CN114001114A - Flexible energy absorption system with concave corner structure - Google Patents

Flexible energy absorption system with concave corner structure Download PDF

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Publication number
CN114001114A
CN114001114A CN202010068049.6A CN202010068049A CN114001114A CN 114001114 A CN114001114 A CN 114001114A CN 202010068049 A CN202010068049 A CN 202010068049A CN 114001114 A CN114001114 A CN 114001114A
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polymer
energy absorption
group
flexible energy
bond
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不公告发明人
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Xiamen Tiance Material Technology Co ltd
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Xiamen Tiance Material Technology Co ltd
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
    • F16F7/00—Vibration-dampers; Shock-absorbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
    • F16F2224/00—Materials; Material properties
    • F16F2224/02—Materials; Material properties solids
    • F16F2224/0225—Cellular, e.g. microcellular foam

Abstract

The invention discloses a flexible energy absorption system with an inner concave angle structure, which is characterized by comprising adjacent holes, wherein at least one side of each hole is opened towards the surface along the thickness direction of the system and is provided with the inner concave angle structure; comprising at least one polymer matrix material having dilatancy properties. The flexible energy absorption system with the inward concave angle structure has extremely wide energy absorption application in the fields of life, production, sports, leisure, entertainment, military affairs, police affairs, security, medical care and the like.

Description

Flexible energy absorption system with concave corner structure
Technical Field
The invention relates to an energy absorption system, in particular to a flexible energy absorption system with an inward concave angle structure.
Background
In practical engineering problems, many shock and vibration problems are involved. Such as military equipment airdrop, car crash, train car crash, elevator stall, spacecraft returnway landing, and the like. In these occasions, too large collision force is necessary to test the safety of the related structures, and in most cases, the impact collision process generates large dynamic stress, so that the mechanical structures are possibly damaged, the safety of personnel in the mechanical structures is harmed, and even huge accidents are caused. In these cases, in order to avoid accidents as much as possible and to protect the mechanical structure and personnel safety of the vehicle to the greatest extent, it is necessary to provide an energy absorbing structure at a suitable location.
Energy absorbing protective materials currently on the market rely primarily on elastomeric foams or relatively soft compressible materials as the energy absorbing material. When the material is applied to human body protection or precision instrument protection, the main defect is that the shock absorption performance is limited, when the material is severely impacted, the common protective material can not effectively dissipate the impact energy or feed back the change condition of the energy, and when the energy exceeds the highest load of the energy absorption material, a strong impact force still acts on a human body or equipment, so that the human body is injured or the equipment is damaged. Therefore, there is a need to develop energy absorbing materials with completely new chemical structures and/or completely new systems for energy absorption to solve the problems in the prior art.
Disclosure of Invention
Against this background, the present invention provides a flexible energy absorbing system with an inside fillet structure, characterized in that it comprises adjacent holes, at least one side of which is open to the surface along the thickness direction of the system and has an inside fillet structure; it contains at least one intrinsically dilatant polymeric matrix material.
In the present invention, the intrinsic dilatant polymer can be used to realize dilatancy by the following methods: dilatant polymers, which are realized by the glass transition of segments in the structure of the polymer itself, are known as "vitrifying dilatant polymers"; dilatant polymers, which are caused by the introduction of dynamic supramolecules and/or dynamic covalent bonds in the structure of the polymer itself, which enable the dilatant process by the dynamic supramolecular action and/or the dynamic dynamics of the dynamic covalent bonds, are known as "dynamic dilatant polymers". In the embodiment of the present invention, the method of achieving the intrinsic dilatancy is not limited to this, and for example, the dilatancy is based on molecular chain entanglement.
In addition, the present invention may optionally contain other dilatant compositions, structures, etc., such as dispersions/components in which solid microparticles are dispersed in a dispersion medium (which may be selected from liquids, solids, gels, emulsions, creams), dilatant dispersions in which the dilatant process is achieved by the fluidity of the dispersion/component, referred to as "dispersive dilatant composition"; by regulating the cell structure of the foam, which is mainly a closed cell structure, but which also contains small-sized open cells, a dilatant polymer structure, which slowly discharges or enters gas when the foam is compressed or recoiled, and thus exhibits dilatant characteristics, is realized, and is referred to as an "aerodynamic dilatant structure". In embodiments of the invention, the method of achieving dilatancy may comprise a combination of two or more different means, including but not limited to physical mixed forms, chemical hybrid forms, the coexistence of physical mixed forms and chemical hybrid forms.
In the present invention, typical strong dynamic covalent bonds include, but are not limited to: boron-containing dynamic covalent bonds, metal acid ester dynamic covalent bonds, dynamic covalent bonds based on reversible free radicals, more preferably saturated five-membered ring organic borate bonds, unsaturated five-membered ring organic borate bonds, saturated six-membered ring organic borate bonds, unsaturated six-membered ring organic borate bonds (especially saturated five-membered ring organic borate bonds/unsaturated five-membered ring organic borate bonds/saturated six-membered ring organic borate bonds/unsaturated six-membered ring organic borate bonds with aminomethyl benzene groups), inorganic borate silicone bonds, organic borate silicone bonds, dynamic titanate silicone bonds; typical strong dynamic supramolecular interactions include, but are not limited to: monodentate hydrogen bonding, bidentate hydrogen bonding, monodentate metal-ligand bonding, bidentate metal-ligand bonding, ionic bonding, ion-dipole bonding, host-guest bonding, metallophilic bonding, dipole-dipole bonding, halogen bonding, lewis acid-base pairing, cation-pi bonding, anion-pi bonding, benzene-fluorobenzene bonding, pi-pi stacking, ionic hydrogen bonding, radical cation dimerization.
In the present invention, the force-sensitive group refers to an entity containing a mechanical force-sensitive moiety (i.e., force-sensitive moiety), wherein the force-sensitive moiety includes, but is not limited to, covalent chemical groups, supramolecular complexes, supramolecular assemblies, compositions, aggregates, which undergo chemical and/or physical changes of structure under mechanical force, including, but not limited to, chemical bond breaking, bonding, isomerization, decomposition, and physical dissociation, disassembly, and separation, thereby directly and/or indirectly generating chemical and/or physical signal changes, generating new groups/new substances, including, but not limited to, color, luminescence, fluorescence, spectral absorption, magnetism, electricity, conductance, heat, nuclear magnetism, infrared, raman, pH, free radical, catalysis, redox, addition, condensation, substitution, exchange, elimination, decomposition, Polymerization, cross-linking, coordination, hydrogen bonding, host-guest bonding, ionic bonding, change of pi-pi stacking signal/performance, ionic bonding, degradation, change of viscosity signal/performance, release of new molecules, generation of new reactive groups, achieving specific response to mechanical force and obtaining force-induced response performance/effect.
According to a preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; wherein the matrix material of the open-cell walls contains an intrinsic dilatant polymer.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the base material of the pore wall of the open pore contains an intrinsic dilatant polymer, and the dilatant polymer is a vitreous dilatant polymer.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the base material of the pore wall of the open pore contains an intrinsic dilatancy polymer, and the dilatancy polymer is a dynamic dilatancy polymer.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the flexible energy absorption system comprises a flexible energy absorption system, wherein a matrix material of the pore walls of the open pores contains an intrinsic dilatancy polymer, and the flexible energy absorption system also contains a dispersive dilatancy polymer.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the flexible energy absorption system comprises a flexible energy absorption system, a flexible energy absorption system and a flexible energy absorption system, wherein the base material of the pore wall of the open pore contains an intrinsic dilatant polymer, and the flexible energy absorption system also contains an aerodynamic dilatant polymer.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; wherein the matrix material of the pore walls of the pores contains an intrinsic dilatant polymer, and wherein the matrix material is a thermoplastic polymer containing side hydrogen bonding.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; wherein the walls of the pores comprise a matrix material comprising an intrinsic dilatant polymer, and wherein the matrix material is a supramolecular polymer free of hydrogen bonds.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the flexible energy absorption system comprises a flexible energy absorption system, a flexible energy absorption system and a flexible energy absorption system, wherein a base material of the pore wall of the pore contains an intrinsic dilatant polymer, the base material contains a thermoplastic polymer with a side hydrogen bond effect, and the flexible energy absorption system also contains a dispersive dilatant polymer.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; wherein the matrix material of the walls of the open cells comprises an intrinsic dilatant polymer, and wherein the matrix material is a covalently cross-linked polymer.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; wherein the matrix material of the pore walls of the pores contains an intrinsic dilatant polymer, and wherein the matrix material is a dynamic covalent cross-linked polymer.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; wherein the matrix material of the pore walls of the open pores contains an intrinsic dilatant polymer, and wherein the matrix material is a hybrid covalently cross-linked polymer.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; wherein, the matrix material of the hole wall of the open hole contains intrinsic dilatant polymer, and the flexible energy absorption system also contains at least one force sensitive group.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the flexible energy absorption system comprises a flexible energy absorption system, a flexible energy absorption system and a flexible energy absorption system, wherein a base material of the pore wall of the pore contains an intrinsic dilatant polymer, the dilatant polymer is a vitreous dilatant polymer, and the flexible energy absorption system also contains at least one force sensitive group.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the flexible energy absorption system comprises a flexible energy absorption system, a flexible energy absorption system and a flexible energy absorption system, wherein a base material of the hole wall of the opening contains an intrinsic dilatancy polymer, the dilatancy polymer is a dynamic dilatancy polymer, and the flexible energy absorption system also contains at least one force sensitive group.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the flexible energy absorption system also comprises a dispersive dilatancy polymer and at least one force sensitive group.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the flexible energy absorption system also comprises an aerodynamic dilatancy polymer, and the flexible energy absorption system also comprises at least one force sensitive group.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the matrix material of the pore wall of the open pore contains an intrinsic dilatant polymer, the matrix material is a thermoplastic polymer containing a side hydrogen bond effect, and the flexible energy absorption system also contains at least one force sensitive group.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the flexible energy absorption system comprises a flexible energy absorption system, a flexible energy absorption system and a flexible energy absorption system, wherein the wall of the opening contains a matrix material containing an intrinsic dilatant polymer, the matrix material is a supramolecular polymer without hydrogen bonds, and the flexible energy absorption system also contains at least one force sensitive group.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the flexible energy absorption system also comprises a dispersive dilatant polymer, and the flexible energy absorption system also comprises at least one force sensitive group.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the flexible energy absorption system comprises a flexible energy absorption system, a flexible energy absorption system and a flexible energy absorption system, wherein a base material of the pore wall of the pore contains an intrinsic dilatant polymer, the base material is a covalent cross-linked polymer, and the flexible energy absorption system also contains at least one force sensitive group.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the flexible energy absorption system comprises a flexible energy absorption system, a flexible energy absorption system and a flexible energy absorption system, wherein a base material of the pore wall of the pore contains an intrinsic dilatant polymer, the base material is a dynamic covalent crosslinked polymer, and the flexible energy absorption system also contains at least one force sensitive group.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the flexible energy absorption system comprises a flexible energy absorption system, a flexible energy absorption system and a flexible energy absorption system, wherein a base material of the pore wall of the pore contains an intrinsic dilatant polymer, the base material is a hybrid covalent cross-linked polymer, and the flexible energy absorption system also contains at least one force sensitive group.
In the present invention, the polymer matrix material for preparing the fillet structure can be selectively added or used as a polymer formulation component by selectively adding or using additives, fillers and swelling agents according to the actual requirements of the preparation process, the forming process, the use performance requirements and the like, which can improve the processing performance of the material, improve the quality and the yield of the product, reduce the product cost or endow the product with certain specific application performance, but the additives or the used substances are not necessary.
The flexible energy absorption system has wide energy absorption application in the fields of life, production, sports, leisure, entertainment, military affairs, police affairs, security, medical care and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a flexible energy absorption system with an inner concave angle structure, which comprises adjacent holes, wherein at least one side of each hole is opened to the surface along the thickness direction of the system and is provided with the inner concave angle structure; it contains at least one intrinsically dilatant polymeric matrix material. When the inner concave angle structure of the hole is stressed, the hole wall is easy to stack, so that the energy absorption system has enough thickness to bear impact objects after being stressed, the impact fracture of materials is avoided, and the impact resistance is greatly improved; the energy absorption system contains at least one intrinsic type dilatancy polymer matrix material, the matrix material forms the hole wall of the energy absorption system, and can directly and rapidly generate dilatancy response to external force when being stressed and impacted, so that the strength of the hole wall is improved while the dilatancy energy absorption is carried out, and the exertion of the structure performance of the inner concave angle is facilitated. Through the design of the concave corner structure and the reasonable selection and design of the polymer matrix material, the energy absorption performance of the energy absorption device is greatly improved and can be adjusted in a large range.
(2) The flexible energy absorption system with the inward concave angle structure provided by the invention contains at least one intrinsic type dilatancy polymer matrix material and optionally other dilatancy components, wherein the dispersive dilatancy components can be dispersed and blended for use, and the energy absorption system with excellent energy absorption performance can be designed and created through organic combination of different dilatancy components. Wherein, various dynamic covalent bonds and supermolecule actions can be contained. Through the introduction of various dynamic covalent bonds and supermolecule effects, the energy absorption structure can show excellent toughness under the action of external force, so that the energy absorption effect with excellent toughness can be obtained; through the dynamic equilibrium reaction in the polymer, the internal defects of the material caused by internal stress can be effectively reduced, so that the obtained energy-absorbing structure has better performance.
(3) The flexible energy absorption system with the inner concave angle structure provided by the invention contains at least one intrinsic dilatancy polymer matrix material and can also contain a force sensitive group, and the force sensitive group and a crosslinking network are combined according to requirements, so that the performances of damping, shock absorption, sound insulation, noise elimination, impact resistance protection and the like of the force-induced response polymer composition can be greatly improved, the characteristics of adjustability, visibility and the like of energy absorption can be realized, the effects of stress enhancement (force-induced crosslinking) and the like can be obtained, and the flexible energy absorption system with the inner concave angle structure has wider energy absorption application in the fields of life, production, movement, leisure, entertainment, military, police affairs, security, medical care and the like.
These and other features and advantages of the present invention will become apparent with reference to the following description of embodiments, examples and appended claims.
Drawings
FIG. 1 is a schematic view of an exemplary reentrant angular configuration of the present invention.
FIG. 2 is a schematic view of an exemplary open-celled reentrant angular configuration of the present invention.
FIG. 3 is a schematic view of an exemplary curved-edge reentrant angular configuration of the present invention.
Detailed Description
A flexible energy absorbing system having a reentrant corner structure, comprising adjacent apertures having at least one side open to a surface along a thickness direction of the system and having a reentrant corner structure; it contains at least one intrinsically dilatant polymeric matrix material.
For simplicity of description, in the description of the present invention, the term "and/or" is used to indicate that the term may include three cases selected from the options described before the conjunction "and/or," or selected from the options described after the conjunction "and/or," or selected from the options described before and after the conjunction "and/or.
The term "energy absorption" used in the present invention refers to absorption, dissipation, dispersion, etc. of energy generated by physical impact in the form of impact, vibration, shock, explosion, sound, etc., but does not include absorption of only thermal energy and/or electrical energy, thereby achieving effects such as impact (protection), damping, shock absorption, buffering, sound insulation, noise elimination, etc.
In the present invention, the term "component" includes both chemical/supramolecular chemical structural components and physically mixed components unless otherwise specified. The term "comprising" is intended to mean either a linkage/bond between chemical structures or a physical mixture of specific structures, unless otherwise specified.
It should be noted that, in the present invention, the terms "group", "series", "subline", "class", "subclass" and "species" used to describe various structures are used to describe groups having a greater scope than the series, a greater scope than the subline, a greater scope than the class, a greater scope than the subclass, and a greater scope than the species, i.e., a group may have a plurality of series, a series may have a plurality of sublines, a subline may have a plurality of classes, a class may have a plurality of subclasses, and a subclass may have a plurality of subclasses. Even if the force sensitive groups, dynamic covalent bonds, supramolecular motifs have the same motif structure, differences in their properties may result due to differences in linkers, substituents, isomers, complex structures, etc. In the present invention, unless otherwise specified, force sensitive groups, dynamic covalent bonds, and supramolecular moieties having the same moiety structure but different structures due to a linker, a substituent, an isomer, a complex structure, and the like are generally regarded as different structures. The invention can reasonably design, select and regulate the force sensitive groups, the dynamic covalent bonds and the supermolecule elements according to the requirements to obtain the best performance, which is also the advantage of the invention. In the present invention, when it is desired to use a plurality of force-sensitive groups, dynamic covalent bonds or supramolecular motif structures, it is preferable to use structures of different classes, more preferably structures of different series, for better orthogonal/coordinated regulation or the like.
The term "polymerization" reaction/action as used in the present invention, unless otherwise specified, refers to a process in which a reactant of lower molecular weight forms a product of higher molecular weight by polycondensation, polyaddition, ring-opening polymerization, or the like, i.e., a chain extension process/action other than crosslinking. The reactant may be a monomer, oligomer, prepolymer, or other compound having a polymerization ability (i.e., capable of polymerizing spontaneously or under the action of an initiator or an external energy). The product resulting from the polymerization of one reactant is called a homopolymer. It is to be noted that the "polymerization" referred to in the present invention includes a linear growth process, a branching process, a ring formation process, etc. of a reactant molecular chain other than the crosslinking process of the reactant molecular chain; in an embodiment of the invention, "polymerization" includes a chain growth process caused by the bonding of covalent bonds as well as the non-covalent interaction of supramolecular interactions.
The term "crosslinking" reaction/action as used in the present invention refers to the process of intermolecular and/or intramolecular formation of a product having a three-dimensional infinite network type by covalent bond and/or supramolecular action. During the crosslinking process, the polymer chains generally grow continuously in two/three dimensions, gradually form clusters (which may be two-dimensional or three-dimensional), and then develop into a three-dimensional infinite network. Thus, crosslinking can be considered a special form of polymerization. The degree of crosslinking, just before a three-dimensional infinite network is reached during crosslinking, is called the gel point, also called the percolation threshold. A crosslinked product above the gel point (inclusive, the same applies hereinafter) having a three-dimensional infinite network structure, the crosslinked network constituting a whole and spanning the entire polymer structure; the crosslinked product below the gel point, which is only a loose inter-chain linking structure, does not form a three-dimensional infinite network structure, and does not belong to a crosslinked network that can constitute a whole across the entire polymer structure. Unless otherwise specified, the crosslinked structure in the present invention is a three-dimensional infinite network structure above the gel point, and the non-crosslinked structure includes linear and nonlinear structures with a degree of crosslinking of zero and a two-dimensional/three-dimensional cluster structure below the gel point.
In the present invention, "backbone" refers to a structure in the chain length direction of a polymer chain. For crosslinked polymers, the term "backbone" refers to any segment present in the backbone of the crosslinked network, i.e., the backbone chain in the crosslinked network that connects adjacent crosslinks. For polymers of non-crosslinked structure, the "backbone", unless otherwise specified, refers to the chain with the most mer. Wherein, the side chain refers to a chain structure which is connected with the main chain of the polymer and is distributed beside the main chain; the "branched chain"/"branched chain" may have a side chain or other chain structure branched from any chain. Wherein, the "side group" refers to a chemical group which is connected with any chain of the polymer and is arranged beside the chain. Wherein, the "terminal group" refers to a chemical group attached to any chain of the polymer and located at the end of the chain. Unless otherwise specified, a pendant group refers specifically to groups and subgroups thereof having a molecular weight of not more than 1000Da attached to the side of the backbone of the polymer chain. When the molecular weight of the side chain, branched chain, does not exceed 1000Da, itself and the groups thereon are considered side groups. For simplicity, when the molecular weight of the side chain, branched chain, exceeds 1000Da, they are collectively referred to as side chains unless otherwise specified. The "side chain" and "side group" may have a multi-stage structure, that is, the side chain/side group may be continued to have a side chain/side group, and the side chain/side group of the side chain/side group may be continued to have a side chain/side group. In the present invention, for hyperbranched and dendritic chains and their related chain structures, the outermost polymer segment may be regarded as a side chain, and the rest as a main chain.
In the present invention, the reentrant angular structure refers to a polygonal and/or circular arc structure with inward reentrant angles. The concave polygon/arc-shaped structure can be regulated and controlled by changing the number of the polygon/arc-shaped topological structures and the number of the concave structures, and the curved edge concave angle type structure can be obtained by changing the shape of the cell wall of the concave polygon/arc-shaped topological structure on the premise of not changing the polygon/arc-shaped topological structure. The structure includes, but is not limited to, those illustrated in fig. 1 to 3.
In the invention, when the inner concave angle structure of the hole is stressed, the hole wall is easy to stack, so that the energy absorption system has enough thickness to bear impact objects after being stressed, the impact fracture of materials is avoided, and the impact resistance is greatly improved.
In the invention, the intrinsic dilatancy polymer means that the polymer has dilatancy and can have dilatancy without compounding, filling, dispersing and other methods with non-polymer components; the extrinsic dilatant polymer needs to be obtained by preparing a composite material, a composition or the like by compounding, filling, dispersing or the like. It should be noted that, in the present invention, an intrinsic dilatant polymer matrix may also be a polymer, which may be a composite of an intrinsic dilatant polymer and an extrinsic dilatant polymer. Furthermore, when non-covalent forces are formed between the components of a polymer composition and dilatancy occurs through the non-covalent forces, the composition is also considered to be an intrinsically dilatant polymer. The intrinsic dilatant polymer (composition) can show creep property or slow rebound property under specific conditions, namely, the polymer can deform when being subjected to external force; after the external force is removed, the material can not rebound; or not immediately but slowly rebounded/recovered with no or only a small residual deformation. In the present invention, the matrix of the energy absorbing structure may or may not contain an intrinsic dilatant polymer, by blending with non dilatant polymers and/or fillers, etc. and/or by network interpenetration. When the matrix of the composite of the energy absorbing structure does not contain an intrinsic dilatant polymer, it may still have dilatancy but may or may not exhibit creep or slow rebound characteristics, or have lower creep or slow rebound, or only high rebound.
In the present invention, when the dilatant polymer is in the form of an elastomer, a gel or a fluid, it preferably has a ball Rebound of less than 80%, more preferably a Rebound of less than 50%, still more preferably less than 25%, still more preferably less than 10%, wherein the test method is ASTM D-2632 "Rubber Property-Resilience by Vertical Rebound" (ASTM D-2632 "Rubber Property-Vertical Rebound"); when the foam is in its form, it preferably has a ball rebound of less than 25%, more preferably less than 10%, more preferably less than 5%, still more preferably less than 1%, wherein the Test method is ASTM D-3574H "Flexible Cellular Materials Slab, Bonded and molded urethane Foams, TestH, Resilience (ball rebound) Test" (ASTM D-3574H, "Flexible Cellular Material-Panel, Bonded and molded polyurethane Foams, Test H, rebound (ball rebound) Test").
In the present invention, the ball rebound resilience is a ratio of a rebound height to a drop height at which a steel ball of a predetermined mass and shape is dropped on a sample surface. That is, a steel ball with a specified mass and shape is dropped onto the surface of a sample from a fixed height, the rebound height of the steel ball is measured, and the percentage of the ratio of the rebound height (denoted as H) to the drop height (denoted as H) is calculated as the rebound ratio (denoted as R) of the sample, which can be calculated by the following formula:
The rebound resilience R is H/H100 percent; wherein h is the rebound height in millimeters (mm); h is the drop height in millimeters (mm).
In the present invention, the time of rebound at normal temperature and pressure of the dilatant polymer having slow rebound is not particularly limited. For an intrinsic polymer having slow rebound resilience, the rebound time is preferably from 0.5 to 120 seconds, more preferably from 1 to 60 seconds, and further preferably from 1 to 10 seconds. For the composite type having slow rebound resilience, the rebound time is preferably from 0.1 to 120 seconds, more preferably from 0.2 to 60 seconds, further preferably from 0.5 to 10 seconds. Wherein, the rebound time refers to the time required for basically restoring the test sample after applying pressure to the sample to cause the sample to generate specified deformation and keeping the specified time.
In the present invention, the intrinsic dilatant polymer can be used to realize dilatancy by the following methods: dilatant polymers, which are realized by the glass transition of segments in the structure of the polymer itself, are known as "vitrifying dilatant polymers"; dilatant polymers, which are caused by the introduction of dynamic supramolecules and/or dynamic covalent bonds in the structure of the polymer itself, which enable the dilatant process by the dynamic supramolecular action and/or the dynamic dynamics of the dynamic covalent bonds, are known as "dynamic dilatant polymers". In the embodiment of the present invention, the method of achieving the intrinsic dilatancy is not limited to this, and for example, the dilatancy is based on molecular chain entanglement.
In the present invention, the energy absorbing system comprises at least one intrinsically dilatant polymer matrix material, i.e. the polymer matrix material of the energy absorbing system comprises at least one of the intrinsically polymer materials. When the polymer matrix material forms the hole wall of the energy absorption system, the polymer matrix material can directly and rapidly generate the dilatant response to external force when being stressed and impacted, the strength of the hole wall is improved while the dilatant energy absorption is carried out, and the exertion of the structure performance of the inner concave angle is facilitated.
In addition, the present invention may optionally contain other dilatant compositions, structures, etc., such as dispersions/components in which solid microparticles are dispersed in a dispersion medium (which may be selected from liquids, solids, gels, emulsions, creams), dilatant dispersions in which the dilatant process is achieved by the fluidity of the dispersion/component, referred to as "dispersive dilatant composition"; by regulating the cell structure of the foam, which is mainly a closed cell structure, but which also contains small-sized open cells, a dilatant polymer structure, which slowly discharges or enters gas when the foam is compressed or recoiled, and thus exhibits dilatant characteristics, is realized, and is referred to as an "aerodynamic dilatant structure". In embodiments of the invention, the method of achieving dilatancy may comprise a combination of two or more different means, including but not limited to physical mixed forms, chemical hybrid forms, the coexistence of physical mixed forms and chemical hybrid forms.
In the present invention, the glassy dilatant polymer has at least one or more glass transition temperatures. In the present invention, having the glass transition temperature is one of the requirements for achieving room temperature dilatancy of the polymer of the present invention, i.e., the dilatancy utilizes at least the glass transition of the polymer, particularly the glass transition of its soft segment structure. The glass transition temperature refers to a transition temperature at which a polymer is transformed from a brittle glass state to an elastic rubbery state, that is, a temperature at which a glass transition occurs, and may be a temperature point or a temperature range (also referred to as a glass transition region). When the temperature of the polymer is reduced to be lower than Tg, the molecular chain and chain segment movement of the polymer are frozen and are shown as brittleness; as the temperature of the polymer rises and exceeds the Tg of the polymer, both molecular chains and chain segments of the polymer can move, and the polymer shows high viscoelasticity or rubbery high elasticity; in the vicinity of Tg, the polymer generates softening movement through the segmental motion of the polymer, molecular chains do not move or the movement is limited, good viscoelasticity is shown, and therefore, the dilatancy performance is obtained. When the Tg of the polymer/s is close to room temperature, the polymer shows room temperature dilatancy, namely, the dilatancy of the polymer can be maximized by regulating the glass transition temperature of the polymer to be close to room temperature, namely, the vitrifiability of the polymer can be realized.
In the present invention, the glass transition temperature (Tg) of the polymer can be measured by a known test method by those skilled in the art. At least the glass transition temperature can be measured by a method commonly used in the art, such as Differential Scanning Calorimetry (DSC), dynamic mechanical analysis/Dynamic Mechanical Analysis (DMA), and dynamic mechanical thermal analysis/Dynamic Mechanical Thermal Analysis (DMTA), for example.
In the present invention, the glass-swellable polymer may have only one glass transition temperature or a plurality of glass transition temperatures, and the soft segment thereof has at least one glass transition temperature of-40 ℃ to 60 ℃. The temperature range (temperature span) of any one of the glass transition temperatures is not particularly limited. When the glass transition temperature range is wide, the polymer can realize viscoelastic transition in a wide temperature range, so that a wide dilatancy temperature range is obtained, the temperature sensitivity of the dilatancy polymer is reduced, and the problem of polymer hardening caused by temperature reduction (namely, the problem of low-temperature hardening) can be avoided to a certain extent; when the glass transition temperature range is narrow, the dilatancy temperature range of the polymer is narrow, the temperature controllability is better, and the temperature dependence is higher.
In the invention, the glass transition temperature of the polymer can be regulated and controlled by regulating the chemical composition and the topological structure of the soft segment of the polymer to be close to the use temperature of the dilatant material, so as to obtain the maximized dilatant/viscoelasticity.
In the embodiment of the present invention, the chemical composition of the polymer/soft segment is not particularly limited, and is selected from, but not limited to, polymer segments whose main chains are carbon chain structures, carbon hetero chain structures, carbon element chain structures, element hetero chain structures, and carbon hetero element chain structures, and preferably carbon chain structures, carbon hetero chain structures, element hetero chain structures, and carbon hetero element chain structures, because the raw materials are easily available and the preparation technology is mature. By way of example, the soft segment polymer chain backbone may be a segment based on the following polymers, but the invention is not limited thereto: homopolymers, copolymers, modifications, derivatives and the like of acrylate polymers, saturated olefin polymers, unsaturated olefin polymers, halogen-containing olefin polymers, polyacrylonitrile polymers, polyvinyl alcohol polymers, polyether polymers, polyester polymers, biopolyester polymers, epoxy polymers, polythioether polymers, silicone polymers and the like; preferred are homopolymers, copolymers, modified products, and derivatives of unsaturated olefin polymers, polyether polymers, epoxy polymers, polysulfide polymers, and polyorganosiloxane polymers. By way of example, the soft segment polymer chain backbone may be a segment based on the following polymers, but the invention is not limited thereto: homopolymers, copolymers, modifications, and derivatives of polyethylene, polyvinyl acetate, polyethylacrylate, polybutylacrylate, polyoctyl acrylate, polyvinylmethylether, polyvinylethylether, ethylene-propylene copolymer, polyisobutylene, polychloroprene, poly cis-1, 4-isoprene, poly trans-1, 4-isoprene, styrene-butadiene copolymer, polynorbornene, polyoxymethylene, polyethylene oxide, polypropylene oxide, polytetrahydrofuran, ethylene oxide-propylene oxide copolymer (such as polyethylene oxide-polypropylene oxide copolymer), polydimethylsiloxane, polydiethylsiloxane, polydiphenylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, and hydrogenpolysiloxane.
In the invention, the vitrification dilatancy caused by polymer vitrification has the characteristic of strong controllability of the working temperature range, and is convenient for obtaining the dilatancy material with a specific working temperature range.
In the invention, the dynamic dilatant polymer may only contain strong dynamic supramolecular action, may only contain strong dynamic covalent bond, or may contain both strong dynamic supramolecular action and strong dynamic covalent bond.
In the embodiment of the present invention, it is preferable that the group constituting the strong dynamic unit in the dynamic dilatant polymer is located in the terminal group, pendant group or side chain of the common covalent cross-linked network/weak dynamic covalent cross-linked network/weak dynamic supramolecular cross-linked network/weak dynamic hybrid dynamic cross-linked network, or exists in the form of polymer in the polymer structure layer, so as to obtain better dynamic property and dilatant property.
In the invention, the dynamic dilatancy caused by the supermolecule and/or dynamic covalent bond with strong dynamics has the characteristics of rich regulation and control means, high dynamic transformation speed and the like.
In the invention, the dynamic constants of the strong dynamic covalent bond and the strong dynamic supermolecule action are generally more than 10^ -5s -1Preferably 100000-0.0001s-1The amount of the surfactant is preferably 1000-0.001s as required according to different performance requirements and application occasions-1Preferably in the range of 100 to 0.01s-1It is also preferably 10 to 0.1s-1. The polymer can show dynamic reversibility under mild conditions, and is beneficial to enabling a dynamic polymer to obtain a dilatant effect, so that a more excellent energy absorption effect is obtained, self-repairability is more easily obtained, and a more uniformly activated polymer is more easily obtained. The dynamic constant of the weak dynamic covalent bond and the weak dynamic supermolecule action is generally less than 10^ -5s-1Which generally require specific conditions (e.g., heat, light, specific pH, catalyst, etc.) to be effectiveThe dynamic property is embodied, and the dynamic bonding-dissociation balance is not generated under the conditions of material working temperature, no external field action and the like. Different kinetic constants are combined with different polymer structures, such as cross-linking degree, polymer chain topology, cross-linked network topology, glass transition temperature, composite structure and the like, so that different force action response rates can be provided, different viscous loss increase, viscous-elastic transition or elastic enhancement can be generated, and different energy absorption effects and rebound responses can be generated. The technical scheme of the invention can skillfully and effectively design and regulate the dynamic dilatancy by designing and selecting a proper dynamic structure and a proper polymer structure so as to meet the requirements of different performances in different occasions to the maximum extent. For example, higher rates meet higher cushioning requirements for older shoes, lower rates meet the requirements for both high rebound and cushioning for sprints, jumps, etc., lower rates meet low creep requirements for shock absorption for precision instruments, and so forth.
In embodiments of the present invention, typical strong dynamic supramolecular interactions include, but are not limited to: a monodentate hydrogen bonding action, a bidentate hydrogen bonding action, a monodentate metal-ligand action, a bidentate metal-ligand action, an ionic clustering action, an ion-dipole action, a host-guest action, a metallophilic action, a dipole-dipole action, a halogen bonding action, a lewis acid-base pair action, a cation-pi action, an anion-pi action, a benzene-fluorobenzene action, a pi-pi stacking action, an ionic hydrogen bonding action, a radical cation dimerization; typical strong dynamic covalent bonds include, but are not limited to: boron-containing dynamic covalent bonds, metal acid ester dynamic covalent bonds, and reversible free radical-based dynamic covalent bonds. Among them, preferred are a bidentate hydrogen bond action, a bidentate metal-ligand action, an ionic cluster action, an ion-dipole action, a host-guest action, a Lewis acid-base pair action, an ionic hydrogen bond action, an inorganic boronic acid monoester bond, a saturated five-membered ring inorganic boronic acid ester bond, an unsaturated five-membered ring inorganic boronic acid ester bond, a saturated six-membered ring inorganic boronic acid ester bond, an unsaturated six-membered ring inorganic boronic acid ester bond, an organic boronic acid monoester bond, a saturated five-membered ring organic boronic acid ester bond, an unsaturated five-membered ring organic boronic acid ester bond, a saturated six-membered ring organic boronic acid ester bond, an unsaturated six-membered ring organic boronic acid ester bond (particularly, a saturated five-membered ring organic boronic acid ester bond/an unsaturated five-membered ring organic boronic acid ester bond/a saturated six-membered ring organic boronic acid ester bond/an unsaturated six-membered ring organic boronic acid ester bond) to which is linked to an aminomethyl benzene group, Inorganic borate silicone bonds, organic borate silicone bonds, dynamic titanate silicone bonds, more preferably a one-tooth hydrogen bonding action, a two-tooth hydrogen bonding action, a one-tooth metal-ligand action, an ionic action, an ion-dipole action, a host-guest action, an ionic hydrogen bonding action, an inorganic borate monoester bond, an organic borate monoester bond, a saturated five-membered ring organic borate bond/an unsaturated five-membered ring organic borate bond/a saturated six-membered ring organic borate bond/an unsaturated six-membered ring organic borate bond, an inorganic borate silicone bond, an organic borate silicone bond, a dynamic titanate silicone bond, because of high dynamic and good controllability.
In the invention, the boron-containing dynamic covalent bond contains boron atoms in the dynamic structure composition, and includes but is not limited to fifteen types of bonds, i.e. organic boron anhydride bond, inorganic boron anhydride bond, organic-inorganic boron anhydride bond, saturated five-membered ring organic borate bond, unsaturated five-membered ring organic borate bond, saturated six-membered ring organic borate bond, unsaturated six-membered ring organic borate bond, saturated five-membered ring inorganic borate bond, unsaturated five-membered ring inorganic borate bond, saturated six-membered ring inorganic borate bond, unsaturated six-membered ring inorganic borate bond, organic borate monoester bond, inorganic borate monoester bond, organic borate silicone bond and inorganic borate silicone bond; wherein, each boron-containing dynamic covalent bond can comprise a plurality of boron-containing dynamic covalent bond structures. When two or more boron-containing dynamic covalent bonds are selected, the boron-containing dynamic covalent bonds can be selected from different structures in the same type of boron-containing dynamic covalent bonds, and also can be selected from different structures in different types of boron-containing dynamic covalent bonds, wherein, in order to achieve orthogonal and/or synergistic dynamic performance, the boron-containing dynamic covalent bonds are preferably selected from different structures in different types of boron-containing dynamic covalent bonds.
In the present invention, the organoboron anhydride linkages are selected from, but not limited to, at least one of the following structures:
Figure BDA0002376545090000081
wherein each boron atom in the organoboron anhydride linkage is connected to at least one carbon atom by a boron-carbon bond, and at least one organic group is connected to the boron atom by said boron-carbon bond;
Figure BDA0002376545090000082
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; difference in the same boron atom
Figure BDA0002376545090000083
Can be linked to form a ring, on different boron atoms
Figure BDA0002376545090000084
May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical organoboronic anhydride bond structures may be exemplified by:
Figure BDA0002376545090000085
in the embodiment of the present invention, the organoboron anhydride linkages, which may be formed by reacting organoboronic acid moieties contained in the compound starting materials with organoboronic acid moieties, may be introduced into the polymer by polymerization/crosslinking reactions between the reactive groups contained in the compound starting materials containing organoboron anhydride linkages.
In the present invention, the inorganic boron anhydride linkage is selected from, but not limited to, the following structures:
Figure BDA0002376545090000086
wherein, Y1、Y2、Y3、Y4Each independently selected from hydrogenAn atom, fluorine atom, chlorine atom, bromine atom, iodine atom, oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom, preferably from oxygen atom, and Y 1、Y2At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom, Y3、Y4At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom;
Figure BDA0002376545090000087
denotes a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein a, b, c, d denote each independently of Y1、Y2、Y3、Y4The number of connected connections; when Y is1、Y2、Y3、Y4When each is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom, a, b, c and d are 0; when Y is1、 Y2、Y3、Y4When each is independently selected from oxygen atom and sulfur atom, a, b, c and d are 1; when Y is1、Y2、Y3、Y4When each is independently selected from nitrogen atom and boron atom, a, b, c and d are 2; when Y is1、Y2、Y3、Y4When each is independently selected from silicon atoms, a, b, c and d are 3; difference on the same atom
Figure BDA0002376545090000099
Can be linked to form a ring, on different atoms
Figure BDA00023765450900000910
May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical inorganic boron anhydride bond structures are exemplified by:
Figure BDA0002376545090000091
in the embodiment of the present invention, the inorganic boron anhydride bond may be formed by the reaction of an inorganic boric acid moiety contained in the compound raw material with an inorganic boric acid moiety, or may be introduced into the polymer by the polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing an inorganic boron anhydride bond.
In the present invention, the organic-inorganic boron anhydride linkage is selected from, but not limited to, the following structures:
Figure BDA0002376545090000092
wherein, Y1、Y2Each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a silicon atom, preferably from an oxygen atom, and Y1、Y2At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom; wherein, the boron atom in the structure is connected with at least one carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond;
Figure BDA00023765450900000911
denotes a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein a, b denote independently from Y1、Y2The number of connected connections; when Y is1、Y2When each is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom, a and b are 0; when Y is1、Y2When each is independently selected from oxygen atom and sulfur atom, a and b are 1; when Y is1、Y2When each is independently selected from nitrogen atom and boron atom, a and b are 2; when Y is1、Y2When each is independently selected from silicon atoms, a, b is 3; difference on the same atom
Figure BDA00023765450900000912
Can be linked to form a ring, on different atoms
Figure BDA00023765450900000913
May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical organic-inorganic boron anhydride bond structures may be exemplified by:
Figure BDA0002376545090000093
In embodiments of the present invention, the organic-inorganic boron anhydride linkages, which may be formed by reaction of organic boronic acid moieties contained in the compound starting materials with inorganic boronic acid moieties, may also be introduced into the polymer by polymerization/crosslinking reactions between the reactive groups contained therein using compound starting materials containing organic-inorganic boron anhydride linkages.
In the invention, the saturated five-membered ring organic boric acid ester bond is selected from but not limited to the following structures:
Figure BDA0002376545090000094
wherein the boron atom is connected with a carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond;
Figure BDA00023765450900000914
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; different on the same carbon atom
Figure BDA00023765450900000915
Can be linked to form a ring, on different carbon atoms
Figure BDA00023765450900000916
And may be linked to form a ring, including but not limited to aliphatic rings, ether rings, condensed rings, and combinations thereof. Typical saturated five-membered ring organoborate bond structures may be exemplified by:
Figure BDA0002376545090000095
in the embodiment of the present invention, the saturated five-membered ring organic boronic acid ester bond can be formed by reacting a 1, 2-diol moiety contained in the compound raw material with an organic boronic acid moiety, or a polymer can be introduced by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing a saturated five-membered ring organic boronic acid ester bond.
In the invention, the unsaturated five-membered ring organic boric acid ester bond is selected from but not limited to the following structures:
Figure BDA0002376545090000096
wherein the boron atom is connected with a carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond;
Figure BDA0002376545090000097
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom;
Figure BDA0002376545090000098
an aromatic ring of any number of members, preferably from a six-membered ring, containing two adjacent carbon atoms in the aromatic ring, which is located in an unsaturated five-membered ring organoboronate bond; the hydrogen atom on the aromatic ring-forming atom may be substituted with any substituent or may not be substituted. Typical unsaturated five-membered ring organoborate bond structures may be exemplified by:
Figure BDA0002376545090000101
in the embodiment of the present invention, the unsaturated five-membered ring organic borate bond may be formed by reacting an ortho-diphenol moiety contained in the compound raw material with an organic borate moiety, or may be introduced into a polymer by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing an unsaturated five-membered ring organic borate bond.
In the present invention, the saturated six-membered ring organic borate bond is selected from, but not limited to, the following structures:
Figure BDA0002376545090000102
Wherein the boron atom is connected with a carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond;
Figure BDA0002376545090000109
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; different on the same carbon atom
Figure BDA00023765450900001010
Can be linked to form a ring, on different carbon atoms
Figure BDA00023765450900001011
And may be linked to form a ring, including but not limited to aliphatic rings, ether rings, condensed rings, and combinations thereof. Typical saturated six-membered ring organoboronate bond structures may be exemplified by:
Figure BDA0002376545090000103
in the embodiment of the present invention, the saturated six-membered ring organoboronate bond may be formed by reacting a 1, 3-diol moiety contained in a compound raw material with an organoboronate moiety, or may be introduced into a polymer by polymerization/crosslinking reaction between reactive groups contained in a compound raw material containing a saturated six-membered ring organoboronate bond.
In the present invention, the unsaturated six-membered ring organic borate bond is selected from, but not limited to, the following structures:
Figure BDA0002376545090000104
wherein the boron atom is connected with a carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond;
Figure BDA0002376545090000105
Represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom;
Figure BDA0002376545090000106
an aromatic ring of any number of members, preferably from a six-membered ring, containing two adjacent carbon atoms in the aromatic ring, which is located in an unsaturated six-membered ring organoboronate bond; the hydrogen atom on the aromatic ring-forming atom may be substituted with any substituent or not; different on the same carbon atom
Figure BDA00023765450900001012
Can be linked to form a ring, on different carbon atoms
Figure BDA00023765450900001013
Or can be connected into a ring. Typical unsaturated six-membered ring organoboronate bond structures may be exemplified by:
Figure BDA0002376545090000107
in the embodiment of the present invention, the unsaturated six-membered ring organoboronate bond may be formed by reacting a 2-hydroxymethylphenol moiety contained in the compound raw material with an organoboronate moiety, or may be introduced into a polymer by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing an unsaturated six-membered ring organoboronate bond.
In the present invention, the saturated five-membered ring organoboronAcid ester bond, unsaturated five-membered ring organic borate bond, saturated six-membered ring organic borate bond, unsaturated six-membered ring organic borate bond, wherein the structure of the ester bond is that boron atom is preferably bonded with aminomethyl benzene group (b)
Figure BDA0002376545090000108
Indicates the position to which the boron atom is attached); the organic boric acid units for forming the saturated five-membered ring organic boric acid ester bond, the unsaturated five-membered ring organic boric acid ester bond, the saturated six-membered ring organic boric acid ester bond and the unsaturated six-membered ring organic boric acid ester bond are preferably aminomethyl phenylboronic acid (ester) units.
As the aminomethyl phenylboronic acid (ester) element has higher reaction activity when reacting with the 1, 2-diol element and/or the catechol element and/or the 1, 3-diol element and/or the 2-hydroxymethylphenol element, the formed boron-containing dynamic covalent bond has stronger dynamic reversibility, can perform dynamic reversible reaction under milder neutral conditions, can show sensitive dynamic characteristics and obvious energy absorption effect, and can embody greater advantages when being used as an energy absorption material.
Typical structures of such boron-containing dynamic covalent bonds with aminomethyl benzene groups are exemplified by:
Figure BDA0002376545090000111
in the invention, the saturated five-membered ring inorganic borate ester bond is selected from but not limited to at least one of the following structures:
Figure BDA0002376545090000112
wherein, Y1Selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom;
Figure BDA0002376545090000118
represents a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein a represents a linkage to Y 1The number of connected connections; when Y is1When the atom is selected from oxygen atom and sulfur atom, a is 1; when Y is1When the atom is selected from nitrogen atom and boron atom, a is 2; when Y is1When selected from silicon atoms, a is 3; different on the same carbon atom
Figure BDA0002376545090000119
Can be linked to form a ring, on different carbon atoms
Figure BDA00023765450900001110
And may be linked to form a ring, including but not limited to aliphatic rings, ether rings, condensed rings, and combinations thereof. Typical saturated five-membered ring inorganic borate bond structures are exemplified by:
Figure BDA0002376545090000113
in the embodiment of the present invention, the saturated five-membered ring inorganic borate bond may be formed by reacting a 1, 2-diol moiety contained in the compound raw material with an inorganic borate moiety, or a polymer may be introduced by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing a saturated five-membered ring inorganic borate bond.
In the present invention, the unsaturated five-membered ring inorganic borate ester bond is selected from, but not limited to, at least one of the following structures:
Figure BDA0002376545090000114
wherein, Y1Selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom;
Figure BDA00023765450900001111
represents a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein a represents a linkage to Y 1The number of connected connections; when Y is1When the atom is selected from oxygen atom and sulfur atom, a is 1; when Y is1When the atom is selected from nitrogen atom and boron atom, a is 2; when Y is1When selected from silicon atoms, a is 3;
Figure BDA0002376545090000115
an aromatic ring of any number of members, preferably from a six-membered ring, containing two adjacent carbon atoms in the aromatic ring, which is located in an unsaturated five-membered ring inorganic borate bond; the hydrogen atom on the aromatic ring-forming atom may be substituted with any substituent or may not be substituted. Typical unsaturated five-membered ring inorganic borate bond structures may be exemplified by:
Figure BDA0002376545090000116
in the embodiment of the present invention, the unsaturated five-membered ring inorganic borate bond may be formed by reacting an ortho-diphenol moiety contained in the compound raw material with an inorganic borate moiety, or may be introduced into a polymer by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing an unsaturated five-membered ring inorganic borate bond.
In the present invention, the saturated six-membered ring inorganic borate bond is selected from, but not limited to, at least one of the following structures:
Figure BDA0002376545090000117
wherein, Y1Selected from oxygen atoms, sulphur atoms, nitrogen atoms, boron atoms, silicon atoms, preferably oxygen atoms;
Figure BDA00023765450900001112
represents a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein a represents a linkage to Y 1The number of connected connections; when Y is1When the atom is selected from oxygen atom and sulfur atom, a is 1; when Y is1When the atom is selected from nitrogen atom and boron atom, a is 2; when Y is1When selected from silicon atoms, a is 3; of the same carbon atomDifference in
Figure BDA00023765450900001113
Can be linked to form a ring, on different carbon atoms
Figure BDA00023765450900001114
And may be linked to form a ring, including but not limited to aliphatic rings, ether rings, condensed rings, and combinations thereof. Typical saturated six-membered ring inorganic borate bond structures may be exemplified by:
Figure BDA0002376545090000121
in the embodiment of the present invention, the saturated six-membered ring inorganic borate bond may be formed by reacting a 1, 3-diol moiety contained in the compound raw material with an inorganic borate moiety, or a polymer may be introduced by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing a saturated six-membered ring inorganic borate bond.
In the present invention, the unsaturated six-membered ring inorganic borate bond is selected from, but not limited to, at least one of the following structures:
Figure BDA0002376545090000122
wherein, Y1Selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom;
Figure BDA0002376545090000126
represents a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein a represents a linkage to Y 1The number of connected connections; when Y is1When the atom is selected from oxygen atom and sulfur atom, a is 1; when Y is1When the atom is selected from nitrogen atom and boron atom, a is 2; when Y is1When selected from silicon atoms, a is 3;
Figure BDA0002376545090000127
an aromatic ring of any number of members, preferably from a six-membered ring, containing two adjacent carbon atoms in the aromatic ring, which is located in an unsaturated six-membered ring inorganic borate bond; the hydrogen atom on the aromatic ring-forming atom may be substituted with any substituent or not; different on the same carbon atom
Figure BDA0002376545090000128
Can be linked to form a ring, on different carbon atoms
Figure BDA0002376545090000129
Or can be connected into a ring. Typical unsaturated six-membered ring inorganic borate bond structures are exemplified by:
Figure BDA0002376545090000123
in the embodiment of the present invention, the unsaturated six-membered ring inorganic borate bond may be formed by reacting a 2-hydroxymethylphenol moiety contained in the compound raw material with an inorganic borate moiety, or may be introduced into a polymer by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing an unsaturated six-membered ring inorganic borate bond.
In the invention, the organoboronic acid monoester bond is selected from but not limited to at least one of the following structures:
Figure BDA0002376545090000124
wherein the boron atom is linked to at least one carbon atom by a boron-carbon bond and at least one organic group is linked to the boron atom by said boron-carbon bond; i is 1Selected from divalent linking groups; i is2Selected from the group consisting of a double bond directly attached to two carbon atoms, a trivalent carbene group directly attached to two carbon atoms
Figure BDA00023765450900001210
A divalent non-carbon atom, a linking group containing at least two backbone atoms;
Figure BDA00023765450900001211
an aromatic ring of any number of members, preferably selected from six-membered rings; the hydrogen atom on the aromatic ring-forming atom may be substituted with any substituent or not;
Figure BDA00023765450900001212
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; different in the same carbon atom, boron atom
Figure BDA00023765450900001213
Can be connected into a ring, on different carbon atoms and boron atoms
Figure BDA00023765450900001214
Can also be connected into a ring or can be connected with I1、I2The substituent atoms (substituents) in the (A) form a ring together, the ring comprises but is not limited to an aliphatic ring, an ether ring, a condensation ring and a combination thereof, wherein the organic boric acid single ester bond formed after the 6 and 7 structures form the ring is not the saturated five-membered ring organic boric acid ester bond, the unsaturated five-membered ring organic boric acid ester bond, the saturated six-membered ring organic boric acid ester bond and the unsaturated six-membered ring organic boric acid ester bond which are described in the previous description. Typical organic boronic acid monoester bond structures are exemplified by:
Figure BDA0002376545090000125
in the embodiment of the present invention, the organoboronate monoester bond may be formed by reacting a monol moiety contained in a compound raw material with an organoboronic acid moiety, or a polymer may be introduced by polymerization/crosslinking reaction between reactive groups contained in a compound raw material containing an organoboronate monoester bond.
In the present invention, the inorganic boronic acid monoester bond is selected from, but not limited to, at least one of the following structures:
Figure BDA0002376545090000131
wherein, Y1～Y13Each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a silicon atom, preferably from an oxygen atom, and Y1、Y2；Y3、Y4；Y5、Y6、Y7、Y8；Y9、Y10、Y11、Y12At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom; y is14Selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom; i is1Selected from divalent linking groups; i is2Selected from the group consisting of a double bond directly attached to two carbon atoms, a trivalent carbene group directly attached to two carbon atoms
Figure BDA0002376545090000132
A divalent non-carbon atom, a linking group containing at least two backbone atoms;
Figure BDA0002376545090000137
represents a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein a to n each represent a linkage to Y1～Y14The number of connected connections; when Y is1～Y13When each is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom, a-m is 0; when Y is1～Y14When each is independently selected from oxygen atom and sulfur atom, a to n are 1; when Y is1～Y14When each is independently selected from nitrogen atom and boron atom, a to n are 2; when Y is1～Y14Each independently selected from silicon atoms, a to n is 3;
Figure BDA0002376545090000138
An aromatic ring having an arbitrary number of elements, preferably from six-memberedA ring; the hydrogen atom on the aromatic ring-forming atom may be substituted with any substituent or not; different on the same carbon atom
Figure BDA0002376545090000139
Can be linked to form a ring, on different carbon atoms
Figure BDA00023765450900001310
Can also be connected into a ring or can be connected with I1、I2The substituted atoms (substituents) in the (A) form a ring together, the ring comprises but is not limited to aliphatic ring, ether ring, condensed ring and combination thereof, wherein the inorganic boric acid monoester bond formed after the 5, 6, 7 and 8 structures form the ring is not the saturated five-membered ring inorganic boric acid ester bond, the unsaturated five-membered ring inorganic boric acid ester bond, the saturated six-membered ring inorganic boric acid ester bond and the unsaturated six-membered ring inorganic boric acid ester bond which are described before. Typical inorganic boronic acid monoester bond structures are exemplified by:
Figure BDA0002376545090000133
in the embodiment of the present invention, the inorganic boronic acid monoester bond can be formed by reacting a monol moiety contained in a compound raw material with an inorganic boronic acid moiety, and a polymer can also be introduced by a polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing the inorganic boronic acid monoester bond.
In the invention, the organic boric acid silicon ester bond is selected from but not limited to at least one of the following structures:
Figure BDA0002376545090000134
Wherein the boron atom is linked to at least one carbon atom by a boron-carbon bond and at least one organic group is linked to the boron atom by said boron-carbon bond;
Figure BDA00023765450900001311
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; difference on the same atom
Figure BDA00023765450900001312
Can be linked to form a ring, on different atoms
Figure BDA00023765450900001313
May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical silicon organoborate bond structures may be exemplified by:
Figure BDA0002376545090000135
in the embodiment of the present invention, the organoboronate silicone bond may be formed by reacting a silanol moiety contained in the compound raw material with an organoboronic acid moiety, or a polymer may be introduced by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing an organoboronate silicone bond.
In the present invention, the inorganic borate silicone bond is selected from, but not limited to, at least one of the following structures:
Figure BDA0002376545090000136
wherein, Y1、Y2、Y3Each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a silicon atom, preferably from an oxygen atom, and Y 1、Y2At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom;
Figure BDA0002376545090000146
denotes a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein a, b, c are each independentlyIs shown with Y1、Y2、 Y3The number of connected connections; when Y is1、Y2、Y3When each is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom, a, b and c are 0; when Y is1、Y2、Y3When each is independently selected from oxygen atom and sulfur atom, a, b and c are 1; when Y is1、Y2、Y3When each is independently selected from nitrogen atoms and boron atoms, a, b and c are 2; when Y is1、Y2、Y3When each is independently selected from silicon atoms, a, b and c are 3; difference on the same atom
Figure BDA0002376545090000147
Can be linked to form a ring, on different atoms
Figure BDA0002376545090000148
May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical inorganic silicon borate ester bond structures include, for example:
Figure BDA0002376545090000141
in the embodiment of the present invention, the inorganic borate silicone bond may be formed by reacting a silanol moiety contained in the compound raw material with an inorganic borate moiety, or a polymer may be introduced by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing an inorganic borate silicone bond.
The organic boronic acid moiety in the embodiments of the present invention is selected from, but not limited to, any of the following structures:
Figure BDA0002376545090000142
wherein, K1、K2、K3Is a monovalent organic group directly attached to an oxygen atom or a monovalent radicalA silicone group, directly linked to an oxygen atom through a carbon atom or a silicon atom, selected from any one of the following structures: small molecule hydrocarbyl, small molecule silyl, polymer chain residues; k4Is a divalent organic or divalent organosilicon group directly attached to two oxygen atoms, directly attached to the oxygen atoms through a carbon or silicon atom, selected from any of the following structures: a divalent small molecule hydrocarbon group, a divalent small molecule silane group, a divalent polymer chain residue; m1 +、M2 +、M3 +Is a monovalent cation, preferably Na+、K+、NH4 +；M4 2+Is a divalent cation, preferably Mg2+、Ca2+、Zn2+、Ba2+；X1、X2、X3Is a halogen atom, preferably selected from chlorine and bromine atoms; d1、D2Is a group bound to a boron atom, D1、D2Are different and are each independently selected from hydroxyl (-OH), ester (-OK)1) Salt group (-O-M)1 *) Halogen atom (-X)1) Wherein, K is1、M1 +、X1The definitions of (A) and (B) are consistent with those described above, and are not described herein again; wherein, the boron atom in the structure is connected with a carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond;
Figure BDA0002376545090000149
Represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; difference in the same boron atom
Figure BDA00023765450900001410
May be linked to form a ring including, but not limited to, aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof.
The inorganic boronic acid moiety described in the embodiments of the present invention is selected from, but not limited to, the following structures:
Figure BDA0002376545090000143
wherein, W1、W2、W3Each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a silicon atom, preferably from an oxygen atom, and W1、W2、W3At least one selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom;
Figure BDA00023765450900001411
represents a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein x, y, z each represent a linkage to W1、W2、W3The number of connected connections; when W is1、W2、W3X, y, z is 0 when each is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom; when W is1、W2、W3When each is independently selected from oxygen atom and sulfur atom, x, y and z are 1; when W is1、W2、W3When each is independently selected from nitrogen atom and boron atom, x, y and z are 2; when W is1、W2、W3Each independently selected from the group consisting of silicon atom, x, y, z ═ 3; difference on the same atom
Figure BDA00023765450900001412
Can be linked to form a ring, on different atoms
Figure BDA00023765450900001413
May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof.
The inorganic boric acid moiety described in the embodiment of the present invention is preferably introduced by using inorganic borane, inorganic boric acid, inorganic boric anhydride, inorganic borate ester, inorganic boron halide as a raw material.
1, 2-bis described in the embodiments of the present inventionAlcohol moiety which is ethylene glycol
Figure BDA0002376545090000144
And substituted forms thereof which have been deprived of at least one non-hydroxyl hydrogen atom;
the 1, 3-diol moiety described in the embodiments of the present invention is 1, 3-propanediol
Figure BDA0002376545090000145
And substituted forms thereof which have been deprived of at least one non-hydroxyl hydrogen atom;
for the 1, 2-diol moiety and the 1, 3-diol moiety, they may be linear structures or cyclic group structures.
For linear 1, 2-diol motif structures, it may be selected from any one or several of the B-like structures and isomeric forms thereof:
class B:
Figure BDA0002376545090000151
for linear 1, 3-diol motif structures, it may be selected from any one or several of the C-like structures and isomeric forms thereof:
class C:
Figure BDA0002376545090000152
wherein R is1～R3Is a monovalent group attached to the 1, 2-diol moiety; r 4～R8Is a monovalent group attached to the 1, 3-diol moiety;
Figure BDA00023765450900001510
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; wherein R is1～R8Each independently selected from any one of the following structures: hydrogen atom, heteroatom group, small molecule hydrocarbon group and polymer chain residue.
Wherein, the isomeric forms of B1-B4 and C1-C6 are respectively and independently selected from any one of position isomerism, conformational isomerism and chiral isomerism.
For a cyclic 1, 2-diol elementary structure, two carbon atoms in an ethylene glycol molecule are connected through the same group; wherein, the cyclic group structure is 3-200 rings, preferably 3-10 rings, more preferably 3-6 rings, the number of the cyclic group structure is 1,2 or more, and the cyclic group structure is selected from but not limited to any one of the following: aliphatic rings, ether rings, condensed rings, and combinations thereof; suitable cyclic group structures are exemplified by:
Figure BDA0002376545090000153
for cyclic 1, 3-diol motif structures, it can be formed by linking two carbon atoms in the 1, 3-propanediol molecule through the same group; wherein, the cyclic group structure is 3-200 rings, preferably 3-10 rings, more preferably 3-6 rings, the number of the cyclic group structure is 1,2 or more, and the cyclic group structure is selected from but not limited to any one of the following: aliphatic rings, ether rings, condensed rings, and combinations thereof; suitable cyclic group structures are exemplified by:
Figure BDA0002376545090000154
The catechol moiety in the present invention is a catechol
Figure BDA0002376545090000155
And substituted forms thereof, hybridized forms thereof, and combinations thereof, having lost at least one non-hydroxyl hydrogen atom, suitable catechol motif structures being exemplified by:
Figure BDA0002376545090000156
2-hydroxymethylphenol as described in the present inventionThe motif being 2-hydroxymethylphenol
Figure BDA0002376545090000157
And substituted forms thereof and hybridized forms thereof and combinations thereof, with suitable 2-hydroxymethylphenol motifs such as:
Figure BDA0002376545090000158
the monool moiety in the embodiment of the present invention refers to a structural moiety consisting of a hydroxyl group and a carbon atom directly bonded to the hydroxyl group (
Figure BDA0002376545090000159
Wherein, the carbon atom can be a non-aromatic carbon atom, and can also be an aromatic carbon atom), and in the case that the 1, 2-diol unit, the catechol unit, the 1, 3-diol unit and the 2-hydroxymethylphenol unit form an unsaturated/saturated five-membered ring organic borate bond, an unsaturated/saturated six-membered ring organic borate bond, an unsaturated/saturated five-membered ring inorganic borate bond and an unsaturated/saturated six-membered ring inorganic borate bond, the monoalcohol unit is not the hydroxyl group in the 1, 2-diol unit, the catechol unit, the 1, 3-diol unit and the 2-hydroxymethylphenol unit, and besides this, the monoalcohol unit can also be selected from any suitable dihydric (polybasic) alcohol compound and/or any hydroxyl group in the group. Suitable structures containing monoalcohol moieties may be mentioned, for example:
Figure BDA0002376545090000161
The silanol moiety in the embodiment of the present invention refers to a structural moiety consisting of a silicon atom and a hydroxyl group or a group hydrolyzable to the silicon atom to obtain a hydroxyl group (
Figure BDA0002376545090000162
Or
Figure BDA0002376545090000163
Wherein Z can be selected from halogen, cyano, oxygen cyano, sulfur cyano, alkoxy, amino, sulfate group, borate group, acyl, acyloxy, acylamino, ketoxime group, alkoxide group and the like, and preferably halogen and alkoxy).
The boron-containing dynamic covalent bond selected by the invention has strong dynamic property and mild dynamic reaction condition, can realize the synthesis and dynamic reversible effect of the polymer under the conditions of no need of a catalyst, no need of high temperature, illumination or specific pH, can further improve the preparation efficiency, reduce the limitation of the use environment and expand the application range of the polymer.
In the present invention, the boron-free dynamic covalent bond does not contain boron atom in its dynamic structure composition, and includes, but is not limited to, dynamic sulfur linkage, dynamic selenium sulfur linkage, dynamic selenium nitrogen linkage, acetal dynamic covalent linkage, dynamic covalent linkage based on carbon-nitrogen double bond, dynamic covalent linkage based on reversible free radical, exchangeable acyl linkage, dynamic covalent linkage based on steric effect induction, reversible addition-fragmentation chain transfer dynamic covalent linkage, dynamic siloxane linkage, dynamic silicon-ether linkage, exchangeable dynamic covalent linkage based on alkyl nitrogen heterocyclic onium, unsaturated carbon-carbon double bond capable of olefin cross metathesis reaction, unsaturated carbon-carbon triple bond capable of alkyne cross metathesis reaction, [2+2] cycloaddition dynamic covalent linkage, [4+4] cycloaddition dynamic covalent linkage, boron atom-free dynamic covalent linkage, and reversible free radical-based on reversible free radical, and exchangeable acyl linkage, Twenty-seven groups of bonds including a mercapto-Michael addition dynamic covalent bond, an amine alkene-Michael addition dynamic covalent bond, a triazolinedione-indole-based dynamic covalent bond, a diazacarbene-based dynamic covalent bond, a benzoyl-based dynamic covalent bond, a hexahydrotriazine-based dynamic covalent bond, a dynamically exchangeable trialkylsulfonium bond, a dynamic acid ester bond and a diketoenamine dynamic covalent bond; wherein, each group of boron-free dynamic covalent bonds can contain a plurality of types of boron-free dynamic covalent bond structures. When two or more than two boron-free dynamic covalent bonds are selected, the boron-free dynamic covalent bonds can be selected from different structures in the same type of dynamic covalent bonds in the same group of boron-free dynamic covalent bonds, different structures in different types of dynamic covalent bonds in the same group of boron-free dynamic covalent bonds, and different structures in different groups of boron-free dynamic covalent bonds, wherein in order to achieve orthogonal and/or synergistic dynamic performance, the boron-free dynamic covalent bonds are preferably selected from different structures in different groups of boron-free dynamic covalent bonds.
In the invention, the dynamic sulfur-connecting bond comprises a dynamic disulfide bond and a dynamic polysulfide bond, which can be activated under certain conditions, and the dissociation, bonding and exchange reaction of the bond occur, thus showing the dynamic reversible characteristic; the dynamic sulfur linkage described in the present invention is selected from the following structures:
Figure BDA0002376545090000164
wherein x is the number of S atoms, x is more than or equal to 2,
Figure BDA0002376545090000166
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Typical dynamic sulfur linkage structures may be exemplified by:
Figure BDA0002376545090000165
Figure BDA0002376545090000171
in the embodiment of the present invention, the "certain condition" for activating the dynamic reversibility of the dynamic sulfur linkage includes, but is not limited to, temperature adjustment, addition of redox agent, addition of catalyst, addition of initiator, illumination, radiation, microwave, plasma action, pH adjustment, and the like. For example, the dynamic sulfur linkage can be broken to form a sulfur radical by heating, so that dissociation and exchange reaction of the dynamic sulfur linkage can be carried out, and the dynamic sulfur linkage is reformed and stabilized after cooling, so that the polymer can obtain self-repairability and reworkability. The dynamic sulfur linkage can be broken to form sulfur free radical by illumination, so that dissociation and exchange reaction of disulfide bond can be generated, and the dynamic sulfur linkage is reformed after the illumination is removed, so that the polymer can obtain self-repairability and reprocessing property. Radiation, microwave and plasma can generate free radicals in the system to act with dynamic sulfur-connecting bond, so that self-repairability and reworkability are obtained. The presence of a catalyst, including but not limited to tetrakis (triphenylphosphine) rhodium hydride, 1, 8-diazabicyclo (5.4.0) undec-7-ene, cuprous chloride, methacrylate-copper complex catalysts, alkyl phosphines (e.g., triphenylphosphine, tributylphosphine, tricyclohexylphosphine, diphenylcyclohexylphosphine, dicyclohexylphenylphosphine), promotes the formation and exchange of dynamic sulfur linkages, thereby accelerating the self-healing process and achieving rework. In the embodiment of the invention, the dynamic reaction of disulfide bonds can also be realized by adding a redox agent to the system. Wherein the reducing agent can promote the dissociation of dynamic sulfur bond to form sulfydryl, thereby obtaining recyclability and reprocessing performance; the oxidizing agent can promote the formation of dynamic sulfur-connecting bonds, thereby obtaining secondary formability. Wherein, the reducing agent includes, but is not limited to, sodium hyposulfite, sodium borohydride, dithiothreitol, 2-mercaptoethanol, glutathione, alkyl mercaptan (such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, etc.), alkyl phosphine (such as triphenylphosphine, tributylphosphine, tricyclohexylphosphine, diphenylcyclohexylphosphine, dicyclohexylphenylphosphine, etc.), etc.; such oxidizing agents include, but are not limited to, air, lead dioxide, manganese dioxide, organic peroxides (e.g., dibenzoyl peroxide, hydrogen peroxide, ozone, p-quinone dioxime, disulfide), and the like. The dynamic polymer can also be self-repairing or recyclable by adding an initiator into the system and then generating free radicals under the action of heating, illumination, radiation, microwaves and plasmas to promote the dissociation or exchange of dynamic sulfur-connecting bonds. Wherein, the initiator includes but is not limited to any one or any several of the following initiators: photoinitiators, such as 2, 2-dimethoxy-2-phenylacetophenone (DMPA), 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenylketone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), benzophenone, 2-hydroxy-4- (2-hydroxyethoxy) -2-methylpropiophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone and alpha-ketoglutaric acid; organic peroxides such as lauroyl peroxide, Benzoyl Peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxybenzoate, t-butylperoxypivalate, di-t-butyl peroxide, diisopropylbenzene hydroperoxide; azo compounds, such as Azobisisobutyronitrile (AIBN), azobisisoheptonitrile; inorganic peroxides such as ammonium persulfate, potassium persulfate, and the like; wherein, the initiator is preferably 2, 2-dimethoxy-2-phenylacetophenone, azobisisobutyronitrile, lauroyl peroxide, benzoyl peroxide and potassium persulfate.
In the embodiment of the present invention, the dynamic sulfur linkage may be formed by a bonding reaction of a sulfur radical through an oxidative coupling reaction of a mercapto group contained in a compound raw material, or may be introduced into a polymer through a polymerization/crosslinking reaction between reactive groups contained in a compound raw material containing a disulfide linkage. Among these, the compound raw material containing a disulfide bond is not particularly limited, and a polyol, isocyanate, epoxy compound, alkene, alkyne, carboxylic acid, ester, amide, sulfur, and mercapto compound containing a disulfide bond are preferable, and a polyol, isocyanate, epoxy compound, alkene, and alkyne containing a disulfide bond are more preferable.
In the invention, the dynamic selenium-connecting bond comprises a dynamic double selenium bond and a dynamic multiple selenium bond, which can be activated under certain conditions and generate bond dissociation, bonding and exchange reaction to embody dynamic reversible characteristics; the dynamic selenium linkage bond in the invention is selected from the following structures:
Figure BDA0002376545090000181
wherein x is the number of S atoms, x is more than or equal to 2,
Figure BDA0002376545090000183
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Typical dynamic selenium linkage structures may be mentioned, for example:
Figure BDA0002376545090000182
In the embodiment of the present invention, the "certain condition" for activating the dynamic reversibility of the dynamic selenium linkage includes, but is not limited to, temperature regulation, addition of redox agent, addition of catalyst, addition of initiator, illumination, radiation, microwave, plasma action and other action modes, so that the polymer shows good self-repairability, recycling property, stimulus responsiveness and the like. For example, the dynamic selenium-connected bond can be broken to form a selenium free radical by heating, so that dissociation and exchange reaction of the dynamic bond can be carried out, the dynamic selenium-connected bond is reformed and stabilized after cooling, and the self-repairability and the reworkability are shown; the polymer containing dynamic bonds can obtain good self-repairing performance through laser irradiation; the radiation, microwave and plasma can generate free radicals in the system to react with the dynamic selenium-connected bond, so that the self-repairability and the reprocessing performance are obtained. The dynamic polymer can also be recycled by adding a redox agent into the system; wherein the reducing agent is capable of promoting dissociation of the dynamic selenium linkage into selenol such that the dynamic polymer dissociates; the oxidant can oxidize selenol to form dynamic selenium linkage, so as to obtain reprocessing performance. Wherein, the reducing agent includes but is not limited to sodium hyposulfite, sodium borohydride, dithiothreitol, 2-mercaptoethanol, glutathione, tris (2-carbonylethyl) phosphate, alkyl mercaptan (such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, etc.), alkyl phosphine (such as triphenylphosphine, tributylphosphine, tricyclohexylphosphine, diphenylcyclohexylphosphine, dicyclohexylphenylphosphine, etc.); the oxidant species include, but are not limited to, air, lead dioxide, manganese dioxide, organic peroxides (e.g., dibenzoyl peroxide, hydrogen peroxide, ozone, p-quinonedioxime, disulfide), and the like. The dynamic polymer can also be self-repairing or recyclable by adding an initiator into the system and then generating free radicals under the action of heating, illumination, radiation, microwaves and plasma to promote the dissociation or exchange of dynamic selenium-connected bonds. Wherein, the initiator includes but is not limited to any one or any several of the following initiators: photoinitiators, such as 2, 2-dimethoxy-2-phenylacetophenone (DMPA), 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenylketone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), benzophenone, 2-hydroxy-4- (2-hydroxyethoxy) -2-methylpropiophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone and alpha-ketoglutaric acid; organic peroxides such as lauroyl peroxide, Benzoyl Peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxybenzoate, t-butylperoxypivalate, di-t-butyl peroxide, diisopropylbenzene hydroperoxide; azo compounds, such as Azobisisobutyronitrile (AIBN), azobisisoheptonitrile; inorganic peroxides such as ammonium persulfate, potassium persulfate, and the like; wherein, the initiator is preferably 2, 2-dimethoxy-2-phenylacetophenone, azobisisobutyronitrile, lauroyl peroxide, benzoyl peroxide and potassium persulfate.
In the embodiment of the present invention, the dynamic selenium linkage may be formed by an oxidative coupling reaction of selenol contained in the compound raw material or a bonding reaction of a selenium radical, or may be introduced into the polymer by a polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing the dynamic selenium linkage. Among these, the raw material of the compound having a kinetic selenium linkage is not particularly limited, and a polyol, an isocyanate, an epoxy compound, an alkene, an alkyne, a carboxylic acid, and a diselenide having a kinetic selenium linkage (e.g., sodium diselenide and dichlorodiselenide) are preferable, and a polyol, an isocyanate, an epoxy compound, an alkene, and an alkyne having a kinetic selenium linkage are more preferable.
In the invention, the dynamic selenium-sulfur bond can be activated under certain conditions, and bond dissociation, bonding and exchange reaction occur, thus showing the dynamic reversible characteristic; the dynamic selenium-sulfur bond in the invention is selected from at least one of the following structures:
Figure BDA0002376545090000191
wherein the content of the first and second substances,
Figure BDA0002376545090000193
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Typical dynamic selenium-sulfur bond structures may be exemplified by:
Figure BDA0002376545090000192
in the embodiment of the present invention, the "certain conditions" for activating the dynamic reversibility of the dynamic selenium-sulfur bond include, but are not limited to, temperature regulation, addition of redox agent, addition of catalyst, addition of initiator, illumination, radiation, microwave, plasma action, etc., so that the polymer exhibits good self-repairability, recycling recoverability, stimulus responsiveness, etc. For example, the dynamic selenium-sulfur bond can be broken to form a sulfur radical and a selenium radical by heating, so that dissociation and exchange reaction of the dynamic bond can be carried out, the dynamic selenium-sulfur bond is reformed and stabilized after cooling, and the self-repairability and the reworkability are shown; the polymer containing the sulfur-selenium bond can obtain good self-repairing performance through laser irradiation; the radiation, microwave and plasma can generate free radicals to react with the dynamic selenium-sulfur bond in the system, so that the self-repairability and the reprocessing performance are obtained. The dynamic polymer can also be recycled by adding a redox agent to the system. Wherein, the reducing agent includes but is not limited to sodium hyposulfite, sodium borohydride, dithiothreitol, 2-mercaptoethanol, glutathione, tris (2-carbonylethyl) phosphate, alkyl mercaptan (such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, etc.), alkyl phosphine (such as triphenylphosphine, tributylphosphine, tricyclohexylphosphine, diphenylcyclohexylphosphine, dicyclohexylphenylphosphine, etc.); the oxidant species include, but are not limited to, air, lead dioxide, manganese dioxide, organic peroxides (e.g., dibenzoyl peroxide, hydrogen peroxide, ozone, p-quinonedioxime, disulfide), and the like. The dynamic polymer can also be self-repairing or recyclable by adding an initiator into the system and then generating free radicals under the action of heating, illumination, radiation, microwaves and plasma to promote the dissociation or exchange of dynamic selenium-sulfur bonds. Wherein, the initiator includes but is not limited to any one or any several of the following initiators: photoinitiators, such as 2, 2-dimethoxy-2-phenylacetophenone (DMPA), 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenylketone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), benzophenone, 2-hydroxy-4- (2-hydroxyethoxy) -2-methylpropiophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone and alpha-ketoglutaric acid; organic peroxides such as lauroyl peroxide, Benzoyl Peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxybenzoate, t-butylperoxypivalate, di-t-butyl peroxide, diisopropylbenzene hydroperoxide; azo compounds, such as Azobisisobutyronitrile (AIBN), azobisisoheptonitrile; inorganic peroxides such as ammonium persulfate, potassium persulfate, and the like; wherein, the initiator is preferably 2, 2-dimethoxy-2-phenylacetophenone, azobisisobutyronitrile, lauroyl peroxide, benzoyl peroxide and potassium persulfate.
In the embodiment of the present invention, the dynamic selenothio bond may be formed by a bond formation reaction of a sulfur radical and a selenium radical through an oxidative coupling reaction of thiol and selenol contained in the compound raw materials, or may be introduced into the polymer through a polymerization/crosslinking reaction between reactive groups contained in the compound raw materials containing a selenothio bond. Among these, the raw material of the compound having a sulfur-selenium bond is not particularly limited, and a polyol, an isocyanate, an epoxy compound, an alkene, an alkyne, and a carboxylic acid having a sulfur-selenium bond are preferable, and a polyol, an isocyanate, an epoxy compound, an alkene, and an alkyne having a sulfur-selenium bond are more preferable.
In the invention, the dynamic selenium-nitrogen bond can be activated under a certain condition, and dissociation, bonding and exchange reaction of the bond occur, thus showing the dynamic reversible characteristic; the dynamic selenium nitrogen bond described in the present invention is selected from the following structures:
Figure BDA0002376545090000201
wherein X is selected from halogen ions, preferably chloride ions and bromide ions,
Figure BDA0002376545090000204
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Typical dynamic selenium nitrogen bond structures can be exemplified by:
Figure BDA0002376545090000202
in the embodiment of the invention, the "certain condition" for activating the dynamic reversibility of the dynamic selenium nitrogen bond includes, but is not limited to, temperature regulation, addition of an acid-base catalyst, and the like, so that the polymer shows good self-repairability, recycling recoverability, stimulus responsiveness, and the like. Wherein, the acid-base catalyst can be selected from: (1) inorganic acid, organic acid and acid salt catalyst thereof. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, phosphoric acid, and the like; examples of the organic acid include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and the like; examples of the salts include sulfate, hydrogen sulfate, and hydrogen phosphate. (2) Examples of the group IA alkali metal and its compound include lithium, lithium oxide, lithium acetylacetonate, sodium methoxide, sodium ethoxide, sodium hydroxide, potassium carbonate, and cobalt carbonate. (3) Examples of the group IIA alkali metal and compounds thereof include calcium, calcium oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, magnesium ethoxide and the like. (4) Aluminum metal and its compounds, for example, aluminum powder, alumina, sodium aluminate, hydrous alumina And sodium hydroxide, alkoxy aluminum compounds, and the like. (5) Examples of the organic compound include ammonium chloride, triethylamine hydrochloride, pyridine, hydroxylamine hydrochloride, hydroxylamine sulfate, N-methylhydroxylamine hydrochloride, benzylamine hydrochloride, o-benzylhydroxylamine hydrochloride, butyraldehyde oxime, benzaldehyde oxime, hydrazine monohydrate, N' -diphenylthiourea, scandium trifluoromethanesulfonate (Sc (OTf))3) And the like. (6) Examples of the divalent copper compound include copper acetate. (7) Examples of the trivalent iron compound include an aqueous ferric chloride solution, ferric sulfate hydrate, and ferric nitrate hydrate. Among them, sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, calcium hydroxide, triethylamine, pyridine, and copper acetate are preferable.
In an embodiment of the present invention, the dynamic selenazonitrogen bond can be formed by reacting a selenium halide contained in a compound raw material with a pyridine derivative.
In the invention, the acetal dynamic covalent bond comprises a dynamic ketal bond, a dynamic acetal bond, a dynamic thioketal bond and a dynamic thioketal bond, can be activated under certain conditions, and generates bond dissociation, ketal reaction and exchange reaction, thus showing dynamic reversible characteristics; the "certain conditions" for activating the dynamic reversibility of acetal dynamic covalent bond means heating, appropriate acidic aqueous conditions, and the like. The acetal-based dynamic covalent bond described in the present invention is selected from at least one of the following structures:
Figure BDA0002376545090000203
Wherein, X1、X2、X3、X4Each independently selected from oxygen atom, sulfur atom, nitrogen atom, preferably from oxygen atom, sulfur atom; r1、R2Each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; r3、R4Each independently selected from the group consisting of a single bond, a heteroatom linking group, a divalent or polyvalent small molecule hydrocarbon group, a divalent or polyvalent polymer chain residue;
Figure BDA0002376545090000214
denotes a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein
Figure BDA0002376545090000215
May be linked to form a ring including, but not limited to, aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical acetal-based dynamic covalent bond structures include, for example:
Figure BDA0002376545090000211
in the embodiment of the present invention, the acetal dynamic covalent bond can be dissociated in an acidic aqueous solution and formed under anhydrous acidic conditions, and has good pH stimulus responsiveness, so that dynamic reversibility can be obtained by adjusting an acidic environment.
In embodiments of the present invention, acids that may be used in the dynamic ketal reaction include, but are not limited to, p-toluenesulfonic acid, pyridinium p-toluenesulfonate, hydrochloric acid, sulfuric acid, oxalic acid, carbonic acid, propionic acid, nonanoic acid, silicic acid, acetic acid, nitric acid, chromic acid, phosphoric acid, 4-chloro-benzenesulfinic acid, p-methoxybenzoic acid, 1, 4-phthalic acid, 4, 5-difluoro-2-nitrophenylacetic acid, 2-bromo-5-fluorophenylpropionic acid, bromoacetic acid, chloroacetic acid, phenylacetic acid, adipic acid, and the like. The acid used in the present invention may be in the form of a simple acid, an organic acid solution, an aqueous acid solution, or a vapor of an acid, without limitation. The invention can also use different states of the acid in a combined mode, such as promoting the formation of dynamic covalent bonds by using an organic solution of p-toluenesulfonic acid, and dissociating the dynamic covalent bonds by using an aqueous solution of hydrochloric acid to obtain recycling property and the like.
In the embodiment of the present invention, the acetal dynamic covalent bond may be formed by condensation reaction of a ketone group, an aldehyde group, a hydroxyl group, and a thiol group contained in a compound raw material, may be formed by exchange reaction of an acetal dynamic covalent bond with an alcohol, a thiol, an aldehyde, and a ketone, or may be introduced into a polymer by polymerization/crosslinking reaction between reactive groups contained in a compound raw material containing an acetal dynamic covalent bond. Among these, the raw material of the compound having the acetal dynamic covalent bond is not particularly limited, and a polyol, a polythiol, a polyamine, an isocyanate, an epoxy compound, an alkene, an alkyne, and a carboxylic acid having the acetal dynamic covalent bond are preferable, and a polyol, a polyamine, an isocyanate, an epoxy compound, an alkene, and an alkyne having the acetal dynamic covalent bond are more preferable.
According to the invention, the dynamic covalent bond based on the carbon-nitrogen double bond comprises a dynamic imine bond, a dynamic oxime bond, a dynamic hydrazone bond and a dynamic acylhydrazone bond, and can be activated under certain conditions, and dissociation, condensation and exchange reactions of the dynamic covalent bond are carried out, so that the dynamic reversible characteristic is embodied; herein, the "certain condition" for activating the dynamic covalent bond dynamic reversibility based on a carbon-nitrogen double bond refers to an appropriate pH aqueous condition, an appropriate catalyst presence condition, a heating condition, a pressurizing condition, and the like. The dynamic covalent bond based on carbon-nitrogen double bond in the invention is selected from at least one of the following structures:
Figure BDA0002376545090000212
Wherein R is1Is a divalent or polyvalent small molecule hydrocarbon group;
Figure BDA0002376545090000216
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Typical dynamic covalent bond structures based on carbon-nitrogen double bonds may be mentioned, for example:
Figure BDA0002376545090000213
in the embodiment of the present invention, the suitable pH aqueous condition for promoting the dissociation and condensation reaction of the dynamic covalent bond based on carbon-nitrogen double bond refers to that the dynamic polymer is swelled in an aqueous solution with a certain pH value or the surface thereof is wetted with an aqueous solution with a certain pH value, so that the dynamic covalent bond based on carbon-nitrogen double bond in the dynamic polymer has dynamic reversibility. The aqueous solution can be all aqueous solution, or organic solution containing water, oligomer, plasticizer and ionic liquid. The pH of the aqueous solution selected varies depending on the type of the selected dynamic covalent bond based on carbon-nitrogen double bond, for example, for the dynamic phenylimide bond, an acidic solution having a pH of 6.5 or less may be selected for hydrolysis, and for the dynamic acylhydrazone bond, an acidic solution having a pH of 4 or less may be selected for hydrolysis.
Wherein, the acid-base catalyst for the dissociation, condensation and exchange reaction of the dynamic covalent bond based on carbon-nitrogen double bond can be selected from: (1) inorganic acid, organic acid and acid salt catalyst thereof. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, phosphoric acid, and the like; examples of the organic acid include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and the like; examples of the salts include sulfate, hydrogen sulfate, and hydrogen phosphate. (2) Examples of the group IA alkali metal and its compound include lithium, lithium oxide, lithium acetylacetonate, sodium methoxide, sodium ethoxide, sodium hydroxide, potassium carbonate, and cobalt carbonate. (3) Examples of the group IIA alkali metal and compounds thereof include calcium, calcium oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, magnesium ethoxide and the like. (4) Aluminum metal and its compounds, for example, aluminum powder, alumina, sodium aluminate, a complex of hydrous alumina and sodium hydroxide, an aluminum alkoxide-based compound, and the like can be cited. (5) Examples of the organic compound include ammonium chloride, triethylamine hydrochloride, pyridine, hydroxylamine hydrochloride, hydroxylamine sulfate, N-methylhydroxylamine hydrochloride, benzylamine hydrochloride, o-benzylhydroxylamine hydrochloride, butyraldehyde oxime, benzaldehyde oxime, hydrazine monohydrate, N' -diphenylthiourea, scandium trifluoromethanesulfonate (Sc (OTf)) 3) And the like. (6) Examples of the divalent copper compound include copper acetate. (7) The ferric iron compound includes, for example, ferric trichloride aqueous solution, ferric sulfate hydrate, nitric acidIron hydrates, and the like. Among them, sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, calcium hydroxide, triethylamine, pyridine, and copper acetate are preferable.
In the embodiment of the present invention, the dynamic covalent bond based on carbon-nitrogen double bond may be formed by condensation reaction of ketone group, aldehyde group, acyl group and amino group, hydrazine group, hydrazide group contained in the compound raw material, or may be introduced into the polymer by polymerization/crosslinking reaction between the reactive groups contained in the compound raw material containing the dynamic covalent bond based on carbon-nitrogen double bond. Among these, the raw material of the compound having a dynamic covalent bond based on a carbon-nitrogen double bond is not particularly limited, and a polyol, a polythiol, a polyamine, an isocyanate, an epoxy compound, an alkene, an alkyne, and a carboxylic acid having a dynamic covalent bond based on a carbon-nitrogen double bond are preferable, and a polyol, a polyamine, an isocyanate, an epoxy compound, an alkene, and an alkyne having a dynamic covalent bond based on a carbon-nitrogen double bond are more preferable.
In the invention, the dynamic covalent bond based on the reversible free radical can be activated under certain conditions to generate free radicals and generate bonding or exchange reaction of the bond, thus showing dynamic reversible characteristics; the "exchange reaction of dynamic covalent bonds based on reversible free radicals" means that intermediate state free radicals formed after the dissociation of old dynamic covalent bonds in the polymer form new dynamic covalent bonds elsewhere, thereby generating exchange of chains and change of polymer topology. The reversible radical-based dynamic covalent bond described in the present invention is selected from at least one of the following structures:
Figure BDA0002376545090000221
Wherein each W is independently selected from an oxygen atom, a sulfur atom;
wherein, W1Each independently selected from single bonds, ether groups, thioether groups, secondary amine groups and substituents thereof, divalent methyl groups and substituents thereof, preferably from direct bonds, ether groups, thioether groups; w at different positions1Are the same or different;
wherein, W2Each independently selected from ether groups, thioether groups, secondary amine groups and substituents thereof, divalent methyl groups and substituents thereof, preferably from thioether groups, secondary amine groups; w at different positions2Are the same or different;
wherein, W3Each independently selected from ether groups, thioether groups, preferably ether groups; w at different positions3Are the same or different;
wherein, W4Each independently selected from ether groups, thioether groups, secondary amine groups and substituents thereof, preferably from ether groups; w at different positions4Are the same or different;
wherein V, V ' are independently selected from carbon atom and nitrogen atom, different positions have the same or different structure of V, V ', when V, V ' is selected from nitrogen atom, the compound is connected with V, V
Figure BDA0002376545090000222
Is absent;
wherein Z is selected from selenium atom, tellurium atom, antimony atom and bismuth atom; wherein k is linked to Z
Figure BDA0002376545090000223
The number of (2); when Z is a selenium atom or a tellurium atom, k is 1, meaning that there is only one
Figure BDA0002376545090000224
Is connected with Z; when Z is an antimony atom or a bismuth atom, k is 2, which means that there are two
Figure BDA0002376545090000225
To Z are two
Figure BDA0002376545090000226
Are the same or different in structure;
wherein R is1Each independently selected from a hydrogen atom, a halogen atom, a hetero atom group, C1-20Hydrocarbyl/heterohydrocarbyl, substituted C1-20Hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing; r1Each of which isIndependently preferably selected from hydrogen atom, hydroxyl group, cyano group, carboxyl group, C1-20Alkyl radical, C1-20Aryl radical, C1-20Heteroaromatic hydrocarbon group and C substituted by acyl, acyloxy, acylamino, oxyacyl, sulfuryl, aminoacyl, phenylene1-20Hydrocarbyl/heterohydrocarbyl; r1Further preferably selected from the group consisting of a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, phenyl group, hydroxyl group, cyano group, carboxyl group, methyloxyacyl group, ethyloxyacyl group, propyloxyacyl group, butyloxyacyl group, methylaminoacyl group, ethylaminoacyl group, propylaminoylgroup, butylaminoacyl group;
wherein R is2Each independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain; each R is2Are the same or different; when R is2When selected from substituents, it is selected from, but not limited to: hydroxy, phenyl, phenoxy, C1-10Alkyl radical, C 1-10Alkoxy radical, C1-10Alkoxyacyl group, C1-10An alkanoyloxy group, a trimethylsilyloxy group, a triethylsiloxy group; wherein, the substituent atom or the substituent group is not particularly limited, and is selected from any one or more of halogen atom, alkyl substituent group and heteroatom-containing substituent group;
wherein R is3Each independently selected from cyano, C1-10Alkoxyacyl group, C1-10Alkyl acyl radical, C1-10Alkylaminoacyl, phenyl, substituted phenyl, arylalkyl, substituted arylalkyl; wherein, the substituent atom or the substituent group is not particularly limited, and is selected from any one or more of halogen atom, alkyl substituent group and heteroatom-containing substituent group;
wherein R is1、R2、R3、R4Each independently selected from hydrogen atom, halogen atom, heteroatom group, substituent; r1、R2、R3、R4Each independently preferably selected from a hydrogen atom, a halogen atom, a hetero atom group, C1-20Hydrocarbyl radical, C1-20Heterohydrocarbyl, substituted C1-20Hydrocarbyl or substituted C1-20Heterohydrocarbyl and combinations of two or more of the foregoingA substituent of (1); more preferably from hydrogen atom, hydroxy group, cyano group, carboxy group, C1-20Alkyl radical, C1-20Heteroalkyl, cyclic structure C1-20Alkyl, C of cyclic structure1-20Heteroalkyl group, C1-20Aryl radical, C1-20A heteroaryl group;
Wherein R is5、R6、R7、R8Each independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain; when R is5、R6、 R7、R8When each is independently selected from the group consisting of a substituent, the substituent is preferably a substituent having a steric hindrance effect; the substituents with steric hindrance are selected from, but not limited to: cyano radicals, C1-20Alkyl radical, C1-20Cycloalkyl, aralkyl, heteroaralkyl and the groups formed by the above groups substituted by any substituent atom or substituent group; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent; by way of example, typical sterically hindered substituents include, but are not limited to: cyano, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, adamantyl, phenyl, pyridyl, C1-5Alkyl-substituted phenyl, C1-5Alkoxy-substituted phenyl, C1-5Alkylthio-substituted phenyl, C1-5Alkylamino substituted phenyl, cyano substituted phenyl;
wherein each L is independently selected from the group consisting of a heteroatom linking group, a heteroatom group linking group, a divalent C1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C 1-20A divalent linking group formed from hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent; l is each independently preferably selected from the group consisting of acyl, acyloxy, acylthio, acylamino, oxyacyl, thioacyl, phenylene, divalent C1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C1-20Hydrocarbyl/heterohydrocarbyl(ii) a Wherein said substituted divalent C1-20The structure of the substituent group in the hydrocarbon group/heterohydrocarbon group is preferably an acyl group, an acyloxy group, an acylthio group, an acylamino group, an oxyacyl group, a thioacyl group, an aminoacyl group, a phenylene group, and more preferably the substituted divalent C1-20The hydrocarbyl/heterohydrocarbyl group being linked to R via said substituent group1To the carbon atom(s) of (a);
wherein the content of the first and second substances,
Figure BDA0002376545090000237
represents that the ring has a conjugated structure; wherein the content of the first and second substances,
Figure BDA0002376545090000231
is a five-membered nitrogen heterocyclic structure with a conjugated structure; wherein the content of the first and second substances,
Figure BDA0002376545090000232
the two five-membered nitrogen heterocycles form a carbon-carbon single bond, a carbon-nitrogen single bond or a nitrogen-nitrogen single bond between the two ring-forming atoms; according to different connection modes, the connection modes are different,
Figure BDA0002376545090000233
including but not limited to one or more of the following isomers:
Figure BDA0002376545090000234
Figure BDA0002376545090000235
It should be noted that under appropriate conditions, interconversion between the various isomers can occur, and therefore, the six isomer motifs described above are regarded as the same structural motif in the present invention;
wherein the content of the first and second substances,
Figure BDA0002376545090000236
is a nitrogen-containing aliphatic heterocyclic ring, the number of ring-forming atoms of the ring is not particularly limited, and is preferably from 3 to 10, more preferably from 5 to 8; the aliphatic heterocyclic ring has at least one ring-constituting atom other thanOne ring-forming atom is a nitrogen atom, the remaining ring-forming atoms are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, boron atoms, phosphorus atoms, silicon atoms, and the hydrogen atoms attached to the ring-forming atoms are substituted or unsubstituted by any suitable substituent atom, substituent group; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent;
wherein the content of the first and second substances,
Figure BDA0002376545090000241
indicates that n is connected with
Figure BDA0002376545090000242
Wherein n is 0, 1 or an integer greater than 1; wherein, the symbols are the sites connecting with other structures in the formula; said
Figure BDA0002376545090000243
Preferably at least one of the following structures, but the invention is not limited thereto:
Figure BDA0002376545090000244
said
Figure BDA0002376545090000245
More preferably at least one of the following structures, but the present invention is not limited thereto:
Figure BDA0002376545090000246
wherein the content of the first and second substances,
Figure BDA0002376545090000247
is an aromatic ring; the ring structure of the aromatic ring is selected from a monocyclic structure, a polycyclic structure, a spiro structure and a fused ring structure; the number of ring-forming atoms of the ring is not particularly limited;the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, boron atoms, phosphorus atoms, silicon atoms, and the hydrogen atoms attached to the ring-forming atoms are optionally substituted by any suitable substituent atom, substituent group or not; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent;
wherein the content of the first and second substances,
Figure BDA0002376545090000248
indicates that n is connected with
Figure BDA00023765450900002410
Of an aromatic ring of (a) in different positions
Figure BDA00023765450900002411
Are the same or different; wherein, the symbols are the sites connecting with other structures in the formula;
wherein the content of the first and second substances,
Figure BDA00023765450900002412
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; each one of
Figure BDA00023765450900002413
The structures are the same or different; is different
Figure BDA00023765450900002414
May be linked to form a ring including, but not limited to, aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof.
Typical dynamic covalent bond structures based on reversible free radicals may be mentioned, for example:
Figure BDA0002376545090000249
Figure BDA0002376545090000251
Figure BDA0002376545090000261
Figure BDA0002376545090000271
Figure BDA0002376545090000281
wherein, W, W1、W2、W3、W4、
Figure BDA0002376545090000283
The definition, selection range and preferable range of (2) are as described above.
In the embodiment of the present invention, the "certain conditions" for activating the dynamic reversibility of the dynamic covalent bond based on the reversible free radicals include, but are not limited to, temperature regulation, initiator addition, illumination, radiation, microwave, plasma action and other action modes. For example, the dynamic covalent bond can be broken to form a free radical by heating, so that dissociation and exchange reaction of the dynamic covalent bond can be carried out, and the dynamic covalent bond is reformed and stabilized after cooling, so that the polymer can obtain self-repairability and reworkability. The dynamic covalent bond can be broken to form free radicals by illumination, so that dissociation and exchange reaction of the dynamic covalent bond can be carried out, the dynamic covalent bond is reformed after the illumination is removed, and the polymer can obtain self-repairability and reprocessing property. Radiation, microwaves and plasmas can generate free radicals in a system to react with dynamic covalent bonds so as to obtain self-repairability and reprocessing performance. The initiator is capable of generating free radicals, promoting dissociation or exchange of dynamic covalent bonds, and obtaining self-repairability or recyclability. Wherein, the initiator includes but is not limited to any one or any several of the following initiators: photoinitiators, such as 2, 2-dimethoxy-2-phenylacetophenone (DMPA), 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenylketone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), benzophenone, 2-hydroxy-4- (2-hydroxyethoxy) -2-methylpropiophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone and alpha-ketoglutaric acid; organic peroxides such as lauroyl peroxide, Benzoyl Peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxybenzoate, t-butylperoxypivalate, di-t-butyl peroxide, diisopropylbenzene hydroperoxide; azo compounds, such as Azobisisobutyronitrile (AIBN), azobisisoheptonitrile; inorganic peroxides such as ammonium persulfate, potassium persulfate, and the like; wherein, the initiator is preferably 2, 2-dimethoxy-2-phenylacetophenone, azobisisobutyronitrile, lauroyl peroxide, benzoyl peroxide and potassium persulfate.
In an embodiment of the present invention, the reversible radical-based dynamic covalent bond contained in the polymer may be formed by a bonding reaction or other suitable coupling reaction of radicals contained in the compound raw materials; it can be generated in situ in the polymer or can be introduced into the polymer by polymerization/crosslinking reactions between the reactive groups it contains using a compound starting material containing a dynamic covalent bond based on a reversible free radical. Among these, the raw material of the compound having a dynamic covalent bond based on a reversible radical is not particularly limited, and a polyol, a polythiol, a polyamine, an isocyanate, an epoxy compound, an alkene, an alkyne, and a carboxylic acid having a dynamic covalent bond based on a reversible radical are preferable, and a polyol, a polyamine, an isocyanate, an epoxy compound, an alkene, and an alkyne having a dynamic covalent bond based on a reversible radical are more preferable.
In the present invention, the binding exchangeable acyl bond can be activated under certain conditions and undergoes a binding acyl exchange reaction (e.g., a binding transesterification reaction, a binding amide exchange reaction, a binding carbamate exchange reaction, a binding vinylogous amide or vinylogous carbamate exchange reaction, etc.) with a nucleophilic group, thereby exhibiting a dynamic reversible property; wherein, the 'associative acyl exchange reaction' means that the associative exchangeable acyl bonds are firstly combined with nucleophilic groups to form an intermediate structure, and then the acyl exchange reaction is carried out to form a new dynamic covalent bond, thereby generating exchange of chains and change of a topological structure of the polymer, wherein the crosslinking degree of the polymer can be kept unchanged; wherein the "certain conditions" for activating the dynamic reversibility of the binding exchangeable acyl bond means suitable catalyst existence conditions, heating conditions, pressurizing conditions, etc.; the "nucleophilic group" refers to a reactive group such as hydroxyl, sulfhydryl and amino group, which is present in a polymer system for a binding acyl exchange reaction, and the nucleophilic group may be on the same polymer network/chain as the binding exchangeable acyl bond, may be on a different polymer network/chain, or may be introduced through a small molecule or a polymer containing the nucleophilic group. The binding exchangeable acyl bond as described in the present invention is selected from at least one of the following structures:
Figure BDA0002376545090000282
Wherein, X1、X2Selected from carbon atoms, oxygen atoms, sulfur atoms, nitrogen atoms and silicon atoms; y is selected from the group consisting of an oxygen atom, a sulfur atom and a secondary amine group; z1、Z2Selected from oxygen atom, sulfur atom; r5Selected from the group consisting of hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; wherein, when X1、X2When it is an oxygen atom or a sulfur atom, R1、R2、R3、R4Is absent; when X is present1、X2When it is a nitrogen atom, R1、R3Exist, R2、R4Is absent, and R1、 R3Each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; when X is present1、X2When it is a carbon atom or a silicon atom, R1、R2、R3、R4Exist, and areEach independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
Figure BDA0002376545090000293
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Wherein the binding exchangeable acyl bond is preferably selected from the group consisting of a binding exchangeable ester bond, a binding exchangeable thioester bond, a binding exchangeable amide bond, a binding exchangeable urethane bond, a binding exchangeable thiocarbamate bond, a binding exchangeable urea bond, a binding exchangeable vinyl amide bond, and a binding exchangeable vinyl carbamate bond. Typical binding exchangeable acyl bond structures may be exemplified by:
Figure BDA0002376545090000291
Among them, the acyl bond having an exchangeable binding property to a nucleophilic group is more preferable, and typical structures thereof are, for example:
Figure BDA0002376545090000292
in the present invention, some of the bonded acyl exchange reactions need to be carried out under catalytic conditions, and the catalysts include catalysts for transesterification (including esters, thioesters, carbamates, thiocarbamates, etc.) and amine exchange (including amides, carbamates, thiocarbamates, ureas, vinylogous amides, vinylogous carbamates, etc.). By adding the catalyst, the occurrence of the combined acyl exchange reaction can be promoted, so that the dynamic polymer shows good dynamic characteristics.
Wherein the catalyst for the transesterification reaction may be selected from: (1) inorganic acid, organic acid and acid salt catalyst thereof. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, phosphoric acid, and the like; examples of the organic acid include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and the like(ii) a Examples of the salts include sulfate, hydrogen sulfate, and hydrogen phosphate. (2) Examples of the group IA alkali metal and its compound include lithium, lithium oxide, lithium acetylacetonate, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium carbonate, and cobalt carbonate. (3) The alkali metal of group IIA and its compounds are exemplified by calcium, calcium oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, and magnesium ethoxide. (4) Aluminum metal and its compounds, for example, aluminum powder, alumina, sodium aluminate, a complex of hydrous alumina and sodium hydroxide, and an aluminum alkoxide-based compound can be cited. (5) Tin compounds include inorganic tin compounds and organic tin compounds. Examples of the inorganic tin include tin oxide, tin sulfate, stannous oxide, and stannous chloride. Examples of the organotin include dibutyltin oxide, dibutyltin dilaurate, dibutyltin dichloride, tin tributylacetate, tributyltin chloride and trimethyltin chloride. Examples of the group IVB element compound (6) include titanium dioxide, tetramethyl titanate, isopropyl titanate, isobutyl titanate, tetrabutyl titanate, zirconium oxide, zirconium sulfate, zirconium tungstate, and tetramethyl zirconate. (7) Anionic layered column compounds, the main component of which is generally composed of hydroxides of two metals, called double metal hydroxides LDH, and the calcined product of which is LDO, such as hydrotalcite { Mg } 6(CO3)[Al(OH)6]2(OH)4·4H2O }. (8) Supported solid catalysts, which may be mentioned by way of example KF/CaO, K2CO3/CaO、KF/γ-Al2O3、 K2CO3/γ-Al2O3、KF/Mg-La、K2O/activated carbon, K2CO3Coal ash powder, KOH/NaX, KF/MMT (montmorillonite) and other compounds. (9) Examples of the organozinc compound include zinc acetate and zinc acetylacetonate. (10) Examples of the organic compound include 1,5, 7-triazabicyclo [4.4.0]Dec-5-ene (TBD), 2-methylimidazole (2-MI), triphenylphosphine, and the like. Among them, preferred are organotin compounds, titanate compounds, organozinc compounds, supported solid catalysts, TBD, 2-MI; more preferably, TBD and zinc acetate are mixed and used for concerted catalysis, and 2-MI and zinc acetylacetonate are mixed and used for concerted catalysis.
Among them, the catalyst for amine exchange reaction can be selected from: nitric acid, hydrochloric acid, aluminum chloride, ammonium chloride, triethylamine hydrochloride, hydroxylamine hydrochloride, hydroxylamine sulfate, N-methylhydroxylamine hydrochloride, benzylamine hydrochloride, o-benzylhydroxylamine hydrochloride, butyraldehyde oxime, benzaldehyde oxime, hydrazine monohydrate, N' -diphenylthiourea, scandium trifluoromethanesulfonate (Sc (OTf)3) Montmorillonite KSF, hafnium tetrachloride (HfCl)4)、Hf4Cl5O24H24、 HfCl4KSF-polyDMAP, transglutaminase (TGase); divalent copper compounds, such as copper acetate; examples of the trivalent iron compound include an aqueous ferric chloride solution, ferric sulfate hydrate, and ferric nitrate hydrate. Among them, copper acetate is preferable; sc (OTf) 3And HfCl4Mixing and sharing synergistic catalysis; HfCl4KSF-polyDMAP; the glycerol, the boric acid and the ferric nitrate hydrate are mixed to share the synergistic catalysis.
In the present embodiment, some of the coupling acyl exchange reactions may be performed by microwave irradiation or heating. For example, common urethane bonds, thiourethane bonds and urea bonds can be heated to 160-180 ℃ under the pressure of 4MPa to perform acyl exchange reaction; the vinylogous amide bond and the vinylogous carbamate bond can generate acyl exchange reaction through Michael addition when being heated to more than 100 ℃;
Figure BDA0002376545090000301
the urethane bond of the structure can be heated to more than 90 ℃ to carry out acyl exchange reaction with the molecular chain containing the phenolic hydroxyl or the benzyl hydroxyl structure. The present invention preferably performs the reversible reaction under normal temperature and normal pressure conditions by adding a catalyst that can be used for the binding acyl exchange reaction.
In the embodiment of the present invention, the binding exchangeable acyl bond may be formed by condensation reaction of an acyl group, a thioacyl group, an aldehyde group, a carboxyl group, an acid halide, an acid anhydride, an active ester, an isocyanate group, a hydroxyl group, an amino group, and a thiol group contained in the compound raw material, or may be introduced into the polymer by polymerization/crosslinking reaction between the reactive groups contained in the compound raw material containing the binding exchangeable acyl bond. Among these, the starting material of the compound having the exchangeable acyl bond is not particularly limited, and a polyol, a polythiol, a polyamine, an isocyanate, an epoxy compound, an alkene, an alkyne, and a carboxylic acid having the exchangeable acyl bond are preferable, and a polyol, a polyamine, an isocyanate, an epoxy compound, an alkene, and an alkyne having the exchangeable acyl bond are more preferable.
In the invention, the dynamic covalent bond based on steric effect induction contains a large group with steric effect, can be activated at room temperature or under a certain condition, and generates bond dissociation, bonding and exchange reaction, thereby showing the dynamic reversible characteristic. The steric effect induced dynamic covalent bond as described in the present invention is selected from at least one of the following structures:
Figure BDA0002376545090000302
wherein, X1、X2Selected from carbon atoms, silicon atoms and nitrogen atoms, preferably carbon atoms, nitrogen atoms; z1、Z2Selected from oxygen atoms and sulfur atoms, preferably oxygen atoms; when X is present1、X2When it is a nitrogen atom, R1、R3Exist, R2、R4Is absent, and R1、R3Each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; when X is present1、X2When it is a carbon atom or a silicon atom, R1、R2、R3、R4Are present and are each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; wherein R isbIs a bulky group with steric hindrance directly bonded to the nitrogen atom, and is selected from C3-20Alkyl, ring C3-20Alkyl, phenyl, benzyl, aromatic and unsaturated forms, substituted forms, hybridized forms of the above groups and combinations thereof, more preferably from isopropyl, benzyl, phenyl, benzyl, substituted and hybridized forms of the above groups, more preferably from isopropyl, benzyl, phenyl, benzyl, and combinations thereof,Tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, phenyl, benzyl, methylbenzyl, most preferably selected from tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, phenyl, benzyl, methylbenzyl;
Figure BDA0002376545090000303
Nitrogen-containing rings having an arbitrary number of atoms, which may be aliphatic rings or aromatic rings, which may be aliphatic rings, aromatic rings, ether rings, condensed rings, or combinations thereof, wherein the ring-forming atoms are each independently selected from a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, or another hetero atom, and the hydrogen atoms on the ring-forming atoms may be substituted with any substituent or not, and the resulting rings are preferably pyrrole rings, imidazole rings, pyrazole rings, piperidine rings, pyridine rings, pyridazine rings, pyrimidine rings, or pyrazine rings; n represents the number of linkages to the ring-forming atoms of the cyclic group structure. Typical steric effect-based induced dynamic covalent bond structures may be exemplified by:
Figure BDA0002376545090000304
Figure BDA0002376545090000311
the large group with steric hindrance effect in the invention is directly connected with a nitrogen atom or forms a ring structure with the nitrogen atom, and can weaken the chemical bond strength between a carbon atom in carbonyl and thiocarbonyl and an adjacent nitrogen atom, so that the carbon-nitrogen bond shows the property of a dynamic covalent bond, and the dynamic reversible reaction can be carried out at room temperature or under certain conditions. It is to be noted that the larger the steric effect in the "bulky group having steric effect" is, the better, the moderate size is, and the appropriate dynamic reversibility of the carbon-nitrogen bond is imparted. Said The method is used for activating the 'certain condition' of dynamic reversibility of dynamic covalent bonds induced by steric effect, and comprises the action modes of heating, pressurizing, illuminating, radiating, microwave, plasma action and the like, so that the polymer has good self-repairing property, recycling property, stimulus responsiveness and the like. For example,
Figure BDA0002376545090000312
the dynamic covalent bond of the structure can carry out dynamic exchange reaction at 60 ℃, and shows dynamic characteristics.
In the present invention, the steric effect induced dynamic covalent bond is preferably selected from steric effect induced amide bond, steric effect induced urethane bond, steric effect induced thiourethane bond, and steric effect induced urea bond.
In the embodiment of the present invention, the steric effect induced dynamic covalent bond may be formed by condensation reaction of an acyl group, a thioacyl group, an aldehyde group, a carboxyl group, an acyl halide, an acid anhydride, an active ester, an isocyanate group contained in a compound raw material and an amino group to which a bulky group having steric effect is attached, or may be introduced into a polymer by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing the steric effect induced dynamic covalent bond. Among these, the raw material of the compound having a dynamic covalent bond induced by steric hindrance is not particularly limited, and a polyol, a polythiol, a polyamine, an isocyanate, an epoxy compound, an alkene, an alkyne, or a carboxylic acid having a dynamic covalent bond induced by steric hindrance is preferably contained, and a polyol, a polyamine, an isocyanate, an epoxy compound, an alkene, or an alkyne having a dynamic covalent bond induced by steric hindrance is more preferably contained.
In the invention, the reversible addition fragmentation chain transfer dynamic covalent bond can be activated in the presence of an initiator, and a reversible addition fragmentation chain transfer reaction is carried out, so that the dynamic reversible characteristic is embodied. The reversible addition fragmentation chain transfer dynamic covalent bond described in the present invention is selected from at least one of the following structures:
Figure BDA0002376545090000313
wherein R is1～R10Each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; x1、X2、X3Each independently selected from single bond, divalent or polyvalent small molecule hydrocarbon group, preferably from divalent C1-20Alkyl groups and substituted forms thereof, hybridized forms thereof, and combinations thereof, more preferably selected from the group consisting of divalent isopropyl groups, divalent cumyl groups, divalent isopropyl ester groups, divalent isopropylcarboxyl groups, divalent isopropyl nitrile groups, divalent nitrile cumyl groups, divalent acrylic acid group n-mers, divalent acrylic ester group n-mers, divalent styrene group n-mers and substituted forms thereof, hybridized forms thereof, and combinations thereof, wherein n is greater than or equal to 2; z1、Z2、Z3Each independently selected from a single bond, a heteroatom linking group, a divalent or polyvalent small molecule hydrocarbyl group, preferably from a heteroatom linking group having or associated with a group having an electro-absorption effect, a divalent or polyvalent small molecule hydrocarbyl group having or associated with a group having an electro-absorption effect; wherein as Z 2、Z3Preferably, it can be selected from the group consisting of ether group, sulfide group, selenium group, divalent silicon group, divalent amine group, divalent phosphoric acid group, divalent phenyl group, methylene group, ethylene group, divalent styrene group, divalent isopropyl group, divalent cumyl group, divalent isopropyl ester group, divalent isopropylcarboxyl group, divalent isopropylnitrile group, divalent nitrile cumyl group; wherein, the group having the electric absorption effect includes, but is not limited to, carbonyl group, aldehyde group, nitro group, ester group, sulfonic group, amido group, sulfone group, trifluoromethyl group, aryl group, cyano group, halogen atom, alkene, alkyne and combination thereof;
Figure BDA0002376545090000314
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom.
The reversible addition fragmentation chain transfer dynamic covalent bonds described herein are preferably polyacrylic and ester groups, polymethacrylic and ester groups, polystyrene, polymethylstyrene, allyl sulfide groups, dithioester groups, diseleno groups, trithiocarbonate groups, triselenocarbonate groups, diseleno thiocarbonate groups, dithioselenocarbonate groups, bisthioester groups, bisseleno groups, bistrothiocarbonate groups, bistriselenocarbonate groups, dithiocarbamato groups, diseleno carbamate groups, dithiocarbonate groups, diseleno carbonate groups, and derivatives thereof.
Typical reversible addition fragmentation chain transfer dynamic covalent bond structures may be exemplified by:
Figure BDA0002376545090000321
wherein n is the number of the repeating units, can be a fixed value or an average value, and n is more than or equal to 1.
The "reversible addition fragmentation chain transfer reaction" described in the present invention means that when a reactive radical reacts with the reversible addition fragmentation chain transfer dynamic covalent bond described in the present invention to form an intermediate, the intermediate can be fragmented to form a new reactive radical and a new reversible addition fragmentation chain transfer dynamic covalent bond, and this process is a reversible process. This process is similar to, but not exactly identical to, the reversible addition fragmentation chain transfer process in reversible addition fragmentation chain transfer polymerization. Firstly, reversible addition fragmentation chain transfer polymerization is a solution polymerization process, and the reversible addition fragmentation chain transfer reaction can be carried out in solution or solid; in addition, in the reversible addition fragmentation chain transfer reaction, a proper amount of a substance capable of generating an active free radical can be added to generate the active free radical under a certain condition, so that the reversible addition fragmentation chain transfer dynamic covalent bond has good dynamic reversibility, and the progress of the reversible addition fragmentation chain transfer reaction is promoted.
Wherein, the initiator used in the reversible addition-fragmentation chain transfer exchange reaction includes but is not limited to any one or more of the following: photoinitiators, such as 2, 2-dimethoxy-2-phenylacetophenone (DMPA), 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenylketone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), benzophenone, 2-hydroxy-4- (2-hydroxyethoxy) -2-methylpropiophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone and alpha-ketoglutaric acid; organic peroxides such as lauroyl peroxide, Benzoyl Peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxybenzoate, t-butylperoxypivalate, di-t-butyl peroxide, diisopropylbenzene hydroperoxide; azo compounds, such as Azobisisobutyronitrile (AIBN), azobisisoheptonitrile; inorganic peroxides such as ammonium persulfate, potassium persulfate, and the like; wherein, the initiator is preferably 2, 2-dimethoxy-2-phenylacetophenone, azobisisobutyronitrile, lauroyl peroxide, benzoyl peroxide and potassium persulfate.
In embodiments of the present invention, the reversible addition fragmentation chain transfer dynamic covalent bond may be introduced into the polymer by a polymerization/crosslinking reaction between the reactive groups contained therein using a compound starting material containing the reversible addition fragmentation chain transfer dynamic covalent bond.
In the invention, the dynamic siloxane bond can be activated under the condition of catalyst or heating, and siloxane exchange reaction is carried out, so that the dynamic reversible property is embodied; the term "siloxane exchange reaction" refers to the formation of new siloxane bonds elsewhere with concomitant dissociation of old siloxane bonds, resulting in exchange of chains and a change in polymer topology. A dynamic siloxane linkage as described in the present invention, selected from the following structures:
Figure BDA0002376545090000322
wherein the content of the first and second substances,
Figure BDA0002376545090000323
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom;
Figure BDA0002376545090000324
may be looped or not looped.
In the present invention, the siloxane reaction is carried out in the presence of a catalyst or under heating, wherein the dynamic siloxane bond is preferably subjected to a siloxane bond exchange reaction in the presence of a catalyst. The catalyst can promote the siloxane equilibrium reaction, so that the dynamic polymer has good dynamic characteristics. Among them, the catalyst for the siloxane equilibrium reaction can be selected from: (1) examples of the alkali metal hydroxide include lithium hydroxide, potassium hydroxide, sodium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, and calcium hydroxide. (2) Examples of the alkali metal alkoxide and the alkali metal polyalcohol salt include potassium methoxide, sodium methoxide, lithium methoxide, potassium ethoxide, sodium ethoxide, lithium ethoxide, potassium propoxide, potassium n-butoxide, potassium isobutoxide, sodium t-butoxide, potassium t-butoxide, lithium pentoxide, potassium ethylene glycol, sodium glycerol, potassium 1, 4-butanediol, sodium 1, 3-propanediol, lithium pentaerythritol, and sodium cyclohexanolate. (3) Examples of the silicon alkoxide include potassium triphenylsilanolate, sodium dimethylphenylsilicolate, lithium tri-tert-butoxysilicolate, potassium trimethylsilolate, sodium triethylsilanolate, lithium (4-methoxyphenyl) dimethylsilolate, tri-tert-pentoxysilicolate, potassium diphenylsilanediol, and potassium benzyltrimethylammonium bis (catechol) phenylsilicolate. (4) Examples of the quaternary ammonium bases include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), trimethylbenzylammonium hydroxide, tetrabutylammonium hydroxide, (1-hexadecyl) trimethylammonium hydroxide, methyltriethylammonium hydroxide, phenyltrimethylammonium hydroxide, tetra-N-hexylammonium hydroxide, tetrapropylammonium hydroxide, tetraoctylammonium hydroxide, triethylbenzylammonium hydroxide, choline, [3- (methacrylamido) propyl ] dimethyl (3-thiopropyl) ammonium hydroxide inner salt, phenyltriethylammonium hydroxide, N, N, N-trimethyl-3- (trifluoromethyl) aniline hydroxide, N-ethyl-N, N-dimethyl-ethylammonium hydroxide, tetradecylammonium hydroxide, tetrapentylammonium hydroxide, N, N, n-trimethyl-1-adamantylammonium hydroxide, forty-eight alkyl ammonium hydroxide, N-dimethyl-N- [3- (thioxo) propyl ] -1-nonane ammonium hydroxide inner salt, (methoxycarbonylsulfamoyl) triethylammonium hydroxide, 3-sulfopropyldodecyl dimethyl betaine, 3- (N, N-dimethyl palmitylamino) propane sulfonate, methacryloylethyl sulfobetaine, N-dimethyl-N- (3-sulfopropyl) -1-octadecamonium inner salt, tributylmethyl ammonium hydroxide, tris (2-hydroxyethyl) methyl ammonium hydroxide, tetradecyl sulfobetaine, and the like. In the present invention, the catalyst used for the siloxane equilibrium reaction is preferably a catalyst of quaternary ammonium base, silanol type, or alkali metal hydroxide type, and more preferably a catalyst of lithium hydroxide, potassium trimethylsilanolate, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), or the like.
In the embodiment of the present invention, the dynamic siloxane bond may be formed by a condensation reaction between a silicon hydroxyl group and a silicon hydroxyl group precursor contained in the compound raw material, or may be introduced into the polymer by a polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing the dynamic siloxane bond. Among these, the raw material of the compound having a dynamic siloxane bond is not particularly limited, and a polyol, a polyamine, an isocyanate, a siloxane compound, a hydrosiloxane compound, an epoxy compound, an alkene, and an alkyne having a dynamic siloxane bond are preferable, and a polyol, an isocyanate, a siloxane compound, a hydrosiloxane compound, and an alkene having a dynamic siloxane bond are more preferable. Wherein the silicon hydroxyl precursor refers to a structural unit (Si-X) consisting of a silicon atom and a group which can be hydrolyzed to obtain a hydroxyl group and is connected with the silicon atom1) Wherein X is1A group hydrolyzable to give a hydroxyl group, which may be selected from halogen, cyano, oxacyano, thiocyano, alkoxy, amino, sulfate, borate, acyl, acyloxy, acylamino, ketoximeA base group, an alkoxide group. Examples of suitable silicon hydroxyl precursors are: Si-Cl, Si-CN, Si-CNS, Si-CNO, Si-SO 4CH3，Si-OB(OCH3)2，Si-NH2，Si-N(CH3)2，Si-OCH3，Si-COCH3，Si-OCOCH3， Si-CONH2，Si-O-N＝C(CH3)2，Si-ONa。
In the invention, the dynamic silicon ether bond can be activated under heating condition, and silicon ether bond exchange reaction is carried out, thus showing dynamic reversible characteristic; the "exchange reaction of the silyl ether bond" refers to the formation of a new silyl ether bond elsewhere with concomitant dissociation of the old silyl ether bond, resulting in exchange of the chains and a change in the topology of the polymer. A dynamic silicon ether linkage as described in the present invention selected from the following structures:
Figure BDA0002376545090000331
wherein the content of the first and second substances,
Figure BDA0002376545090000333
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom;
Figure BDA0002376545090000334
may be looped or not looped. Among them, the dynamic silicon ether bond is more preferably selected from the following structures:
Figure BDA0002376545090000332
in the embodiment of the present invention, the dynamic silicon ether bond can be formed by condensation reaction of silicon hydroxyl group contained in the compound raw material, silicon hydroxyl group precursor and hydroxyl group in the system, or can be introduced into the polymer by polymerization/crosslinking reaction between the reactive groups contained in the compound raw material containing the dynamic silicon ether bond. Wherein for the compound containing dynamic silicon ether bondThe material is not particularly limited, and is preferably a polyol, a polyamine, an isocyanate, a siloxane compound, a hydrosiloxane, an epoxy compound, an alkene, or an alkyne having a dynamic silicon ether bond, and more preferably a polyol, an isocyanate, a siloxane compound, a hydrosiloxane, or an alkene having a dynamic silicon ether bond. Wherein the silicon hydroxyl precursor refers to a structural unit (Si-X) consisting of a silicon atom and a group which can be hydrolyzed to obtain a hydroxyl group and is connected with the silicon atom 1) Wherein X is1Groups which are hydrolyzable to give hydroxyl groups may be selected from the group consisting of halogen, cyano, oxacyano, thiocyano, alkoxy, amino, sulfate, borate, acyl, acyloxy, amido, ketoxime, alkoxide groups. Examples of suitable silicon hydroxyl precursors are: Si-Cl, Si-CN, Si-CNS, Si-CNO, Si-SO4CH3，Si-OB(OCH3)2，Si-NH2，Si-N(CH3)2，Si-OCH3，Si-COCH3，Si-OCOCH3， Si-CONH2，Si-O-N＝C(CH3)2，Si-ONa。
In the invention, the exchangeable dynamic covalent bond based on the alkyl azacyclo-onium can be activated under certain conditions and has dynamic exchange reaction with halogenated alkyl, thus showing dynamic reversible characteristics. The exchangeable dynamic covalent bond based on azacyclium in the present invention is selected from at least one of the following structures:
Figure BDA0002376545090000341
wherein, X—Is negative ion selected from bromide ion and iodide ion, preferably bromide ion;
Figure BDA0002376545090000345
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Typical alkylazacyclonium-based exchangeable dynamic covalent bond structures are exemplified by:
Figure BDA0002376545090000342
in the embodiment of the present invention, the haloalkyl group, which may be an aliphatic haloalkyl group or an aromatic haloalkyl group, may be present in any suitable terminal group, side group and/or side chain in the dynamic polymer, or may be present in any suitable form in other components such as small molecules, oligomers, etc., and may be on the same polymer network/chain with exchangeable dynamic covalent bonds based on alkyl nitrogen azides, or on different polymer networks/chains, or may be introduced through small molecules or polymers containing haloalkyl groups.
In the present embodiment, the "certain conditions" for activating the dynamic reversibility of the exchangeable dynamic covalent bond based on the alkylazacyclonium means in the presence of the halogenated alkyl group and the solvent and under suitable conditions of temperature, humidity, pressure, etc.
In the embodiment of the present invention, the alkyl azacyclic onium-based exchangeable dynamic covalent bond may be formed by the action of a triazole/pyridyl compound with a halogenated hydrocarbon, or may be introduced into a polymer by a polymerization/crosslinking reaction between reactive groups contained therein using a compound raw material containing an alkyl azacyclic onium-based exchangeable dynamic covalent bond. Wherein, the triazole-based compound can be generated by using azide groups contained in compound raw materials to react with alkyne; wherein the halogenated hydrocarbon includes, but is not limited to, saturated halogenated hydrocarbon (for example, methyl chloride, bromocyclohexane, 1, 2-dibromoethane, triiodomethane, etc.), unsaturated halogenated hydrocarbon (for example, vinyl bromide, 3-chlorocyclohexene, 4-bromo-1-buten-3-yne, 1-bromo-2-iodocyclobutene, etc.), halogenated aromatic hydrocarbon (for example, chlorobenzene, β -bromonaphthalene, chloromethane, o-dichlorobenzene, etc.), etc.; among these, the raw material of the compound having an exchangeable dynamic covalent bond based on an alkylazacycloium is not particularly limited, and a polyol, an isocyanate, an epoxy compound, an alkene, an alkyne, a carboxylic acid, an ester, and an amide having an exchangeable dynamic covalent bond based on an alkylazacycloium are preferable, and a polyol, an isocyanate, an epoxy compound, an alkene, and an alkyne having an exchangeable dynamic covalent bond based on an alkylazacycloium are more preferable.
In the invention, the unsaturated carbon-carbon double bond capable of generating olefin cross metathesis double decomposition reaction can be activated in the presence of a catalyst and generates olefin cross metathesis double decomposition reaction, thus showing dynamic reversible characteristic; wherein, the olefin cross metathesis double decomposition reaction refers to the carbon skeleton rearrangement reaction between unsaturated carbon-carbon double bonds catalyzed by metal catalyst; wherein, the rearrangement reaction refers to the generation of new carbon-carbon double bonds at other places and the dissociation of old carbon-carbon double bonds, thereby generating the exchange of chains and the change of polymer topological structure. The structure of the unsaturated carbon-carbon double bond capable of undergoing olefin cross metathesis reaction in the present invention is not particularly limited, and is preferably selected from the following structures having low steric hindrance and high reactivity:
Figure BDA0002376545090000343
in embodiments of the present invention, the catalyst for catalyzing olefin cross metathesis reaction includes, but is not limited to, metal catalysts based on ruthenium, molybdenum, tungsten, titanium, palladium, nickel, etc.; among them, the catalyst is preferably a catalyst based on ruthenium, molybdenum, tungsten, more preferably a ruthenium catalyst having higher catalytic efficiency and being insensitive to air and water, particularly a catalyst which has been commercialized such as Grubbs 'first generation, second generation, third generation catalysts, Hoveyda-Grubbs' first generation, second generation catalysts, etc. Among these, examples of catalysts useful in the present invention for catalyzing olefin cross metathesis reactions include, but are not limited to, the following:
Figure BDA0002376545090000344
Figure BDA0002376545090000351
Wherein Py is3Is composed of
Figure BDA0002376545090000352
Mes is
Figure BDA0002376545090000353
Ph is phenyl, Et is ethyl, i-Pr is isopropyl, t-Bu is tert-butyl, and PEG is polyethylene glycol.
In the invention, the unsaturated carbon-carbon triple bond capable of generating alkyne cross metathesis reaction can be activated in the presence of a catalyst and generate alkyne cross metathesis reaction, thus showing dynamic reversible characteristic; wherein, the alkyne cross metathesis double decomposition reaction refers to the carbon skeleton rearrangement reaction between unsaturated carbon-carbon triple bonds catalyzed by a metal catalyst; the rearrangement reaction refers to the formation of new triple bonds between carbon and the dissociation of old triple bonds between carbon and carbon, resulting in exchange of chains and change of polymer topology. The structure of the unsaturated carbon-carbon triple bond in which the alkyne cross metathesis reaction can occur in the present invention is not particularly limited, and is preferably selected from the structures shown below which are small in steric hindrance and high in reactivity:
Figure BDA0002376545090000354
in embodiments of the present invention, the catalyst for catalyzing alkyne cross-metathesis reaction includes, but is not limited to, metal catalysts based on molybdenum, tungsten, and the like; among them, the catalyst is preferably a catalyst having compatibility with the functional group, such as catalysts 15 to 20 in the exemplified structure, etc.; the catalyst is also preferably a catalyst having higher catalytic efficiency and being insensitive to air, such as catalysts 1, 18-20, etc. in the exemplified structure; the catalyst is also preferably a catalyst which can function catalytically at ambient temperature or in the ambient temperature range, such as catalyst 11 in the illustrated construction. Examples of catalysts useful in the present invention for catalyzing alkyne cross metathesis reactions include, but are not limited to, the following:
Figure BDA0002376545090000361
Wherein Py is3Is composed of
Figure BDA0002376545090000362
Ph is phenyl and t-Bu is tert-butyl.
In the embodiment of the present invention, the unsaturated carbon-carbon double bond capable of olefin cross metathesis reaction and the unsaturated carbon-carbon triple bond capable of alkyne cross metathesis reaction may be derived from a selected polymer precursor containing the unsaturated carbon-carbon double bond/unsaturated carbon-carbon triple bond, or may be generated or introduced on the basis of a polymer precursor containing no unsaturated carbon-carbon double bond/unsaturated carbon-carbon triple bond. However, since the reaction conditions for forming the carbon-carbon double bond/carbon-carbon triple bond are generally harsh, it is preferable to use a polymer precursor having carbon-carbon double bond/carbon-carbon triple bond to carry out the reaction, thereby achieving the purpose of introducing carbon-carbon double bond/carbon-carbon triple bond.
Among them, polymer precursors which already contain unsaturated carbon-carbon double bonds/unsaturated carbon-carbon triple bonds include, by way of example and not limitation, butadiene rubber, 1, 2-butadiene rubber, isoprene rubber, polynorbornene, chloroprene rubber, styrene-butadiene rubber, nitrile rubber, polychloroprene, brominated polybutadiene, ethylene-propylene-diene rubber (EPDM), acrylonitrile-butadiene-styrene copolymer (ABS), styrene-butadiene rubber (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), unsaturated polyester, unsaturated polyether and its copolymer, 1, 4-butylene glycol, 1, 5-di-p-hydroxyphenyl-1, 4-pentadien-3-one, unsaturated carbon-carbon triple bonds, Glyceryl monoricinoleate, maleic acid, fumaric acid, trans-methylbutenedioic acid (mesaconic acid), cis-methylbutenedioic acid (citraconic acid), chloromaleic acid, 2-methylenesuccinic acid (itaconic acid), 4' -diphenylenedicarboxylic acid, 1, 5-di-p-hydroxyphenyl-1, 4-pentadien-3-one, fumaroyl chloride, 1, 4-phenylenediacryloyl chloride, citraconic anhydride, maleic anhydride, dimethyl fumarate, monoethyl fumarate, diethyl fumarate, dimethyl citraconate, 1, 4-dichloro-2-butene, 1, 4-dibromo-2-butene, etc., and oligomers having a carbon-carbon double bond/carbon-carbon triple bond in the terminal-functionalized chain skeleton may also be used.
In the invention, the [2+2] cycloaddition dynamic covalent bond is formed based on the [2+2] cycloaddition reaction, can be activated under a certain condition, and generates bond dissociation, bonding and exchange reaction, thus showing the dynamic reversible characteristic; wherein, the [2+2] cycloaddition reaction refers to a reaction that one unsaturated double bond and another unsaturated double bond or unsaturated triple bond respectively provide 2 pi electrons to react and add with each other to form a quaternary ring structure. The [2+2] cycloaddition dynamic covalent bond described in the present invention is selected from at least one of the following structures:
Figure BDA0002376545090000371
wherein D is1～D6Each independently selected from carbon atom, oxygen atom, sulfur atom, selenium atom, nitrogen atom, silicon atom, preferably from carbon atom, D1、 D2At least one of them is selected from carbon atom or oxygen atom or nitrogen atom or silicon atom; a is1～a6Respectively represent with D1～D6The number of connected connections; when D is present1～D6Each independently selected from oxygen atom, sulfur atom, selenium atom1～a60; when D is present1～D6Each independently selected from nitrogen atoms, a1～a61 is ═ 1; when D is present1～D6Each independently selected from carbon atom and silicon atom, a1～a6＝2；Q1～Q6Each independently selected from carbon atoms, oxygen atoms; b1～b6Respectively represent and Q1～Q6The number of connected connections; when Q is1～Q6Each independently selected from oxygen atoms, b 1～b60; when Q is1～Q6Each independently selected from carbon atoms, b1～b6＝2；
Figure BDA0002376545090000373
Represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; difference on the same atom
Figure BDA0002376545090000374
Can be linked to form a ring, on different atoms
Figure BDA0002376545090000375
May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typically [2+2]]Examples of cycloaddition dynamic covalent bond structures are:
Figure BDA0002376545090000372
in an embodiment of the present invention, the unsaturated double bond for performing the [2+2] cycloaddition reaction may be selected from a carbon-carbon double bond, a carbon-oxygen double bond, a carbon-sulfur double bond, a carbon-nitrogen double bond, a nitrogen-nitrogen double bond; unsaturated triple bonds, which may be selected from carbon-carbon triple bonds, for forming said [2+2] cycloaddition dynamic covalent bond; wherein, the unsaturated double bond and the unsaturated triple bond are preferably directly connected with an electroabsorption effect group or an electrosupply effect group, and the electroabsorption effect group comprises but is not limited to carbonyl, aldehyde group, nitro, ester group, sulfonic group, acylamino, sulfonyl, trifluoromethyl, aryl, cyano, halogen atom, alkene, alkyne and combination thereof; the electron donating effector groups include, but are not limited to, hydroxyl, p-methoxyphenyl, thioether, amino, secondary amine, tertiary amine, methyl, ethyl, isopropyl, isobutyl, and combinations thereof.
In the embodiment of the present invention, the [2+2] cycloaddition dynamic covalent bond can be formed by using unsaturated carbon-carbon double bond, azo group, carbonyl group, aldehyde group, thiocarbonyl group, imino group, cumulative diene group and ketene group contained in the compound raw material, or by [2+2] cycloaddition reaction between the unsaturated carbon-carbon double bond, azo group, carbonyl group, aldehyde group, thiocarbonyl group, imino group, cumulative diene group and ketene group, or by using the compound raw material containing the [2+2] cycloaddition dynamic covalent bond to introduce polymer by polymerization/crosslinking reaction between the reactive groups contained in the compound raw material; among them, the raw material of the compound having an unsaturated carbon-carbon double bond is preferably ethylene, propylene, acrolein, acrylonitrile, acrylate, methacrylate, butenedicarboxylic acid, cinnamyl alcohol, cinnamyl aldehyde, cinnamic acid, cinnamide, coumarin, pyrimidine, chalcone, giant knotweed, α, β -unsaturated nitro compound, cyclooctene, norbornene, maleic anhydride, p-benzoquinone, butynedicarboxylic acid, azodicarboxylate, bisthioester, maleimide, fullerene, or a derivative thereof; among these, the raw material of the compound having a [2+2] cycloaddition dynamic covalent bond is not particularly limited, and a polyol, an isocyanate, an epoxy compound, an alkene, an alkyne, a carboxylic acid, an ester, an amide, sulfur, and a mercapto compound having a [2+2] cycloaddition dynamic covalent bond are preferable, and a polyol, an isocyanate, an epoxy compound, an alkene, and an alkyne having a [2+2] cycloaddition dynamic covalent bond are more preferable.
In the invention, the [4+2] cycloaddition dynamic covalent bond is formed based on the [4+2] cycloaddition reaction, can be activated under a certain condition, and generates bond dissociation, bonding and exchange reaction, thus showing the dynamic reversible characteristic; wherein the [4+2] cycloaddition reaction refers to a reaction in which 4 pi electrons are provided by a diene group and 2 pi electrons are provided by a dienophile group to form a cyclic group structure by addition. The [4+2] cycloaddition dynamic covalent bond described in the present invention is selected from at least one of the following structures:
Figure BDA0002376545090000381
wherein, K1、K2、K5～K10Each independently selected from carbon atom, oxygen atom, sulfur atom, nitrogen atom, silicon atom, selenium atom, and at K1、 K2Or K5、K6Or K7、K8Or K9、K10In which at least one atom is selected from carbon atoms or nitrogen atoms or silicon atomsA seed; c. C1～c10Respectively represent and K1～K10The number of connected connections; when K is1、K2、K5～K10Each independently selected from oxygen atom, sulfur atom, selenium atom, c1、c2、c5～c100; when K is1、K2、K5～K10Each independently selected from nitrogen atoms, c1、c2、c5～c101 is ═ 1; when K is1、K2、K5～K10Each independently selected from carbon atom and silicon atom, c1、c2、c5～c10＝2；K3、K4Each independently selected from oxygen atom, sulfur atom, nitrogen atom; c. C3、c4Respectively represent and K3、 K4The number of connected connections; when K is3、K4Each independently selected from an oxygen atom and a sulfur atom, c 3、c40; when K is3、K4Each independently selected from nitrogen atoms, c3、c4＝1；I1、I2Each independently selected from the group consisting of an oxygen atom, a sulfur atom, a secondary amine group and substituted forms thereof, an amide group, an ester group, a divalent small hydrocarbon group, more preferably from the group consisting of an oxygen atom, a methylene group, a 1, 2-diethylene group, a 1, 2-vinylidene group, a 1, 1' -vinyl group, substituted forms of a secondary amine group, an amide group, an ester group;
Figure BDA0002376545090000383
the ring group structure is an aromatic ring or a hybrid aromatic ring, the ring atoms of the ring group structure are independently selected from carbon atoms, nitrogen atoms or other hetero atoms, the ring group structure is preferably 6-50-membered rings, more preferably 6-12-membered rings; the hydrogen atoms on each ring-forming atom may be substituted or unsubstituted, wherein, when the ring-forming atoms are selected from nitrogen atoms, the nitrogen atoms may carry a positive charge; the structure of the cyclic group is preferably benzene ring, naphthalene ring, anthracene ring and substituted forms of the above groups; n represents the number of linkages to the ring-forming atoms of the cyclic group structure;
Figure BDA0002376545090000384
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; difference on the same atom
Figure BDA0002376545090000385
Can be linked to form a ring, on different atoms
Figure BDA0002376545090000386
May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical [4+2 ] ]Examples of cycloaddition dynamic covalent bond structures are:
Figure BDA0002376545090000382
Figure BDA0002376545090000391
wherein, the [4+2] cycloaddition dynamic covalent bond can be connected with the light-control locking element to form the light-control DA structure. The light-operated locking element can react with the dynamic covalent bond and/or the light-operated locking element under a specific illumination condition to change the structure of the dynamic covalent bond, thereby achieving the purpose of locking/unlocking DA reaction; wherein, when the dynamic covalent bond is locked, it is unable or more difficult to perform DA equilibrium reaction, and when the dynamic covalent bond is unlocked, it is able to perform DA equilibrium reaction, realizing dynamic characteristics.
In the invention, the light control locking element comprises the following structural units:
Figure BDA0002376545090000392
wherein the content of the first and second substances,
Figure BDA0002376545090000393
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; difference on the same atom
Figure BDA0002376545090000394
Can be linked to form a ring, on different atoms
Figure BDA0002376545090000395
May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof;
a photo-controlled [4+2] cycloaddition dynamic covalent bond attached to a photo-control locking motif, preferably selected from at least one of the following general structures:
Figure BDA0002376545090000401
wherein, K1、K2、K3、K4、K5、K6Each independently selected from carbon atom, oxygen atom, sulfur atom, nitrogen atom, and at K 1、K2Or K3、 K4Or K5、K6At least one of them is selected from carbon atoms; a is1、a2、a3、a4、a5、a6Respectively represent and K1、K2、K3、K4、K5、K6The number of connected connections; when K is1、K2、K3、K4、K5、K6Each independently selected from an oxygen atom and a sulfur atom1、a2、a3、a4、a5、a60; when K is1、K2、K3、K4、K5、K6Each independently selected from nitrogen atoms, a1、a2、a3、a4、a5、a61 is ═ 1; when K is1、K2、K3、K4、 K5、K6Each independently selected from carbon atoms, a1、a2、a3、a4、a5、a6＝2；I1、I2、I3Each independently absent or each independently selected from the group consisting of an oxygen atom, a 1,1 '-carbonyl group, a methylene group and substituted forms thereof, a 1, 2-ethylene group and substituted forms thereof, a 1,1' -vinyl group and substituted forms thereof; when I is1、 I2、I3Each independently absent, b ═ 2; when I is1、I2、I3Each independently selected from the group consisting of an oxygen atom, 1 '-carbonyl, methylene and substituted forms thereof, 1, 2-ethylene and substituted forms thereof, 1' -vinyl and substituted forms thereof, b ═ 1; m is selected from the group consisting of an oxygen atom, a nitrogen atom, a divalent alkoxy chain: (
Figure BDA0002376545090000402
n ═ 2, 3, 4), preferably an oxygen atom or a nitrogen atom; c represents the number of connections to M; when M is selected from an oxygen atom, a divalent alkoxy chain, c ═ 0; when M is selected from nitrogen atoms, c ═ 1; c1、C2、C3、C4、C5、C6Represent carbon atoms in different positions; difference on the same atom
Figure BDA0002376545090000406
Can be linked to form a ring, on different atoms
Figure BDA0002376545090000407
Can also be linked to form a ring, where K is preferred1And K2K to3And K 4K to5And K6C to1And C2C to3And C4C to5And C6Forming a ring; the ring may be any number of rings, preferably five-membered and six-membered rings, and may be aliphatic, aromatic, ether, condensed, or combinations thereof, the ring-forming atoms are each independently selected from carbon, oxygen, nitrogen, sulfur, silicon, selenium, or other heteroatoms, and the hydrogen atom on the ring-forming atomsMay be substituted with any substituent or may be unsubstituted; wherein, K1And K2K to3And K4K to5And K6The ring formed between preferably has the following structure:
Figure BDA0002376545090000403
C1and C2C to3And C4The ring formed between preferably has the following structure:
Figure BDA0002376545090000404
C5and C6The ring formed between preferably has the following structure:
Figure BDA0002376545090000405
in the embodiment of the present invention, the diene group used for the [4+2] cycloaddition reaction may be any suitable group containing conjugated diene and its derivatives, such as butadiene, pentadiene, hexadiene, cyclopentadiene, cyclohexadiene, tetrazine, benzene, anthracene, furan, fulvene, graphene and its derivatives, etc.; dienophile groups for forming the [4+2] cycloaddition dynamic covalent bonds containing any suitable unsaturated double or triple bonds, such as carbon-carbon double bonds, carbon-carbon triple bonds, carbon-oxygen double bonds, carbon-sulfur double bonds, carbon-nitrogen double bonds, nitrogen-nitrogen double bonds, and the like; wherein, the diene group, unsaturated double bond or unsaturated triple bond in the dienophile group are preferably directly connected with the electric absorption effect group or the electric supply effect group, and the electric absorption effect group comprises but is not limited to carbonyl, aldehyde group, nitro group, ester group, sulfonic group, acylamino group, sulfonyl group, trifluoromethyl, aryl, cyano group, halogen atom, alkene, alkyne and combination thereof; the electron donating effector groups include, but are not limited to, hydroxyl, p-methoxyphenyl, thioether, amino, secondary amine, tertiary amine, methyl, ethyl, isopropyl, isobutyl, and combinations thereof.
In the embodiment of the present invention, the [4+2] cycloaddition dynamic covalent bond may be formed by a [4+2] cycloaddition reaction between a compound raw material containing a diene group and a compound raw material containing a dienophile group, or may be introduced into a polymer by a polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing a [4+2] cycloaddition dynamic covalent bond. Wherein the compound raw material containing diene group can be selected from butadiene, pentadiene, hexadiene, cyclopentadiene, cyclohexadiene, tetrazine, benzene, anthracene, furan, fulvene, graphene and derivatives of the above compounds; wherein the compound raw material containing dienophile group can be selected from ethylene, propylene, acrolein, acrylonitrile, acrylic ester, methacrylic ester, butenedicarboxylic acid, cinnamyl alcohol, cinnamyl aldehyde, cinnamic acid, cinnamyl amide, coumarin, pyrimidine, chalcone, giant knotweed rhizome, alpha, beta-unsaturated nitro compound, cyclooctene, norbornene, maleic anhydride, p-benzoquinone, butynedicarboxylic acid, azodicarboxylate, bisthioester, maleimide, fullerene and derivatives of the above compounds; among these, the raw material of the compound having a [4+2] cycloaddition dynamic covalent bond is not particularly limited, and a polyol, an isocyanate, an epoxy compound, an alkene, an alkyne, a carboxylic acid, an ester, an amide, sulfur, and a mercapto compound having a [4+2] cycloaddition dynamic covalent bond are preferable, and a polyol, an isocyanate, an epoxy compound, an alkene, and an alkyne having a [4+2] cycloaddition dynamic covalent bond are more preferable.
In the invention, the [4+4] cycloaddition dynamic covalent bond is formed based on the [4+4] cycloaddition reaction, can be activated under a certain condition, and generates bond dissociation, bonding and exchange reaction, thus showing dynamic reversible characteristics; wherein the [4+4] cycloaddition reaction refers to a reaction in which two conjugated diene groups each provide 4 pi electrons to form a cyclic group structure by addition. The [4+4] cycloaddition dynamic covalent bond described in the present invention is selected from the following structures:
Figure BDA0002376545090000411
wherein the content of the first and second substances,
Figure BDA0002376545090000412
the ring group structure is an aromatic ring or a hybrid aromatic ring, the ring atoms of the ring group structure are independently selected from carbon atoms, nitrogen atoms or other hetero atoms, the ring group structure is preferably 6-50-membered rings, more preferably 6-12-membered rings; the hydrogen atoms on each ring-forming atom may be substituted or unsubstituted, wherein, when the ring-forming atoms are selected from nitrogen atoms, the nitrogen atoms may carry a positive charge; the structure of the cyclic group is preferably benzene ring, naphthalene ring, anthracene ring, aza benzene, aza naphthalene, aza anthracene and substituted forms of the above groups; i is6～I14Each independently selected from the group consisting of an oxygen atom, a sulfur atom, an amide group, an ester group, an imine group, and a divalent small hydrocarbon group, more preferably from the group consisting of an oxygen atom, a methylene group, 1, 2-diethylene, 1, 2-vinylidene, an amide group, an ester group, and an imine group;
Figure BDA0002376545090000414
Represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; difference on the same atom
Figure BDA0002376545090000415
Can be linked to form a ring, on different atoms
Figure BDA0002376545090000416
And may be linked to form a ring, including but not limited to aliphatic rings, ether rings, condensed rings, and combinations thereof. Typically [4+4]]Examples of cycloaddition dynamic covalent bond structures are:
Figure BDA0002376545090000413
Figure BDA0002376545090000421
in an embodiment of the present invention, the conjugated diene group used for the [4+4] cycloaddition reaction may be any suitable group containing conjugated diene and its derivatives, such as benzene, anthracene, naphthalene, furan, cyclopentadiene, cyclohexadiene, pyrone, pyridone and its derivatives, and the like.
In the embodiment of the present invention, the [4+4] cycloaddition dynamic covalent bond may be formed by a [4+4] cycloaddition reaction between the compound raw materials containing the conjugated diene group, or may be introduced into the polymer by a polymerization/crosslinking reaction between the reactive groups contained in the compound raw materials containing the [4+4] cycloaddition dynamic covalent bond.
In the embodiment of the present invention, the "certain condition" for activating the dynamic reversibility of the [2+2] cycloaddition dynamic covalent bond, [4+4] cycloaddition dynamic covalent bond includes, but is not limited to, the action modes of temperature regulation, catalyst addition, illumination, radiation, microwave, etc. For example, the [2+2] cycloaddition dynamic covalent bond can be dissociated by heating at a higher temperature, and then the [2+2] cycloaddition dynamic covalent bond is reformed by heating at a lower temperature; furan and maleimide can carry out a [4+2] cycloaddition reaction at room temperature or under a heating condition to form a dynamic covalent bond, the formed dynamic covalent bond can be dissociated at a temperature higher than 110 ℃, and the dynamic covalent bond can be reformed through cooling. For another example, the [2+2] cycloaddition dynamic covalent bond can be subjected to [2+2] cycloaddition reaction under the long-wavelength light irradiation condition to form a dynamic covalent bond, and then the dynamic covalent bond is dissociated under the short-wavelength light irradiation condition to obtain an unsaturated carbon-carbon double bond again; for example, the cinnamoyl unsaturated carbon-carbon double bond can be subjected to a [2+2] cycloaddition reaction under the ultraviolet irradiation condition that the lambda is more than 280nm to form a dynamic covalent bond, and the bond dissociation is carried out under the ultraviolet irradiation condition that the lambda is less than 280nm to obtain the cinnamoyl unsaturated carbon-carbon double bond again; the coumarin unsaturated carbon-carbon double bond can be subjected to [2+2] cycloaddition reaction under the condition that lambda is larger than 319nm ultraviolet irradiation to form a dynamic covalent bond, and the bond dissociation is carried out under the condition that lambda is smaller than 319nm ultraviolet irradiation to obtain the coumarin unsaturated carbon-carbon double bond again. For another example, anthracene and maleic anhydride can undergo a [4+2] cycloaddition reaction under ultraviolet irradiation at λ 250 nm to form a dynamic covalent bond. For another example, anthracene can undergo a [4+4] cycloaddition reaction under uv irradiation at λ 365nm to form a dynamic covalent bond, and then undergo bond dissociation under uv irradiation at λ less than 300 nm. In addition, the [2+2], [4+4] cycloaddition reaction can be carried out under the catalytic condition of a catalyst to form a dynamic covalent bond, wherein the catalyst comprises but is not limited to Lewis acid, Lewis base and metal catalyst; the lewis acid includes, but is not limited to, metal chloride, metal iodide, trifluoromethanesulfonate, alkylmetal compound, borane, boron trifluoride and its derivatives, arylboron difluoride, scandium trifluoroalkylsulfonate, and the like, preferably titanium tetrachloride, aluminum trichloride, aluminum tribromide, ethylaluminum dichloride, iron tribromide, iron trichloride, tin tetrachloride, borane, boron trifluoride etherate, scandium trifluoromethanesulfonate; the Lewis bases, which include, but are not limited to, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene (TBD), azacyclocarbene (NHC), quinidine, quinine, etc.; the metal catalyst includes, but is not limited to, catalysts based on iron, cobalt, palladium, ruthenium, nickel, copper, silver, gold, molybdenum, and examples of the metal catalyst used in the present invention for catalyzing the [2+2], [4+4] cycloaddition include, but are not limited to, the following:
Figure BDA0002376545090000431
In the invention, the dynamic covalent bond of the mercapto-Michael addition can be activated under certain conditions, and bond dissociation, bonding and exchange reaction occur, thus showing the dynamic reversible characteristic; the dynamic covalent mercapto-michael addition bond described in the present invention is selected from at least one of the following structures:
Figure BDA0002376545090000432
wherein X is selected from ketone group, ester group, amide group, thiocarbonyl group and sulfone group; y is an electron withdrawing effect group including, but not limited to, aldehyde groups, carboxyl groups, nitro groups, phosphate groups, sulfonate groups, amide groups, sulfone groups, trifluoromethyl groups, cyano groups, halogen atoms, and combinations thereof;
Figure BDA0002376545090000434
denotes a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein the difference is on the same carbon atom
Figure BDA0002376545090000435
Can be linked to form a ring, on different carbon atoms
Figure BDA0002376545090000436
Or may be linked to form a ring, the carbon atom being attached to X
Figure BDA0002376545090000437
May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical mercapto-michael addition dynamic covalent bond structures may be exemplified by:
Figure BDA0002376545090000433
in the embodiment of the present invention, the "certain conditions" for activating the dynamic reversibility of the thiol-michael addition dynamic covalent bond include, but are not limited to, temperature adjustment, catalyst addition, pH adjustment, and the like. For example, the dissociated mercapto-michael addition dynamic covalent bonds can be regenerated by heating or exchanged to allow the polymer to achieve self-repairability and re-processability. For another example, for a thiol-michael addition dynamic covalent bond, it can be dissociated with a neutral or weakly alkaline solution to be in a dynamic reversible equilibrium. As another example, the presence of a catalyst that promotes the formation and exchange of dynamic covalent bonds, such mercapto-Michael addition reaction catalysts include, but are not limited to, Lewis acids, organophosphates, organo-base catalysts, nucleophilic catalysts, ionic liquid catalysts, and the like; the Lewis acid includes, but is not limited to, metal chloride, metal iodide, trifluoromethanesulfonate, alkyl metal compound, borane, boron trifluoride and its derivative, aryl boron difluoride, scandium trifluoroalkyl sulfonate, etc.; the organic phosphide includes, but is not limited to potassium phosphate, tri-n-propyl phosphine, dimethyl phenyl phosphine, methyl diphenyl phosphine, triphenyl phosphine; organic base catalysts including, but not limited to, ethylenediamine, triethanolamine, triethylamine, pyridine, diisopropylethylamine, and the like; the nucleophilic catalyst comprises 4-dimethylaminopyridine, tetrabutylammonium bromide, tetramethylguanidine, 1, 5-diazabicyclo [4,3,0] non-5-ene, 1, 8-diazabicyclo [5,4,0] -undec-7-ene, 1,5, 7-triazabicyclo [4,4,0] dec-5-ene, 1, 4-diazabicyclo [2,2,2] octane, imidazole and 1-methylimidazole; the ionic liquid catalyst includes but is not limited to 1-butyl-3-methylimidazolium hexafluorophosphate, 1- (4-sulfonic) butylpyridine, 1-butyl-3-methylimidazolium tetrahydroborate, 1-allyl-3-methylimidazolium chloride and the like.
In the embodiment of the present invention, the thiol-michael addition dynamic covalent bond may be formed by a thiol-michael addition reaction between a thiol group contained in a compound raw material and a conjugated olefin or a conjugated alkyne, or may be introduced into a polymer by a polymerization/crosslinking reaction between reactive groups contained in a compound raw material containing a thiol-michael addition dynamic covalent bond. Wherein the compound material containing conjugated olefin or conjugated alkyne can be selected from acrolein, acrylic acid, acrylate, propiolate, methacrylate, acrylamide, methacrylamide, acrylonitrile, crotonate, butenedioate, butynedioate, itaconic acid, cinnamate, vinyl sulfone, maleic anhydride, maleimide and derivatives thereof; among these, the raw material of the compound having a dynamic covalent bond of mercapto-michael addition is not particularly limited, and a polyol, an isocyanate, an epoxy compound, an alkene, an alkyne, a carboxylic acid, an ester, and an amide having a dynamic covalent bond of mercapto-michael addition are preferable, and a polyol, an isocyanate, an epoxy compound, an alkene, and an alkyne having a dynamic covalent bond of mercapto-michael addition are more preferable.
In the invention, the amine alkene-Michael addition dynamic covalent bond can be activated under a certain condition, and the dissociation, bonding and exchange reaction of bonds occur, thus showing the dynamic reversible characteristic; an amine alkene-michael addition dynamic covalent bond as described in the present invention is selected from the following structures:
Figure BDA0002376545090000442
wherein the content of the first and second substances,
Figure BDA0002376545090000443
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom.
In the embodiment of the present invention, the "certain conditions" for activating the dynamic reversibility of the amine alkene-michael addition dynamic covalent bond include, but are not limited to, temperature adjustment, pH adjustment, and the like. For example, for amine alkene-Michael addition dynamic covalent bonds, a weakly acidic (pH 5.3) solution can be used to cause dissociation and thus dynamic reversible equilibrium. As another example, the dissociated amine alkene-Michael addition dynamic covalent bond can be regenerated by heating at 50-100 deg.C or exchanged to allow the polymer to achieve self-repairability and re-processability.
In an embodiment of the present invention, the amine alkene-michael addition dynamic covalent bond may be formed by preparing an intermediate product from terephthalaldehyde, malonic acid, and malonic diester, and reacting the intermediate product with an amino compound through amine alkene-michael addition.
In the invention, the dynamic covalent bond based on triazolinedione-indole can be activated under certain conditions, and the bond dissociation, bonding and exchange reaction occur, so that the dynamic reversible characteristic is embodied; the triazolinedione-indole-based dynamic covalent bond described in the present invention is selected from the following structures:
Figure BDA0002376545090000441
wherein the content of the first and second substances,
Figure BDA0002376545090000444
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom.
In the embodiment of the present invention, the "certain conditions" for activating the dynamic covalent bond dynamic reversibility based on triazolinedione-indole include, but are not limited to, temperature regulation, pressurization, addition of a catalyst, and the like. For example, the indole and the oxazoline diketone can generate a dynamic covalent bond based on triazoline diketone-indole at the temperature of 0 ℃, the bond dissociation is realized by heating, and the dynamic covalent bond is regenerated by cooling or the exchange of the dynamic covalent bond is carried out, so that the polymer can obtain self-repairability and reprocessing property. For another example, for dynamic covalent bonds based on triazolinedione-indole, they may optionally be dissociated in neutral or slightly alkaline solution to be in dynamic reversible equilibrium. As another example, the presence of a catalyst capable of promoting the formation and exchange of dynamic covalent bonds, said addition reaction catalyst being selected from Lewis acids; the lewis acid includes, but is not limited to, metal chloride, metal iodide, trifluoromethanesulfonate, alkyl metal compound, borane, boron trifluoride and its derivative, aryl boron difluoride, scandium trifluoroalkyl sulfonate, and the like.
In an embodiment of the present invention, the dynamic covalent bond based on triazolinedione-indole may be formed by an alder-olefin addition reaction between a bisoxazolinedione group and a derivative thereof contained in a compound raw material and indole and a derivative thereof. Wherein the indole or its derivative is selected from indole-3-propionic acid, indole-3-butyric acid, indole-4-carboxylic acid, indole-5-carboxylic acid, indole-6-carboxylic acid, 4- (aminomethyl) indole, 5- (aminomethyl) indole, 3- (2-hydroxyethyl) indole, indole-4-methanol, indole-5-methanol, 3-mercaptoindole, 3-acetylenoindole, 5-amino-2 phenylindole, 2-phenyl-1H-indol-6 amine, 2-phenyl-1H-indol-3-acetaldehyde, (2-phenyl-1H-indol-3-alkyl) carboxylic acid, 6-amino-2-phenyl-1H-indole-3-carboxylic acid ethyl ester Esters, 2- (2-aminophenyl) indole, 2-phenylindole-3-acetonitrile, 4, 6-diamidino-2-phenylindole dihydrochloride, and the like.
In the invention, the dynamic covalent bond based on the dinitrogen heterocarbene can be activated under certain conditions, and the dissociation, bonding and exchange reaction of the bond are generated, thus showing the dynamic reversible characteristic; the dinitrocarbene-based dynamic covalent bond described in the present invention is selected from at least one of the following structures:
Figure BDA0002376545090000453
Wherein the content of the first and second substances,
Figure BDA0002376545090000454
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; in which, on different carbon atoms
Figure BDA0002376545090000455
May be linked to form a ring including, but not limited to, aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical bis-azacarbene based dynamic covalent bond structures may be exemplified by:
Figure BDA0002376545090000451
wherein Me represents a methyl group, Et represents an ethyl group, nBu represents an n-butyl group, Ph represents a phenyl group, and Mes represents a trimethylphenyl group.
In the embodiment of the present invention, the "certain conditions" for activating the dynamic reversibility of the double-nitrogen heterocarbene-based dynamic covalent bond include, but are not limited to, temperature regulation, solvent addition and other action modes. For example, the polymer can obtain self-repairability and reworkability by heating the dynamic covalent bond based on the diazacarbone under the temperature condition of higher than 90 ℃ to dissociate the dynamic covalent bond into a diazacarbone structure, and then reducing the temperature to regenerate the dynamic covalent bond or exchange the dynamic covalent bond.
In the embodiment of the invention, the dynamic covalent bond based on the diazacarbone can be formed by utilizing a diazacarbone group contained in a compound raw material or reacting the diazacarbone group with a thiocyano group.
In the invention, the benzoyl-based dynamic covalent bond can be activated under certain conditions and is broken to form a free radical, and the free radical can be reversibly coupled or exchanged to form the dynamic covalent bond again, thereby showing the dynamic reversible characteristic. The benzoyl-based dynamic covalent bond described in the present invention is selected from at least one of the following structures:
Figure BDA0002376545090000452
wherein each Z is independently selected from a germanium atom or a tin atom; each W is independently selected from an oxygen atom or a sulfur atom, preferably from an oxygen atom;
Figure BDA0002376545090000456
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Typical benzoyl-based dynamic covalent bond structures may be exemplified by:
Figure BDA0002376545090000461
in the embodiment of the present invention, the "certain conditions" for activating the dynamic reversibility of the benzoyl-based dynamic covalent bond include, but are not limited to, temperature regulation, illumination, radiation, microwave, and the like. For example, the dynamic covalent bond can be broken to form a free radical by heating, so that dissociation and exchange reaction of the dynamic covalent bond can be carried out, and the dynamic covalent bond is reformed and stabilized after cooling, so that the polymer can obtain self-repairability and reworkability. The dynamic covalent bond can be broken to form free radicals by illumination, so that dissociation and exchange reaction of the dynamic covalent bond can be carried out, the dynamic covalent bond is reformed after the illumination is removed, and the polymer can obtain self-repairability and reprocessing property. The radiation and the microwave can generate free radicals in the system to react with dynamic covalent bonds, so that the self-repairability and the reworkability are obtained.
In the invention, the hexahydrotriazine dynamic covalent bond can be activated under certain conditions, and bond dissociation, bonding and exchange reaction are carried out, thus showing dynamic reversible characteristics; the "certain condition" for activating the dynamic reversibility of the hexahydrotriazine dynamic covalent bond refers to an appropriate pH condition, heating condition, or the like. The hexahydrotriazine dynamic covalent bond disclosed by the invention is selected from at least one of the following structures:
Figure BDA0002376545090000462
wherein the content of the first and second substances,
Figure BDA0002376545090000464
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Typical hexahydrotriazine dynamic covalent bond structures may be mentioned, for example:
Figure BDA0002376545090000463
Figure BDA0002376545090000471
in the embodiment of the invention, the suitable pH condition for carrying out the hexahydrotriazine dynamic covalent bond dynamic reversible reaction refers to that the dynamic polymer is swelled in a solution with a certain pH value or the surface of the dynamic polymer is wetted by a solution with a certain pH value, so that the hexahydrotriazine dynamic covalent bond in the dynamic polymer shows dynamic reversibility. For example, hexahydrotriazine dynamic covalent bonds can be dissociated at a pH < 2 and reformed at neutral pH, allowing the polymer to be self-healing and re-processing. Wherein, the acid-base reagent for adjusting pH can be selected from: (1) inorganic acid, organic acid and acid salt catalyst thereof. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, phosphoric acid, and the like; examples of the organic acid include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and the like; examples of the salts include sulfate, hydrogen sulfate, and hydrogen phosphate. (2) Examples of the group IA alkali metal and compounds thereof include lithium, lithium oxide, lithium acetylacetonate, sodium methoxide, sodium ethoxide, sodium hydroxide, potassium carbonate, brilliant carbonate, and potassium tert-butoxide. (3) Examples of the group IIA alkali metal and compounds thereof include calcium, calcium oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, magnesium ethoxide and the like. (4) Aluminum metal and its compounds, for example, aluminum powder, alumina, sodium aluminate, a complex of hydrous alumina and sodium hydroxide, an aluminum alkoxide-based compound, and the like can be cited. (5) Examples of the organic compound include ammonium chloride, triethylamine hydrochloride, pyridine, hydroxylamine hydrochloride, hydroxylamine sulfate, N-methylhydroxylamine hydrochloride, benzylamine hydrochloride, o-benzylhydroxylamine hydrochloride, butyraldehyde oxime, benzaldehyde oxime, hydrazine monohydrate, N' -diphenylthiourea, scandium trifluoromethanesulfonate (Sc (OTf)) 3) And the like. (6) Examples of the divalent copper compound include copper acetate. (7) Examples of the trivalent iron compound include an aqueous ferric chloride solution, ferric sulfate hydrate, and ferric nitrate hydrate. Among them, sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, calcium hydroxide, triethylamine, pyridine, copper acetate, and potassium tert-butoxide are preferable.
In the embodiment of the invention, the hexahydrotriazine dynamic covalent bond can be formed by performing a polycondensation reaction on an amino group and an aldehyde group contained in a compound raw material at a low temperature (such as 50 ℃) to form a hexahydrotriazine dynamic covalent bond of a (I) type, and then heating the hexahydrotriazine dynamic covalent bond of a (II) type at a high temperature (such as 200 ℃); the starting compounds containing hexahydrotriazine dynamic covalent bonds can also be used to introduce polymers by polymerization/crosslinking reactions between the reactive groups they contain. Among these, the starting materials of the hexahydrotriazine compound having a dynamic covalent bond are not particularly limited, and polyols, isocyanates, epoxy compounds, alkenes, alkynes, carboxylic acids, esters, and amides having a dynamic covalent bond of hexahydrotriazine are preferable, and polyols, isocyanates, epoxy compounds, alkenes, alkynes having a dynamic covalent bond of hexahydrotriazine are more preferable.
In the invention, the dynamic exchangeable trialkyl sulfonium bond can be activated under the heating condition and undergoes alkyl exchange reaction, thus showing dynamic reversible characteristics; wherein the "transalkylation reaction" refers to the formation of new trialkylsulfonium bonds elsewhere with concomitant dissociation of old trialkylsulfonium bonds, resulting in exchange of chains and changes in polymer topology. In the present invention, the transalkylation reaction is preferably carried out under the heating conditions of 130-160 ℃. The dynamically exchangeable trialkylsulfonium linkage described in this invention is selected from the following structures:
Figure BDA0002376545090000472
wherein, X—Selected from sulfonates, preferably benzenesulfonates, more preferably p-bromobenzenesulfonates;
Figure BDA0002376545090000474
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom.
In the embodiment of the present invention, the dynamically exchangeable trialkylsulfonium bond can be formed by a mercapto-michael addition reaction between a mercapto group contained in a compound raw material and an unsaturated carbon-carbon double bond, and a sulfonate is added as an alkylating agent.
In the present invention, the dynamic acid ester bond is selected from at least one of the following structures:
Figure BDA0002376545090000473
wherein X is selected from carbon atom or silicon atom; y is selected from titanium atom, aluminum atom, chromium atom, tin atom, zirconium atom, phosphorus atom, preferably titanium atom, aluminum atom, phosphorus atom;
Figure BDA0002376545090000483
Represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; wherein a represents the number of connections to Y; when Y is selected from aluminum atom, chromium atom and phosphorus atom, a is 2; when Y is selected from titanium atom, tin atom and zirconium atom, a is 3; difference on the same atom
Figure BDA0002376545090000484
Can be linked to form a ring, on different atoms
Figure BDA0002376545090000485
May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. In the invention, the dynamic acid ester bond is preferably a dynamic titanate bond, a dynamic aluminate bond and a dynamic phosphite bond. Typical dynamic acid ester bond structures may be exemplified by:
Figure BDA0002376545090000481
in the embodiment of the present invention, the dynamic acid ester bond can be formed by reacting an alcohol or silanol moiety contained in the compound raw material with a corresponding acid or lithium ion hydride or chloride, or can be introduced by using the compound raw material containing the dynamic acid ester bond through a polymerization/crosslinking reaction between reactive groups contained therein.
In the invention, the diketone enamine dynamic covalent bond can be activated under certain conditions, and bond dissociation, bonding and exchange reaction occur, thus showing dynamic reversible characteristics; the diketoenamine dynamic covalent bond described in the present invention is selected from the following structures:
Figure BDA0002376545090000482
Wherein the content of the first and second substances,
Figure BDA0002376545090000486
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom.
In embodiments of the present invention, the "certain conditions" for activating the dynamic covalent bond reversibility of the diketoenamine include, but are not limited to, heating, suitable acidic aqueous conditions, and the like, such that the polymer exhibits good self-healing, recycling and recoverability, stimulus responsiveness, and the like. In the embodiment of the invention, the dynamic covalent bond of the diketone enamine can be dissociated in a strong acid aqueous solution and formed under anhydrous neutral conditions, and the dynamic reversibility can be obtained by adjusting an acid environment because the dynamic covalent bond has good pH stimulus responsiveness. In embodiments of the present invention, acids that may be used to provide the dynamic reaction include, but are not limited to, permanganic acid, hydrochloric acid (hydrochloric acid), sulfuric acid, nitric acid, perchloric acid, selenic acid, hydrobromic acid, hydroiodic acid, chloric acid, and the like. The acid used in the present invention may be in the form of a simple acid, an organic acid solution, an aqueous acid solution, or a vapor of an acid, without limitation.
In an embodiment of the present invention, the diketone enamine dynamic covalent bond may be formed by reacting 2-acetyl-5, 5-dimethyl-1, 3-cyclohexanedione contained in a compound raw material with an amino compound.
The boron-free dynamic covalent bond contained in the polymer can be kept stable under specific conditions, so that the purposes of providing a balanced structure and mechanical strength are achieved, and dynamic reversibility can be realized under other specific conditions, so that the material can be subjected to complete self-repairing, recycling and plastic deformation; meanwhile, different types of boron-free dynamic covalent bonds exist, so that the polymer can show different response effects to external stimuli such as heat, illumination, pressure, pH, oxidation reduction and the like, and dynamic reversible balance can be promoted or slowed down in a proper environment by selectively controlling external conditions, so that the dynamic polymer is in a required state.
In order to achieve dynamic reversible equilibrium of the boron-free dynamic covalent bond in the invention, thereby having dynamic reversibility and showing good dynamic reversible effect, the boron-free dynamic covalent bond is required to have dynamic reversibility through the modes of temperature regulation, addition of an oxidation-reduction agent, addition of a catalyst, illumination, radiation, microwave, plasma action, pH regulation and the like. Among them, the temperature adjustment means that can be used in the present invention includes, but is not limited to, water bath heating, oil bath heating, electric heating, microwave heating, laser heating, and the like. The type of illumination employed in the present invention is not limited, and ultraviolet light (UV), infrared light, visible light, laser, chemiluminescence, and more preferably ultraviolet light, infrared light, visible light are preferred. Radiation employed in the present invention includes, but is not limited to, high energy ionizing radiation such as alpha rays, beta rays, gamma rays, x rays, electron beams, and the like. The plasma action used in the present invention means a catalytic action by an ionized gaseous substance composed of positive and negative ions generated by ionizing atoms and radicals from which part of electrons are deprived. The microwave used in the present invention means an electromagnetic wave having a frequency of 300MHz to 300 GHz.
In the present invention, the supramolecular action includes, but is not limited to, the following series: in the present invention, the supramolecular interactions include, but are not limited to, metal-ligand interactions, ionic cluster interactions, ion-dipole interactions, host-guest interactions, metallophilic interactions, dipole-dipole interactions, halogen bond interactions, lewis acid-base pair interactions, cation-pi interactions, anion-pi interactions, benzene-fluorobenzene interactions, pi-pi stacking interactions, ionic hydrogen bonding interactions, radical cation dimerization interactions, phase separation, crystallization interactions, hydrogen bonding interactions.
The supramolecular effect can be a weak dynamic supramolecular effect which does not dissociate/break in the normal use process of the dynamic dilatant polymer, and the dynamic supramolecular effect can not undergo dynamic dissociation and generate interconversion dynamic behavior under the conditions of material working temperature, no external field effect and the like; or the dynamic polymer has dynamic strong dynamic supramolecular action in the normal use process of the dynamic dilatant polymer, and can generate dynamic dissociation and generate interconversion dynamic behavior under the conditions of material working temperature, no external field action and the like; the working temperature of the material is generally not higher than 60 ℃ and preferably not higher than 25 ℃. In the polymer containing strong dynamic supermolecule action, the exchange speed of the supermolecule action is high, and monomers at different positions can be exchanged, so that the force sensitive groups can be activated to a greater extent, and the polymer which is activated more uniformly can be obtained more easily. Dissociation/fragmentation can also occur under certain conditions, such as weak dynamic supramolecular interactions at high temperatures, strong competitive substances, strong mechanical forces, etc. In the present invention, supramolecular action is, unless otherwise specified, considered only as supramolecular action and not as force sensitive moiety/group; when the force-sensitive group also contains a group/unit capable of forming supramolecules and the group is one of the characteristic groups constituting the force-sensitive group, the group/unit is considered only as part of the force-sensitive group and not as a supramolecular moiety alone, unless otherwise specified; as a non-specific indication, supramolecular interactions which are regarded as force sensitive elements/groups are used only as said force sensitive elements/groups.
The non-covalent dynamics of supramolecular interactions refer to the rate of transition between their dissociative and associated/bound states, with faster rates being more dynamic. The more dynamic supramolecular action is advantageous in that self-repairability can be more easily obtained, and therefore, the supramolecular action having high strength and strong dynamics is preferable. In the present invention, when a plurality of force-sensitive groups exist in the dynamic dilatant polymer, it is not necessary that each force-sensitive group is activated by force, and such a design can make some specific force-sensitive groups not activated after the material is destroyed, for example, the activation force of some force-sensitive groups is higher than that of supramolecules, but can produce many beneficial effects, such as testing the strength of the material, the strength of supramolecules, etc.
Among them, the metal-ligand interaction described in the present invention refers to a supramolecular interaction established by a coordination bond formed by a ligand group (represented by L) and a metal center (represented by M). The ligand group is selected from cyclopentadiene or a structural unit containing at least one coordination atom or ion (represented by A). The metal center can be selected from metal ions, metal centers of metal chelates, metal centers of metal organic compounds and metal centers of metal inorganic compounds. Wherein, a coordinating atom or ion may form one or more coordination bonds with one or more metal centers, and a metal center may also form one or more coordination bonds with one or more coordinating atoms or ions. The number of coordination bonds a ligand group forms with the metal center is referred to as the number of teeth of the ligand group. In the embodiment of the present invention, in the same system, one metal center can form a metal-ligand action with one or more of a bidentate ligand, a bidentate ligand and a tridentate ligand, and different ligands can also form a ring through the metal center connection, so that the present invention can effectively provide dynamic metal-ligand actions with sufficient variety, quantity and performance, and the structures shown in the following general formulas are some examples, but the present invention is not limited thereto:
Figure BDA0002376545090000491
Wherein A is a coordinating atom or ion, M is a metal center, an A-M bond formed by each ligand group and the same metal center is a tooth, wherein the single bond connects A to indicate that the coordinating atoms or ions belong to the same ligand group, when a ligand group contains two or more coordinating atoms or ions, A can be the same atom or different atoms,selected from the group including but not limited to boron, nitrogen, oxygen, sulfur, phosphorus, silicon, arsenic, selenium, tellurium; preferably boron, nitrogen, oxygen, sulfur, phosphorus; more preferably nitrogen, oxygen; most preferably nitrogen. Incidentally, sometimes a exists in the form of negative ions;
Figure BDA0002376545090000492
is a cyclopentadiene ligand. In the present invention, it is preferable that one coordinating atom or ion form only one coordination bond with one metal center, and therefore the number of coordinating atoms or ions contained in a ligand group is the number of teeth of the ligand group. The ligand group interacts with the metal-ligand formed by the metal center (as M-L)xRepresenting the number of ligand groups interacting with the same metal center) is related to the kind and number of coordinating atoms or ions on the ligand groups, the kind and valence of the metal center, and the like.
In embodiments of the invention, where supramolecular interactions crosslinks above the gel point are formed, one metal center must be capable of forming a metal-ligand interaction with at least two of the ligand groups (i.e., M-L) in order to be able to form crosslinks based on metal-ligand interactions2Structure) or a metal-ligand interaction may be formed by multiple ligands with the same metal center, where two or more ligand groups may be the same or different. The coordination number of one metal center is limited, and the more the coordinating atoms or ions of the ligand groups, the fewer the number of ligands that one metal center can coordinate, the lower the degree of supramolecular cross-linking based on metal-ligand interaction; however, since the more denticity each ligand forms with the metal center, the stronger the coordination, the lower the dynamic properties, and thus, in the present invention, it is preferable that the number of ligand groups not exceed tridentate.
In embodiments of the invention, there may be only one ligand in a polymer chain or in a dynamic dilatant polymer system, or any suitable combination of ligands may be present simultaneously. The ligand refers to a core ligand structure, and a skeleton ligand, a side group ligand and a terminal group ligand can have the same core ligand structure, and the difference is that the connection points and/or positions of the core ligand structure connected to the polymer chain or the small molecule are different. The appropriate ligand combination can effectively prepare dynamic dilatant polymer with specific properties, for example, the synergistic and/or orthogonal effects are achieved, and the comprehensive properties of the material are improved. Suitable ligand groups (core ligand structures) may be exemplified by, but are not limited to:
Examples of monodentate ligand groups are as follows:
Figure BDA0002376545090000501
bidentate ligand groups are exemplified as follows:
Figure BDA0002376545090000502
tridentate ligand groups are exemplified below:
Figure BDA0002376545090000503
tetradentate ligand groups are exemplified below:
Figure BDA0002376545090000504
the polydentate ligands are exemplified by:
Figure BDA0002376545090000505
in embodiments of the present invention, the metal center M may be the metal center of any suitable metal ion or compound/chelate or the like, which may be selected from any suitable ionic form, compound/chelate form and combinations thereof of any one of the metals of the periodic table of the elements.
The metal is preferably a metal of the first to seventh subgroups and group eight. The metals of the first to seventh subgroups and group VIII also include the lanthanides (i.e., La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and the actinides (i.e., Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, Lr).
More preferably, the metal is a metal of the first subgroup (Cu, Ag, Au), a metal of the second subgroup (Zn, Cd), a metal of the eighth group (Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt), a metal of the lanthanide series (La, Eu, Tb, Ho, Tm, Lu), or a metal of the actinide series (Th). Further preferably, Cu, Zn, Fe, Co, Ni, Pd, Ag, Pt, Au, La, Ce, Eu, Tb, Th are selected to obtain stronger dynamic property.
In the embodiment of the present invention, the metal organic compound is not limited, and suitable examples include the following:
Figure BDA0002376545090000511
other suitable metal organic compounds capable of providing a metal center include, but are not limited to, metal-organic cages, metal-organic frameworks. Such metal organic compounds may be used alone or introduced into the polymer chain at suitable locations by means of suitable covalent chemical linkages. Those skilled in the art may implement the present invention reasonably and effectively in light of the logic and spirit of the present invention.
In the embodiment of the present invention, the metal inorganic compound is preferably an oxide or sulfide particle of the above metal, particularly a nanoparticle.
In embodiments of the present invention, the metal chelate compound which can provide a suitable metal center is preferably a chelate compound having a vacancy in a coordination site, or a chelate compound in which a part of the ligands can be substituted with the skeletal ligand of the present invention.
In the embodiment of the present invention, the combination of the ligand group and the metal center is not particularly limited as long as the ligand can form a suitable metal-ligand interaction with the metal center. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:
Figure BDA0002376545090000512
Figure BDA0002376545090000521
The ionic interaction in the present invention refers to a supramolecular interaction which contains at least one pair of ionic groups with positive and negative charges in a dynamic dilatant polymer structure and is formed by coulomb force between the positive ionic group and the negative ionic group. The cationic group refers to a group having a positive charge, and examples thereof include:
Figure BDA0002376545090000522
preference is given to
Figure BDA0002376545090000523
The anionic group refers to a group having a negative charge, and examples thereof include: -O-、
Figure BDA0002376545090000524
Preference is given to
Figure BDA0002376545090000525
Figure BDA0002376545090000526
Wherein the anionic groups may also be present in clay minerals including, but not limited to, kaolinite, antigorite, pyrophyllite, talc, montmorillonite, saponite, stone, hydromicas, micas, chlorite, palygorskite, sepiolite. In special cases, the positive and negative ionic groups may be in the same compound structure, such as choline glycerophosphate, 2-methacryloyloxyethyl phosphorylcholine, l-carnitine, methacryloylethyl sulfobetaine, etc. The ionic action being stable in the polymer and being possible by modification of the ionic groupsThe concentration and the type can well control the strength of the ion action.
In the embodiment of the present invention, the combination of the positive ionic group and the negative ionic group is not particularly limited as long as the positive ionic group can form a suitable ionic action with the negative ionic group. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:
Figure BDA0002376545090000527
the ion cluster action in the present invention is formed by aggregating ten or more to several tens of pairs of anions and cations. Wherein the anionic group is an organic group which is relatively susceptible to losing a proton, and the cationic group is an organic group which is relatively susceptible to accepting a proton or a metal ion which is relatively susceptible to losing an electron. By way of example, anions that can be incorporated into the polymer include, but are not limited to, negative oxygen ions, carboxylates, sulfonates, phosphates, phosphites, and the like, and counter cations with which cation-anion pairs can be formed include, but are not limited to, alkali metal ions, alkaline earth metal ions, transition metal ions, ammonium, pyridinium, and the like; cations that may be incorporated into the polymer include, but are not limited to, ammonium, pyridinium, and the like, and counter anions with which cation-anion pairs may be formed include, but are not limited to, fluoride, chloride, bromide, iodide, tosylate, and the like. The ion cluster effect has humidity sensitivity, and the counter ions are not directly connected with the polymer, and the strength of the ion cluster effect can be regulated and controlled by changing the quantity and the types of the counter ions and the like.
In the embodiment of the present invention, when the ion cluster effect exists, the cations and anions do not have any limitation on the position in the polymer molecule.
In the embodiment of the present invention, the anion and cation pairs that can form ion clusters are not particularly limited, and some suitable anion and cation pairs may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000528
the ion-dipole effect in the present invention refers to a supramolecular effect formed by interaction between an electric dipole and a charged ionic group, wherein when two atoms with different electronegativities are bonded, the electric charge distribution is not uniform due to the induction of the atom with the greater electronegativity, resulting in asymmetric distribution of electrons. The ionic group may be any suitable charged group, such as the following, but the invention is not limited thereto:
Figure BDA0002376545090000531
preference is given to
Figure BDA0002376545090000532
Figure BDA0002376545090000533
The electric dipole may be generated by bonding any suitable two atoms with different electronegativities, such as the following, but the invention is not limited thereto: C-H, C ≡ N, C ≡ N, C ≡ O, C-O, C-S, C ≡ S, C-F, C-Cl, C-Br, C-I, H-O, H-S, H-N, preferably C ≡ N, C ≡ O, C-F, H-O. The ion-dipole effect can stably exist in an electrochemical environment, the acting force is easy to regulate and control, and the conditions of generating and dissociating the acting force are mild.
In the embodiment of the present invention, the combination of the ionic group and the electric dipole is not particularly limited as long as the ionic group can form a suitable ion-dipole action with the electric dipole. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:
Figure BDA0002376545090000534
where in the present invention host-guest interaction is used, it is meant any suitable host of supramolecular interaction established by host-guest interaction. Wherein, the main body (represented by H) is a compound (macromolecule or inorganic organic ion framework) with a cavity capable of realizing molecular recognition; the guest (denoted by G) is a compound (small molecule or ionic group) that can be recognized by the host and inserted into the cavity of the host. One host molecule can recognize and bond to a plurality of guest molecules, and in the embodiment of the present invention, it is preferable that one host molecule recognizes at most two guest molecules. The host molecule includes but is not limited to ether (including crown ether, crypt ether, spherulite, hemispheric ether, pod ether, lasso ether, benzocrown ether, heterocrown ether, heterocrypt ether, mixed crypt ether), cyclodextrin, cyclophane, cucurbituril, calixarene, pillararene and suitable inorganic organic ionic frameworks, preferably crown ether, beta-cyclodextrin, cucurbit [8] urea, calix [4] arene, and pillararene. The guest molecule includes, but is not limited to, long-chain alkane, cycloalkane, heterocyclic alkane, aromatic hydrocarbon, heteroarene, fused ring structure compound, heterocyclic structure compound, monocyclic structure compound, polycyclic structure compound, spiro structure compound, bridged ring structure compound, and suitable ionic group, preferably long-chain alkane, heterocyclic compound, polycyclic compound, bridged ring compound, and suitable ionic group. The host molecule and the guest molecule can exist in the polymer stably, the formed host and guest have moderate action strength, and can interact or dissociate under mild conditions, so that the dynamic property of the dynamic dilatant polymer can be realized under ordinary conditions.
Suitable host molecules may be exemplified by, but are not limited to:
Figure BDA0002376545090000535
Figure BDA0002376545090000541
Ni(PDC)(H2O)2skeleton, Zn3(PTC)2(H2O)8·4H2An O skeleton;
suitable guest molecules may be exemplified by, but are not limited to:
Figure BDA0002376545090000542
in the embodiment of the present invention, the combination of the host molecule and the guest molecule is not particularly limited as long as the host can form a suitable host-guest interaction with the guest. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:
Figure BDA0002376545090000543
wherein, the term "metallophilic" as used in the present invention means when the two outermost electronic structures are d10Or d8The metal ions of (a) are brought closer to less than the sum of their van der waals radii; wherein, the two metal ions which have the effect of the metallophilic can be the same or different. The outermost electronic structure is d10Metal ions of (2) include, but are not limited to, Cu+、Ag+、Au+、Zn2+、Hg2+、Cd2+Preferably of Au+、 Cd2+(ii) a The outermost electronic structure is d8Metal ions of (2) include, but are not limited to, Co+、Ir+、Rh+、Ni2+、Pt2+、Pb2+Preferably Pt2+、 Pb2+. The metallophilic action can exist stably in the polymer, has moderate action strength, certain directionality and no obvious saturation, can be aggregated to form a polynuclear complex, is less influenced by the external environment, and can ensure that the dynamic property of the prepared polymer is more sufficient.
In the embodiment of the present invention, the combination of forming the metallophilic action is not particularly limited as long as a suitable metallophilic action is formed between metal ions. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:
Cu—Cu、Ag—Ag、Au—Au、Zn—Zn、Hg—Hg、Cd—Cd、Co—Co、Ir—Ir、Rh—Rh、Ni—Ni、Pt—Pt、 Pb—Pb、Cu—Ag、Cu—Au、Ag—Au、Cu—Zn、Cu—Co、Cu—Pt、Zn—Co、Zn—Pt、Co—Pt、Co—Rh、 Ni—Pb。
herein, the dipole-dipole effect in the present invention refers to that when two atoms with different electronegativities are bonded, the charge distribution is not uniform due to the induction of the atom with the greater electronegativity, resulting in asymmetric distribution of electrons, resulting in electric dipoles, and the interaction between the two electric dipoles. The electric dipole may be generated by bonding any suitable two atoms with different electronegativities, such as the following, but the invention is not limited thereto: C-N, C ≡ N, C ≡ N, C ≡ O, C-O, C-S, C ≡ S, C-F, C-Cl, C-Br, C-I, H-O, H-S, H-N, preferably C ≡ N, C ≡ O, C-F, H-O, and more preferably C ≡ N. The dipole-dipole effect can stably exist in the polymer and is easy to regulate, and the pairing of the acting groups can generate a micro-domain, so that the interaction is more stable; at higher temperatures, the dipole-dipole effect is reduced or even eliminated, and thus polymers containing dipole-dipole effects may exhibit differences in dynamics depending on the temperature differences.
In the embodiment of the present invention, the combination between the electric dipoles is not particularly limited as long as an appropriate dipole-dipole action can be formed between the electric dipoles. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:
Figure BDA0002376545090000544
among them, the halogen bond interaction in the present invention refers to a non-covalent interaction formed between a halogen atom and a neutral or negatively charged lewis base, and is essentially an interaction between a sigma-anti bond orbital of the halogen atom and an atom or pi-electron system having a lone electron pair. Halogen bond interactions can be represented by-X.Y-, wherein X can be selected from Cl, Br, I, preferably Br, I; y can be selected from F, Cl, Br, I, N, O, S, pi bond, preferably Br, I, N, O. The halogen bond has directional and linear inclined geometric characteristics; as the atomic number of halogen increases, the number of electron donors that can be bonded increases, and the strength of the halogen bond formed increases. Based on halogen bond effect, ordered and self-repairing dynamic dilatant polymer can be designed.
In the embodiment of the present invention, the combination of atoms forming the halogen bond function is not limited as long as a stable halogen bond function can be formed in the dynamic dilatant polymer. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:
—Cl···Cl—、—Cl···F—、—Cl···Br—、—Cl···I—、—Cl···N—、—Cl···O—、—Cl···S—、—Cl···π—、—Br···Br—、—Br···F—、—Br···I—、—Br···N—、—Br···O—、—Br···S—、—Br···π—、—I···I—、—I···F—、—I···N—、—I···O—、—I···S—、—I···π—。
Herein, the Lewis acid-base pair referred to in the present invention refers to a non-covalent interaction formed between a Lewis acid and a Lewis base. Wherein, the lewis acid refers to a substance (including molecules, ions or atomic groups) capable of accepting an electron pair, and can be selected from positive ion groups (such as alkyl positive ions, nitro positive ions, quaternary ammonium positive ions, imidazole positive ions and the like), metal ions (such as sodium ions, potassium ions, calcium ions, magnesium ions and the like), electron-deficient compounds (such as boron trifluoride, organoborane, aluminum chloride, ferric chloride, sulfur trioxide, dichlorocarbene, trifluoromethanesulfonate and the like), and the lewis acid is preferably alkyl positive ions, quaternary ammonium positive ions, imidazole positive ions, organoborane, and more preferably organoborane; the Lewis base refers to a substance (including a molecule, an ion or an atomic group) capable of giving an electron pair, which may be selected from the group consisting of an anionic group (e.g., a halide, an oxide, a sulfide, a hydroxide, a carbonate, a nitrate, a sulfate, a phosphate, an alkoxide, an olefin, an aromatic compound, etc.), a compound having a lone pair of electrons (e.g., ammonia, an amine, an imine, an azo compound, a nitroso compound, cyanogen, an isocyanate, an alcohol, an ether, a thiol, monooxide Carbon dioxide, nitrogen monoxide, nitrous oxide, sulfur dioxide, organophosphanes, carbenes, etc.), the lewis base being preferably an alkoxide, an alkene, an aromatic compound, an amine, an azo compound, a nitroso compound, an isocyanate, carbon dioxide, an organophosphane, more preferably an amine, an azo compound, a nitroso compound, an organophosphane. Wherein, the Lewis acid-base pair action is preferably a 'hindered Lewis acid-base pair action', and the 'hindered Lewis acid-base pair action' means that at least one of Lewis acid and Lewis base in the Lewis acid-base pair action needs to be connected with a 'bulky group with steric effect'; said "bulky group with steric hindrance" may weaken the strength of the coordination bond between the Lewis acid and the Lewis base, thereby allowing the Lewis acid-base pair to exhibit the property of a strong dynamic supramolecule selected from the group consisting of C3-20Alkyl, ring C3-20Alkyl, phenyl, benzyl, aralkyl and unsaturated forms, substituted forms, hybridized forms of the above groups and combinations thereof, more preferably from isopropyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, phenyl, trimethylphenyl, fluorophenyl, benzyl, methylbenzyl, most preferably from tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, phenyl, trimethylphenyl, fluorophenyl, benzyl, methylbenzyl. Wherein the azo compound is preferably selected from azomethane, azotert-butane, N-methylazomethylamine, N-methylazoethylamine, N-ethylazoethylamine, azodiacetic acid, azobenzene, azodiphenylamine, dichloroazobenzene, azobisisobutyronitrile, azodicarbonamide, dimethyl azodicarboxylate, diethyl azodicarboxylate, diisopropyl azodicarboxylate, di-tert-butyl azodicarboxylate; the nitroso compound is preferably selected from the group consisting of nitrosomethane, nitrosotert-butane, N-nitrosoethanolamine, nitrosobenzene, nitrosotoluene, nitrosochlorobenzene, nitrosonaphthalene, and N-nitrosourea. The Lewis acid-base pair has good dynamic reversibility and can The rapid dissociation is carried out under slight heating or in the presence of an organic solvent, thereby realizing self-repairing or reshaping.
In the embodiment of the present invention, the combination of the formation of the lewis acid-base pair effect is not limited as long as a stable lewis acid-base pair effect can be formed in the dynamic dilatant polymer. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:
Figure BDA0002376545090000551
Figure BDA0002376545090000561
wherein, in the present invention, the cation-pi action refers to the non-covalent interaction formed between a cationic group and an aromatic pi system. There are three main classes of cation-pi action, the first group being simple inorganic cations or ionic groups (e.g. Na)+、K+、Mg2+、NH4 +、Ca2+) And aromatic pi systems; the second group is the interaction between organic cations (e.g., quaternary ammonium cations) and aromatic pi systems; the third type is the interaction between positively charged atoms in dipole bonds (e.g., H atoms in N-H bonds) and aromatic π systems. The cation-pi effect has rich varieties and moderate strength, can stably exist in various environments, and can prepare dynamic dilatant polymer with rich performance based on the cation-pi effect.
In the embodiment of the present invention, the kind of the cation-. pi.function is not particularly limited as long as it can form a stable cation-. pi.function in the dynamic dilatant polymer. Some suitable cationic groups may be exemplified by, but are not limited to:
Figure BDA0002376545090000562
Na+、K+、Li+、Mg2+、Ca2 +、Be2+、 H-O、H-S、H-N。
Wherein, in the present invention, anion-pi interaction refers to non-covalent interaction formed between an anionic group and an electron-deficient aromatic pi system. The anionic groups may be simple inorganic non-metallic ions or ionic groups (e.g. Cl)-、Br-、I-、OH-) (ii) a Or an organic anionic group (e.g., a benzenesulfonic acid group); it may also be a negatively charged atom in a dipole bond (e.g. a chlorine atom in a C-Cl bond). The electron-deficient aromatic pi system means that due to different electronegativities of ring-forming atoms, the density distribution of pi electron clouds of rings is not uniform, and pi electrons mainly deviate to the electronegativity high electron direction, so that the density distribution of the pi electron clouds of aromatic rings is reduced, such as pyridine, fluorobenzene and the like. The anion-pi action has reversibility and controllable identification, and can be used for constructing dynamic dilatant polymers with special properties.
In the embodiment of the present invention, the kind of the anion-. pi.action is not particularly limited as long as it can form a stable anion-. pi.action in the dynamic dilatant polymer. Some suitable anionic groups may be exemplified by, but are not limited to:
Figure BDA0002376545090000563
Cl-、Br-、I-、OH-、SCN-；
some suitable electron deficient aromatic pi systems may be exemplified, but the invention is not limited thereto: pyridine, pyridazine, fluorobenzene, nitrobenzene, tetraoxacalix [2] arene [2] triazine and benzene tri-imide.
In the present invention, the benzene-fluorobenzene reaction refers to a non-covalent interaction between an aromatic hydrocarbon and a polyfluorinated aromatic hydrocarbon, which is composed of the combination of dispersive force and quadrupole moment. Because the ionization potential of fluorine atoms is very high and the atomic polarizability and atomic radius are both small, the fluorine atoms around the polyfluorinated aromatic hydrocarbon are negatively charged due to large electronegativity, and the skeleton of the central carbon ring is positively charged due to small electronegativity. Because the electronegativity of the carbon atom is greater than that of the hydrogen atom, the direction of the electric quadrupole moment of the aromatic hydrocarbon is opposite to that of the polyfluorinated aromatic hydrocarbon, and because the volume of the fluorine atom is very small, the volume of the polyfluorinated aromatic hydrocarbon is similar to that of the aromatic hydrocarbon, the aromatic hydrocarbon and the polyfluorinated aromatic hydrocarbon are stacked in an alternate face-to-face mode to form a columnar stacking structure, and the stacking mode is basically not influenced by the introduced functional group. The reversibility and stacking effect of the benzene-fluorobenzene action are utilized to prepare the dynamic dilatant polymer with special functions.
In the embodiment of the present invention, the kind of the benzene-fluorobenzene action is not limited as long as a stable benzene-fluorobenzene action can be formed in the dynamic dilatant polymer. Some suitable benzene-fluorobenzene reactions may be exemplified by, but the invention is not limited to:
Figure BDA0002376545090000564
Wherein, the pi-pi stacking effect in the invention refers to the pi-pi stacking effect formed by overlapping pi-bond electron clouds due to the fact that the dynamic dilatant polymer contains an aromatic pi system capable of providing the pi-bond electron clouds. Pi-pi stacking functions in three ways, including face-to-face stacking, offset stacking, and edge-to-face stacking. The surface accumulation means that the interactive ring surfaces are parallel to each other, the distance between the centers of the parallel ring surfaces is almost equal to the distance between the ring surfaces, the pi-pi action of the accumulation mode is electrostatic mutual exclusion and is relatively unstable, but when the electron-withdrawing property of a substituent group connected to the ring surfaces is relatively strong, the pi-pi action of the surface accumulation becomes relatively obvious; the offset accumulation means that the action ring surfaces are parallel to each other, but the center of the ring has certain offset, namely the distance of the center of the ring is larger than the distance between the ring surfaces, the accumulation mode relieves the mutual exclusion action between the two ring surfaces, correspondingly increases the attraction of sigma-pi, and is a common accumulation mode; stacking other than planar stacking and offset stacking is called edge-planar stacking, which has the smallest energy and the smallest intermolecular repulsion, and is often found between ring-conjugated molecules having smaller van der waals surfaces or between ring-conjugated molecules having flexible linkers.
Aromatic pi systems capable of providing pi-bonded electron clouds, including but not limited to most condensed ring compounds and some heterocyclic compounds in which pi-pi conjugation occurs, suitable aromatic pi systems may be exemplified by, but are not limited to, the following:
Figure BDA0002376545090000571
Figure BDA0002376545090000572
preference is given to
Figure BDA0002376545090000573
The pi-pi stacking effect has simple forming mode, can stably exist in the polymer, is less influenced by the external environment, and can be conveniently regulated and controlled by changing the conjugated compound and the content.
In the embodiment of the present invention, the combination of the aromatic pi systems providing the pi-bond electron cloud is not particularly limited as long as a suitable pi-pi stacking effect is formed between the aromatic pi systems. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:
Figure BDA0002376545090000574
the ionic hydrogen bonding in the invention is composed of a positive ionic group and a negative ionic group which can form hydrogen bonding, and simultaneously forms hydrogen bonding and coulomb interaction between positive ions and negative ions, or is composed of a positive/negative ionic group which can form hydrogen bonding and a neutral hydrogen bonding group, and simultaneously forms hydrogen bonding and ion-dipole interaction between positive ions and negative ions and the neutral group.
In the embodiments of the present invention, some suitable combinations of ionic hydrogen bonding can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000575
Figure BDA0002376545090000581
Herein, the radical cationic dimerization referred to in the present invention refers to a supramolecular interaction established by interaction between radical cationic groups containing both radical and cation. By way of example, the radical cationic groups that can form radical cationic dimerization include, but are not limited to, the following:
Figure BDA0002376545090000582
in an embodiment of the present invention, some suitable combinations of free radical cationic dimerization may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000583
herein, the phase separation effect in the present invention refers to an unstable tendency of separation between phases due to a change in a certain environmental condition in a multi-phase system, and includes phase separation caused during a supramolecular action such as coordination, recombination, assembly, combination, aggregation, etc., phase separation caused by an incompatible phase, phase separation caused by an incompatible block structure, etc.
In the embodiments of the present invention, the phase topology (phase morphology) formed by phase separation is not limited, and includes, but is not limited to, spherical, cylindrical, helical, lamellar, and combinations thereof. Any phase, including different phases, can be dispersed in another phase, can form interpenetrating double/multiple continuous phases with other phases, can be mutually independent continuous phases, and can also be in a mixed form. In the embodiment of the present invention, it is preferable that one phase is dispersed in the other phase in a spherical shape as phase-separated physical crosslinking, so that the polymer can more conveniently have better flexibility and elasticity and more suitably exert dynamic properties.
In the present invention, the crystallization refers to a process in which polymer chains are arranged and folded to form ordered domains, and includes crystallization caused by a supramolecular interaction process such as coordination, recombination, assembly, combination, aggregation, etc., crystallization caused by an incompatible phase, crystallization caused by an incompatible block structure, crystallization caused by a regular easy-to-crystallize segment, crystallization caused by a liquid crystal, etc. The liquid crystal chain segment is introduced, and crystallization caused by liquid crystal can be utilized to effectively regulate and control crystallization, so that dynamic reversible transformation can be realized under the stimulation conditions of heat, light, pH, chemical change and the like; wherein, the liquid crystal chain segment can be introduced by liquid crystal polymers (such as poly-p-benzamide, poly-p-phenylene terephthamide, poly-benzothiazole, poly-benzoxazole and the like), mesogens (such as 4, 4' -dimethoxyazobenzene, ethylene-p-methoxyphenyl terephthalate, mesogenic diacrylate and the like) and the like.
In the present invention, the phase separation and crystallization may be independent of each other, or may be simultaneously carried out by the same unit structure. The phase separation and/or crystallization generated by the supermolecule effect not only has the functions of increasing the apparent molecular weight of the supermolecule and regulating the topological structure of the supermolecule and the microstructure of the polymer, but also has the self-reinforcing effect, and can improve the properties of the polymer, such as strength, modulus and the like.
In an embodiment of the present invention, the dynamic dilatant polymer having said phase separation/crystallization may be a segment based on, but not limited to, the following polymer segments, groups or any combination thereof: amorphous polymer segments with high glass transition temperatures (i.e., glass transition temperatures above the upper limit of the material's operating temperature, typically above 40 ℃, preferably not less than 100 ℃), such as polystyrene, polymethylmethacrylate, polyvinylpyridine, hydrogenated polynorbornene, polyether, polyester, polyetheretherketone, polyaromatic carbonate, polysulfone, and the like; hydrogen bond group-rich polymer segments, groups such as polyamides, polypeptides, urea bond-rich segments, urethane bond-rich segments, ureido pyrimidinone-based segments, and the like; polymer segments, groups rich in crystalline phases, such as crystalline polyethylene, crystalline polypropylene, crystalline polyester, crystalline polyether, liquid crystal polymer, liquid crystal groups, and the like; ionic polymer segments such as polyacrylate, polymethacrylate, polyacrylamide, polystyrene sulfonate, and the like; polymer chain segments rich in conjugated structures, such as polyacetylene, polyphenylacetylene, polyphenyl, polyfluorene, polythiophene and the like. Among them, amorphous polymer segments with high glass transition temperature, polymer segments/groups rich in hydrogen bonding groups, and polymer segments/groups rich in crystalline phases are preferable in order to design and control the molecular structure of the dynamic dilatant polymer to obtain the best performance.
The hydrogen bonding in the present invention is any suitable supramolecular interaction established by hydrogen bonding, and is generally a hydrogen bonding linkage in the form of Z-H … Y formed by hydrogen mediated between Z and Y through a hydrogen atom covalently linked to atom Z with large electronegativity and atom Y with large electronegativity and small radius, wherein Z, Y is any suitable atom with large electronegativity and small radius, which may be the same kind of element or different kind of element, and may be selected from atoms of F, N, O, C, S, Cl, P, Br, I, etc., more preferably F, N, O atom, and more preferably O, N atom. The hydrogen bond function can exist as supramolecular polymerization and/or crosslinking and/or intrachain cyclization, namely the hydrogen bond can only play a role of connecting two or more chain segment units to increase the size of a polymer chain but not play a role of supramolecular crosslinking, or the hydrogen bond only plays a role of interchain supramolecular crosslinking, or only plays a role of intrachain cyclization, or the combination of any two or more of the three. The present invention also does not exclude that the hydrogen bonds play a grafting role.
In embodiments of the present invention, the hydrogen bonds may be any number of teeth. Wherein the number of teeth refers to the number of hydrogen bonds formed by a donor (H, i.e., a hydrogen atom) and an acceptor (Y, i.e., an electronegative atom that accepts a hydrogen atom) of hydrogen bonding groups, each H … Y combining into one tooth. In the following formula, the hydrogen bonding of monodentate, bidentate and tridentate hydrogen bonding groups is schematically illustrated, respectively.
Figure BDA0002376545090000591
The bonding of the monodentate, bidentate and tridentate hydrogen bonds can be specifically exemplified as follows:
Figure BDA0002376545090000592
the more the number of teeth of the hydrogen bond, the greater the synergistic effect and the greater the strength of the hydrogen bond. In the embodiment of the present invention, the number of teeth of the hydrogen bond is not limited. If the number of teeth of the hydrogen bond is large, the strength is high, the dynamic property of the hydrogen bond action is weak, and the dynamic dilatant polymer can be promoted to keep a balanced structure and improve the mechanical properties (modulus and strength). If the number of teeth of the hydrogen bond is small, the strength is low, and the dynamics of the hydrogen bonding action is strong. In embodiments of the invention, preferably no more than four teeth hydrogen bonding are involved.
In embodiments of the invention, the hydrogen bonding may be effected by the presence of non-covalent interactions between any suitable hydrogen bonding groups. Wherein, the hydrogen bond group can only contain a hydrogen bond donor, only contain a hydrogen bond acceptor, or contain both the hydrogen bond donor and the hydrogen bond acceptor, preferably contain both the hydrogen bond donor and the hydrogen bond acceptor. Wherein, the hydrogen bonding group preferably comprises the following structural components:
Figure BDA0002376545090000593
more preferably at least one of the following structural components:
Figure BDA0002376545090000594
further preferably at least one of the following structural components:
Figure BDA0002376545090000595
Wherein the content of the first and second substances,
Figure BDA0002376545090000596
refers to a linkage to a polymer chain, cross-link, or any other suitable group/atom, including a hydrogen atom. In the embodiments of the present invention, the hydrogen bonding group is preferably selected from amide groups, carbamate groups, urea groups, thiocarbamate groups, thiourea groups, pyrazolyl groups, imidazolyl groups, imidazolinyl groups, triazolyl groups, purine groups, porphyrin groups, derivatives thereof, and the like.
In the present invention, said hydrogen bonding groups may be present only on the polymer chain backbone (including side chains/branches/bifurcations), referred to as backbone hydrogen bonding groups; or may be present only in pendant groups (also including multilevel structures of pendant groups), referred to as pendant hydrogen bonding groups; or may be present only on the polymer chain/small molecule end group, referred to as an end hydrogen bonding group; or may be present in at least two of the polymer chain backbone, the polymer chain pendant group, the polymer chain/small molecule end group. When present on at least two of the polymer chain backbone, the polymer chain pendant groups, and the polymer chain/small molecule end groups at the same time, hydrogen bonds may be formed between hydrogen bonding groups in different positions, in particular instances, for example, the backbone hydrogen bonding groups may form hydrogen bonds with the pendant hydrogen bonding groups. The hydrogen bonding groups may also be present in polymer constituents such as small molecule compounds or fillers, referred to as other hydrogen bonding groups.
Among these, suitable backbone hydrogen bonding groups are exemplified by (but the invention is not limited to):
Figure BDA0002376545090000601
among these, suitable pendant hydrogen bonding groups/terminal hydrogen bonding groups may have the above-mentioned skeleton hydrogen bonding group structure, and are exemplified by (but the invention is not limited to) the following:
Figure BDA0002376545090000602
Figure BDA0002376545090000611
wherein m and n are the number of repeating units, and may be fixed values or average values, and are preferably less than 20, and more preferably less than 5.
Other hydrogen bonding groups in the present invention may be any suitable hydrogen bonding structure.
In the invention, the same polymer system may contain one or more than one hydrogen bonding group, and the same cross-linking network may also contain one or more than one hydrogen bonding group, that is, the dynamic dilatant polymer may contain a combination of one or more than one hydrogen bonding group. The hydrogen bonding groups may be formed by reaction between any suitable groups, for example: formed by covalent reaction between carboxyl groups, acid halide groups, acid anhydride groups, ester groups, amide groups, isocyanate groups and amino groups; formed by covalent reaction between isocyanate groups and hydroxyl, mercapto and carboxyl groups; formed by covalent reaction between the succinimide group and amino, hydroxyl, sulfhydryl groups. The hydrogen bonding can be generated in the process of dynamic supermolecular crosslinking of the dynamic dilatant polymer; or the dynamic supermolecule crosslinking is carried out after the hydrogen bond action is generated in advance; it is also possible to generate hydrogen bonding during the subsequent shaping of the dynamic dilatant polymer after the formation of dynamic supramolecular crosslinks, but the invention is not limited thereto.
In the invention, the dynamic dilatancy polymer for energy absorption has the advantages of rich component structure, various performances, wide raw material sources and strong controllability. By controlling the parameters of the molecular structure, the number of functional groups, the molecular weight and the like of the compound serving as the raw material, the dynamic dilatant polymer with different apparent characteristics, adjustable performance and wide application can be prepared. For example, by controlling the number of functional groups and the number of other reactive groups of the compound used as the raw material, dynamic dilatant polymers having different topologies can be prepared, thereby preparing polymer materials having different energy absorbing effects.
In the invention, the same polymer system may contain one or more than one hydrogen bonding group, and the same cross-linking network may also contain one or more than one hydrogen bonding group, that is, the dynamic dilatant polymer may contain a combination of one or more than one hydrogen bonding group. The hydrogen bonding groups may be formed by reaction between any suitable groups, for example: formed by covalent reaction between carboxyl groups, acid halide groups, acid anhydride groups, ester groups, amide groups, isocyanate groups and amino groups; formed by covalent reaction between isocyanate groups and hydroxyl, mercapto and carboxyl groups; formed by covalent reaction between the succinimide group and amino, hydroxyl, sulfhydryl groups.
In the embodiment of the present invention, by utilizing and combining the advantages of the supramolecular action, the dynamic dilatant polymer has various other properties in addition to dynamic, self-repairing, and stress sensitivity: such as directionality of halogen bond action, cation-pi action, anion-pi action, controllable selectivity and controllable identification of small molecules/ions/groups in host-guest action, orderliness of benzene-fluorobenzene action and pi-pi stacking action, pH, concentration sensitivity and conductivity of ion action, ion-dipole action and ion hydrogen bond action, special photoelectricity of metallophilic interaction and free radical cation dimerization action, and the like, and supermolecule acting groups/units can be reasonably selected according to requirements for molecular design. Endows the material with unique functional characteristics on the basis of good performance.
In the present invention, one or more of the supramolecules may be included in one of the dynamic dilatant polymers. When a plurality of said supramolecular interactions are present, it is preferred that said plurality of supramolecular interactions are orthogonal and/or synergistic, and that different types of supramolecular interactions are preferred, more preferably different series of supramolecular interactions. The orthogonality refers to that the formation, dissociation and other responses of the various supramolecular interactions do not affect each other; by synergy is meant that the formation and/or dissociation and/or other response of one or more of the different supramolecular interactions triggers the formation and/or dissociation and/or other response of the other supramolecular interactions or occurs simultaneously with the formation and/or dissociation and/or other response of the other supramolecular interactions and produces a greater effect than a linear superposition of the various supramolecular interactions. Preferably both orthogonal and synergistic.
In the embodiments of the present invention, the "supramolecular moiety" refers to a group or molecule or structural unit for forming various types of supramolecules, which includes, but is not limited to, hydrogen bonding group, ligand group, metal center, ionic group, electric dipole, host molecule, guest molecule, metal ion, halogen atom, lewis base, lewis acid, aromatic pi system, arene, polyfluorinated arene, radical cationic group, phase-separable polymer segment, crystalline polymer segment, etc. The supramolecular motif may be located at any suitable position on the dynamic dilatant polymer, including but not limited to, end groups, side groups, backbones. In the particulate supramolecular polymers, the supramolecular motif may be contained by the inorganic/organic particles themselves, or obtained by reaction/grafting of small and/or large molecules on the surface or inside the particles.
In the present invention, the dispersion/component having dispersibility dilatancy comprises solid microparticles and a dispersion medium, wherein the volume fraction of the solid microparticles is preferably not less than 20%, more preferably not less than 30%, more preferably not less than 40%.
Wherein, the solid microparticles comprise two types of nanoparticles and microparticles; by way of example, the former include, but are not limited to, nano-silica, nano-alumina, nano-montmorillonite, nano-calcium carbonate, graphene, cellulose crystallites, nano-polymethylmethacrylate particles, nano-polystyrene particles, nano-iron oxide particles, nano-mica, nano-silicon nitride, and the like; the latter include, but are not limited to, submicron or micron sized silica particles, alumina particles, polymethylmethacrylate particles, polystyrene particles, starch particles, mica, silicon nitride, and the like. The shape of the solid microparticles can be spheres, ellipsoids, discs, other regular and irregular polyhedrons and the like, the surface of the solid microparticles can be smooth or rough, and spheres and ellipsoids are preferred; the surface of which is optionally also modified organically and/or inorganically.
Wherein, when the dispersion medium is selected from liquid, it includes but is not limited to organic matter, mineral oil, polymer matrix, etc., and specifically, as examples, the dispersion medium includes but is not limited to water, polyethylene glycol, polypropylene glycol, liquid paraffin, vegetable oil, mineral oil, silicone oil, ionic liquid, plasticizer, liquid metal, dilatant fluid (such as boron-containing dynamic polymer), and mixtures thereof, etc.; when the dispersion medium is selected from solids, it includes, but is not limited to, low Tg crosslinked polymers, gels, dilatant crosslinked polymers (e.g., boron containing crosslinked dynamic polymers and hybrid crosslinked dynamic polymers).
In the embodiment of the present invention, when the dispersion liquid contains inorganic solid microparticles and organic dispersion medium, the dispersion liquid may optionally contain a coupling agent and/or a surfactant, so that the solid microparticles can be more uniformly dispersed in the dispersion medium, for example, silane coupling agents such as KH550, KH560 and a1120, and coupling agents such as titanates, aluminates, organochromosomes, phosphates, zirconates and stannates.
In the present invention, it is particularly noted that the dispersion liquid with dispersive dilatancy is preferably used not as a dispersion continuous phase by itself, but as a dispersed phase, or is used as a continuous phase and/or a dispersed phase by coating or impregnating in a structure of pores or cavities with self-supporting properties, or is mixed with other matrix materials.
In the invention, the solid microparticles and the dispersion liquid/dispersion required for realizing the dispersibility dilatancy are rich in commercial sources, and the dispersion process does not need to carry out complex chemical reaction, thereby having the characteristic of high performance controllability. The dispersion of inorganic particles is also characterized by puncture resistance.
In embodiments of the invention, the aerodynamic dilatancy can be controlled by controlling the open-cell structure of the foam, and as the open-cell surface area fraction is generally reduced, the rebound time increases and the dilatancy increases. In order to obtain suitable dilatancy, it is preferred that the ratio of open cell area to cell surface area is from 3% to 20%, more preferably from 5% to 15%, more preferably from 5% to 10%.
In the present invention, the cell structure of the polymer foam having aerodynamic dilatancy can be obtained at least by adding a suitable amount of a cell opener/porogen. The cell opener/porogen acts to break the cell walls as the polymer reacts to form a foam, thereby promoting the formation of an open cell structure. The types and the adding contents of the pore-forming agent/pore-foaming agent are not particularly limited, and can be reasonably regulated and controlled according to actual needs to obtain the polymer foam with different open area ratios and adjustable dilatancy. By way of example, for polyurethane foams, the cell opener/porogen may be selected from, but is not limited to: ethylene oxide homopolymer polyol or random copolymer polyol of ethylene oxide and a small amount of propylene oxide with the molecular weight of more than 5000Da and the hydroxyl functionality of not less than 5, and propylene oxide homopolymer monohydric alcohol with the molecular weight of 1000-8500 Da and the hydroxyl functionality of 1.
In the present invention, the aerodynamic dilatancy is characterized by low temperature sensitivity.
In the invention, the matrix material of the flexible energy absorbing system can be common covalent polymer, dynamic covalent polymer or supermolecular polymer; wherein, the crosslinking forms such as dynamic covalent crosslinking, supermolecule crosslinking, common covalent crosslinking, dynamic covalent-supermolecule hybridization crosslinking, dynamic covalent-common covalent hybridization crosslinking, supermolecule-common covalent hybridization crosslinking and the like can be contained; the time for realizing the crosslinking of the base material can be crosslinking after printing is finished, simultaneously crosslinking when printing is carried out, and crosslinking after printing is finished when partial printing is carried out; the means to achieve crosslinking may be thermally induced crosslinking, photocrosslinking, frontal polymerization crosslinking, and the like.
In the invention, the polymer raw material for the flexible energy absorption system can also contain a force-sensitive component, and the force-sensitive component generates chemical and/or physical changes under the action of mechanical force to realize force-induced response.
In the present invention, the force sensitive component comprises a force sensitive group covalently and/or non-covalently attached to a polymer chain, and a force responsive component in physical blend.
In the present invention, the mechanical force source includes, but is not limited to, stretching, compressing, expanding, ultrasound, rubbing, scraping, shearing, cutting, swelling (for cross-linked polymers), bending, twisting, i.e. the force-induced response is obtained by providing a mechanical force including, but not limited to, stretching, compressing, expanding, ultrasound, rubbing, scraping, shearing, cutting, swelling (for cross-linked polymers), bending, twisting.
In the present invention, the force-sensitive group refers to an entity containing a mechanical force-sensitive moiety (i.e., force-sensitive moiety), wherein the force-sensitive moiety includes, but is not limited to, covalent chemical groups, supramolecular complexes, supramolecular assemblies, compositions, aggregates, which undergo chemical and/or physical changes of structure under mechanical force, including, but not limited to, chemical bond breaking, bonding, isomerization, decomposition, and physical dissociation, disassembly, and separation, thereby directly and/or indirectly generating chemical and/or physical signal changes, generating new groups/new substances, including, but not limited to, color, luminescence, fluorescence, spectral absorption, magnetism, electricity, conductance, heat, nuclear magnetism, infrared, raman, pH, free radical, catalysis, redox, addition, condensation, substitution, exchange, elimination, decomposition, Polymerization, cross-linking, coordination, hydrogen bonding, host-guest bonding, ionic bonding, change of pi-pi stacking signals/properties, ionic bonding, degradation, change of viscosity signals/properties, release of new molecules, generation of new reactive groups, achieving specific response to mechanical force and obtaining force-induced response properties/effects.
In the present invention, the force-sensitive moiety includes covalent type and non-covalent type. Wherein, the covalent type force sensitive element is mainly related to chemical changes such as breaking, eliminating, bonding, isomerization and the like of covalent bonds under the action of mechanical force, and comprises but not limited to homolytic cleavage, heterolytic cleavage, reverse cyclization, electrocyclic ring opening, bending activation, elimination, addition, isomerization and the like; the non-covalent force sensitive element mainly relates to physical changes such as dissociation of a supramolecular complex, disassembly and assembly of an assembly body, separation of a composition, separation of an aggregate and the like under the action of mechanical force.
In the present invention, the force sensitive groups include single force sensitive groups and complex force sensitive groups. Wherein the single force-sensitive moiety comprises only one force-sensitive element or only one force-sensitive element in its structure can be activated by force and is not tethered by a tethering structure, which is not an essential component for generating a force-responsive signal, comprising both covalent single force-sensitive moieties and non-covalent single force-sensitive moieties. Wherein, the composite force-sensitive group is formed by tying and/or combining one or more of the covalent and/or non-covalent force-sensitive elements/single force-sensitive groups, and includes but not limited to tying structures, gating structures, parallel structures, tandem structures, and two or more of tying, gating, parallel and tandem structures, and multi-composite structures formed by multi-stage combination of the force-sensitive elements/single force-sensitive groups. The complex force sensitive groups may thus be covalent complex force sensitive groups, non-covalent complex force sensitive groups, covalent-non-covalent complex force sensitive groups. The flexibility and variety of the composite force sensing clusters provide the invention with flexible polymer design and rich force-induced responsiveness.
In the present invention, the force-responsive component, which is not a polymer in itself, can generate force response by directly applying mechanical force to itself, and can generate force response by applying mechanical force after being blended with the slow rebound polymer, so that the slow rebound polymer has force responsiveness, including but not limited to force-responsive crystals, force-responsive assemblies, force-responsive aggregates, and force-responsive compositions. The responsive component is blended and dispersed in the slow rebound polymer or the composition thereof in a physical blending mode, and optionally generates force-induced response performance/effect in a synergistic and/or orthogonal mode with the force sensitive groups contained on the slow rebound polymer chain.
In the invention, the force-responsive crystal is generally a small molecular dye crystal, which is generally formed by crystallization/self-assembly followed by crystallization, and under the action of mechanical force, the crystalline state/assembly state of the force-responsive crystal changes to generate changes of color, fluorescence, luminescence and the like, so as to realize force response; typical structures of the compounds include small molecule crystals such as spiropyran, spirothiopyran, spirooxazine, spirothiazine, rhodamine, etc., crystalline small molecule assemblies, small molecule aggregates, and small molecule compositions.
In the present invention, the force-responsive assembly may be selected from a donor-receptor type, a diketopyrrolopyrrole type, a conjugated type, a platinum coordination type, a gold coordination type, a beryllium coordination type, a copper coordination type, an iridium coordination type, a boron coordination type, a phenothiazine type, a dioxaborolane type, and a dye molecule type; the typical structure of which can be referred to the structure described in the present invention in the previous paragraph based on non-covalent single force sensitive groups of supramolecular assemblies.
In the present invention, the force-responsive aggregate may be selected from the group consisting of a divinylanthracene type, a tetraarylethylene type, a cyanoethylene type, a berberine type, a maleimide type, a 4-hydropyran type; the typical structure of which can be referred to as the structure described in the invention above for the non-covalent aggregate-based force-sensitive groups.
In the present invention, the division is made by a force-activated reaction mechanism, and the covalent single force sensitive groups include, but are not limited to, the following groups: covalent single-force sensitive groups based on homolytic mechanism, covalent single-force sensitive groups based on heterolytic mechanism, covalent single-force sensitive groups based on reverse cyclization mechanism, covalent single-force sensitive groups based on electrocyclization mechanism, covalent single-force sensitive groups based on flexural activation mechanism, and covalent single-force sensitive groups based on other mechanisms.
In the present invention, covalent single force sensitive groups based on the homolytic mechanism include, but are not limited to, the following series: peroxide series, disulfo/polysulfide series, diselenide/polyselenide series, azonitrile series, bisarylfuranone series, bisarylcyclic ketone series, bisarylcyclopentenedione series, bisarylchromene series, arylbiimidazole series, arylethane series, dicyanotetrarylethane series, arylpinacol series, chain transfer series, cyclohexadienone series, tetracyanoethane series, cyanoacylethane series, adamantane-substituted ethane series, bifluorene series, allylthioether series, thio/selenoate series, benzoyl series covalent monomelic groups.
In the invention, the covalent single force-sensitive group of the peroxide series homolysis mechanism refers to a force-sensitive group containing a peroxide force-sensitive element, and the structural general formula of the covalent single force-sensitive group includes but is not limited to the following types:
Figure BDA0002376545090000641
wherein the content of the first and second substances,
Figure BDA0002376545090000648
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
A typical structure of the formula 1-A-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000642
wherein the content of the first and second substances,
Figure BDA0002376545090000649
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the present invention, the covalent single force-sensitive group of the disulfide/polysulfide series homolytic mechanism refers to a force-sensitive group containing disulfide/polysulfide force-sensitive elements, and the structural formula thereof includes but is not limited to the following types:
Figure BDA0002376545090000643
wherein m is the number of sulfur atoms connected by a single bond, and the value of m is a certain specific integer value of more than or equal to 2, preferably 2-20, and more preferably 2-10; wherein, each W is independently selected from but not limited to oxygen atom and sulfur atom;
wherein the content of the first and second substances,
Figure BDA0002376545090000644
indicates that n is connected with
Figure BDA00023765450900006410
An aromatic ring of (2); wherein the value of n is 0, 1 or an integer greater than 1; the symbols are the sites connected with other structures in the formula, and if not specifically noted, the symbols appearing hereinafter have the same meaning and are not repeated; the ring structure of the aromatic ring is selected from a monocyclic structure, a polycyclic structure, a spiro structure and a fused ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and the hydrogen atoms connected to the ring-forming atoms are substituted or unsubstituted by any suitable substituent atom, substituent group; wherein, the substituent atom or substituent is not particularly limited, and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent. At different positions
Figure BDA0002376545090000645
Are the same or different; in order to increase the conjugation effect and the steric hindrance, promote the homolytic fracture of the force sensitive group under the action of the mechanical force, facilitate the stabilization of the formed free radical and obtain the reversible force-activated characteristic,
Figure BDA0002376545090000646
preferably at least one of the following structures, but the invention is not limited thereto:
Figure BDA0002376545090000647
Figure BDA0002376545090000651
said
Figure BDA0002376545090000652
Further preferred is at least one of the following structures, but the present invention is not limited thereto:
Figure BDA0002376545090000653
wherein L is1Are divalent linking groups, each independently selected from, but not limited to:
Figure BDA0002376545090000654
l in different positions1Are the same or different; wherein L is2Are divalent linking groups, each independently selected from, but not limited to: a direct bond,
Figure BDA0002376545090000655
Figure BDA0002376545090000656
L in different positions2Are the same or different;
wherein R is1、R2、R3、R4Each independently selected from any suitable atom (including hydrogen atoms), substituent; the substituent contains a heteroatom or does not contain a heteroatom, the number of carbon atoms is not particularly limited, preferably 1 to 20, more preferably 1 to 10, the structure of the substituent is not particularly limited, and the substituent includes a linear structure, a branched structure or a cyclic structure selected from an aliphatic ring, an aromatic ring, an ether ring, a condensed ring and combinations thereof, preferably an aliphatic ring and an aromatic ring. In general terms, R 1、R2、R3、R4Each independently preferably selected from a hydrogen atom, a halogen atom, a hetero atom group, C1-20Hydrocarbyl radical, C1-20Heterohydrocarbyl, substituted C1-20Hydrocarbyl or substituted C1-20Heterohydrocarbyl and two of the above groupsOr a combination of more than one. In order to increase the steric hindrance of nitrogen atoms in the force-sensitive groups, promote the homolytic cleavage of the force-sensitive groups under the action of mechanical force, facilitate the stabilization of the formed free radicals, promote the coupling of the free radicals or the reversible exchange of the force-sensitive groups, and obtain good reversible performance, R1、R2、R3、R4Each independently preferably selected from hydrogen atom, hydroxyl group, cyano group, carboxyl group, C1-20Alkyl radical, C1-20Heteroalkyl, cyclic structure C1-20Alkyl, C of cyclic structure1-20Heteroalkyl group, C1-20Aryl radical, C1-20A heteroaryl group; in general terms, the structures in the general formulae 1-B-5, 1-B-7
Figure BDA0002376545090000657
Preferably at least one of the following structures, but the invention is not limited thereto:
Figure BDA0002376545090000658
said
Figure BDA0002376545090000659
More preferably at least one of the following structures, but the present invention is not limited thereto:
Figure BDA00023765450900006510
wherein the content of the first and second substances,
Figure BDA00023765450900006511
is a nitrogen-containing aliphatic heterocyclic ring, the number of ring-forming atoms of the ring is not particularly limited, and is preferably from 3 to 10, more preferably from 5 to 8; except that at least one of the ring-forming atoms of the aliphatic ring is a nitrogen atom, the rest of the ring-forming atoms are selected from but not limited to carbon atoms, nitrogen atoms, oxygen atoms and sulfur atoms, and hydrogen atoms connected to the ring-forming atoms are substituted or unsubstituted by any suitable substituent atom, substituent group; wherein said substitution is The atom or substituent is not particularly limited, and is selected from any one or more of halogen atom, hydrocarbyl substituent, and heteroatom-containing substituent;
wherein the content of the first and second substances,
Figure BDA0002376545090000661
indicates that n is connected with
Figure BDA0002376545090000667
Wherein n is 0, 1 or an integer greater than 1; in order to increase the steric hindrance of the nitrogen atom in the force-sensitive group, promote homolytic cleavage of the force-sensitive group under the action of mechanical forces, facilitate stabilization of the free radicals formed, and promote coupling of said free radicals
Figure BDA0002376545090000662
Preferably at least one of the following structures, but the invention is not limited thereto:
Figure BDA0002376545090000663
said
Figure BDA0002376545090000664
More preferably at least one of the following structures, but the present invention is not limited thereto:
Figure BDA0002376545090000665
wherein the content of the first and second substances,
Figure BDA0002376545090000668
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation. It is to be expressly noted that, when in a structure "
Figure BDA0002376545090000669
Each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain which may or may not participate in force activation, "at least one of the left and right sides of the activatable bond in the structure or a force-sensitive group comprising the structure
Figure BDA00023765450900006610
With substituted or supramolecular polymer chains participating in force activation, the force being transmitted through these chains
Figure BDA00023765450900006611
Acting on the force sensitive groups, wherein the included angle formed by the acting forces on the left side and the right side is not higher than 180 degrees, and preferably smaller than 180 degrees; unless otherwise indicated, appear hereinafter "
Figure BDA00023765450900006612
Each independently linked to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation "have the same meaning and are not repeated.
Typical structures of the general formulae 1-B-1 to 1-B-7 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000666
Figure BDA0002376545090000671
wherein the content of the first and second substances,
Figure BDA0002376545090000674
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Specifically, the typical structures of the formulae 1-B-1 to 1-B-7 may be further exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000672
wherein the content of the first and second substances,
Figure BDA0002376545090000675
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the diselenide/polyselene series homolysis mechanism refers to a force sensitive group containing diselenide/polyselene force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following groups:
Figure BDA0002376545090000673
Figure BDA0002376545090000681
wherein m is the number of selenium atoms connected by a single bond, and the value of m is a certain specific integer value greater than or equal to 2, preferably 2-20, and more preferably 2-10; wherein, each W is independently selected from but not limited to oxygen atom and sulfur atom; wherein the content of the first and second substances,
Figure BDA0002376545090000682
The definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-3; wherein R is1、R2、R3、R4The definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-5; wherein the content of the first and second substances,
Figure BDA0002376545090000683
the definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-6;
Figure BDA0002376545090000686
each independently of the others, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation。
Typical structures of the formulae 1-C-1 to 1-C-7 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000684
wherein the content of the first and second substances,
Figure BDA0002376545090000687
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Specifically, typical structures of the formulae 1-C-1 to 1-C-7 may be further exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000685
Figure BDA0002376545090000691
wherein the content of the first and second substances,
Figure BDA0002376545090000699
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the azonitrile series homolytic mechanism refers to a force sensitive group containing azonitrile force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0002376545090000692
wherein R is5、R6、R7、R8Each independently selected from, but not limited to, a hydrogen atom, a halogen atom, a heteroatom group, C1-20Hydrocarbyl/heterohydrocarbyl, substituted C 1-20Hydrocarbyl radicalA heterohydrocarbyl group, and combinations of two or more of the foregoing, preferably selected from hydrogen, halogen, C1-20Alkyl radical, C1-20Heteroalkyl group, more preferably selected from hydrogen atom, C1-5Alkyl radical, C1-5Heteroalkyl, more preferably selected from cyano, methyl, ethyl, propyl, butyl;
Figure BDA00023765450900006910
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
A typical structure of the formula 1-D-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000693
wherein the content of the first and second substances,
Figure BDA00023765450900006911
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the bisaryl furanone series homolytic mechanism refers to a force sensitive group containing bisaryl furanone force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0002376545090000694
wherein, each W is independently selected from but not limited to oxygen atom and sulfur atom; w1Is a divalent linking group, each of which is independently selected from, but not limited to
Figure BDA0002376545090000695
Figure BDA0002376545090000696
Is preferably selected from
Figure BDA00023765450900006914
Each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, any two of the same ring structure
Figure BDA00023765450900006913
With or without looping.
Wherein the structure represented by formula 1-E-1 is preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090000698
wherein each G is independently selected from
Figure BDA0002376545090000701
Said
Figure BDA0002376545090000702
The definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-3; wherein, W, W1、
Figure BDA0002376545090000707
The definition, selection range and preferable range of (A) are the same as those of the general formula 1-E-1;
wherein the content of the first and second substances,
Figure BDA0002376545090000703
to be connected with n
Figure BDA0002376545090000708
An aromatic ring of (2); wherein the ring structure of the aromatic ring is selected from a monocyclic structure, a polycyclic structure, a spiro structure, and a fused ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and the hydrogen atoms connected to the ring-forming atoms are substituted or unsubstituted by any suitable substituent atom, substituent group; wherein the substituent atom or substituent is not particularly limited and is selected from, but not limited to, halogenAny one or more of an atom, a hydrocarbyl substituent, and a heteroatom-containing substituent; at different positions in the same general formula
Figure BDA0002376545090000709
Are the same or different; by way of example, the
Figure BDA00023765450900007010
May be selected from at least one of the following structures, but the invention is not limited thereto:
Figure BDA0002376545090000704
said
Figure BDA00023765450900007011
More preferably at least one of the following structures, but the present invention is not limited thereto:
Figure BDA0002376545090000705
Wherein L is1、L2The definitions, selection ranges, preferred ranges of (a) are as described in the previous sections of this series.
A typical structure of the formula 1-E-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000706
wherein, W, W1、
Figure BDA0002376545090000712
The definition, selection range and preferable range of (A) are the same as those of the general formula 1-E-1; l is1The definitions, selection ranges, preferred ranges of (a) are as described in the previous sections of this series.
Specifically, the typical structure of the formula 1-E-1 can be further exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000711
Figure BDA0002376545090000721
wherein the content of the first and second substances,
Figure BDA0002376545090000722
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the biaryl cyclic ketone series homolysis mechanism refers to a force sensitive group containing biaryl cyclic ketone force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0002376545090000731
wherein, each W is independently selected from but not limited to oxygen atom and sulfur atom; w2Is a divalent linking group, each of which is independently selected from, but not limited to
Figure BDA0002376545090000732
Figure BDA0002376545090000733
Is preferably selected from
Figure BDA0002376545090000734
Each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, any two of the same ring structure
Figure BDA0002376545090000738
With or without looping.
Wherein the structure represented by formula 1-F-1 is preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090000735
Wherein, W, W2、
Figure BDA0002376545090000739
The definition, selection range and preferable range of (A) are the same as those of the general formula 1-F-1; g is defined, selected and preferably in the same range as the general formula 1-E-1-1;
Figure BDA00023765450900007310
the definition, selection range and preferable range of (A) are the same as those of the general formula 1-E-1-4.
A typical structure of the formula 1-F-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000736
wherein, W, W2、
Figure BDA00023765450900007311
The definition, selection range and preferable range of (A) are the same as those of the general formula 1-F-1; l is1The definitions, selection ranges, preferred ranges of (a) are as described in the previous sections of this series.
Specifically, the typical structure of the formula 1-F-1 can be further exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000737
Figure BDA0002376545090000741
wherein the content of the first and second substances,
Figure BDA0002376545090000755
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the diarylcyclopentenedione series homolytic mechanism refers to a force sensitive group containing diarylcyclopentenedione force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following groups:
Figure BDA0002376545090000751
wherein, each W is independently selected from but not limited to oxygen atom and sulfur atom;
Figure BDA0002376545090000756
each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, any two of the same ring structure
Figure BDA0002376545090000757
With or without looping.
Wherein the structure represented by formula 1-G-1 is preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090000752
wherein, W,
Figure BDA0002376545090000758
The definition, selection range and preferable range of (A) are the same as those of the general formula 1-G-1; g is defined, selected and preferably in the same range as the general formula 1-E-1-1;
Figure BDA0002376545090000759
the definition, selection range and preferable range of (A) are the same as those of the general formula 1-E-1-4.
A typical structure of the formula 1-G-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000753
wherein, W,
Figure BDA00023765450900007510
The definition, selection range and preferable range of (A) are the same as those of the general formula 1-G-1; l is1The definitions, selection ranges, preferred ranges of (a) are as described in the previous sections of this series.
Specifically, the typical structure of the general formula 1-G-1 can be further exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000754
Figure BDA0002376545090000761
wherein the content of the first and second substances,
Figure BDA0002376545090000776
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the bisaryl chromene series homolytic mechanism refers to a force sensitive group containing bisaryl chromene force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0002376545090000771
wherein, W3Is a divalent linking group, each of which is independently selected from, but not limited to
Figure BDA0002376545090000772
V, V' are each independently selected from carbon atoms, nitrogen atoms; when V, V 'is a nitrogen atom, V, V' is linked to
Figure BDA0002376545090000777
Is absent;
Figure BDA0002376545090000778
each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, any two of the same ring structure
Figure BDA0002376545090000779
With or without looping.
Wherein the structure represented by formula 1-H-1 is preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090000773
wherein, W3、V、V’、
Figure BDA00023765450900007710
The definition, selection range and preferable range of (A) are the same as those of the general formula 1-H-1;
Figure BDA00023765450900007711
the definition, selection range and preferable range of (A) are the same as those of the general formula 1-E-1-4.
Among them, the structure represented by the general formula 1-H-1 further preferably has a structure represented by the following formula:
Figure BDA0002376545090000774
wherein, W3、V、V’、
Figure BDA00023765450900007712
The definition, selection range and preferable range of (A) are the same as those of the general formula 1-H-1; g is defined, selected and preferably in the same range as the general formula 1-E-1-1;
Figure BDA00023765450900007713
definition and selection ofThe selection range and the preferred range are the same as those of the general formula 1-E-1-4.
A typical structure of the formula 1-H-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000775
Figure BDA0002376545090000781
wherein, W3、
Figure BDA0002376545090000783
The definition, selection range and preferred range of (1-H-1) are the same; l is1The definitions, selection ranges, preferred ranges of (a) are as described in the previous sections of this series.
Specifically, the typical structure of the formula 1-H-1 can be further exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000782
Figure BDA0002376545090000791
Figure BDA0002376545090000801
Figure BDA0002376545090000811
wherein the content of the first and second substances,
Figure BDA0002376545090000825
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the aryl biimidazole series homolytic mechanism refers to a force sensitive group containing aryl biimidazole force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0002376545090000821
wherein the content of the first and second substances,
Figure BDA0002376545090000826
represents that the ring has a conjugated structure; wherein the content of the first and second substances,
Figure BDA0002376545090000827
is a five-membered nitrogen heterocyclic structure with a conjugated structure; wherein the content of the first and second substances,
Figure BDA0002376545090000828
the two five-membered nitrogen heterocycles form a polycyclic structure formed by a carbon-carbon single bond, a carbon-nitrogen single bond or a nitrogen-nitrogen single bond through respective ring-forming atoms; according to different
Figure BDA0002376545090000829
The linkage, formula 1-I-1 includes but is not limited to one or more of the following isomers:
Figure BDA00023765450900008210
Figure BDA0002376545090000822
it should be noted that under appropriate conditions, interconversion between the various isomers can occur, and therefore, the six isomer motifs are regarded as the same structural motif in the present invention;
Figure BDA00023765450900008211
each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, in the same ring structureTwo are provided
Figure BDA00023765450900008212
With or without looping.
Wherein the structure represented by the general formula 1-I-1 is preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090000823
wherein the content of the first and second substances,
Figure BDA00023765450900008213
the definition, selection range and preferable range of the formula (I) are the same as those of the general formula 1-I-1; g is defined, selected and preferably in the same range as the general formula 1-E-1-1;
Figure BDA00023765450900008214
The definition, selection range and preferable range of (A) are the same as those of the general formula 1-E-1-4.
The typical structure of the formula 1-I-1 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000824
wherein the content of the first and second substances,
Figure BDA00023765450900008215
the definition, selection range and preferable range of the formula (I) are the same as those of the general formula 1-I-1; l is1The definitions, selection ranges, preferred ranges of (a) are as described in the previous sections of this series.
Specifically, the typical structure of the general formula 1-I-1 can be further exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000831
Figure BDA0002376545090000841
wherein the content of the first and second substances,
Figure BDA0002376545090000844
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the aryl ethane series homolysis mechanism refers to a force sensitive group containing aryl ethane force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0002376545090000842
wherein R is2Each independently selected from any suitable atom (including a hydrogen atom), substituent selected from hydroxy, phenyl, phenoxy, C, and substituted polymer chain with or without participation in force activation1-10Alkyl radical, C1-10Alkoxy radical, C1-10Alkoxyacyl group, C1-10An alkanoyloxy group, a trimethylsilyloxy group, a triethylsiloxy group; wherein the content of the first and second substances,
Figure BDA0002376545090000845
the definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-3; wherein the content of the first and second substances,
Figure BDA0002376545090000846
Each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula 1-J-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000843
Figure BDA0002376545090000851
wherein R is2The definition, selection range and preferable range of (A) are the same as those of the general formula 1-J-1;
Figure BDA0002376545090000854
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the dicyano tetraarylethane series homolysis mechanism refers to a force sensitive group containing dicyano tetraarylethane force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0002376545090000852
wherein the content of the first and second substances,
Figure BDA0002376545090000855
the definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-3; wherein the content of the first and second substances,
Figure BDA0002376545090000856
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula 1-K-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000853
Figure BDA0002376545090000861
wherein the content of the first and second substances,
Figure BDA0002376545090000866
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the aryl pinacol series homolysis mechanism refers to a force sensitive group containing an aryl pinacol force sensitive element, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0002376545090000862
Wherein, W4Is a divalent linking group, each of which is independently selected from, but not limited to, a direct bond,
Figure BDA0002376545090000863
Preferably from a direct bond,
Figure BDA0002376545090000864
Each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula 1-L-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000865
Figure BDA0002376545090000871
wherein, W4The definition, selection range and preferable range of (A) are the same as those of the general formula 1-L-1;
Figure BDA0002376545090000873
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the present invention, the covalent single force-sensitive group of the chain transfer series homolytic mechanism refers to a force-sensitive group containing a chain transfer force-sensitive element, and the structural general formula thereof includes but is not limited to the following classes:
Figure BDA0002376545090000872
wherein R is2And
Figure BDA0002376545090000874
the definition, selection range and preferable range of (A) are the same as those of the general formula 1-J-1; w4The definition, selection range and preferable range of (A) are the same as those of the general formula 1-L-1; r1、R2、R3、R4The definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-5;
Figure BDA0002376545090000875
the definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-6;
wherein R is1Each independently selected from atoms (including hydrogen atoms), substituents, R at different positions1Are the same or different in structure; wherein the substituent contains or does not contain a heteroatom, the number of carbon atoms is not particularly limited, preferably the number of carbon atoms is 1 to 20, more preferably 1 to 10, the structure of the substituent is not particularly limited, and the substituent includes a linear structure, a branched structure containing a pendant group, or a cyclic structure selected from the group consisting of an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and combinations thereof, preferably an aliphatic ring and an aromatic ring; in general terms, R 1Each independently preferably selected from a hydrogen atom, a halogen atom, a hetero atom group, C1-20Hydrocarbyl/heterohydrocarbyl, substituted C1-20Hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing. In order to promote the homolytic fracture of the force sensitive group under the action of mechanical force, increase the oxidation resistance of the formed carbon free radical, stabilize the formed carbon free radical, facilitate the coupling of the further free radical or participate in other free radical reactions, and obtain the reversible force-induced activation characteristic, the self-repairing performance and the self-enhancing performance, R1Each independently preferably selected from hydrogen atom, hydroxyl group, cyano group, carboxyl group, C1-20Alkyl radical, C1-20Aryl radical, C1-20Heteroaromatic hydrocarbon groups and acyl, acyloxy, acylamino, oxyacyl, thioacyl,Aminoacyl, phenylene substituted C1-20Hydrocarbyl/heterohydrocarbyl; r1Further preferably selected from the group consisting of a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, phenyl group, hydroxyl group, cyano group, carboxyl group, methyloxyacyl group, ethyloxyacyl group, propyloxyacyl group, butyloxyacyl group, methylaminoacyl group, ethylaminoacyl group, propylaminoylgroup, butylaminoacyl group;
wherein, V3Selected from selenium atom, tellurium atom, antimony atom, bismuth atom; wherein k is and V 3Connected to each other
Figure BDA0002376545090000876
The number of (2); when V is3In the case of selenium or tellurium, k is 1 and represents only one
Figure BDA0002376545090000877
And V3Connecting; when V is3When it is an antimony atom or a bismuth atom, k is 2, which means that there are two
Figure BDA0002376545090000878
And V3Are connected with two
Figure BDA0002376545090000885
Are the same or different in structure;
wherein, L 'is a divalent linking group, and the structures of L' at different positions are the same or different; the divalent linking group contains or does not contain a heteroatom, the number of carbon atoms is not particularly limited, preferably 1 to 20, more preferably 1 to 10, the structure of the divalent linking group is not particularly limited, and the divalent linking group includes, but is not limited to, a linear structure, a branched structure containing a pendant group, or a cyclic structure selected from the group consisting of an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and combinations thereof, preferably an aliphatic ring and an aromatic ring. In general terms, each of said L' is independently selected from the group consisting of a heteroatom linking group, a heteroatom group linking group, a divalent C1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C1-20Hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing. Wherein the substituent atom or substituent groupThere is no particular limitation, and it is selected from, but not limited to, any one or more of halogen atoms, hydrocarbon-based substituents, and heteroatom-containing substituents. In order to promote homolytic cleavage of the force sensitive group under the action of mechanical force, increase oxidation resistance of the formed carbon free radical, stabilize the formed carbon free radical, facilitate further coupling of the free radical or participate in other free radical reactions, and obtain reversible force-induced activation property, self-repairing property and self-enhancing property, L' is respectively and independently preferably selected from acyl, acyloxy, acylthio, acylamino, oxyacyl, sulfuryl, phenylene and divalent C 1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C1-20Hydrocarbyl/heterohydrocarbyl; wherein said substituted divalent C1-20The structure of the substituent group in the hydrocarbon group/heterohydrocarbon group is preferably an acyl group, an acyloxy group, an acylthio group, an acylamino group, an oxyacyl group, a thioacyl group, an aminoacyl group, a phenylene group, and more preferably the substituted divalent C1-20The hydrocarbyl/heterohydrocarbyl group being linked to R via said substituent group1To the carbon atom(s) of (a);
in general terms, of the formulae 1-M-1 to 1-M-8
Figure BDA0002376545090000881
Preferably, the present invention is not limited to one selected from the following structures:
Figure BDA0002376545090000882
wherein R is selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation; wherein R represents the number of R connected with a benzene ring, and the value of R is an integer selected from 0 to 5; wherein m is the number of repeating units, which can be a fixed value or an average value;
said
Figure BDA0002376545090000886
Further preferred is at least one of the following structures, but the present invention is not limited thereto:
Figure BDA0002376545090000883
wherein, the definitions, selection ranges and preferred ranges of R, R and m are as described in the primary structure;
wherein the content of the first and second substances,
Figure BDA0002376545090000887
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula 1-M-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000884
Figure BDA0002376545090000891
wherein R is2The definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-1;
Figure BDA0002376545090000895
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Typical structures of the general formula 1-M-2 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000892
wherein, the definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-2;
Figure BDA0002376545090000896
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Typical structures of the general formulae 1 to M-3 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000893
wherein, W4The definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-3;
Figure BDA0002376545090000897
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Typical structures of the general formulae 1 to M-4 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000894
Figure BDA0002376545090000901
wherein, the definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-4;
Figure BDA0002376545090000904
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Typical structures of the general formulae 1 to M-5 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000902
wherein, the definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-5;
Figure BDA0002376545090000905
Each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Typical structures of the general formulae 1 to M-6 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000903
Figure BDA0002376545090000911
wherein, the definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-6;
Figure BDA0002376545090000914
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Typical structures of the general formulae 1 to M-7 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000912
wherein, the definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-7;
Figure BDA0002376545090000915
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Typical structures of the formulae 1 to M-8 may be illustrated below, but the present invention is not limited thereto:
Figure BDA0002376545090000913
Figure BDA0002376545090000921
wherein, the definition, the selection range and the preferred range of M are the same as those of the general formula 1-M-8;
Figure BDA0002376545090000926
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the cyclohexadienone series homolytic mechanism refers to a force sensitive group containing cyclohexadienone force sensitive elements, and the structural general formula of the covalent single force sensitive group comprises but is not limited to the following types:
Figure BDA0002376545090000922
wherein the content of the first and second substances,
Figure BDA0002376545090000927
the definition, selection range and preferable range of (A) are the same as those of the general formula 1-E-1-4;
Figure BDA0002376545090000928
Each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the formulae 1-N-1 to 1-N-3 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000923
wherein the content of the first and second substances,
Figure BDA0002376545090000929
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the tetracyanoethane series homolysis mechanism refers to a force sensitive group containing tetracyanoethane force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0002376545090000924
wherein the content of the first and second substances,
Figure BDA00023765450900009210
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 1-O-1 is preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090000925
wherein the content of the first and second substances,
Figure BDA00023765450900009211
the definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-3;
Figure BDA00023765450900009212
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of formula 1-O-1 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000931
Figure BDA0002376545090000941
wherein the content of the first and second substances,
Figure BDA0002376545090000949
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the present invention, the covalent single force-sensitive group of the cyanoacyl ethane series homolysis mechanism refers to a force-sensitive group containing cyanoacyl ethane force-sensitive elements, and the structural general formula thereof includes but is not limited to the following types:
Figure BDA0002376545090000942
wherein, each W is independently selected from but not limited to oxygen atom and sulfur atom; wherein, W5Is a divalent linking group, each of which is independently selected from, but not limited to, a direct bond,
Figure BDA0002376545090000943
Is preferably selected from
Figure BDA0002376545090000944
More preferably from
Figure BDA0002376545090000945
Each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, any two of the same ring structure
Figure BDA00023765450900009410
With or without looping.
Wherein the structure represented by formula 1-P-1 is preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090000946
wherein, W, W5、
Figure BDA00023765450900009411
The definition, selection range and preferable range of (A) are the same as those of the general formula 1-P-1.
A typical structure of the formula 1-P-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000947
wherein the content of the first and second substances,
Figure BDA00023765450900009412
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the adamantane substituted ethane series homolytic mechanism refers to a force sensitive group containing adamantane substituted ethane force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0002376545090000948
Wherein Ad is selected from the group consisting of bivalent or multivalent adamantyl and dimeric or multimeric derivatives thereof; by way of example, the Ad is selected from, but not limited to:
Figure BDA0002376545090000951
wherein the content of the first and second substances,
Figure BDA0002376545090000955
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula 1-Q-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000952
wherein the content of the first and second substances,
Figure BDA0002376545090000956
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the bifluorene series homolysis mechanism refers to a force sensitive group containing bifluorene force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0002376545090000953
wherein R is3Each independently selected from cyano, C1-10Alkoxyacyl group, C1-10Alkyl acyl radical, C1-10An alkylaminoacyl group, a phenyl group, a substituted phenyl group, an aromatic hydrocarbon group, a substituted aromatic hydrocarbon group, wherein the substituent atom or the substituent group is not particularly limited and is selected from any one or more of a halogen atom, a hydrocarbon group substituent group, and a heteroatom-containing substituent group; wherein the content of the first and second substances,
Figure BDA0002376545090000957
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the general formula 1-R-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000954
Figure BDA0002376545090000961
wherein the content of the first and second substances,
Figure BDA0002376545090000963
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force-sensitive group of the homolytic mechanism of the allyl sulfide series refers to a force-sensitive group containing allyl sulfide force-sensitive elements, and the structural general formula of the covalent single force-sensitive group includes but is not limited to the following types:
Figure BDA0002376545090000962
wherein, C1、C2、C3Represents carbon atoms, and the numbers at the upper right corner of the carbon atoms are used for distinguishing carbon atoms at different positions so as to facilitate the accuracy and the conciseness of description;
wherein R is1 1、R1 2、R1 3、R1 4Each independently selected from atoms (including hydrogen atoms), substituents; r1 1、R1 2、R1 3、R1 4Each independently preferably selected from a hydrogen atom, a halogen atom, C1-20Hydrocarbyl/heterohydrocarbyl, substituted C1-20A hydrocarbon group/heterohydrocarbon group, the substituent atom or substituent group being not particularly limited; r1 1、R1 2、R1 3、R1 4Each independently more preferably from a hydrogen atom, a halogen atom, C1-20Alkyl radical, C1-20Aryl radical, C1-20Heterohydrocarbyl radical, C1-20Hydrocarbyloxyacyl group, C1-20Hydrocarbyl thioacyl, C1-20Hydrocarbyl aminoacyl groups and substituents formed from combinations of two or more of the above groups; r1 1、R1 2、R1 3、R1 4Each independently of the others is preferably selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl;
wherein Z is 2Is a divalent linking atom or a divalent linking group; when Z is2When selected from divalent linking atoms, it is selected from S atoms; when Z is2When the divalent linking group is selected, the divalent linking group contains a hetero atom or does not contain a hetero atom, and the number of carbon atoms is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10; the structure thereof is not particularly limited, and includes, but is not limited to, a linear structure, a branched structure or a cyclic structure; the cyclic structure is selected from the group consisting of an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and combinations thereof, preferably an aliphatic ring and an aromatic ring; in general terms, Z2Selected from, but not limited to, divalent C1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C1-20Hydrocarbyl/heterohydrocarbyl and two of the aboveOne or more divalent linking groups formed by combination, wherein the substituent atom or substituent group is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent group and heteroatom-containing substituent group; z2More preferably divalent acrylic or methacrylic acid and its corresponding esters, divalent acrylamides or methacrylamides, N-mers of divalent styrene or methylstyrene (N.gtoreq.2) such as trimers, tetramers;
when Z is2Selected from divalent linking atoms, Z 1Is and C2A divalent linking group in which the atoms are directly linked; the divalent linking group contains or does not contain a heteroatom, the number of carbon atoms is not particularly limited, preferably 1 to 20, more preferably 1 to 10, the structure of the divalent linking group is not particularly limited, and the divalent linking group includes, but is not limited to, a linear structure, a branched structure containing a pendant group, or a cyclic structure selected from an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and a combination thereof, preferably an aromatic ring; in general terms, the divalent linking group is selected from, but not limited to, divalent C1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C1-20A divalent linking group formed from hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing; z1More preferably from divalent C1-20Alkyl, divalent C1-20Aromatic hydrocarbon radical, divalent C1-20Alkoxy, divalent C1-20Aryloxy, divalent C1-20Alkylthio, divalent C1-20Arylthio, most preferably selected from divalent C1-20An alkylthio group; in particular, Z1Preferably from methylene, methylene sulfide, ethylene, propylene, butylene, pentylene, hexylene, divalent phenyl ether, divalent benzyl, divalent ethoxy, divalent butoxy, divalent hexyloxy, most preferably selected from methylene sulfide; when Z is 2Selected from said divalent linking groups, Z1Is and C2A divalent linking group in which the atoms are directly linked; the divalent linking group contains a hetero atom or does not contain a hetero atom, the number of carbon atoms is not particularly limited, preferably the number of carbon atoms is 1 to 20, more preferably 1 to 10, the structure is not particularly limited, and the divalent linking group includes, but is not limited to, a linear structure and a linear structureA branched or cyclic structure of a pendant group, said cyclic structure selected from the group consisting of an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and combinations thereof, preferably an aromatic ring; in general terms, the divalent linking group is selected from, but not limited to: divalent heteroatom radical linking group, divalent C1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C1-20A divalent linking group formed from hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing; z1More preferably from divalent connecting group with electron-withdrawing effect, divalent connecting group substituted by electron-withdrawing effect substituent, so as to facilitate the homolytic cleavage of the force sensitive group and obtain more remarkable force-induced response effect; wherein, the divalent linking group with electron-withdrawing effect includes but is not limited to acyl, acyloxy, acylthio, acylamino, phenylene; the divalent linking group substituted by the substituent having the electron-withdrawing effect includes, but is not limited to, acyl group, acyloxy group, acylthio group, amide group, phenylene group, nitro group, sulfonic acid group, aromatic hydrocarbon group, cyano group, halogen atom, and divalent C group substituted by trifluoromethyl group 1-20Hydrocarbyl/heterohydrocarbyl; by way of example, the divalent linking group substituted with an electron-withdrawing substituent includes, but is not limited to, an acyl group, an acyloxy group, an acylthio group, an amide group, a phenylene group, a nitro group, a sulfonic acid group, an aromatic hydrocarbon group, a cyano group, a halogen atom, a trifluoromethyl-substituted phenylene group, a benzylidene group, a naphthylidene group, a pyrrolylidene group, a pyridylidene group;
wherein the content of the first and second substances,
Figure BDA0002376545090000974
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
A typical structure of the formula 1-S-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000971
wherein n is the number of repeating units, can be a fixed value or an average value, and is an integer greater than or equal to 1;
Figure BDA0002376545090000975
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the thio/seleno ester series homolytic mechanism refers to a force sensitive group containing thio/seleno ester force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0002376545090000972
wherein, W6Each independently selected from a sulfur atom or a selenium atom;
wherein Z is3A divalent linking group containing or not containing a heteroatom, the number of carbon atoms of which is not particularly limited, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, the structure of which is not particularly limited, including but not limited to a linear structure, a branched structure, or a cyclic structure selected from the group consisting of an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and combinations thereof, preferably an aliphatic ring and an aromatic ring; by way of example, Z 3Selected from, but not limited to, divalent heteroatom linkers, divalent heteroatom group linkers, divalent C1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C1-20A divalent linking group formed from hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent;
wherein Z is4A divalent linking group containing a heteroatom or not, the number of carbon atoms of which is not particularly limited, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, the structure of which is not particularly limited, including but not limited to a linear structure, a branched structure, or a cyclic structure selected from an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and a combination thereof, preferably an aromatic ring; the divalent linking group is selected fromNot restricted to divalent C1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C1-20A divalent linking group formed from hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing; z4More preferably C substituted by cyano, alkyl, aryl, ester, amide, urea, carbamate 1-20Hydrocarbyl/heterohydrocarbyl;
wherein the content of the first and second substances,
Figure BDA0002376545090000976
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by formula 1-T-1 is preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090000973
wherein, W6、Z4、
Figure BDA0002376545090000977
The definition, selection range and preferable range of (A) are the same as those of the general formula 1-T-1;
wherein Z is5Selected from oxygen atom, sulfur atom, selenium atom, silicon atom, carbon atom, nitrogen atom; when Z is5When it is an oxygen atom, a sulfur atom, or a selenium atom, R1 5、R1 6、R1 7Is absent; when Z is5When it is a nitrogen atom, R1 5Exist, R1 6、R1 7Is absent; when Z is5When it is a silicon atom or a carbon atom, R1 5、R1 6Exist, R1 7Is absent;
wherein R is1 5、R1 6、R1 7、R1 8Each independently selected from an atom (including a hydrogen atom), a substituent; r1 5、R1 6、R1 7、R1 8Each is independentPreferably selected from hydrogen atom, halogen atom, C1-20Hydrocarbyl/heterohydrocarbyl, substituted C1-20Hydrocarbyl/heterohydrocarbyl; r1 5、R1 6、R1 7、R1 8Each independently more preferably from a hydrogen atom, a halogen atom, C1-20Alkyl radical, C1-20Alkenyl radical, C1-20Aryl radical, C1-20Alkoxyacyl group, C1-20Alkoxythioacyl, C1-20Aryloxy acyl group, C1-20Aryloxythioacyl, C1-20Alkylthio acyl radical, C1-20An arylthioacyl group;
wherein Z is6Is a divalent linking group; the divalent linking group contains or does not contain a heteroatom, the number of carbon atoms is not particularly limited, preferably 1 to 20, more preferably 1 to 10, and the structure thereof is not particularly limited, and includes, but is not limited to, a linear structure, a branched structure containing a pendant group, or a cyclic structure selected from an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and a combination thereof, preferably an aromatic ring. The divalent linking group is selected from, but not limited to: divalent heteroatom radical linking group, divalent C 1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C1-20A divalent linking group formed from hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing; z6The divalent connecting group is preferably selected from a divalent connecting group with an electron-withdrawing effect and a divalent connecting group substituted by an electron-withdrawing effect substituent, so that the force sensitive group is split evenly and more remarkable force-induced response effect is obtained; wherein, the divalent linking group with electron-withdrawing effect includes but is not limited to acyl, acyloxy, acylthio, acylamino, phenylene; the divalent linking group substituted by the substituent having the electron-withdrawing effect includes, but is not limited to, acyl group, acyloxy group, acylthio group, amide group, phenylene group, nitro group, sulfonic acid group, aromatic hydrocarbon group, cyano group, halogen atom, and divalent C group substituted by trifluoromethyl group1-20Hydrocarbyl/heterohydrocarbyl. By way of example, the divalent linking group substituted with an electron-withdrawing substituent includes, but is not limited to, acyl, acyloxy, acylthio, amide, phenylene, nitro, sulfonic acid groupsAn aromatic hydrocarbon group, a cyano group, a halogen atom, a trifluoromethyl-substituted phenylene group, a benzylidene group, a naphthylidene group, a pyrrolylidene group, a pyridylidene group.
A typical structure of the formula 1-T-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000981
Wherein the content of the first and second substances,
Figure BDA0002376545090000983
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the benzoyl series homolysis mechanism refers to a force sensitive group containing benzoyl force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0002376545090000982
wherein each Z is independently selected from carbon atom, silicon atom, germanium atom and tin atom, preferably selected from carbon atom, germanium atom and tin atom; each W is independently selected from an oxygen atom or a sulfur atom, preferably from an oxygen atom; wherein the content of the first and second substances,
Figure BDA0002376545090000984
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the general formulae 1-S-1, 1-S-2, 1-S-3 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000991
in the present invention, covalent single force sensitive groups based on heterolytic mechanisms include, but are not limited to, the following series: triaryl sulfur salt series, o-phthalaldehyde series, sulfonic acid series, seleno/seleno-sulfur/seleno-nitrogen series, and mercapto-Michael addition bond series.
In the invention, the covalent single force sensitive group of the triaryl sulfate series heterolysis mechanism refers to a force sensitive group containing triaryl sulfate force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0002376545090000992
Wherein the content of the first and second substances,
Figure BDA0002376545090000995
each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, wherein any two of the same ring structure
Figure BDA0002376545090000996
With or without looping.
A typical structure of the formula 2-A-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090000993
wherein the content of the first and second substances,
Figure BDA0002376545090000997
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the ortho-phthalaldehyde series heterolysis mechanism refers to a force sensitive group containing ortho-phthalaldehyde force sensitive elements, and the structural general formula of the covalent single force sensitive group comprises but is not limited to the following groups:
Figure BDA0002376545090000994
wherein, the ring of M is aliphatic ring, ether ring or the combination of the aliphatic ring, the ether ring and the aromatic ring, the ring-forming atoms of the ring structure are respectively and independently carbon atoms, nitrogen atoms or other hetero atoms, and at least one ring-forming atom is oxygen atom; the hydrogen atoms attached to the ring-forming atoms may be substituted or unsubstituted with any suitable substituent atom, substituent group; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent;
Wherein the content of the first and second substances,
Figure BDA0002376545090001007
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula 2-B-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001001
wherein the content of the first and second substances,
Figure BDA0002376545090001008
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force-sensitive group of the sulfonic acid group series heterolysis mechanism refers to a force-sensitive group containing a sulfonic acid group force-sensitive element, and the structural general formula of the covalent single force-sensitive group includes but is not limited to the following types:
Figure BDA0002376545090001002
wherein the content of the first and second substances,
Figure BDA0002376545090001009
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
A typical structure of the formula 2-C-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001003
wherein the content of the first and second substances,
Figure BDA00023765450900010010
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force-sensitive group of the seleno-oxo/seleno-thio/seleno-nitrogen series heterofission mechanism refers to a force-sensitive group containing seleno-oxo/seleno-thio/seleno-nitrogen force-sensitive elements, and the structural general formula includes but is not limited to the following types:
Figure BDA0002376545090001004
wherein each W is independently selected from an oxygen atom, a sulfur atom; wherein the content of the first and second substances,
Figure BDA00023765450900010011
each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, to the same atom
Figure BDA00023765450900010012
With or without looping.
Wherein the structures represented by the general formulae 2-D-1 and 2-D-2 are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001005
wherein W is as defined for formula 2-D-1; wherein the content of the first and second substances,
Figure BDA00023765450900010013
the definition, selection range and preferable range of (A) are the same as those of the general formula 1-B-3; wherein the content of the first and second substances,
Figure BDA00023765450900010014
indicates that n is connected with
Figure BDA00023765450900010015
A nitrogen-containing aromatic ring of (a); the number of ring-forming atoms of the ring is not particularly limited, and is preferably from 5 to 8; except that at least one of the ring-forming atoms is a nitrogen atom and the ring and the selenium atom are connected through the nitrogen atom, the remaining ring-forming atoms are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, and the hydrogen atoms connected to the ring-forming atoms may be substituted or unsubstituted with any suitable substituent atom, substituent group; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent; wherein the value of n is 0, 1 or an integer greater than 1; at different positions
Figure BDA00023765450900010016
Are the same or different; said
Figure BDA00023765450900010017
The structure of (a) is preferably selected from pyridine rings and substituted forms thereof;
Figure BDA00023765450900010018
any two of which are each independently attached to the same atom, including a hydrogen atom, a substituent, and a substituted polymer chain, with or without participation in force activation
Figure BDA00023765450900010019
With or without rings, any two of the same ring structure
Figure BDA00023765450900010020
With or without looping.
Typical structures of the general formulae 2-D-1, 2-D-2 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001006
Figure BDA0002376545090001011
wherein X is selected from but not limited to fluorine atom, chlorine atom, bromine atom, cyano group, and isothiocyanato group, preferably from chlorine atom and bromine atom;
Figure BDA0002376545090001014
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the present invention, the covalent single force-sensitive group of the mercapto-michael addition bond series heterolysis mechanism refers to a force-sensitive group containing a mercapto-michael addition bond force-sensitive element, and the structural formula thereof includes but is not limited to the following types:
Figure BDA0002376545090001012
wherein X is selected from carbon group, ester group, amide group, thiocarbonyl group, thioester group, thioamide group, sulfone group, sulfonate group and phosphate group; y is an electron-withdrawing effect group including, but not limited to, aldehyde group, carbon group, ester group, carboxyl group, amide group, cyano group, nitro group, trifluoromethyl group, phosphoric acid group, sulfonic acid group, halogen atom;
Figure BDA0002376545090001015
each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, to the same atom
Figure BDA0002376545090001016
With or without rings, on different carbon atoms
Figure BDA0002376545090001017
Or may be linked to form a ring, the carbon atom being attached to X
Figure BDA0002376545090001018
May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof.
Typical structures of the general formulae 2-E-1, 2-E-2, 2-E-3, 2-E-4 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001013
wherein the content of the first and second substances,
Figure BDA0002376545090001019
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the present invention, covalent single force sensitive groups based on the reverse cyclization mechanism include, but are not limited to, the following series: cyclobutane series, monoepoxybutane series, dioxetane series, dinitrocyclobutane series, cyclobutene series, triazole ring series, DA series, hetero DA series, light-controlled DA series, and [4+4] cycloaddition series.
In the invention, the covalent single force sensitive group of the cyclobutane series reverse cyclization mechanism refers to a single force sensitive group containing cyclobutane force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0002376545090001021
wherein, Q is independently selected from oxygen atom and carbon atom, and Q at different positions can be the same or different; b represents the number of connections to Q, respectively; when each Q is independently selected from oxygen atoms, b ═ 0; when each Q is independently selected from carbon atoms, b ═ 2;
Figure BDA0002376545090001025
Denotes the linkage to a polymer chain, cross-linkingA linked network chain or any other suitable group/atom linkage; difference on the same atom
Figure BDA0002376545090001026
Can be linked to form a ring, on different atoms
Figure BDA0002376545090001027
May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof;
among them, the force sensitive group of the formula 3-A-1 is preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001022
wherein J is independently selected from oxygen atom, sulfur atom, secondary amine group and substitution form thereof, and J at different positions can be same or different; ar is independently selected from aryl, preferably phenyl, and Ar at different positions can be the same or different; n represents the number of connections to Ar; x0Each independently selected from a halogen atom, preferably from a fluorine atom, a chlorine atom, a bromine atom;
Figure BDA0002376545090001028
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; difference on the same atom
Figure BDA0002376545090001029
Can be linked to form a ring, on different atoms
Figure BDA00023765450900010210
May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof;
among them, the force sensitive group of the general formula 3-A-1-1 is preferably selected from the following general structure:
Figure BDA0002376545090001023
Wherein J is independently selected from oxygen atom, sulfur atom, secondary amine group and substitution form thereof, and J at different positions can be same or different; j 'is independently selected from oxygen atom and sulfur atom, and J' at different positions can be the same or different;
a typical structure of the formula 3-A-1-1 can be exemplified as follows:
Figure BDA0002376545090001024
Figure BDA0002376545090001031
wherein J is independently selected from oxygen atom, sulfur atom, secondary amine group and substitution form thereof, and J at different positions can be same or different; j 'is independently selected from oxygen atom and sulfur atom, and J' at different positions can be the same or different; r, R1、R2Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
among them, the force sensitive group of the general formula 3-A-1-2 is preferably selected from the following general structure:
Figure BDA0002376545090001041
wherein J is independently selected from oxygen atom, sulfur atom, secondary amine group and substitution form thereof, and J at different positions can be same or different; j 'is independently selected from oxygen atom and sulfur atom, and J' at different positions can be the same or different;
a typical structure of the formula 3-A-1-2 can be exemplified as follows:
Figure BDA0002376545090001042
Figure BDA0002376545090001051
wherein J is independently selected from oxygen atom, sulfur atom, secondary amine group and substitution form thereof, and J at different positions can be same or different; j' is selected from oxygen atom and sulfur atom; r, R 1、R2Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, micromolecular hydrocarbon groups and polymer chain residues, wherein R at different positions can be the same or different;
among them, the force sensitive group of the general formula 3-A-1-3 is preferably selected from the following general structure:
Figure BDA0002376545090001052
wherein J is independently selected from oxygen atom, sulfur atom, secondary amine group and substitution form thereof, and J at different positions can be same or different;
typical structures of the general formula 3-A-1-3 can be exemplified as follows:
Figure BDA0002376545090001053
wherein R is1、R2Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
among them, the force sensitive group of the general formula 3-A-1-4 is preferably selected from the following general structure:
Figure BDA0002376545090001054
wherein J is independently selected from oxygen atom, sulfur atom, secondary amine group and substitution form thereof, and J at different positions can be same or different;
typical structures of the general formula 3-A-1-4 can be exemplified as follows:
Figure BDA0002376545090001055
wherein R is1、R2Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
among them, the force sensitive group of the general formula 3-A-1-5 is preferably selected from the following general structure:
Figure BDA0002376545090001056
wherein J is selected from the group consisting of an oxygen atom, a sulfur atom, a secondary amine group, and substituted forms thereof;
Typical structures of the general formula 3-A-1-5 can be exemplified as follows:
Figure BDA0002376545090001057
wherein R is selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
among them, the force sensitive group of the general formula 3-A-1-6 is preferably selected from the following general structure:
Figure BDA0002376545090001061
typical structures of the general formula 3-A-1-6 can be exemplified as follows:
Figure BDA0002376545090001062
wherein, R, R1、R2、R3Each independently selected from any one of the following structures: hydrogenAtoms, heteroatom groups, small molecule hydrocarbyl groups, polymer chain residues;
among them, the force sensitive group of the general formula 3-A-1-7 is preferably selected from the following general structure:
Figure BDA0002376545090001071
wherein J is selected from the group consisting of an oxygen atom, a sulfur atom, a secondary amine group, and substituted forms thereof; j' is selected from oxygen atom and sulfur atom;
typical structures of the general formula 3-A-1-7 can be exemplified as follows:
Figure BDA0002376545090001072
wherein, R, R1、R2、R3、R4Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
among them, the force sensitive group of the general formula 3-A-1-8 is preferably selected from the following general structure:
Figure BDA0002376545090001081
wherein J is selected from the group consisting of an oxygen atom, a sulfur atom, a secondary amine group, and substituted forms thereof; j' is selected from oxygen atom and sulfur atom;
typical structures of the general formula 3-A-1-8 can be exemplified as follows:
Figure BDA0002376545090001082
wherein, R, R1、R2Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
Among them, the force sensitive group of the general formula 3-A-1-9 is preferably selected from the following general structure:
Figure BDA0002376545090001083
wherein J is selected from the group consisting of an oxygen atom, a sulfur atom, a secondary amine group, and substituted forms thereof; j' is selected from oxygen atom and sulfur atom;
typical structures of the general formula 3-A-1-9 can be exemplified as follows:
Figure BDA0002376545090001084
wherein, R, R1、R2Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
typical structures of the general formula 3-A-1-10 can be exemplified as follows:
Figure BDA0002376545090001091
typical structures of the general formula 3-A-1-11 can be exemplified as follows:
Figure BDA0002376545090001092
among them, the force sensitive group of the general formula 3-A-1-12 is preferably selected from the following general structure:
Figure BDA0002376545090001093
typical structures of the general formula 3-A-1-12 can be exemplified as follows:
Figure BDA0002376545090001094
in addition, the typical structure of the covalent single force sensitive group of the cyclobutane series reverse cyclization mechanism can also be exemplified as follows:
Figure BDA0002376545090001095
wherein R is selected from any one of the following structures: hydrogen atoms, heteroatom groups, micromolecular hydrocarbon groups and polymer chain residues, wherein R at different positions can be the same or different; j' is selected from the group consisting of an oxygen atom, a sulfur atom, a secondary amine group, and substituted forms thereof;
a typical structure of the formula 3-A-2 can be exemplified as follows:
Figure BDA0002376545090001096
typical structures of the general formula 3-A-3 can be exemplified as follows:
Figure BDA0002376545090001097
wherein R is1、R2Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
Typical structures of the general formula 3-A-4 can be exemplified as follows:
Figure BDA0002376545090001098
wherein R is1、R2Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
in the present invention, the covalent single force-sensitive group of the reverse cyclization mechanism of the mono-heterocyclic butane series refers to a single force-sensitive group containing a mono-heterocyclic butane force-sensitive element, and the structural general formula thereof includes but is not limited to the following types:
Figure BDA0002376545090001099
wherein Q is selected from oxygen atom and carbon atom; b represents the number of connections to Q; when Q is selected from oxygen atom, b ═ 0; when Q is selected from carbon atoms, b ═ 2; d is selected from oxygen atom, sulfur atom, selenium atom, nitrogen atom and silicon atom; a represents the number of connections to D; when D is selected from oxygen atom, sulfur atom and selenium atom, a is 0; when D is selected from a nitrogen atom, a ═ 1; when D is selected from a silicon atom, a ═ 2;
Figure BDA0002376545090001104
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; difference on the same atom
Figure BDA0002376545090001105
Can be linked to form a ring, on different atoms
Figure BDA0002376545090001106
May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof;
a typical structure of the formula 3-B-1 can be exemplified as follows:
Figure BDA0002376545090001101
Wherein, R, R1、R2Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
among them, the force sensitive group of the general formula 3-B-2 is preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001102
in the present invention, the covalent single force-sensitive group of the reverse cyclization mechanism of the dioxetane series refers to a single force-sensitive group containing dioxetane force-sensitive elements, and the structural general formula thereof includes but is not limited to the following types:
Figure BDA0002376545090001103
wherein J is selected from the group consisting of a direct bond, an oxygen atom, a sulfur atom, a secondary amine group and substituted forms thereof, a methylene group and substituted forms thereof; wherein Ar is selected from aromatic rings selected from monocyclic structures, polycyclic structures and condensed ring structures; the number of ring-forming atoms of the ring is not particularly limited, and a five-membered ring or a six-membered ring is preferable; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, boron atoms, phosphorus atoms, and silicon atoms, and the hydrogen atoms attached to the ring-forming atoms may be substituted with any suitable substituent atom, substituent, or may be unsubstituted; wherein, the substituent atom or substituent group is not particularly limited and is selected from but not limited to heteroatom group, small molecule hydrocarbyl group, polymer chain residue; the substituent atoms or substituents are preferably selected from: halogen atom, cyano group, nitro group, trifluoromethyl group, C 1-20Alkyl radical, C1-20Alkylsiloxy group, C1-20Acyloxy, C1-20Alkoxyacyl group, C1-20Alkoxy radical, C1-20Alkylthio radical, C1-20An alkylamino group. By way of example, suitable Ar may be selected from the following structures:
Figure BDA0002376545090001111
wherein, the symbol is the site connecting with other structures in the formula, if not specifically noted, the following symbol is the same meaning, and the description is not repeated; l is1Is a divalent linking group selected from, but not limited to, oxygen atoms, sulfur atoms, secondary amine groups and substituted forms thereof, methylene groups and substituted forms thereof; l is2Is a divalent linking group selected from, but not limited to, a direct bond, an oxygen atom, a sulfur atom, a secondary amine group and substituted forms thereof, a methylene group and substituted forms thereof, a carbonyl group, a thiocarbonyl group;
typical structures of covalent single force sensitive groups of the reverse cyclization mechanism of the dioxetane series can be exemplified as follows:
Figure BDA0002376545090001112
wherein, R, R1、R2Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
in the invention, the covalent single force sensitive group of the reverse cyclization mechanism of the diazocyclobutane series refers to a single force sensitive group containing a diazobutane force sensitive element, and the structural general formula of the covalent single force sensitive group comprises but is not limited to the following groups:
Figure BDA0002376545090001121
wherein R is 1、R2Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
a typical structure of the formula 3-D-1 can be exemplified as follows:
Figure BDA0002376545090001122
wherein, R, R1、R2Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
a typical structure of the general formula 3-D-2 can be exemplified as follows:
Figure BDA0002376545090001123
wherein R is1、R2Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
a typical structure of the general formula 3-D-3 can be exemplified as follows:
Figure BDA0002376545090001124
wherein, R, R1、R2Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
in the invention, the covalent single force sensitive group of the cyclobutene series reverse cyclization mechanism refers to a single force sensitive group containing cyclobutene force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0002376545090001125
wherein the content of the first and second substances,
Figure BDA0002376545090001126
the ring structure is aromatic ring or hybrid aromatic ring, the ring atoms of the ring structure are independently selected from carbon atom, nitrogen atom or other hetero atoms, the ring structure is preferably 6-50 membered ring, more preferably 6-12 membered ring; the hydrogen atoms on each ring-forming atom may be substituted or unsubstituted, wherein, when the ring-forming atoms are selected from nitrogen atoms, the nitrogen atoms may carry a positive charge; the ring structure is preferably a benzene ring, a naphthalene ring, an anthracene ring and substituted forms of the above ring structures; n represents the number of linkages to the ring-forming atoms of the cyclic structure; each R is independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, micromolecular hydrocarbon groups and polymer chain residues, wherein R at different positions can be the same or different;
A typical structure of the formula 3-E-1 can be exemplified as follows:
Figure BDA0002376545090001127
Figure BDA0002376545090001131
wherein, R, R1、R2Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
a typical structure of the general formula 3-E-2 can be exemplified as follows:
Figure BDA0002376545090001132
typical structures of the general formula 3-E-3 can be exemplified as follows:
Figure BDA0002376545090001133
typical structures of the general formula 3-E-4 can be exemplified as follows:
Figure BDA0002376545090001134
wherein, R, R1Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
in the invention, the covalent single-force sensitive groups of the cyclobutane series, the monoheterocyclic butane series, the dioxetane series, the dinitrocyclobutane series and the cyclobutene series reverse cyclization mechanism can also be activated by other actions except mechanical force, for example, the covalent single-force sensitive groups of the cyclobutane series can be subjected to reverse cyclization reaction under the irradiation of ultraviolet light with certain frequency so as to dissociate the force sensitive groups; the dioxetane series covalent single force sensitive group can be subjected to reverse cyclization reaction under one or more of the activation effects of chemistry, biology, heat and the like so as to dissociate the force sensitive group.
In the invention, the covalent single force sensitive group of the triazole ring series reverse cyclization mechanism is a single force sensitive group containing a triazole ring force sensitive element, and the structural general formula of the covalent single force sensitive group comprises but is not limited to the following groups:
Figure BDA0002376545090001135
Wherein the content of the first and second substances,
Figure BDA0002376545090001138
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom;
among them, the force sensitive group of the formula 3-F-1 is preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001136
in the invention, the covalent single force sensitive group of the DA series reverse cyclization mechanism refers to a single force sensitive group containing DA force sensitive elements, and the structural general formula of the covalent single force sensitive group comprises but is not limited to the following classes:
Figure BDA0002376545090001137
Figure BDA0002376545090001141
wherein I is selected from oxygen atom, sulfur atom, secondary amine group and substitution form thereof, amide group, ester group, divalent small molecule hydrocarbon group, more preferably from oxygen atom, methylene group, 1, 2-ethylene group, 1' -vinyl group, substitution form of secondary amine group, amide group, ester group;
Figure BDA0002376545090001148
the ring structure is aromatic ring or hybrid aromatic ring, the ring atoms of the ring structure are independently selected from carbon atom, nitrogen atom or other hetero atoms, the ring structure is preferably 6-50 rings, more preferably 6-12 rings; the hydrogen atoms on each ring-forming atom may be substituted, or not substituted, wherein,when the ring-forming atoms are selected from nitrogen atoms, the nitrogen atoms may carry a positive charge; the ring structure is preferably a benzene ring, a naphthalene ring, an anthracene ring and substituted forms of the above groups; n represents the number of linkages to the ring-forming atoms of the cyclic structure;
Figure BDA0002376545090001149
Represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; difference on the same atom
Figure BDA00023765450900011410
Can be linked to form a ring, on different atoms
Figure BDA00023765450900011411
May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof;
among them, the force sensitive group of the formula 3-G-1 is preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001142
wherein each R is independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, micromolecular hydrocarbon groups and polymer chain residues, wherein R at different positions can be the same or different;
a typical structure of the formula 3-G-1-1 can be exemplified as follows:
Figure BDA0002376545090001143
wherein, R, R1、R2Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
a typical structure of the formula 3-G-1-2 can be exemplified as follows:
Figure BDA0002376545090001144
typical structures of the general formula 3-G-1-3 can be exemplified as follows:
Figure BDA0002376545090001145
typical structures of the general formula 3-G-1-4 can be exemplified as follows:
Figure BDA0002376545090001146
a typical structure of the formula 3-G-2 can be exemplified as follows:
Figure BDA0002376545090001147
wherein R is selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
Among them, the force sensitive groups of formula 3-G-3 are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001151
wherein R is1、R2Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
a typical structure of the formula 3-G-3-1 can be exemplified as follows:
Figure BDA0002376545090001152
wherein, R, R1、R2Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
a typical structure of the general formula 3-G-3-2 can be exemplified as follows:
Figure BDA0002376545090001153
wherein R is selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
typical structures of the general formula 3-G-3-3 can be exemplified as follows:
Figure BDA0002376545090001154
typical structures of the general formula 3-G-3-4 can be exemplified as follows:
Figure BDA0002376545090001161
typical structures of the general formula 3-G-3-5 can be exemplified as follows:
Figure BDA0002376545090001162
typical structures of the general formula 3-G-3-6 can be exemplified as follows:
Figure BDA0002376545090001163
typical structures of the general formula 3-G-3-7 can be exemplified as follows:
Figure BDA0002376545090001164
wherein, R, R1、R2Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
typical structures of the general formula 3-G-3-13 can be exemplified as follows:
Figure BDA0002376545090001165
wherein, R, R1、R2Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
Typical structures of the general formula 3-G-3-14 can be exemplified as follows:
Figure BDA0002376545090001166
wherein R is selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
typical structures of the general formula 3-G-3-19 can be exemplified as follows:
Figure BDA0002376545090001167
wherein, R, R1、R2Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
among them, the force sensitive groups of formula 3-G-4 are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001168
a typical structure of the formula 3-G-4-1 can be exemplified as follows:
Figure BDA0002376545090001169
Figure BDA0002376545090001171
wherein R is selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
a typical structure of the general formula 3-G-4-2 can be exemplified as follows:
Figure BDA0002376545090001172
wherein R is selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
typical structures of the general formula 3-G-4-3 can be exemplified as follows:
Figure BDA0002376545090001173
wherein R is selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
typical structures of the general formula 3-G-4-4 can be exemplified as follows:
Figure BDA0002376545090001174
wherein R is selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
Among them, the force sensitive groups of formula 3-G-5 are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001175
among them, the force sensitive group of the general formula 3-G-5-1 is preferably selected from the following general structure:
Figure BDA0002376545090001176
wherein R is1、R2Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
a typical structure of the general formula 3-G-5-1-1 can be exemplified as follows:
Figure BDA0002376545090001177
wherein, R, R1、R2Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
a typical structure of the general formula 3-G-5-1-2 can be exemplified as follows:
Figure BDA0002376545090001181
wherein, R, R1Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
among them, the force sensitive group of the general formula 3-G-5-2 is preferably selected from the following general structure:
Figure BDA0002376545090001182
wherein R is1、R2Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
among them, the force sensitive group of the general formula 3-G-5-3 is preferably selected from the following general structure:
Figure BDA0002376545090001183
wherein R is1、R2Each independently selected from any one of the following structures: hydrogen atom, hetero atom group, small molecule hydrocarbon group, polymer chain residue ；
Among them, the force sensitive groups of formula 3-G-6 are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001184
a typical structure of the formula 3-G-6-1 can be exemplified as follows:
Figure BDA0002376545090001185
wherein, R, R1Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
among them, the force sensitive groups of formula 3-G-7 are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001186
among them, the force sensitive group of the general formula 3-G-7-1 is preferably selected from the following general structure:
Figure BDA0002376545090001187
wherein R is1、R2Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
among them, the force sensitive group of the general formula 3-G-7-2 is preferably selected from the following general structure:
Figure BDA0002376545090001191
wherein R is1、R2Each independently selected from any one of the following structures: hydrogen atom, hetero atom group, small molecule hydrocarbon group, polymer chain residueA group;
among them, the force sensitive groups of formula 3-G-8 are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001192
in the invention, the covalent single force sensitive group of the hetero DA series reverse cyclization mechanism refers to a single force sensitive group containing a hetero DA force sensitive element, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0002376545090001193
wherein, P 1Selected from oxygen atom, sulfur atom, nitrogen atom, silicon atom, selenium atom; p2Selected from carbon atoms, nitrogen atoms, silicon atoms; c. C1、c2Respectively represent and P1、P2The number of connected connections; when P is present1When selected from oxygen atom, sulfur atom, selenium atom, c10; when P is present1、P2When selected from nitrogen atoms, c1、c 21 is ═ 1; when P is present1、P2When selected from carbon atoms, silicon atoms, c22; i is selected from oxygen atom, sulfur atom, secondary amine group and substitution form thereof, amide group, ester group, divalent small molecule hydrocarbon group, more preferably from oxygen atom, methylene group, 1, 2-ethylene group, 1' -vinyl group, substitution form of secondary amine group, amide group, ester group;
Figure BDA0002376545090001194
the ring structure is aromatic ring or hybrid aromatic ring, the ring atoms of the ring structure are independently selected from carbon atom, nitrogen atom or other hetero atoms, the ring structure is preferably 6-50 rings, more preferably 6-12 rings; the hydrogen atoms on each ring-forming atom may be substituted or unsubstituted, wherein, when the ring-forming atoms are selected from nitrogen atoms, the nitrogen atoms may carry a positive charge; the cyclic structure is preferably benzene ring, naphthalene ring or anthracene ringAnd substituted forms of the above groups; n represents the number of linkages to the ring-forming atoms of the cyclic structure;
Figure BDA0002376545090001195
Represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; difference on the same atom
Figure BDA0002376545090001196
Can be linked to form a ring, on different atoms
Figure BDA0002376545090001197
May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof;
among them, the force sensitive group of the general formula 3-H-1 is preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001198
a typical structure of the formula 3-H-1-1 can be exemplified as follows:
Figure BDA0002376545090001199
wherein R is selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
a typical structure of the formula 3-H-1-2 can be exemplified as follows:
Figure BDA00023765450900011910
wherein R is selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
typical structures of the general formula 3-H-1-3 can be exemplified as follows:
Figure BDA0002376545090001201
wherein R is selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
typical structures of the general formula 3-H-1-4 can be exemplified as follows:
Figure BDA0002376545090001202
wherein R is selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
typical structures of the general formula 3-H-1-5 can be exemplified as follows:
Figure BDA0002376545090001203
Among them, the force sensitive group of the general formula 3-H-2 is preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001204
among them, the force sensitive group of the general formula 3-H-3 is preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001205
among them, the force sensitive groups of the general formula 3-H-4 are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001206
a typical structure of the formula 3-H-4-1 can be exemplified as follows:
Figure BDA0002376545090001207
wherein R is selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
a typical structure of the formula 3-H-4-2 can be exemplified as follows:
Figure BDA0002376545090001211
wherein R is selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
typical structures of the general formula 3-H-4-3 can be exemplified as follows:
Figure BDA0002376545090001212
wherein, R, R1Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
typical structures of the general formula 3-H-4-7 can be exemplified as follows:
Figure BDA0002376545090001213
wherein R is selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
typical structures of the general formula 3-H-4-8 can be exemplified as follows:
Figure BDA0002376545090001214
wherein R is selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
Typical structures of the general formula 3-H-4-9 can be exemplified as follows:
Figure BDA0002376545090001215
wherein R is selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
typical structures of the general formula 3-H-4-10 can be exemplified as follows:
Figure BDA0002376545090001216
wherein R is selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
typical structures of the general formula 3-H-4-13 can be exemplified as follows:
Figure BDA0002376545090001217
wherein R is selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
typical structures of the general formula 3-H-4-14 can be exemplified as follows:
Figure BDA0002376545090001218
wherein R is selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
typical structures of the general formula 3-H-4-15 can be exemplified as follows:
Figure BDA0002376545090001219
wherein, R, R1Each independently selected from any one of the following structures: hydrogenAtoms, heteroatom groups, small molecule hydrocarbyl groups, polymer chain residues;
typical structures of the general formula 3-H-4-16 can be exemplified as follows:
Figure BDA0002376545090001221
wherein R is selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
typical structures of the general formula 3-H-4-19 can be exemplified as follows:
Figure BDA0002376545090001222
Wherein R is selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
typical structures of the general formula 3-H-4-20 can be exemplified as follows:
Figure BDA0002376545090001223
wherein R is selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
typical structures of the general formula 3-H-4-21 can be exemplified as follows:
Figure BDA0002376545090001224
wherein, R, R1Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
typical structures of the general formula 3-H-4-22 can be exemplified as follows:
Figure BDA0002376545090001225
wherein R is selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
among them, the force sensitive groups of the general formula 3-H-5 are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001226
a typical structure of the formula 3-H-5-1 can be exemplified as follows:
Figure BDA0002376545090001227
wherein, R, R1Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
a typical structure of the formula 3-H-5-2 can be exemplified as follows:
Figure BDA0002376545090001231
wherein R is selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
Typical structures of the general formula 3-H-5-3 can be exemplified as follows:
Figure BDA0002376545090001232
wherein, R, R1Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
typical structures of the general formula 3-H-5-4 can be exemplified as follows:
Figure BDA0002376545090001233
wherein, R, R1Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
typical structures of the general formula 3-H-5-5 can be exemplified as follows:
Figure BDA0002376545090001234
wherein R is1Selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
among them, the force sensitive groups of the general formula 3-H-6 are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001235
in the invention, the covalent single force sensitive group of the light-controlled DA series reverse cyclization mechanism refers to a single force sensitive group containing a light-controlled locking element and a DA element sensitive to mechanical force, wherein the DA element can be used as a part of the light-controlled locking element; the existence of the light-operated locking element enables the force-sensitive clusters to have different structures under different illumination conditions and show different response effects on mechanical force, thereby achieving the purpose of locking/unlocking the force-sensitive elements; under the condition of light-operated unlocking, the DA force-sensitive element can perform inverse DA chemical reaction under the action of mechanical force, so that the polymer directly and/or indirectly generates chemical signal change, specific response to mechanical force is achieved, and force-induced response performance/effect is obtained; when the force-sensitive element is locked, it cannot be activated by mechanical force to express the force-sensitive property, or is more difficult to be activated by mechanical force to express the force-sensitive property. By utilizing the characteristics, the mechanochemical performance of the material can be regulated and controlled by selecting specific illumination conditions, the locking/unlocking regulation effect is achieved, and the applicability and the functional responsiveness of the force sensitive group are improved. Wherein, ultraviolet light (generally, ultraviolet light with a wavelength range of 310-380 nm) is selected to lock the force sensitive groups, and visible light (generally, visible light with a wavelength range of more than 420 nm) is selected to unlock the force sensitive groups. The ultraviolet light and the visible light used as the light source in the present invention have various and unlimited sources, and may be ultraviolet light or visible light directly generated by a high pressure mercury lamp, a metal halogen lamp, a mercury lamp, a xenon lamp, an LED lamp, etc. with a desired wavelength, or ultraviolet light or visible light obtained by energy transfer (including up-conversion fluorescence or down-conversion fluorescence) of a fluorophore; the fluorophore may be selected from organic fluorophores, organometallic fluorophores, organic elemental fluorophores, biological fluorophores, inorganic fluorophores, organic-inorganic hybrid fluorophores, and the like.
In the invention, the light control locking element comprises the following structural units:
Figure BDA0002376545090001241
wherein the content of the first and second substances,
Figure BDA0002376545090001244
represents a linkage to a polymer chain, a cross-linked network chain, a force-sensitive group, or any other suitable group/atom; difference on the same atom
Figure BDA0002376545090001245
Can be linked to form a ring, on different atoms
Figure BDA0002376545090001246
May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof.
In the invention, the Diels-Alder force-sensitive element contains at least one of the following structural units:
Figure BDA0002376545090001242
wherein, K0Selected from carbon atom, oxygen atom, sulfur atom, nitrogen atom; a is0Represents a group K0The number of connected connections; when K is0When selected from oxygen atom, sulfur atom, a00; when K is0When selected from nitrogen atoms, a01 is ═ 1; when K is0When selected from carbon atoms, a0＝2。
In the invention, the covalent single force sensitive group of the reverse cyclization mechanism of the light-operated DA series has a structural general formula including but not limited to the following classes:
Figure BDA0002376545090001243
wherein, K1、K2、K3、K4、K5、K6Each independently selected from carbon atom, oxygen atom, sulfur atom, nitrogen atom, and at K1、K2Or K3、 K4Or K5、K6At least one of them is selected from carbon atoms; a is1、a2、a3、a4、a5、a6Respectively represent and K1、K2、K3、K4、K5、K6The number of connected connections; when K is1、K2、K3、K4、K5、K6Each independently selected from an oxygen atom and a sulfur atom 1、a2、a3、a4、a5、a60; when K is1、K2、K3、K4、K5、K6Each independently selected from nitrogen atoms, a1、a2、a3、a4、a5、a61 is ═ 1; when K is1、K2、K3、K4、 K5、K6Each independently selected from carbon atoms, a1、a2、a3、a4、a5、a6＝2；I1、I2、I3Each independently absent or each independently selected from the group consisting of an oxygen atom, a 1,1 '-carbonyl group, a methylene group and substituted forms thereof, a 1, 2-ethylene group and substituted forms thereof, a 1,1' -vinyl group and substituted forms thereof; when I is1、 I2、I3Each independently absent, b ═ 2; when I is1、I2、I3Each independently selected from the group consisting of an oxygen atom, 1 '-carbonyl, methylene and substituted forms thereof, 1, 2-ethylene and substituted forms thereof, 1' -vinyl and substituted forms thereof, b ═ 1; m is selected from the group consisting of an oxygen atom, a nitrogen atom, a divalent alkoxy chain: (
Figure BDA0002376545090001251
n ═ 2, 3, 4), preferably an oxygen atom or a nitrogen atom; c represents the number of connections to M; when M is selected from an oxygen atom, a divalent alkoxy chain, c ═ 0; when M is selected from nitrogen atoms, c ═ 1; c1、C2、C3、C4、C5、C6Represent carbon atoms in different positions; difference on the same atom
Figure BDA0002376545090001256
Can be linked to form a ring, on different atoms
Figure BDA0002376545090001257
Can also be linked to form a ring, where K is preferred1And K2K to3And K4K to5And K6C to1And C2C to3And C4C to5And C6Forming a ring; the ring may be any number of rings, preferably five-membered and six-membered rings, which may be aliphatic, aromatic, ether, condensed, or combinations thereof, the ring-forming atoms are each independently selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, selenium atoms, or other heteroatoms, and the hydrogen atoms on the ring-forming atoms may be substituted with any substituent or not; wherein, K 1And K2K to3And K4K to5And K6Formed byPreferably the following structure:
Figure BDA0002376545090001252
C1and C2C to3And C4The ring formed between preferably has the following structure:
Figure BDA0002376545090001253
C5and C6The ring formed between preferably has the following structure:
Figure BDA0002376545090001254
among them, the force sensitive group of the general formula 3-I-1 is preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001255
Figure BDA0002376545090001261
wherein R is1、R2Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; e1、 E2Each independently selected from any one of the following structures:
Figure BDA0002376545090001262
a typical structure of the formula 3-I-1 can be exemplified as follows:
Figure BDA0002376545090001263
wherein each R is independently selected from any one of the following structures: hydrogen atom, heteroatom group, small molecule hydrocarbon group, polymer chain residue, R is more preferably hydrogen atom, fluorine atom, chlorine atom, bromine atom, hydroxyl group, amino group, carboxyl group, ester group, cyano group, methyl group, ethyl group, propyl group, vinyl group, trifluoromethyl group, phenyl group, pyridyl group, more preferably hydrogen atom, fluorine atom, cyano group, methyl group, phenyl group; r1Selected from any one of the following structures: hydrogen atoms, small hydrocarbon groups, polymer chain residues; r0Each independently selected from the group consisting of: -H, -CH3、-F、-Cl、-Br、-COOH、-CN、
Figure BDA0002376545090001264
Figure BDA0002376545090001271
Figure BDA0002376545090001272
R, R at different locations0May be the same or different;
Among them, the force sensitive group of the general formula 3-I-2 is preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001273
wherein E is1、E2Each independently selected from any one of the following structures:
Figure BDA0002376545090001274
a typical structure of the general formula 3-I-2 can be exemplified as follows:
Figure BDA0002376545090001275
wherein R is eachIndependently selected from any one of the following structures: hydrogen atom, heteroatom group, small molecule hydrocarbon group, polymer chain residue, R is more preferably hydrogen atom, fluorine atom, chlorine atom, bromine atom, hydroxyl group, amino group, carboxyl group, ester group, cyano group, methyl group, ethyl group, propyl group, vinyl group, trifluoromethyl group, phenyl group, pyridyl group, more preferably hydrogen atom, fluorine atom, cyano group, methyl group, phenyl group; r1Selected from any one of the following structures: hydrogen atoms, small hydrocarbon groups, polymer chain residues; r0Each independently selected from the group consisting of: -H, -CH3、-F、-Cl、-Br、-COOH、-CN、
Figure BDA0002376545090001276
Figure BDA0002376545090001277
Figure BDA0002376545090001278
R, R at different locations0May be the same or different;
among them, the force sensitive groups of formula 3-I-3 are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001281
wherein R is1、R2、R3、R4Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; e is selected from any one of the following structures:
Figure BDA0002376545090001282
typical structures of the general formula 3-I-3 can be exemplified as follows:
Figure BDA0002376545090001283
Figure BDA0002376545090001291
Wherein each R is independently selected from any one of the following structures: hydrogen atom, heteroatom group, small molecule hydrocarbon group, polymer chain residue, R is more preferably hydrogen atom, fluorine atom, chlorine atom, bromine atom, hydroxyl group, amino group, carboxyl group, ester group, cyano group, methyl group, ethyl group, propyl group, vinyl group, trifluoromethyl group, phenyl group, pyridyl group, more preferably hydrogen atom, fluorine atom, cyano group, methyl group, phenyl group; r1、R2Each independently selected from any one of the following structures: hydrogen atoms, small hydrocarbon groups, polymer chain residues; r0Each independently selected from the group consisting of: -H, -CH3、-F、-Cl、-Br、 -COOH、-CN、
Figure BDA0002376545090001292
Figure BDA0002376545090001293
R, R at different locations0May be the same or different;
among them, the force sensitive groups of the general formula 3-I-4 are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001294
wherein E is selected from any one of the following structures:
Figure BDA0002376545090001295
Figure BDA0002376545090001301
typical structures of the general formula 3-I-4 can be exemplified as follows:
Figure BDA0002376545090001302
wherein each R is independently selected from any one of the following structures: hydrogen atom, heteroatom group, small molecule hydrocarbon group, polymer chain residue, R is more preferably hydrogen atom, fluorine atom, chlorine atom, bromine atom, hydroxyl group, amino group, carboxyl group, ester group, cyano group, methyl group, ethyl group, propyl group, vinyl group, trifluoromethyl group, phenyl group, pyridyl group, more preferably hydrogen atom, fluorine atom, cyano group, methyl group, phenyl group; r 1、R2Each independently selected from any one of the following structures: hydrogen atoms, small hydrocarbon groups, polymer chain residues; r0Each independently selected from the group consisting of: -H, -CH3、-F、-Cl、-Br、 -COOH、-CN、
Figure BDA0002376545090001303
Figure BDA0002376545090001304
R, R at different locations0May be the same or different;
among them, the force sensitive groups of the general formula 3-I-5 are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001305
Figure BDA0002376545090001311
wherein R is1、R2、R3、R4、R5、R6Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
typical structures of the general formula 3-I-5 can be exemplified as follows:
Figure BDA0002376545090001312
wherein each R is independently selected from any one of the following structures: hydrogen atom, heteroatom group, small molecule hydrocarbon group, polymer chain residue, R is more preferably hydrogen atom, fluorine atom, chlorine atom, bromine atom, hydroxyl group, amino group, carboxyl group, ester group, cyano group, methyl group, ethyl group, propyl group, vinyl group, trifluoromethyl group, phenyl group, pyridyl group, more preferably hydrogen atom, fluorine atom, cyano group, methyl group, phenyl group; r1、R2、R3Each independently selected from any one of the following structures: hydrogen atoms, small hydrocarbon groups, polymer chain residues; r at different positions can be the same or different;
among them, the force sensitive groups of the general formula 3-I-6 are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001321
Typical structures of the general formula 3-I-6 can be exemplified as follows:
Figure BDA0002376545090001322
wherein each R is independently selected from any one of the following structures: hydrogen atom, heteroatom group, small molecule hydrocarbon group, polymer chain residue, R is more preferably hydrogen atom, fluorine atom, chlorine atom, bromine atom, hydroxyl group, amino group, carboxyl group, ester group, cyano group, methyl group, ethyl group, propyl group, vinyl group, trifluoromethyl group, phenyl group, pyridyl group, more preferably hydrogen atom, fluorine atom, cyano group, methyl group, phenyl group; r1、R2、R3Each independently selected from any one of the following structures: hydrogen atoms, small hydrocarbon groups, polymer chain residues; r at different positions can be the same or different;
among them, the force sensitive groups of the general formulae 3-I-7 are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001323
wherein R is1、R2Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; e is selected from any one of the following structures:
Figure BDA0002376545090001331
f is selected from any one of the following structures:
Figure BDA0002376545090001332
typical structures of the general formulae 3 to I-7 can be illustrated as follows:
Figure BDA0002376545090001333
Figure BDA0002376545090001341
wherein each R is independently selected from any one of the following structures: hydrogen atom, heteroatom group, small molecule hydrocarbon group, polymer chain residue, R is more preferably hydrogen atom, fluorine atom, chlorine atom, bromine atom, hydroxyl group, amino group, carboxyl group, ester group, cyano group, methyl group, ethyl group, propyl group, vinyl group, trifluoromethyl group, phenyl group, pyridyl group, more preferably hydrogen atom, fluorine atom, cyano group, methyl group, phenyl group; r 1Selected from any one of the following structures: hydrogen atoms, small hydrocarbon groups, polymer chain residues; r0Selected from the following groups: -H, -CH3、-F、-Cl、-Br、-COOH、-CN、
Figure BDA0002376545090001342
Figure BDA0002376545090001343
R at different positions can be the same or different;
among them, the force sensitive groups of the general formula 3-I-8 are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001344
wherein E is selected from any one of the following structures:
Figure BDA0002376545090001345
f is selected from any one of the following structures:
Figure BDA0002376545090001346
typical structures of the general formulae 3 to I-8 can be illustrated as follows:
Figure BDA0002376545090001347
Figure BDA0002376545090001351
wherein each R is independently selected from any one of the following structures: hydrogen atom, heteroatom group, small molecule hydrocarbon group, polymer chain residue, R is more preferably hydrogen atom, fluorine atom, chlorine atom, bromine atom, hydroxyl group, amino group, carboxyl group, ester group, cyano group, methyl group, ethyl group, propyl group, vinyl group, trifluoromethyl group, phenyl group, pyridyl group, more preferably hydrogen atom, fluorine atom, cyano group, methyl group, phenyl group; r1Selected from any one of the following structures: hydrogen atoms, small hydrocarbon groups, polymer chain residues; r0Selected from the following groups: -H, -CH3、-F、-Cl、-Br、-COOH、-CN、
Figure BDA0002376545090001352
Figure BDA0002376545090001353
R at different positions can be the same or different;
among them, the force sensitive groups of the general formula 3-I-9 are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001354
wherein R is1、R2Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; g is selected from any one of the following structures:
Figure BDA0002376545090001355
Typical structures of the general formulae 3 to I-9 can be illustrated as follows:
Figure BDA0002376545090001356
Figure BDA0002376545090001361
wherein each R is independently selected from any one of the following structures: hydrogen atom, heteroatom group, small molecule hydrocarbon group, polymer chain residue, R is more preferably hydrogen atom, fluorine atom, chlorine atom, bromine atom, hydroxyl group, amino group, carboxyl group, ester group, cyano group, methyl group, ethyl group, propyl group, vinyl group, trifluoromethyl group, phenyl group, pyridyl group, more preferably hydrogen atom, fluorine atom, cyano group, methyl group, phenyl group; r at different positions can be the same or different; r1Selected from any one of the following structures: hydrogen atom, small molecule hydrocarbon group, polymer chain residue；
Among them, the force sensitive groups of the general formula 3-I-10 are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001362
wherein G is selected from any one of the following structures:
Figure BDA0002376545090001363
typical structures of the general formula 3-I-10 can be exemplified as follows:
Figure BDA0002376545090001371
wherein each R is independently selected from any one of the following structures: hydrogen atom, heteroatom group, small molecule hydrocarbon group, polymer chain residue, R is more preferably hydrogen atom, fluorine atom, chlorine atom, bromine atom, hydroxyl group, amino group, carboxyl group, ester group, cyano group, methyl group, ethyl group, propyl group, vinyl group, trifluoromethyl group, phenyl group, pyridyl group, more preferably hydrogen atom, fluorine atom, cyano group, methyl group, phenyl group; r at different positions can be the same or different; r 1Selected from any one of the following structures: hydrogen atoms, small hydrocarbon groups, polymer chain residues;
among them, the force sensitive groups of the general formula 3-I-11 are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001372
wherein R is1、R2、R3、R4Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; f is selected from any one of the following structures:
Figure BDA0002376545090001373
typical structures of the general formula 3-I-11 can be exemplified as follows:
Figure BDA0002376545090001374
Figure BDA0002376545090001381
wherein each R is independently selected from any one of the following structures: hydrogen atom, heteroatom group, small molecule hydrocarbon group, polymer chain residue, R is more preferably hydrogen atom, fluorine atom, chlorine atom, bromine atom, hydroxyl group, amino group, carboxyl group, ester group, cyano group, methyl group, ethyl group, propyl group, vinyl group, trifluoromethyl group, phenyl group, pyridyl group, more preferably hydrogen atom, fluorine atom, cyano group, methyl group, phenyl group; r1、R2Each independently selected from any one of the following structures: hydrogen atoms, small hydrocarbon groups, polymer chain residues; r at different positions can be the same or different;
among them, the force sensitive groups of the general formula 3-I-12 are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001382
wherein, F is selected from any one of the following structures:
Figure BDA0002376545090001383
Typical structures of the general formulae 3 to I-12 can be illustrated as follows:
Figure BDA0002376545090001391
wherein each R is independently selected from any one of the following structures: hydrogen atom, heteroatom group, small molecule hydrocarbon group, polymer chain residue, R is more preferably hydrogen atom, fluorine atom, chlorine atom, bromine atom, hydroxyl group, amino group, carboxyl group, ester group, cyano group, methyl group, ethyl group, propyl group, vinyl group, trifluoromethyl group, phenyl group, pyridyl group, more preferably hydrogen atom, fluorine atom, cyano group, methyl group, phenyl group; r1、R2Each independently selected from any one of the following structures: hydrogen atoms, small hydrocarbon groups, polymer chain residues; r at different positions may be the same or different.
In the invention, the covalent single force sensitive group of DA series, hybrid DA series and light-operated DA series reverse cyclization mechanism can also carry out reverse cyclization reaction through thermal activation so as to dissociate the force sensitive group.
In the present invention, the covalent single force sensitive group of the [4+4] cycloaddition series reverse cyclization mechanism refers to a single force sensitive group containing [4+4] cycloaddition force sensitive elements, and the structural general formula thereof includes but is not limited to the following classes:
Figure BDA0002376545090001392
wherein the content of the first and second substances,
Figure BDA0002376545090001393
the ring structure is aromatic ring or hybrid aromatic ring, the ring atoms of the ring structure are independently selected from carbon atom, nitrogen atom or other hetero atoms, the ring structure is preferably 6-50 rings, more preferably 6-12 rings; the hydrogen atoms on each ring-forming atom may be substituted or unsubstituted, wherein, when the ring-forming atoms are selected from nitrogen atoms, the nitrogen atoms may carry a positive charge; the ring structure is preferably a benzene ring, a naphthalene ring, an anthracene ring, an aza-benzene, an aza-naphthalene, an aza-anthracene or a substituted form of the above groups; i is 6～I14Each independently selected from the group consisting of an oxygen atom, a sulfur atom, an amide group, an ester group, an imide group, and a divalent small hydrocarbon group, more preferably from the group consisting of an oxygen atom, a methylene group, 1, 2-diethylene, 12-ethenylene, amide, ester, imine;
Figure BDA0002376545090001395
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; difference on the same atom
Figure BDA0002376545090001396
Can be linked to form a ring, on different atoms
Figure BDA0002376545090001397
Or linked to form a ring, including but not limited to aliphatic rings, ether rings, condensed rings, and combinations thereof;
among them, the force sensitive group of formula 3-J-1 is preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001394
wherein R is1、R2、R3、R4Each independently selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
a typical structure of the formula 3-J-1 can be exemplified as follows:
Figure BDA0002376545090001401
among them, the force sensitive group of formula 3-J-2 is preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001402
a typical structure of the formula 3-J-2 can be exemplified as follows:
Figure BDA0002376545090001403
among them, the force sensitive groups of formula 3-J-3 are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001404
typical structures of the general formula 3-J-3 can be exemplified as follows:
Figure BDA0002376545090001411
among them, the force sensitive groups of formula 3-J-4, which are preferably selected from a subset of the following general structures:
Figure BDA0002376545090001412
Typical structures of the general formula 3-J-4 can be exemplified as follows:
Figure BDA0002376545090001413
among them, the force sensitive groups of formula 3-J-5, which are preferably selected from a subset of the following general structures:
Figure BDA0002376545090001414
typical structures of the general formula 3-J-5 can be exemplified as follows:
Figure BDA0002376545090001415
among them, the force sensitive groups of formula 3-J-6, which are preferably selected from a subset of the following general structures:
Figure BDA0002376545090001416
typical structures of the general formula 3-J-6 can be exemplified as follows:
Figure BDA0002376545090001417
wherein R is1Selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
among them, the force sensitive groups of formula 3-J-7 are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001418
typical structures of the general formula 3-J-7 can be exemplified as follows:
Figure BDA0002376545090001419
among them, the force sensitive groups of formula 3-J-8 are preferably selected from at least a subset of the following general structures:
Figure BDA00023765450900014110
typical structures of the general formula 3-J-8 can be exemplified as follows:
Figure BDA0002376545090001421
among them, the force sensitive groups of formula 3-J-9, which are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001422
among them, the force sensitive groups of formula 3-J-10, which are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001423
among them, the force sensitive groups of formula 3-J-11 are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001424
typical structures of the general formula 3-J-11 can be exemplified as follows:
Figure BDA0002376545090001425
wherein R is 1Selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
among them, the force sensitive groups of formula 3-J-12, which are preferably selected from a subset of the following general structures:
Figure BDA0002376545090001426
among them, the force sensitive groups of formula 3-J-13, which are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001431
typical structures of the general formula 3-J-13 can be exemplified as follows:
Figure BDA0002376545090001432
wherein R is1Selected from any one of the following structures: hydrogen atom, hetero atom radicalGroups, small hydrocarbon groups, polymer chain residues;
among them, the force sensitive groups of formula 3-J-14 are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001433
among them, the force sensitive groups of formula 3-J-15 are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001434
among them, the force sensitive groups of formula 3-J-16, which are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001435
typical structures of the general formula 3-J-16 can be exemplified as follows:
Figure BDA0002376545090001436
Figure BDA0002376545090001441
wherein R is1Selected from any one of the following structures: hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
among them, the force sensitive groups of formula 3-J-17, which are preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001442
typical structures of the general formula 3-J-17 can be exemplified as follows:
Figure BDA0002376545090001443
in the invention, the covalent single force-sensitive group of the [4+4] cycloaddition series reverse cyclization mechanism can also carry out reverse cyclization reaction under the irradiation of ultraviolet light with certain frequency so as to dissociate the force-sensitive group.
In the present invention, covalent single force sensitive groups based on the electrocyclization mechanism include, but are not limited to, the following series: six-membered ring series, five-membered ring series, three-membered ring series.
In the present invention, the covalent single force sensitive group of the six-membered ring series electrical cyclization mechanism refers to a single force sensitive group containing six-membered ring force sensitive elements, and the structural general formula includes but is not limited to the following groups:
Figure BDA0002376545090001451
wherein X is selected from oxygen atom, sulfur atom, selenium atom, tellurium atom, C-R, N-R, preferably oxygen atom; y is selected from C-R and nitrogen atom; each R is independently any suitable atom, substituent, substituted polymer chain; m is a metal atom selected from Be, Zn, Cu, Co, Hg, Pb, Pt, Fe, Cr, Ni, preferably Be, Zn, Cu, Co;
Figure BDA0002376545090001453
each independently of the other, to any suitable atom (including a hydrogen atom), substituent, substituted polymer chain, whether or not participating in force activation, different on the same atom
Figure BDA0002376545090001454
Can be linked to form a ring, on different atoms
Figure BDA0002376545090001455
Or can be connected into a ring. At different positions of the same structural formula, the groups or structures having the same symbols are independent of each other, and may be the same or differentThe same is true.
The six-membered ring monomer containing the general structural formula (4-A-1) of the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0002376545090001452
Wherein, X1Each independently selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, C-R, N-R, preferably from an oxygen atom; y is1Each independently selected from C-R, nitrogen atom; z1Is selected from C- (R)2Nitrogen atom, sulfur atom, oxygen atom, tellurium atom, preferably C- (R)2A nitrogen atom; z2Selected from sulfur atom, oxygen atom, selenium atom, tellurium atom, C- (R)2Nitrogen atom, preferably C- (R)2A nitrogen atom; when Z is1Or Z2Selected from sulfur atom, oxygen atom, selenium atom, tellurium atom, C- (R)2When connected to it
Figure BDA0002376545090001456
The number is 0;
Figure BDA0002376545090001457
an aromatic ring having an arbitrary number of elements; n is a total number of hydrogen atoms, substituent atoms, substituents, and substituent polymer chains bonded to the ring-constituting atoms, and is 0, 1 or an integer X, Y, R greater than 1,
Figure BDA0002376545090001458
The selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
The six-membered ring monomer having the general structural formula (4-A-1) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0002376545090001461
Figure BDA0002376545090001471
wherein, X, X1、Y、Y1、R、Z1、Z2、
Figure BDA0002376545090001472
n、
Figure BDA0002376545090001474
The selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
The six-membered ring monomer having the general structural formula (4-A-1) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0002376545090001473
Figure BDA0002376545090001481
Wherein, X2Each independently selected from carbon atom, oxygen atom, sulfur atom, N-R; x3Each independently selected from the group consisting of an oxygen atom, a sulfur atom, N-R; x, X1、Y、Y1、R、Z1、Z2、
Figure BDA0002376545090001482
The selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
In the present invention, the six-membered ring monomer having the general structural formula (4-A-1) is exemplified by the following structures:
Figure BDA0002376545090001491
Figure BDA0002376545090001501
Figure BDA0002376545090001511
Figure BDA0002376545090001521
Figure BDA0002376545090001531
Figure BDA0002376545090001541
Figure BDA0002376545090001551
wherein, X, X1、X2、X3、Y、Y1The selection range of R is as described in the series of force-sensitive groups, and is not described in detail herein;
Figure BDA0002376545090001556
each independently associated with a polymer chain or supramolecular polymer chain involved in force activation.
The six-membered ring monomer containing the general structural formula (4-A-2) of the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0002376545090001552
wherein, X, R, Z1、Z2、
Figure BDA0002376545090001553
n、
Figure BDA0002376545090001557
The selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
In the present invention, the six-membered ring monomer having the general structural formula (4-A-2) is exemplified by the following structures:
Figure BDA0002376545090001554
wherein the content of the first and second substances,
Figure BDA0002376545090001558
each independently associated with a polymer chain or supramolecular polymer chain involved in force activation.
The six-membered ring monomer containing the general structural formula (4-A-3) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0002376545090001555
wherein X, M,
Figure BDA0002376545090001559
The selection range of the pressure-sensitive groups is as described in the series of the force-sensitive groups, and the detailed description is omitted.
In the present invention, the six-membered ring monomer having the general structural formula (4-A-3) is exemplified by the following structures:
Figure BDA0002376545090001561
wherein the content of the first and second substances,
Figure BDA0002376545090001564
each independently associated with a polymer chain or supramolecular polymer chain involved in force activation.
The six-membered ring monomer containing the general structural formula (4-A-4) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0002376545090001562
wherein, X, Y, Z1、Z2、
Figure BDA0002376545090001565
The selection range of n is as described above in the series of force-sensitive groups and will not be described in detail here.
In the present invention, the six-membered ring monomer having the general structural formula (4-A-4) is exemplified by the following structures:
Figure BDA0002376545090001563
wherein, the selection range of X, Y is as described in the series of force-sensitive groups, and is not described in detail herein;
Figure BDA0002376545090001566
each independently associated with a polymer chain or supramolecular polymer chain involved in force activation.
The six-membered ring monomer containing the general structural formula (4-A-5) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0002376545090001567
wherein the content of the first and second substances,
Figure BDA0002376545090001568
the selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
In the present invention, the six-membered ring monomer having the general structural formula (4-A-5) is exemplified by the following structures:
Figure BDA0002376545090001571
Wherein the content of the first and second substances,
Figure BDA0002376545090001575
each independently associated with a polymer chain or supramolecular polymer chain involved in force activation.
The six-membered ring monomer containing the general structural formula (4-A-6) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0002376545090001572
wherein X, R,
Figure BDA0002376545090001573
n、
Figure BDA0002376545090001576
The selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
In the present invention, the six-membered ring monomer having the general structural formula (4-A-6) is exemplified by the following structures:
Figure BDA0002376545090001574
Figure BDA0002376545090001581
Figure BDA0002376545090001591
wherein, the selection range of X is as the previous description of the series of force-sensitive groups, and the description is omitted;
Figure BDA0002376545090001594
polymers independently of one another and participating in force activationChains or supramolecular polymer chains.
The six-membered ring monomer containing the general structural formula (4-A-7) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0002376545090001592
wherein, X, Z2、
Figure BDA0002376545090001595
The selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
In the present invention, the six-membered ring monomer having the general structural formula (4-A-7) is exemplified by the following structures:
Figure BDA0002376545090001593
Figure BDA0002376545090001601
wherein the content of the first and second substances,
Figure BDA0002376545090001602
each independently associated with a polymer chain or supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the five-membered ring series electrical cyclization mechanism is a force sensitive group containing five-membered ring force sensitive elements, and the structural general formula of the covalent single force sensitive group comprises but is not limited to the following types:
Figure BDA0002376545090001611
Wherein A is0Is selected from
Figure BDA0002376545090001612
A1Is selected from
Figure BDA0002376545090001613
A2Is selected from
Figure BDA0002376545090001614
Each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Wherein the structure represented by the general formula 4-B-1 is preferably selected from the following general structures:
Figure BDA0002376545090001615
wherein, T1Each independently of the other being a substituent group, preferably an electron-withdrawing group, and two T' s1Can be connected to form a ring;
wherein the content of the first and second substances,
Figure BDA0002376545090001616
is a conjugated ring structure or a heterocyclic ring structure containing double bonds; position 1 is attached to a force-activatable bond and position 2 is attached to another linking atom of the five-membered ring; n is
Figure BDA00023765450900016110
Is 0, 1 or an integer greater than 1, m is the number of R therein, which is 0, 1 or an integer greater than 1; wherein, the ring-forming atom at the 1-position side and
Figure BDA00023765450900016111
the ring-forming atoms on the side of the position 2 and the ring-forming atoms on the symmetry axis shown by the dotted line are connected with R; the ring structure is preferably
Figure BDA0002376545090001617
Because the sensor is sensitive to light at the same time, double response of force and light can be realized;
wherein each R is independently selected from any suitable atom (including hydrogen atoms)) Substituents and substituted polymer chains not involved in force activation;
Figure BDA00023765450900016112
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation;
Specifically, the typical structure of the formula 4-B-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001618
wherein the content of the first and second substances,
Figure BDA00023765450900016113
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Among them, the force sensitive group of the general formula 4-B-2 is further preferably selected from the following general structure:
Figure BDA0002376545090001619
wherein A is0、
Figure BDA00023765450900016114
The definition and the selection range of the formula (I) are the same as those of the general formula 4-B-2;
Figure BDA00023765450900016115
is a positively charged conjugated ring structure or heterocyclic structure, wherein n is
Figure BDA00023765450900016116
The total number of (a) is 0, 1 or an integer greater than 1;
Figure BDA00023765450900016117
is an aromatic ring structure, n is
Figure BDA00023765450900016118
The total number of (a) is 0, 1 or an integer greater than 1;
Figure BDA00023765450900016119
is a conjugated ring structure or a heterocyclic ring structure with strong electron-withdrawing groups and/or heteroatoms, n is
Figure BDA00023765450900016120
The total number of (a) is 0, 1 or an integer greater than 1;
Figure BDA00023765450900016121
is a conjugated ring structure or a conjugated heterocyclic structure, n is
Figure BDA00023765450900016122
The total number of (a) is 0, 1 or an integer greater than 1;
specifically, the typical structure of the formula 4-B-2 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001621
wherein the content of the first and second substances,
Figure BDA0002376545090001624
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Among them, the structure represented by the general formulae 4-B-3 to 4-B-6 is more preferably the following general formula:
Figure BDA0002376545090001622
wherein E is 1Each independently selected from one of two structures shown below:
Figure BDA0002376545090001625
wherein the content of the first and second substances,
Figure BDA0002376545090001626
each independently is an aromatic ring structure, n is the total number of atoms (including hydrogen atoms) bonded to atoms constituting the aromatic ring, substituents, and substituted polymer chains, and is 0, 1, or an integer greater than 1; e2Are any suitable atoms (including hydrogen atoms), substituents, and substituted polymer chains, with or without participation in force activation, preferably E1(ii) a In the same structure, when E2Is selected in the range of E1When E is greater1And E2Are independent of each other; a. the1The definition, selection range and preferable range of (A) are the same as those of the general formula 4-B-3; t is2Each independently a substituent group, preferably an electron-withdrawing group, and two T's in the general formulae 4-B-4-1, 4-B-6-12Can be connected to form a ring;
Figure BDA0002376545090001627
is a heterocyclic ring containing at least one nitrogen atom, AxIs a carbon atom or a nitrogen atom, and n is a ring member attached to a heterocyclic ring
Figure BDA0002376545090001628
The total number of (a) is 1 or an integer greater than 1;
Figure BDA0002376545090001629
is an aromatic ring structure, each R is independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain not involved in force activation; n is the total number of R numbers, and is 0, 1 or an integer more than 1; each R is independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that does not participate in force activation;
Figure BDA00023765450900016210
Each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
In one embodiment of the present invention, the force-sensitive element is preferably connected with some specific structures to realize a structure responding to specific metal ions, so that the force-sensitive group has ion detection function besides force response. By way of example, typical structures that can achieve a response to a particular metal ion are listed below, but the invention is not limited thereto:
Figure BDA0002376545090001623
Figure BDA0002376545090001631
wherein each X is independently selected from,
Figure BDA0002376545090001632
Figure BDA0002376545090001633
Each R is independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain not involved in force activation;
Figure BDA0002376545090001638
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
In another embodiment of the present invention, the force-sensitive element is preferably a structure capable of chelating with metal ions and achieving force-induced ion release, and exemplary structures capable of chelating with metal ions and achieving force-induced ion release are listed below, but the present invention is not limited thereto:
Figure BDA0002376545090001634
wherein each X is independently selected from,
Figure BDA0002376545090001635
Figure BDA0002376545090001636
Each R is independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain not involved in force activation;
Figure BDA0002376545090001639
Each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
In another embodiment of the present invention, the force-sensitive moiety is preferably a structure that can be linked to an energy receptor and that can effect energy transfer upon force activation; by way of example, typical structures that can be attached to an energy receptor and that can effect energy transfer upon force activation are as follows, but the invention is not limited thereto:
Figure BDA0002376545090001637
Figure BDA0002376545090001641
wherein L is any suitable covalent linking group having a length of less than 10 nm; each R is independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain not involved in force activation;
Figure BDA0002376545090001643
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Specifically, other typical structures shown in the general formula 4-B-3 are exemplified below, but the present invention is not limited thereto:
Figure BDA0002376545090001642
Figure BDA0002376545090001651
wherein A is1The definition, selection range and preferable range of (A) are the same as those of the general formula 4-B-3; each X is independently selected from,
Figure BDA0002376545090001652
Figure BDA0002376545090001653
Each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that does not participate in force activation;
Figure BDA0002376545090001654
Each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Specifically, the typical structure shown in the general formula 4-B-4 is exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001655
Figure BDA0002376545090001661
wherein each X is independently selected from,
Figure BDA0002376545090001662
Figure BDA0002376545090001663
Each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Specifically, the typical structure shown in the formula 4-B-5 is exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001664
wherein each X is independently selected from,
Figure BDA0002376545090001665
Figure BDA0002376545090001666
Each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Specifically, the typical structure shown in the general formula 4-B-6 is exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001667
wherein each X is independently selected from,
Figure BDA0002376545090001668
Figure BDA0002376545090001669
Each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein the structure represented by the general formula 4-B-7 is preferably selected from at least a subset of the following general structures:
Figure BDA0002376545090001671
wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that does not participate in force activation;
Figure BDA0002376545090001679
each independently with any suitable atom (including a hydrogen atom), substituent, and substituent with or without participation in force activation The object chains are connected; e1、E2The definition, selection range and preferable range of (A) are the same as those of the general formula 4-B-3-1;
Figure BDA0002376545090001672
is an aromatic ring structure, is a linking position, wherein position 1 is linked to a carbon atom and position 2 is linked to an oxygen atom; wherein the ring-forming atom at the 1-position side and the ring-forming atom on the axis of symmetry indicated by the dotted line are bonded to R, and the ring-forming atom at the 2-position side and
Figure BDA00023765450900016710
connecting; n is the total number of R's bonded to the atoms constituting the aromatic ring, and m is
Figure BDA00023765450900016711
The total number of the number; t is3Each independently selected from one of two structures shown below:
Figure BDA0002376545090001673
two T in the same type3When selected from the same structure, T3The specific structures of the components can be the same or different; wherein the content of the first and second substances,
Figure BDA0002376545090001674
each independently is an aromatic ring structure, and n is the total number of atoms (including hydrogen atoms) bonded to atoms constituting the aromatic ring, substituents, and substituted polymer chains, and is 0, 1, or an integer greater than 1.
Specifically, typical structures of the formula 4-B-7 are exemplified below, but the present invention is not limited thereto:
Figure BDA0002376545090001675
wherein the content of the first and second substances,
Figure BDA00023765450900016712
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
The spiro force sensitive group can regulate and control heat, light and force-induced activation and generate coordination under the existence of metal ions, protons and other ligands, so as to regulate and control the properties of thermochromism, photochromism, photocrosslinking, mechanochromism, mechanocrosslinking and the like; by designing and adjusting the substituent of the spiro force sensitive group, particularly the coordination or the substituent containing the coordination group, the coordination of the activated spiro force sensitive group and ligands such as metal ions and the like, such as coordination number, coordination strength, optical characteristics, catalytic characteristics and the like, can be further regulated and controlled, and more extensive and adjustable photoinduced, thermotropic and force-induced properties and the like can be obtained.
In the present invention, the covalent single force-sensitive group of the electrical cyclization mechanism of the three-membered ring series refers to a force-sensitive group containing three-membered ring (including three-membered ring and four-membered/five-membered ring) force-sensitive elements, and the structural general formula includes but is not limited to the following groups:
Figure BDA0002376545090001676
wherein the content of the first and second substances,
Figure BDA00023765450900016713
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation; a is selected from-O-, -S-),
Figure BDA0002376545090001677
Wherein, each E is independently selected from hydrogen atom, halogen atom, alkyl and alkoxy.
Wherein, the structure represented by the general formula 4-C-1-1 is further preferably selected from the following general structures:
Figure BDA0002376545090001678
wherein E isXEach independently selected from a halogen atom, preferably a fluorine atom, a bromine atom, a chlorine atom; r is each independentlySelected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain not involved in force activation;
Figure BDA0002376545090001684
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation;
wherein, E in the general formula 4-C-1-1xWhen the bromine atom is bromine atom, the bromine atom can react with carboxyl in a system after being activated, so that the special effect of enhancing crosslinking caused by force is realized; the hydrogen halide can be released after the structural force shown in the general formula 4-C-1-2 is activated, so that the change of the force pH value is realized; after the force activation, the five-membered ring at the center of the general formula 4-C-1-10 can form furyl which can react with other proper groups in the system to realize the special effect of strengthening the force-induced crosslinking; the force sensitive groups shown in the general formula 4-C-1-12 can react with carboxyl in a system after being activated, so that the special effect of force-induced enhancement is realized; the force sensitive groups shown in the general formula 4-C-1-13 change color after being activated by force, not only can realize force-induced color change, but also can react with groups such as dialkenyl, alkynyl and the like in a system to realize the special effect of enhancing force-induced crosslinking, so that the method is more preferable.
A typical structure of the formula 4-C-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001681
wherein the content of the first and second substances,
Figure BDA0002376545090001685
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the present invention, the covalent single force-sensitive group of the bending activation mechanism of the alkyne-furan adduct series refers to a force-sensitive group containing alkyne-furan adduct force-sensitive elements, and the structural general formula thereof includes but is not limited to the following types:
Figure BDA0002376545090001682
wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain not involved in force activation;
Figure BDA0002376545090001686
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
A typical structure of the formula 5-A-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001683
wherein the content of the first and second substances,
Figure BDA0002376545090001687
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the present invention, the covalent single force-sensitive group of the bending activation mechanism of the anthracene-triazoline-dione adduct series refers to a force-sensitive group containing anthracene-triazoline-dione adduct force-sensitive elements, and the structural general formula of the covalent single force-sensitive group includes but is not limited to the following types:
Figure BDA0002376545090001691
wherein each R is independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain not involved in force activation;
Figure BDA0002376545090001697
Each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation; the anthracene group generated after the force-sensitive group is activated by force has a fluorescence effect, can realize special effects including but not limited to force-induced fluorescence and the like, and is preferably connected with other functional groups with a fluorescence enhancement effect to enable the force to be enhancedThe fluorescence effect is more obvious; the triazolinedione group generated after the force-sensitive group is activated by force can be subjected to addition reaction with groups such as diene group and the like, and when R is a substituted polymer chain which does not participate in the force activation or is connected with the triazolinedione group in another force-sensitive group and the system simultaneously contains the groups such as diene group and the like, special effects including but not limited to force-induced chemical reaction, force-induced crosslinking enhancement and the like can be realized, so that the triazolinedione group is also preferable.
A typical structure of the formula 5-B-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001692
wherein the content of the first and second substances,
Figure BDA0002376545090001698
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the covalent single force sensitive group of the alkynyl series bending activation mechanism refers to a force sensitive group containing alkynyl force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following:
Figure BDA0002376545090001693
Wherein the content of the first and second substances,
Figure BDA0002376545090001699
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation; after being bent and activated, the series of force sensitive groups can generate azide-alkyne click reaction without catalysts with azide groups, and special effects including but not limited to force-induced crosslinking and the like are realized.
A typical structure of the formula 5-C-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001694
wherein the content of the first and second substances,
Figure BDA00023765450900016910
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the present invention, the covalent single force sensitive group of the bending activation mechanism of the azophenyl series refers to a force sensitive group containing azophenyl force sensitive elements, and the structural general formula includes but is not limited to the following:
Figure BDA0002376545090001695
wherein the content of the first and second substances,
Figure BDA00023765450900016911
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation; the series of force sensitive groups can generate phase change after being activated by bending, and achieve special effects including but not limited to force-induced softening and the like.
A typical structure of the formula 5-D-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001696
wherein the content of the first and second substances,
Figure BDA00023765450900016912
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the present invention, covalent single force sensitive groups based on other mechanisms include, but are not limited to, the following series: a double nitrite series, a 1, 1' -linked condensed ring series, a dithiomaleimide series and a Michael reaction series.
In the invention, the covalent single force-sensitive group of the other mechanism of the double-nitrite series refers to a single force-sensitive group containing a double-nitrite force-sensitive element, and the structural general formula of the covalent single force-sensitive group includes but is not limited to the following groups:
Figure BDA0002376545090001701
wherein X is selected from oxygen atom, sulfur atom, preferably oxygen atom;
Figure BDA0002376545090001706
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. In different positions of the same structural formula, groups or structures having the same symbols are independent of each other, and may be the same or different.
In the present invention, the structure of the covalent single-force sensitive group of the other mechanism of the double nitrite series can be exemplified as follows:
Figure BDA0002376545090001702
wherein;
Figure BDA0002376545090001707
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. In different positions of the same structural formula, groups or structures having the same symbols are independent of each other, and may be the same or different.
In the invention, the covalent single force sensitive group of other mechanisms of the 1,1 '-linked condensed ring series refers to a single force sensitive group containing 1, 1' -linked condensed ring force sensitive elements, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following types:
Figure BDA0002376545090001703
Wherein each R is independently any suitable atom, substituent, substituted polymer chain;
Figure BDA0002376545090001704
an aromatic ring having an arbitrary number of elements; the aromatic ring can be any aromatic ring or aromatic heterocyclic ring, and the ring-forming atoms are respectively and independently carbon atoms or hetero atoms; the heteroatom can be selected from nitrogen atom, oxygen atom, sulfur atom, phosphorus atom, silicon atom and boron atom; the hydrogen atom on the aromatic ring-forming atom may be substituted with an optional substituent or may be unsubstituted; it may be a monocyclic structure, a polycyclic structure, or a fused ring structure.
Figure BDA0002376545090001708
Refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. In different positions of the same structural formula, groups or structures having the same symbols are independent of each other, and may be the same or different.
In the present invention, the structure of the covalent single force sensitive group of the other mechanism of the 1, 1' -linked condensed ring series can be exemplified as follows:
Figure BDA0002376545090001705
wherein the content of the first and second substances,
Figure BDA0002376545090001709
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. In different positions of the same structural formula, groups or structures having the same symbols are independent of each other, and may be the same or different.
In the present invention, the covalent single force-sensitive group of the dithiomaleimide series with other mechanisms refers to a single force-sensitive group containing a dithiomaleimide force-sensitive element, and the structural general formula includes but is not limited to the following groups:
Figure BDA0002376545090001711
wherein the content of the first and second substances,
Figure BDA0002376545090001715
an aromatic ring having an arbitrary number of elements; the aromatic ring can be any aromatic ring or aromatic heterocyclic ring, and the ring-forming atoms are respectively and independently carbon atoms or hetero atoms; the heteroatom can be selected from nitrogen atom, oxygen atom, sulfur atom, phosphorus atom, silicon atom and boron atom; the hydrogen atom on the aromatic ring-forming atom may be substituted with an optional substituent or may be unsubstituted; it may be a monocyclic structure, a polycyclic structure, or a fused ring structure.
Figure BDA0002376545090001716
Refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. In different positions of the same structural formula, groups or structures having the same symbols are independent of each other, and may be the same or different.
In the present invention, the structure of the covalent single force sensitive group of the bis-thiolylimide series with other mechanisms can be exemplified as follows:
Figure BDA0002376545090001712
wherein the content of the first and second substances,
Figure BDA0002376545090001717
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. In different positions of the same structural formula, groups or structures having the same symbols are independent of each other, and may be the same or different.
In the invention, the covalent single force sensitive group of other mechanism of the Michael reaction series refers to a single force sensitive group containing a Michael reaction force sensitive element, and the structural general formula of the covalent single force sensitive group includes but is not limited to the following classes:
Figure BDA0002376545090001713
wherein the content of the first and second substances,
Figure BDA0002376545090001718
rings representing arbitrary numbers of elements, on said rings
Figure BDA0002376545090001719
Is attached to the ring by the Michael reaction;
Figure BDA00023765450900017110
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. In different positions of the same structural formula, groups or structures having the same symbols are independent of each other, and may be the same or different. Under the action of mechanical force, a covalent single-force sensitive group of other mechanisms of the Michael reaction series can pull one amido bond away and form an amido bond and a carboxyl group after ring opening.
In the present invention, the structure of the covalent single force sensitive group of the other mechanism of the Michael reaction series can be exemplified as follows:
Figure BDA0002376545090001714
wherein the content of the first and second substances,
Figure BDA00023765450900017111
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. In different positions of the same structural formula, groups or structures having the same symbols are independent of each other, and may be the same or different.
In the present invention, the division is performed in a non-covalent complexing manner, and the non-covalent single force-sensitive groups used to generate the complex force-sensitive groups include, but are not limited to, the following groups: non-covalent single force sensitive groups based on supramolecular complexes, non-covalent single force sensitive groups based on supramolecular assemblies, non-covalent single force sensitive groups based on aggregates, non-covalent single force sensitive groups based on compositions. Non-covalent single force-sensitive groups based on a non-covalent single force-sensitive group of supramolecular complexes and a composition of motifs are preferred as force-sensitive components in a complex force-sensitive group for generating complexes containing non-covalent force-sensitive components. The non-covalent single force sensitive group is capable of specifically responding to mechanical forces and producing significant specific force-induced response properties/effects, such as catalytic, optical, spectroscopic, etc. supramolecular interactions.
In the present invention, the non-covalent single force sensitive groups based on supramolecular complexes include, but are not limited to, the following series: coordination bond series, host-guest interaction series, hydrogen bond interaction series and pi-pi stacking interaction series.
In the present invention, non-covalent single force-sensitive groups based on coordination bonds include, but are not limited to, the following sub-series: complexation of unsaturated carbon-carbon bonds with transition metals, carbene-metal coordination bonds, boron-nitrogen coordination bonds, platinum-phosphorus coordination bonds, metallocene coordination bonds, and ligand-lanthanide metal ion complexation.
In the present invention, the non-covalent single force sensitive group of the complexation of the unsaturated carbon-carbon bond and the transition metal refers to a single force sensitive group containing a complexation force sensitive element of the unsaturated carbon-carbon bond and the transition metal, and the structural general formula thereof includes but is not limited to the following types:
Figure BDA0002376545090001721
wherein the content of the first and second substances,
Figure BDA0002376545090001723
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; each R is independently any suitable atom, substituent, substituted polymer chain; in different positions of the same structural formula, groups or structures having the same symbols are independent of each other, and may be the same or different.
The unsaturated carbon-carbon bond of the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0002376545090001722
Figure BDA0002376545090001731
Wherein the content of the first and second substances,
Figure BDA0002376545090001732
an aromatic ring having an arbitrary number of elements; n is the total number of hydrogen atoms, substituent atoms, substituents, and substituent polymer chains bonded to the atoms constituting the ring, and is 0, 1, or an integer greater than 1;
Figure BDA0002376545090001735
the selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
The structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-1) and the transition metal of the present invention is exemplified by the following:
Figure BDA0002376545090001733
the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-2) and the transition metal of the present invention is exemplified by the following:
Figure BDA0002376545090001734
the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-3) and the transition metal of the present invention is exemplified by the following:
Figure BDA0002376545090001741
the complexation of the transition metal with an unsaturated carbon-carbon bond of the general structural formula (A-4) according to the present invention is further preferably selected from, but not limited to, the following structures:
Figure BDA0002376545090001742
the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-5) and the transition metal of the present invention is exemplified by the following:
Figure BDA0002376545090001743
the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-6) and the transition metal of the present invention is exemplified by the following:
Figure BDA0002376545090001744
The structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-7) and the transition metal of the present invention is exemplified by the following:
Figure BDA0002376545090001745
Figure BDA0002376545090001751
the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-8) and the transition metal of the present invention is exemplified by the following:
Figure BDA0002376545090001752
the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-9) and the transition metal of the present invention is exemplified by the following:
Figure BDA0002376545090001753
the structure of the complex of the unsaturated carbon-carbon bond containing the general structural formula (A-10) and the transition metal of the present invention is exemplified by the following:
Figure BDA0002376545090001754
the structure of the complex of the unsaturated carbon-carbon bond having the general structural formula (A-11) and the transition metal of the present invention is exemplified by the following:
Figure BDA0002376545090001761
in the invention, the non-covalent single force sensitive group of the carbene-metal coordination bond refers to a single force sensitive group containing a carbene-metal coordination bond force sensitive element, and the structural general formula of the single force sensitive group includes but is not limited to the following types:
Figure BDA0002376545090001762
wherein the content of the first and second substances,
Figure BDA0002376545090001763
the selection range of n is as described above in the series of force-sensitive groups and will not be described in detail here.
In the present invention, the carbene-metal coordination bond, carbene ligand, is further preferably selected from, but not limited to, the following structures:
Figure BDA0002376545090001764
wherein, X4Each independently selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, C- (R) 2Preferably from an oxygen atom;
Figure BDA0002376545090001765
the selection range of R is as described above in the series of force-sensitive groups and will not be described in detail herein.
In the present invention, the carbene-metal coordination bond having the general structural formulas (B-1), (B-2), (B-3) and (B-4) can be selected from, but not limited to, the following structures:
Figure BDA0002376545090001766
Figure BDA0002376545090001771
wherein, X4、
Figure BDA0002376545090001772
The selection range of the pressure-sensitive groups is as described in the series of the force-sensitive groups, and the detailed description is omitted; m is a metal center, which may be any suitable ionic form, compound/chelate form, and combinations thereof, of any one of the transition metals; .
In the present invention, the carbene-metal coordination bond having the general structural formulae (B-1), (B-2), (B-3) and (B-4) has the following structure:
Figure BDA0002376545090001773
Figure BDA0002376545090001781
wherein, X4、M、
Figure BDA00023765450900017813
The selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
In the present invention, the non-covalent single force-sensitive group of boron-nitrogen coordination bond refers to a single force-sensitive group containing a force-sensitive element of boron-nitrogen coordination bond, and the structural formula thereof includes but is not limited to the following types:
Figure BDA0002376545090001782
wherein the content of the first and second substances,
Figure BDA0002376545090001783
the selection range of R is as described above in the series of force-sensitive groups and will not be described in detail herein.
The boron-nitrogen coordination bond of the present invention, formula (C-1), may further preferably be selected from, but not limited to, at least one of the following structures:
Figure BDA0002376545090001784
Wherein the content of the first and second substances,
Figure BDA0002376545090001785
r, n, the ranges of choice are as previously described in the series of force-sensitive clusters and will not be further described herein;
Figure BDA0002376545090001786
represents any number of nitrogen heterocycles, including but not limited to aliphatic nitrogen heterocycles, aromatic nitrogen heterocycles, and combinations thereof.
In the present invention, said boron-nitrogen coordination bond having the general structural formula (C-1) is further preferably selected from, but not limited to, the following structures:
Figure BDA0002376545090001787
in the present invention, the boron-nitrogen coordination bond having the general structural formula (C-1) is exemplified by the following structures:
Figure BDA0002376545090001788
in the present invention, the non-covalent single force-sensitive group of platinum-phosphorus coordination bond refers to a single force-sensitive group containing platinum-phosphorus coordination bond force-sensitive elements therein, and the structural formula thereof includes but is not limited to the following types:
Figure BDA0002376545090001789
wherein, X5Each independently selected from a chlorine atom, a bromine atom, an iodine atom, preferably from a chlorine atom;
Figure BDA00023765450900017810
the selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
In the present invention, said platinum-phosphorus coordination bond having the general structural formula (D-1) is further preferably selected from, but not limited to, the following subclasses:
Figure BDA00023765450900017811
wherein, X5、
Figure BDA00023765450900017812
The selection range of n is as described above in the series of force-sensitive groups and will not be described in detail here.
In the present invention, said platinum-phosphorus coordination bond having the general structural formula (D-1) is further preferably selected from, but not limited to, the following structures:
Figure BDA0002376545090001791
Wherein, X5、
Figure BDA0002376545090001792
The selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
In the present invention, the structure of the platinum-phosphorus coordination bond having the general structural formula (D-1) is exemplified as follows:
Figure BDA0002376545090001793
in the present invention, the non-covalent single force-sensitive group of metallocene coordination bond refers to a single force-sensitive group containing a force-sensitive element of metallocene coordination bond, and the structural formula thereof includes but is not limited to the following types:
Figure BDA0002376545090001794
wherein, M is a metal center,
Figure BDA0002376545090001795
is a ligand of cyclopentadiene and a ligand of cyclopentadiene,
Figure BDA0002376545090001796
the selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted. The metal centers are preferably metals of the first to seventh subgroups and of the eighth group. The metals of the first to seventh subgroups and group VIII also include the lanthanides (i.e., La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and the actinides (i.e., Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, Lr). The metal center is more preferably a metal of the first subgroup (Cu, Ag, Au), a metal of the second subgroup (Zn, Cd), a metal of the third subgroup (Sc, Y), a metal of the fourth subgroup (Ti, Zr), a metal of the fifth subgroup (V, Nb), a metal of the sixth subgroup (Cr, Mo), a metal of the seventh subgroup (Mn, Tc), a metal of the eighth group (Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt), a metal of the lanthanoid series (La, Eu, Tb, Ho, Tm, Lu), a metal of the actinide series (Th). More preferably Cu, Zn, Fe, Co, Ni, Zr, Pd, Ag, Pt, Au, La, Ce, Eu, Tb, Th, and still more preferably Fe, Co, Ni, Zr.
In the present invention, the metallocene coordination bond having the general structural formula (E-1) is exemplified by the following structures:
Figure BDA0002376545090001797
wherein the content of the first and second substances,
Figure BDA0002376545090001798
the selection range of the pressure-sensitive material is as described above in the series of force-sensitive clusters, and the description thereof is omitted.
In the invention, the non-covalent single force sensitive group of ligand-lanthanide metal ion complexation refers to a single force sensitive group containing a ligand-lanthanide metal ion complexation force sensitive element, and the single force sensitive group can change the position of the ligand group more easily when being stressed, thereby showing obvious stress response properties, including changes of fluorescence, color and the like.
In embodiments of the present invention, suitable ligand groups may be exemplified by, but are not limited to:
Figure BDA0002376545090001801
in an embodiment of the invention, the lanthanide metal includes La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; preferably lanthanide series Ce, Eu, Tb, Ho, Tm, Lu; more preferably Ce, Eu, Tb, to obtain more remarkable stress responsiveness.
In the embodiment of the present invention, the combination of the ligand group and the metal center is not particularly limited as long as the ligand can form a suitable metal-ligand interaction with the metal center. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:
Figure BDA0002376545090001802
In the present invention, the non-covalent single force sensitive groups based on supramolecular assemblies include, but are not limited to, the following series: the dye molecule series non-covalent single force sensitive group comprises a donor-acceptor series, a diketopyrrolopyrrole series, a conjugated series, a platinum coordination series, a gold coordination series, a beryllium coordination series, a copper coordination series, an iridium coordination series, a boron coordination series, a phenothiazine series, a dioxaborolane series and a dye molecule series.
In the present invention, the non-covalent single force-sensitive group of the donor-acceptor series refers to a force-sensitive group containing a self-assembly aggregate force-sensitive element formed by a donor-acceptor self-assembly element, and the structural general formula thereof includes but is not limited to the following classes:
Figure BDA0002376545090001811
wherein W is an atom or group having an electron withdrawing effect; wherein, the atom with electron-withdrawing effect is selected from but not limited to oxygen atom or sulfur atom, preferably oxygen atom; the group with electron-withdrawing effect is selected from but not limited to:
Figure BDA0002376545090001812
wherein Ar is1、Ar2Each independently selected from aromatic rings having an electron donating effect; wherein the aromatic ring structure is a polycyclic structure or a fused ring structure; by way of example, suitable Ar' s1、Ar2Selected from, but not limited to:
Figure BDA0002376545090001813
wherein the content of the first and second substances,
Figure BDA0002376545090001814
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula F-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001815
wherein the content of the first and second substances,
Figure BDA0002376545090001816
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
A typical structure of the formula F-2 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001817
Figure BDA0002376545090001821
wherein the content of the first and second substances,
Figure BDA0002376545090001822
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
A typical structure of the formula F-3 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001823
wherein the content of the first and second substances,
Figure BDA0002376545090001824
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the non-covalent single force-sensitive group of the diketopyrrolopyrrole series refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by diketopyrrolopyrrole self-assembly elements, and the structural general formula of the non-covalent single force-sensitive group includes but is not limited to the following types:
Figure BDA0002376545090001825
wherein the content of the first and second substances,
Figure BDA0002376545090001826
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula G-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001827
wherein the content of the first and second substances,
Figure BDA0002376545090001828
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the conjugated series of non-covalent single force-sensitive groups refer to force-sensitive groups containing self-assembled aggregate force-sensitive elements formed by conjugated self-assembled elements; wherein, the conjugated self-assembly motif includes but is not limited to the following subseries: polydiacetylene series, polydiphenylacetylene series, polythiophene series, polypyrrole series, anthraquinone series, polyfluorene series, oligomeric p-phenylene vinylene series, bis (benzoxazole) stilbene series, and aza-condensed ring sub-series self-assembly motif.
Wherein, the structural general formula of the polydiacetylene subunit self-assembly unit includes but not limited to the following types:
Figure BDA0002376545090001829
wherein n is the number of the repeating units, and the value range of n is an integer greater than 2, preferably an integer greater than or equal to 5, and more preferably an integer greater than or equal to 10;
Figure BDA00023765450900018210
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula H-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA00023765450900018211
Figure BDA0002376545090001831
wherein n and p are the number of the repeating units, and the value ranges thereof are respectively independent integers more than 2, preferably more than or equal to 5, and more preferably more than or equal to 10;
Figure BDA0002376545090001832
Each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein, the structural general formula of the polydiphenylacetylene self-assembly motif comprises but is not limited to the following types:
Figure BDA0002376545090001833
wherein n is,
Figure BDA0002376545090001834
The definition, selection range and preferable range of (A) are the same as those of the general formula H-1.
A typical structure of the formula H-2 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001835
wherein n, n1、n2Is heavyThe number of the complex units is an integer with the value range of more than 2 independently, preferably an integer with the value range of more than or equal to 5, and more preferably an integer with the value range of more than or equal to 10;
Figure BDA0002376545090001836
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein, the structural general formula of the sub-series self-assembly motif of the polythiophene comprises but is not limited to the following classes:
Figure BDA0002376545090001837
wherein n is the number of the repeating units and the value range of n is an integer larger than 5;
Figure BDA0002376545090001838
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula H-3 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001839
wherein n, n1、n2The number of repeating units is an integer in the range of greater than 5.
Wherein, the structural general formula of the self-assembly motif of the polypyrrolidine series includes but is not limited to the following classes:
Figure BDA00023765450900018310
wherein n is,
Figure BDA00023765450900018311
The definition, selection range and preferable range of (A) are the same as those of the general formula H-3.
A typical structure of the formula H-4 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA00023765450900018312
wherein n, n1、n2The number of repeating units is an integer with a value range of more than 5;
Figure BDA00023765450900018313
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein, the structural general formula of the self-assembly motif of the anthraquinone sub-series includes but is not limited to the following classes:
Figure BDA00023765450900018314
wherein n is,
Figure BDA00023765450900018315
The definition, selection range and preferable range of (A) are the same as those of the general formula H-3.
A typical structure of the formula H-5 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001841
wherein the definition, the selection range and the preferred range of n are the same as those of the general formula H-5;
Figure BDA0002376545090001842
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein, the structural general formula of the polyfluorenesub-series self-assembly motif includes but is not limited to the following classes:
Figure BDA0002376545090001843
wherein n is,
Figure BDA0002376545090001844
The definition, selection range and preferable range of (A) are the same as those of the general formula H-3.
A typical structure of the formula H-6 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001845
Wherein n, n1、n2The number of the repeating units is defined, and the value ranges of the repeating units are respectively independent integers more than 5;
Figure BDA0002376545090001846
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein, the structural general formula of the self-assembly unit of the oligomeric p-phenylene vinylene subunit includes but is not limited to the following types:
Figure BDA0002376545090001847
wherein n is,
Figure BDA0002376545090001848
The definition, selection range and preferable range of (A) are the same as those of the general formula H-1.
A typical structure of the formula H-7 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001849
wherein the definition, the selection range and the preferred range of n are the same as those of the general formula H-7;
Figure BDA00023765450900018410
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein, the structural general formula of the bis (benzoxazole) stilbene sublines self-assembly motif includes but is not limited to the following classes:
Figure BDA00023765450900018411
wherein the content of the first and second substances,
Figure BDA00023765450900018412
selected from, but not limited to, at least one of the following structures:
Figure BDA00023765450900018413
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula H-8 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA00023765450900018414
wherein the content of the first and second substances,
Figure BDA00023765450900018415
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
Wherein, the structural general formula of the self-assembly motif of the aza-condensed ring sub-series includes but is not limited to the following types:
Figure BDA00023765450900018416
wherein the content of the first and second substances,
Figure BDA00023765450900018417
each is independentAre attached to any suitable atom (including hydrogen atoms), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula H-9 can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001851
wherein the content of the first and second substances,
Figure BDA0002376545090001852
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the platinum coordination series non-covalent single force-sensitive group refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by platinum coordination self-assembly elements, and the structural general formula of the force-sensitive group includes but is not limited to the following classes:
Figure BDA0002376545090001853
wherein each V is independently selected from a carbon atom or a nitrogen atom;
wherein Lg is1Is a monodentate ligand coordinated to the platinum atom; wherein the monodentate ligand is selected from, but not limited to: a halogen atom,
Figure BDA0002376545090001854
Figure BDA0002376545090001855
Wherein Lg is2Is a monodentate ligand coordinated to the platinum atom; each Lg2Are the same or different; wherein the monodentate ligand is selected from, but not limited to:
Figure BDA0002376545090001856
wherein the content of the first and second substances,
Figure BDA0002376545090001857
is a bidentate ligand with V and nitrogen atoms as coordinating atoms; by way of example, the bidentate ligand is selected from, but not limited to:
Figure BDA0002376545090001858
Wherein the content of the first and second substances,
Figure BDA0002376545090001859
is a tridentate ligand with V and nitrogen atoms as coordination atoms; by way of example, the tridentate ligand is selected from, but not limited to:
Figure BDA00023765450900018510
wherein the content of the first and second substances,
Figure BDA00023765450900018511
is a tetradentate ligand taking V and nitrogen atoms as coordination atoms; by way of example, the tetradentate ligand is selected from, but not limited to:
Figure BDA00023765450900018512
wherein the content of the first and second substances,
Figure BDA00023765450900018513
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the formulae I-1 to I-4 may be illustrated below, but the present invention is not limited thereto:
Figure BDA0002376545090001861
wherein the content of the first and second substances,
Figure BDA0002376545090001862
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the gold coordination series non-covalent single force-sensitive group refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by gold coordination self-assembly elements, and the structural general formula of the force-sensitive group includes but is not limited to the following classes:
Figure BDA0002376545090001863
wherein Lg is3Is a monodentate ligand coordinated to a gold atom; each Lg3Are the same or different; wherein the monodentate ligand is selected from, but not limited to:
Figure BDA0002376545090001864
wherein the content of the first and second substances,
Figure BDA0002376545090001865
indicates that n is connected with
Figure BDA0002376545090001866
Wherein n is 0, 1 or an integer greater than 1; the ring structure of the aromatic ring is selected from a monocyclic structure, a polycyclic structure and a condensed ring structure; the number of ring-forming atoms of the ring is not particularly limited and is selected from, but not limited to, a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, a boron atom, a phosphorus atom, a silicon atom; the hydrogen atoms on the ring-forming atoms may be substituted with any suitable substituent atom or substituent; wherein, the substituent atom or substituent is not particularly limited, and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent. By way of example, those that are suitable
Figure BDA0002376545090001867
May be selected from at least one of the following structures, but the invention is not limited thereto:
Figure BDA0002376545090001868
wherein the content of the first and second substances,
Figure BDA0002376545090001871
the definition, selection range and preferable range of the formula (I) are the same as those of the general formula (I-2);
wherein the content of the first and second substances,
Figure BDA0002376545090001872
is a bidentate ligand with a sulfur atom and a nitrogen atom as coordination atoms; by way of example, those that are suitable
Figure BDA0002376545090001873
May be selected from at least one of the following structures, but the invention is not limited thereto:
Figure BDA0002376545090001874
wherein the content of the first and second substances,
Figure BDA0002376545090001875
is a bidentate ligand taking a phosphorus atom as a coordination atom, wherein, the metal atoms coordinated with phosphine can be the same gold atom or different gold atoms; by way of example, those that are suitable
Figure BDA0002376545090001876
May be selected from at least one of the following structures, but the invention is not limited thereto:
Figure BDA0002376545090001877
wherein the content of the first and second substances,
Figure BDA0002376545090001878
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of formulae J-1 to J-7 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001879
Figure BDA0002376545090001881
wherein the content of the first and second substances,
Figure BDA0002376545090001882
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the beryllium coordinated series non-covalent single force-sensitive group refers to a force-sensitive group containing self-assembled aggregate force-sensitive elements formed by beryllium coordinated self-assembled elements, and the structural general formula of the force-sensitive group includes but is not limited to the following types:
Figure BDA0002376545090001883
Wherein the content of the first and second substances,
Figure BDA0002376545090001887
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula K-1 can be illustrated as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001884
wherein the content of the first and second substances,
Figure BDA0002376545090001888
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the copper coordination series non-covalent single force-sensitive group refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by copper coordination self-assembly elements, and the structural general formula of the force-sensitive group includes but is not limited to the following classes:
Figure BDA0002376545090001885
wherein the content of the first and second substances,
Figure BDA0002376545090001889
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula L-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001886
wherein the content of the first and second substances,
Figure BDA00023765450900018810
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the iridium coordination series non-covalent single force-sensitive group refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by iridium coordination self-assembly elements, and the structural general formula of the force-sensitive group includes but is not limited to the following types:
Figure BDA0002376545090001891
Wherein the content of the first and second substances,
Figure BDA0002376545090001892
is a bidentate ligand with carbon atoms and nitrogen atoms as coordination atoms; by way of example, those that are suitable
Figure BDA0002376545090001893
May be selected from at least one of the following structures, but the invention is not limited thereto:
Figure BDA0002376545090001894
wherein the content of the first and second substances,
Figure BDA0002376545090001895
is a bidentate ligand with nitrogen atoms as coordination atoms; by way of example, those that are suitable
Figure BDA0002376545090001896
May be selected from at least one of the following structures, but the invention is not limited thereto:
Figure BDA0002376545090001897
wherein the content of the first and second substances,
Figure BDA0002376545090001898
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula M-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001899
wherein the content of the first and second substances,
Figure BDA00023765450900018910
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the boron coordination series non-covalent single force-sensitive group refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by boron coordination self-assembly elements, and the structural general formula of the force-sensitive group includes but is not limited to the following classes:
Figure BDA00023765450900018911
wherein, R is respectively and independently selected from halogen atom, cyano-group and C1-10Hydrocarbyl/heterohydrocarbyl, substituted C1-10Hydrocarbyl/heterohydrocarbyl; r is preferably selected from halogen atoms, phenyl, pentafluorophenyl; v, V' are each independently selected from an oxygen atom or a nitrogen atom;
Figure BDA00023765450900018914
Each independently of the other, to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain, with or without participation in force activation, of any two of the same general formula
Figure BDA00023765450900018915
With or without looping.
Wherein the structures represented by the general formulae N-1 to N-5 are preferably selected from at least a subset of the following general structures:
Figure BDA00023765450900018912
wherein the content of the first and second substances,
Figure BDA00023765450900018913
is an aromatic ring; the ring structure of the aromatic ring is selected from a monocyclic structure, a polycyclic structure and a condensed ring structure; the number of ring-forming atoms of the ring is not particularly limited; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent; wherein the content of the first and second substances,
Figure BDA0002376545090001901
to connect n
Figure BDA0002376545090001902
The ring-forming atoms of the ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms; wherein the content of the first and second substances,
Figure BDA0002376545090001903
and
Figure BDA0002376545090001904
to connect n
Figure BDA0002376545090001905
At least one of the ring-forming atoms of the nitrogen-containing aromatic heterocyclic ring is a nitrogen atom, the nitrogen-containing aromatic heterocyclic ring forms a coordinate bond with a boron atom through the nitrogen atom, and the rest ring-forming atoms are selected from but not limited to carbon atoms, nitrogen atoms, oxygen atoms and sulfur atoms; wherein the content of the first and second substances,
Figure BDA0002376545090001906
to connect n
Figure BDA0002376545090001907
At least two of the ring-forming atoms of (1) are carbon atoms, and the remaining ring-forming atoms are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms; wherein the content of the first and second substances,
Figure BDA0002376545090001908
to connect n
Figure BDA0002376545090001909
At least two of the ring-forming atoms of the nitrogen-containing aromatic heterocycle are nitrogen atoms, one of the nitrogen atoms and the boron atom form a coordination bond, and the rest ring-forming atoms are selected from but not limited to carbon atoms, nitrogen atoms, oxygen atoms and sulfur atoms;
wherein R, V, V
Figure BDA00023765450900019010
The definitions, selection ranges and preferred ranges of the general formulas N-1 to N-5 are the same.
Typical structures of the formulae N-1 to N-5 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA00023765450900019011
Figure BDA0002376545090001911
wherein the content of the first and second substances,
Figure BDA0002376545090001912
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the phenothiazine series non-covalent single force-sensitive group refers to a force-sensitive group containing self-assembly aggregate force-sensitive units formed by phenothiazine self-assembly units; wherein, the phenothiazine self-assembly motif comprises but is not limited to the following classes:
Figure BDA0002376545090001913
wherein each R is independently selected from the group consisting of atoms (including hydrogen atoms), substituents, and substituted polymer chains that may or may not participate in force activation; wherein said substituent atoms are selected from, but not limited to: fluorine atom, chlorine atom, bromine atom, iodine atom; the substituent is preferably selected from substituents with electron-withdrawing effect, so that the intermolecular stacking effect is enhanced, and more remarkable force-induced responsiveness is obtained; wherein said substituents having electron withdrawing effect include but are not limited to: trifluoromethyl, trichloromethyl, nitro, cyano, sulfonic group, aldehyde group, alkyl acyl, alkoxy acyl, carboxyl, amide group;
Wherein n is the total number of substituent atoms, substituents, and substituted polymer chains linked to the atoms constituting the ring structure, and is 0, 1, or an integer greater than 1; when n is more than 1, the structures of the R can be the same or different;
wherein the content of the first and second substances,
Figure BDA0002376545090001914
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the general formulae O-1, O-2 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001915
wherein the content of the first and second substances,
Figure BDA0002376545090001916
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the non-covalent single force-sensitive group of the dioxaborolane series refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by self-assembly elements of the dioxaborolane, and the structural general formula of the non-covalent single force-sensitive group comprises the following groups:
Figure BDA0002376545090001917
wherein Ar is an aromatic ring having an electron donating effect; wherein the aromatic ring is a polycyclic structure selected from, but not limited to:
Figure BDA0002376545090001918
wherein the content of the first and second substances,
Figure BDA0002376545090001919
each independently of any suitable atom (including hydrogen), substituent, and participating or participating inSubstituted polymer chains that do not participate in force activation are linked.
A typical structure of the formula P-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001921
Wherein the content of the first and second substances,
Figure BDA0002376545090001922
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the non-covalent single force-sensitive group of the dye molecule series refers to a force-sensitive group containing self-assembly aggregate force-sensitive elements formed by dye molecule self-assembly elements; wherein, the dye molecule self-assembly motif is selected from one of the following structural formulas:
Figure BDA0002376545090001923
wherein the hydrogen atoms on the dye molecules may be substituted or unsubstituted by any suitable atom, substituent, polymer chain; and the dye molecules are linked to the polymer or supramolecular polymer chains by suitable means.
By way of example, the structure of a typical self-assembly motif of a dye molecule is shown below, but the invention is not limited thereto:
Figure BDA0002376545090001924
wherein the content of the first and second substances,
Figure BDA0002376545090001925
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the present invention, non-covalent, single force-sensitive groups based on aggregates include, but are not limited to, the following series: divinylanthracene series, tetraarylethylene series, cyanoethylene series, berberine series, maleimide series, 4-hydropyran series non-covalent single force sensitive groups.
In the invention, the divinylanthracene series non-covalent single force-sensitive group refers to a force-sensitive group containing aggregation-induced emission aggregate force-sensitive elements formed by divinylanthracene aggregation-induced emission elements, and the general structural formula of the group includes but is not limited to the following types:
Figure BDA0002376545090001926
Wherein Ar is1、Ar2Each independently selected from aromatic rings, the ring structure of which is selected from monocyclic structure, polycyclic structure and condensed ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and the hydrogen atoms connected to the ring-forming atoms are substituted or unsubstituted by any suitable substituent atom, substituent group; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent;
Figure BDA0002376545090001931
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the formulae Q-1 to Q-3 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001932
wherein the content of the first and second substances,
Figure BDA0002376545090001933
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the present invention, the non-covalent single force-sensitive group of the tetraarylethylene series refers to a force-sensitive group containing aggregation-induced emission aggregate force-sensitive elements formed by tetraarylethylene aggregation-induced emission elements, and the structural general formula includes but is not limited to the following classes:
Figure BDA0002376545090001934
Wherein each W is independently selected from a direct bond,
Figure BDA0002376545090001935
Wherein Ar is1、Ar2、Ar3、Ar4Each independently selected from aromatic rings, the structure of which is selected from monocyclic structure, polycyclic structure, spiro structure and condensed ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and the hydrogen atoms attached to the ring-forming atoms are substituted or unsubstituted with any suitable substituent atom, substituent group, or substituted polymer chain; wherein the substituted atom, the substituent, the substituted polymer chain are not particularly limited; in order to increase steric hindrance and aggregation-induced emission of the luminescent moiety in a non-planar conformation, and to form loosely-packed aggregates, so as to obtain a more significant force-induced response effect, the ring structure of the aromatic ring is preferably a polycyclic structure or a fused ring structure; by reasonably selecting the polycyclic structure and the condensed ring structure, the spectral property of the formed force sensitive group can be regulated and controlled in a large range, so that the color change and the fluorescence/phosphorescence emission wavelength which can be adjusted in a large range can be obtained, and the use requirements of various application scenes can be met; in order to increase the intramolecular charge transfer property and obtain a more significant force-induced response effect, particularly a force-induced response effect with a significant change in fluorescence wavelength shift and a high force-induced color contrast, it is more preferable that the substituent on the aromatic ring structure is a substituent having a strong electron-donating effect or electron-withdrawing effect;
Wherein the content of the first and second substances,
Figure BDA0002376545090001941
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the formulae R-1 to R-7 may be illustrated below, but the invention is not limited thereto:
Figure BDA0002376545090001942
Figure BDA0002376545090001951
wherein the content of the first and second substances,
Figure BDA0002376545090001952
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the cyanoethylene series non-covalent single force-sensitive group refers to a force-sensitive group containing aggregation-induced emission aggregate force-sensitive elements formed by cyanoethylene aggregation-induced emission elements, and the structural general formula of the group includes but is not limited to the following classes:
Figure BDA0002376545090001953
wherein Ar is1、Ar2Each independently selected from aromatic rings, the structure of which is selected from monocyclic structure, polycyclic structure, spiro structure and condensed ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and the hydrogen atoms attached to the ring-forming atoms are substituted or unsubstituted with any suitable substituent atom, substituent group, or substituted polymer chain; the substituent atom, substituent group, and substituted polymer chain are not particularly limited. To increase steric hindrance and aggregation-induced emission of luminescent moieties in non-planar conformations, loosely packed aggregates are formed to obtain a more compact structure The ring structure of the aromatic ring is preferably a polycyclic structure or a fused ring structure; by reasonably selecting the polycyclic structure and the condensed ring structure, the spectral property of the formed force sensitive group can be regulated and controlled in a large range, so that the color change and the fluorescence/phosphorescence emission wavelength which can be regulated in a large range can be obtained, and the application requirements of various application scenes can be met; in order to obtain more significant force-responsive effects, especially force-responsive effects with significant shift in fluorescence wavelength and high color contrast of force-induced discoloration, it is preferred that a portion of the hydrogen atoms on the aromatic ring be substituted with a heteroatom, a hydrocarbyl substituent, or a heteroatom substituent, by way of example, suitable heteroatoms, hydrocarbyl substituents, heteroatom substituents are selected from, but not limited to: fluorine atom, chlorine atom, bromine atom, iodine atom, trifluoromethyl group, pentafluorothio group, nitro group, cyano group, C1-20Alkyl radical, C1-20Aryl radical, C1-20Alkoxy radical, C1-20Alkylthio radical, C1-20Alkylamino radical, C1-20Aryloxy radical, C1-20Arylthio radical, C1-20An arylamine group. Ar is1、Ar2Preferably at least one of the following structures, but the invention is not limited thereto:
Figure BDA0002376545090001961
by way of example, typical Ar1、Ar2Including but not limited to one or more of the following structures:
Figure BDA0002376545090001962
Wherein Ar is3Is a divalent aromatic ring, the structure of which is selected from a monocyclic structure, a polycyclic structure, a spiro structure and a fused ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and the hydrogen atoms bonded to the ring-forming atoms are substituted with any suitable substituent atom, substituent group, or substituted polymer chainOr is unsubstituted; wherein the substituent atom is preferably selected from fluorine atom, chlorine atom, bromine atom and iodine atom, and the substituent group is preferably selected from C1-20Alkyl radical, C1-20Aryl radical, C1-20Alkoxy radical, C1-20Alkylthio radical, C1-20Alkylamino radical, C1-20Aryloxy radical, C1-20Arylthio radical, C1-20An arylamine group. Ar is3Preferably at least one of the following structures, but the invention is not limited thereto:
Figure BDA0002376545090001963
by way of example, typical Ar3Including but not limited to one or more of the following structures:
Figure BDA0002376545090001971
wherein the content of the first and second substances,
Figure BDA0002376545090001972
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Wherein the structure represented by the general formula S-1 is further preferably selected from the following general structures:
Figure BDA0002376545090001973
wherein Ar is4Definition, selection range, preferred range of (1) and Ar 1(ii) a Wherein Ar is1、Ar2、
Figure BDA0002376545090001974
The definition, selection range and preferable range of (A) are the same as those of the general formula S-1.
Typical structures of the formulae S-1 to S-4 may be illustrated below, but the invention is not limited thereto:
Figure BDA0002376545090001975
Figure BDA0002376545090001981
wherein the content of the first and second substances,
Figure BDA0002376545090001982
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the berberine series non-covalent single force-sensitive group refers to a force-sensitive group containing aggregation-induced emission aggregate force-sensitive elements formed by berberine aggregation-induced emission elements, and the structural general formula of the force-sensitive group includes but is not limited to the following classes:
Figure BDA0002376545090001983
wherein a is an integer of 1-5, preferably 1 or 2;
wherein the content of the first and second substances,
Figure BDA0002376545090001984
indicates that n is connected with
Figure BDA0002376545090001985
Wherein n is 0, 1 or an integer greater than 1; wherein, the symbols are the sites connecting with other structures in the formula; wherein the ring structure of the aromatic ring is selected from a monocyclic structure, a polycyclic structure, and a fused ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and the hydrogen atoms connected to the ring-forming atoms are substituted or unsubstituted by any suitable substituent atom, substituent group; wherein the substituent atom or substituent is not particularly limited and is selected from the group consisting of halogen atom, hydrocarbyl group and the like Any one or more of a group and a substituent containing a hetero atom is preferably selected from substituents having an electron donating effect;
wherein R is selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain; when R is selected from an atom or a substituent, it is preferably selected from an atom or a substituent having an electron-withdrawing effect;
wherein the content of the first and second substances,
Figure BDA0002376545090001991
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
A typical structure of the formula T-1 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090001992
wherein the content of the first and second substances,
Figure BDA0002376545090001993
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the present invention, the maleimide series non-covalent single force-sensitive group refers to a force-sensitive group containing aggregation-induced emission aggregate force-sensitive element formed by maleimide aggregation-induced emission element, and its structural general formula includes but is not limited to the following classes:
Figure BDA0002376545090001994
wherein R is selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain; when R is selected from an atom or a substituent, it is preferably selected from an atom or a substituent having an electron-withdrawing effect; by way of example, said atoms or substituents having an electron-withdrawing effect are selected from, but not limited to: halogen atom, nitro group, pentafluorothio group, trifluoromethyl group, 4-trifluoromethyl-phenyl group;
Wherein the content of the first and second substances,
Figure BDA0002376545090001995
indicates that n is connected with
Figure BDA0002376545090001996
Wherein n is 0, 1 or an integer greater than 1; wherein, the symbols are the sites connecting with other structures in the formula;
wherein the content of the first and second substances,
Figure BDA0002376545090001997
indicates that n is connected with
Figure BDA0002376545090001998
Wherein n is 0, 1 or an integer greater than 1; wherein, the symbols are the sites connecting with other structures in the formula;
wherein the content of the first and second substances,
Figure BDA0002376545090001999
each independently attached to any suitable atom (including a hydrogen atom), substituent, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the general formulae U-1, U-2 may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA00023765450900019910
wherein the content of the first and second substances,
Figure BDA00023765450900019911
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the invention, the 4-hydropyran series non-covalent single force-sensitive group refers to a force-sensitive group containing aggregation-induced emission aggregate force-sensitive elements formed by 4-H pyran aggregation-induced emission elements, and the structural general formula of the force-sensitive group includes but is not limited to the following types:
Figure BDA00023765450900019912
wherein each W is independently selected from
Figure BDA00023765450900019913
Or
Figure BDA00023765450900019914
Wherein each V is independently an atom or group having an electron withdrawing effect, preferably from an oxygen atom or a sulfur atom, more preferably from an oxygen atom; the group with electron-withdrawing effect is selected from but not limited to:
Figure BDA0002376545090002001
Wherein Ar is1、Ar2Each independently selected from aromatic rings having an electron donating effect; wherein the aromatic ring structure is a monocyclic structure, a polycyclic structure or a condensed ring structure; by way of example, suitable Ar' s1、Ar2Selected from, but not limited to:
Figure BDA0002376545090002002
wherein the content of the first and second substances,
Figure BDA0002376545090002003
each independently attached to any suitable hydrogen atom, substituent group, and substituted polymer chain that may or may not participate in force activation.
Typical structures of the formulae V-1 to V-3 may be illustrated below, but the invention is not limited thereto:
Figure BDA0002376545090002004
wherein the content of the first and second substances,
Figure BDA0002376545090002005
each independently linked to a substituted polymer chain or to a supramolecular polymer chain involved in force activation.
In the present invention, non-covalent single force sensitive groups based on the composition include, but are not limited to, the following series: non-covalent single force sensitive groups based on host-guest compositions, non-covalent single force sensitive groups based on energy transfer compositions.
In the present invention, the non-covalent single force-sensitive group based on a host-guest composition refers to a composition comprising at least one host molecule/group and at least one guest molecule/group, and the host molecule/group and the guest molecule/group form a composition through a host-guest interaction, wherein the host molecule/group and/or the guest molecule/group may or may not have force responsiveness, and at least one of the host molecule/group and the guest molecule/group is covalently linked to a polymer chain; under the action of mechanical force, the host-guest composition is stressed and activated to change the luminescent property, the fluorescence/phosphorescence property and the long afterglow luminescent property, and show specific force-induced response.
The host molecule/group can be exemplified as follows, but the invention is not limited thereto:
Figure BDA0002376545090002011
the guest molecules/groups can be exemplified as follows, but the invention is not limited thereto:
Figure BDA0002376545090002012
in the present invention, the non-covalent single force sensitive group based on the energy transfer composition refers to a non-covalent force response element formed by combining a non-mechanical force responsive energy donor and a non-mechanical force responsive energy acceptor which can transfer energy with each other, wherein the energy donor and the energy acceptor are respectively not responded by mechanical force, and when mechanical force is acted, the distance, arrangement form and the like between the energy donor and the energy acceptor are changed, so that the energy transfer process between the energy donor and the energy acceptor is weakened/inhibited or enhanced/promoted, and the fluorescence wavelength shift, fluorescence intensity enhancement or weakening, fluorescence lifetime extension or shortening and the like generated by the change show specific force response.
In the present invention, the "energy transfer" refers specifically to the transfer of photon energy from an energy donor to an energy acceptor; in one case, when an energy donor absorbs a photon of a certain frequency, it is excited to a higher energy state of an electron, and energy transfer to an adjacent energy acceptor is achieved by dipole resonance interaction between the energy donor and the energy acceptor before the electron returns to the ground state; in another case, when the energy donor emits light, energy transfer to the adjacent energy acceptor is achieved through dipole resonance interaction between the energy donor and the energy acceptor. In order to achieve energy transfer between the energy donor and the energy acceptor to achieve the desired force-induced response effect, the following conditions must be satisfied: 1) the emission spectrum of the energy donor and the absorption spectrum of the energy acceptor are partially overlapped; 2) the energy donor and the energy acceptor need to be close enough together, preferably at a distance of no more than 10 nm; 3) The energy donor and the energy acceptor must also be aligned in a suitable manner, with the transfer dipole orientation preferably being approximately parallel.
In the present invention, the energy donor in the non-covalent single force sensitive moiety of the energy transfer composition may be selected from non-mechanical force responsive fluorophores and/or luminophores, and the energy acceptor may be selected from non-mechanical force responsive fluorophores and/or quenchers.
In the present invention, the energy donor and the energy acceptor contained in the non-covalent single force sensitive group of the energy transfer composition may be selected from the group consisting of, but not limited to, pre-existing, photo-activated, thermal-activated, electro-activated, chemical-activated, bio-activated, magnetic-activated moieties, and does not include force-activated moieties. In the present invention, when multiple energy donors and multiple energy acceptors are contained in the same polymer, each of the energy donors and energy acceptors can have more than one source. In a preferred embodiment of the present invention, all energy donors and energy acceptors are pre-existing, which facilitates force-induced activation by controlling mechanical force action alone, resulting in rapid and stable force-induced response; in another preferred embodiment of the invention, the part of the energy donor or energy donor is pre-existing, and the other part of the energy donor and energy acceptor is selected from the group consisting of those generated by photoactivation, those generated by thermal activation, those generated by electrical activation, those generated by chemical activation, those generated by biological activation, those generated by magnetic activation, and thus facilitates the achievement of a force-induced response effect by light control, thermal control, electrical control, chemical stimulation, biological stimulation and mechanical force in a dual or multiple coordinated control; in another preferred embodiment of the present invention, the energy donor and the energy acceptor are selected from one or more of photoactivated, thermoactivated, electroactive, chemically activated, biologically activated and magnetically activated, which is advantageous for obtaining abundant non-mechanical force response and achieving multiple coordinated force-induced response effects with mechanical force control of the composition to meet the needs of various special application scenarios.
In the present invention, the energy donor and the energy acceptor in the non-covalent single force sensitive group of the energy transfer composition may be on the same polymer chain, on different polymer chains, or one of them may be on the polymer chain; wherein the energy donor and the energy acceptor can be linked to the polymer chain by covalent and/or supramolecular interactions. In the embodiment of the present invention, it is preferable that the energy donor and the energy acceptor are spaced from each other by not more than 10nm, and it is more preferable that the energy donor and the acceptor are kept close to each other by supramolecular interaction and spaced from each other by not more than 10 nm. The supramolecular action described herein, which may be any suitable supramolecular action, includes but is not limited to: hydrogen bonding, metal-ligand interaction, ionic interaction, ion-dipole interaction, host-guest interaction, metallophilic interaction, dipole-dipole interaction, halogen bonding, lewis acid-base pairing interaction, cation-pi interaction, anion-pi interaction, benzene-fluorobenzene interaction, pi-pi stacking interaction, ionic hydrogen bonding, radical cation dimerization, phase separation, crystallization; under the action of mechanical force, the supermolecule action is destroyed, so that the energy transfer process is changed, and force-induced responsiveness is obtained; furthermore, due to the reversible nature of the supramolecular interaction, the force sensitive group may also be given a reversible, recyclable force-responsive effect.
In the invention, the energy transfer can be organically regulated and controlled by designing, selecting and adjusting the type, the quantity and the combination of the energy donor/the energy donor, so that excellent diversified and cooperatively controlled energy transfer performance and wide application are obtained.
In the present invention, the energy donor and the energy acceptor in the non-covalent single force sensitive group based on the energy transfer composition may be different or identical, preferably different. When the energy donor and acceptor are the same, at least one of the donor and acceptor must have multiple excitation and/or emission wavelengths.
In the present invention, the energy transfer in the non-covalent single force sensitive groups based on the energy transfer composition may be of only one stage or may be of multiple stages. When the polymer contains a plurality of fluorophores/luminophores (or precursors thereof), under appropriate energy transfer conditions, multi-stage energy transfer can be formed, namely, the fluorescence/cold luminescence wavelength emitted by the first-stage energy donor is taken as the fluorescence excitation wavelength of the first-stage energy acceptor, the fluorescence wavelength emitted by the first-stage energy acceptor after being excited is taken as the fluorescence excitation wavelength of the second-stage energy acceptor, the fluorescence wavelength emitted by the second-stage energy acceptor after being excited is taken as the fluorescence excitation wavelength of the third-stage energy acceptor, and the like, so that the phenomenon of multi-stage energy transfer is realized. Where only the first transfer is present, the energy transfer may be fluorescence quenching; in multiple transfer stages, the energy transfer of the last stage may be fluorescence quenching.
In the invention, the fluorescence refers to a photoluminescence cold luminescence phenomenon that when a fluorophore is irradiated by incident light with a certain wavelength, the fluorophore enters an excited state after absorbing light energy, and is immediately de-excited to emit emergent light with a wavelength longer or shorter than that of the incident light; the wavelength of the incident light is called the excitation wavelength and the wavelength of the outgoing light is called the emission wavelength. When the emission wavelength is longer than the excitation wavelength, it is called down-conversion fluorescence; when the emission wavelength is shorter than the excitation wavelength, it is called up-conversion fluorescence. In addition to photoluminescence, the fluorescence excitation wavelength that can be an energy acceptor or the cold luminescence that can be quenched by an energy acceptor can be any other suitable light that is not emitted by heat generation by a substance, including but not limited to chemiluminescence of a luminophore, bioluminescence of a luminophore. The fluorescence quenching refers to a phenomenon that the fluorescence intensity and fluorescence lifetime of a fluorescent/luminescent substance are reduced due to the presence of a quencher or a change in the fluorescence environment, and includes static quenching, dynamic quenching, and aggregate fluorescence quenching. The static quenching refers to a phenomenon that a complex is generated between a ground state fluorophore/luminophore and a quencher through weak combination, and the complex quenches fluorescence/luminescence; the dynamic quenching refers to that an excited state fluorophore/luminophore collides with a quenching group to quench the fluorescence/luminescence of the excited state fluorophore/luminophore; the fluorescence quenching refers to the property that some fluorophores/luminophores are aggregated to generate fluorescence quenching, and the self-quenching phenomenon is generated when the concentration of the fluorophores/luminophores is too large.
In the present invention, the fluorophore may be selected from the group consisting of organic fluorophores, organometallic fluorophores, organic elemental fluorophores, biological fluorophores, inorganic fluorophores, which may be selected from the group consisting of, but not limited to, covalent groups and non-covalent complexes, self-assemblies, compositions, aggregates and combinations thereof. The fluorophore may be selected from the group including, but not limited to, pre-existing, chemically activated, biologically activated, photoactivated, thermally activated, electroactive, and magnetically activated.
In the present invention, the pre-existing fluorophore refers to a substance that can absorb light energy and enter an excited state without any activation or intervention under the irradiation of incident light with a certain wavelength, and immediately de-excite and emit emergent light with a wavelength shorter or longer than that of the incident light, and includes, but is not limited to, organic fluorophores, organometallic fluorophores, organic elemental fluorophores, biological fluorophores, organic up-conversion fluorophores, inorganic up-conversion fluorophores, which may be selected from the group consisting of, but is not limited to, covalent structures and non-covalent complexes, self-assemblies, compositions, aggregates and combinations thereof.
Among these, the covalent organic fluorophores can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090002021
Figure BDA0002376545090002031
among them, the following are examples of the aggregation-induced emission organic fluorophore, but the present invention is not limited thereto:
Figure BDA0002376545090002032
Figure BDA0002376545090002041
Figure BDA0002376545090002051
the organic fluorophores of the other non-covalent complexes, self-assemblies, aggregates, compositions and various combinations thereof may be selected from any suitable structure. Wherein the composition organic fluorophore may itself be a donor and acceptor composition having energy transfer properties.
Among them, the organometallic fluorophore may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090002052
among them, the organic element fluorophore may be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090002061
among them, the biological fluorophore can be exemplified as follows, but the present invention is not limited thereto:
GFP、EGFP、GFP-S65T、BFP、CFP、YFP、EBFP、Azurite、EBFP2、mTagBFP、TagRFP、EYFP、 ECFP、Cerulean、mTFP、mTurquoise、mCitrine、mVenus、CyPet、YPet、phiYFP、DsRed、mBanana、mOrange、dTomato、mTangerine、mStrawberry、mCherry、mKO、GFP-Phe66、Sirius、mPlum、mKate、 mKate2、Katushka、mNeptune、TagRFP657、IFP1.4、T-Sapphire、mAmetrine、mKeima、mLSS-Kate1、 mLSS-Kate2；
the inorganic fluorophores include but are not limited to sulfide fluorophores, aluminate fluorophores, silicate fluorophores, nitride fluorophores, oxide fluorophores, oxynitride fluorophores, rare earth fluorophores, and inorganic non-metal quantum dots, wherein part of the inorganic fluorophores are mainly composed of a substrate: activator composition, inorganic fluorophores may be exemplified as follows, but the invention is not limited thereto:
CaS:Eu、SrS:Ce、SrGa2S4:Eu、SrAl2O4:Ce、CaAl2O4:Eu、BaAl2O4:Ce、Lu3Al5O12:Eu、Y3Al5O12:Ce、 Tb3Al5O12:Ce、Gd3Al5O12:Eu、Ba2SiO4:Eu、Sr2SiO4:Eu、BaSi2O3:Eu、BaSiO3:Eu、Ba3SiO5:Eu、Ba2Si3O8:Eu、 Ba3Si5O13:Eu、Ba9Sc2Si6O24:Eu、Ca3Mg2Si3O12:Ce、Ca3Sc2Si3O12:Ce、Ca2Si2O7:Eu、SrLi2SiO4:Eu、 CaLi2SiO4:Eu、Ca2Si5N8:Eu、Sr2Si5N8:Eu、CaAlSiN3:Eu、ZnO:Eu、ZnO:Li、SrSi2N2O2:Eu、CaSi2N2O2Eu, CdS/ZnS quantum dot, ZnSe/ZnS quantum dot, InP/ZnS quantum dot, CdSe/ZnS quantum dot, carbon quantum dot, PbS quantum dot with emission wavelength in near infrared region, ZnS: Cu series long afterglow material, CaS: Bi series long afterglow material, SrAl2O4Eu, Dy series long afterglow material, CaAl2O4Eu, Nd series long afterglow material, Sr4Al14O25Eu, Dy series long afterglow material, Zn2SiO4Mn, As series long afterglow material, Sr2MgSi2O7Eu, Dy series long afterglow material, Ca2MgSi2O7Eu, Dy series long afterglow material, MgSiO3Mn, Eu, Dy series long afterglow material, CaTiO3Pr, Al series long afterglow material, Ca8Zn(SiO4)4Cl2Eu series long afterglow material, Ca2Si5N8Eu series long afterglow materials;
inorganic up-converting phosphors typically consist of a host, an activator and a sensitizer, usually doped into nanoparticles or glass by rare earth ions, to absorb long-wavelength radiation and emit short-wavelength fluorescence. Among them, rare earth ions can be exemplified as follows, but the present invention is not limited thereto: scandium ion, yttrium ion, lanthanum ion, cerium ion, neodymium ion, praseodymium ion, promethium ion, europium ion, samarium ion, terbium ion, gadolinium ion, dysprosium ion, holmium ion, erbium ion, thulium ion, lutetium ion, ytterbium ion;
among these, inorganic up-converting fluorophores can be exemplified as follows, but the present invention is not limited thereto:
NaYF4:Er、CaF2:Er、Gd2(MoO4)3:Er、Y2O3:Er、Gd2O2S:Er、BaY2F8:Er、LiNbO3:Er,Yb,Ln、 Gd2O2:Er,Yb、Y3Al5O12:Er,Yb、TiO2:Er,Yb、YF3:Er,Yb、Lu2O3:Yb,Tm、NaYF4:Er,Yb、LaCl3:Pr、 NaGdF4:Yb,Tm@NaGdF4Core-shell nanostructure of Ln, NaYF4:Yb,Tm、Y2BaZnO5:Yb,Ho、 NaYF4:Yb,Er@NaYF4Core-shell nanostructures of Yb, Tm, NaYF4:Yb,Tm@NaGdF4Core-shell nanostructures of Yb.
The organic up-converting fluorophore is preferably an organic composition which achieves up-conversion effect by triplet-triplet annihilation based, said organic composition mainly consisting of a sensitizer and an organic up-converting energy acceptor.
Among them, the following sensitizers can be exemplified, but the present invention is not limited thereto:
Figure BDA0002376545090002071
among them, the organic up-conversion energy acceptor can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090002081
in the present invention, fluorophores such as organic fluorophores, organic metal fluorophores, organic element fluorophores, biological fluorophores, organic upconversion fluorophores, inorganic fluorophores, and inorganic upconversion fluorophores can also form various noncovalent complexes, self-assemblies, aggregates, and combinations thereof, which can be the same or different.
In the present invention, the fluorophore generated by chemical activation refers to a fluorescent structure in which the excitation wavelength and/or emission wavelength of fluorescence generated by a precursor thereof is changed by a structural change due to a chemical reaction. Suitable structures that can be chemically activated to generate fluorophores can be obtained by suitable structural modification and derivatization of suitable fluorophores as described above, although the invention is not limited thereto. The force-sensitive moieties/groups of the invention having force-sensitive properties can also be chemically activated under suitable conditions without a force-sensitive response to generate a fluorophore.
In the present invention, the fluorescence generated by biological activation refers to a structure having fluorescence in which the excitation wavelength and/or emission wavelength of fluorescence generated by a precursor thereof is changed in structure by a biological reaction. Suitable bioactivatable fluorophore generating structures may be obtained by suitable structural modification and derivatization of the above-mentioned suitable fluorophores, although the invention is not limited thereto. The various force-sensitive moieties/groups of the invention having force-sensitive properties can also be biologically activated under suitable conditions without a force-sensitive response to generate a fluorophore.
In the present invention, the photo-activation generated fluorophore refers to a fluorescent structure in which the excitation wavelength and/or emission wavelength of fluorescence generated by a precursor thereof is changed by a structural change due to a photoreaction. Suitable photoactivatable fluorophore-generating structures can be obtained by suitable structural modification and derivatization of the above-mentioned suitable fluorophores. The following may be exemplified, but the invention is not limited thereto:
PA-GFP (trademark), PA-mCherry1 (trademark), Kaede (trademark), PS-CFP2 (trademark), mEosFP (trademark), Dendra2 (trademark), Dronpa (trademark), rsFasLime (trademark), Pandon (trademark), bsDronpa (trademark), Kindling (trademark).
The force-sensitive moieties/groups of the present invention having force-sensitive properties can also be photoactivated under suitable conditions without a force-sensitive response to generate a fluorophore.
In the present invention, the thermally activated fluorophore refers to a fluorescent structure in which the excitation wavelength and/or emission wavelength of fluorescence generated by a precursor of the fluorophore is changed by a structural change due to a thermal reaction. Suitable structures for the heat-activatable fluorophores can be obtained by suitable structural modification and derivatization of the suitable fluorophores mentioned above, but the invention is not limited thereto. The various force-sensitive moieties/groups of the present invention having force-sensitive properties can also be thermally activated under suitable conditions without a force-sensitive response to generate a fluorophore.
In the present invention, the electrically activated fluorophore refers to a fluorescent structure in which the excitation wavelength and/or emission wavelength of fluorescence generated by structural change of its precursor under the action of an electric stress is changed. Suitable structures that can be electroactive to generate fluorophores may be obtained by suitable structural modification and derivatization of suitable fluorophores as described above, although the invention is not limited thereto. The various force-sensitive moieties/groups of the present invention having force-sensitive properties can also be electroactive under suitable conditions without a force-sensitive response to generate a fluorophore.
In the present invention, the magnetically activated fluorophore refers to a fluorescent structure in which the excitation wavelength and/or emission wavelength of fluorescence generated by a precursor thereof is changed by a structural change due to a magnetic reaction. Suitable structures which can be magnetically activated to generate fluorophores may be obtained by suitable structural modification and derivatization of suitable fluorophores as described above, although the invention is not limited thereto. The force-sensitive moieties/groups of the invention having force-sensitive properties can also be magnetically activated under suitable conditions without a force-sensitive response to generate a fluorophore.
In the present invention, the fluorophore-generating precursor, which may also be a covalent and/or non-covalent complex of a suitable fluorescent moiety and a quencher moiety, is in a quenched state before the action of a suitable chemical, biological, optical, thermal, electrical, magnetic, etc., and is activated by the action of a suitable chemical, biological, optical, thermal, electrical, magnetic, etc., to generate fluorescence from the fluorescent moiety, which may be any suitable entity as described above that can generate fluorescence upon excitation with light of a suitable wavelength.
In the present invention, the fluorophore may function as an energy donor under suitable conditions and may function as an energy acceptor under otherwise suitable conditions. By rational utilization of the fluorophores, a desirable combination of energy donors and acceptors can be obtained, resulting in excellent energy transfer properties.
In the present invention, the luminophore may be selected from, but not limited to, chemical activation generated, biological activation generated, photoactivation generated/photoluminescent, thermoactivation generated/thermoluminescable, electroactive generated/electroluminescent, magnetic activation generated/magnetoluminesceable.
In the present invention, the precursor of the luminophore generated by the chemical activation is called a chemiluminescent group, which refers to a chemical group capable of generating a luminescence phenomenon by a structural change after a chemical reaction, and includes, but is not limited to, a suitable dioxetane chemiluminescent system, a luminol chemiluminescent system, an oxalate peroxide chemiluminescent system, an acidic potassium permanganate chemiluminescent system, a tetravalent cerium chemiluminescent system, an acridinium ester chemiluminescent system, and a fluorescein chemiluminescent system.
Wherein the suitable dioxetane chemiluminescent system is comprised of a suitable dioxetane compound and a fluorescer, wherein the suitable dioxetane compound may be exemplified by, but is not limited to:
Figure BDA0002376545090002091
among them, the fluorescent agent may be exemplified as follows, but the present invention is not limited thereto:
5, 12-bis (phenylethynyl) naphthalene, 9, 10-diphenylanthracene, 1-chloro-9, 10-diphenylanthracene, 1-methoxy-9, 10-diphenylanthracene, 1, 5-dichloro-9, 10-diphenylanthracene, 1, 8-dimethoxy-9, 10-diphenylanthracene, pyrene, 9, 10-bis (phenylethynyl) anthracene, 1-chloro-9, 10-bis (phenylethynyl) anthracene, 1-methoxy-9, 10-bis (phenylethynyl) anthracene, rubrene, 5, 12-bis (phenylethynyl) tetracene, 2-chloro-bis (phenylethynyl) tetracene, rhodamine B, 6-chloro-bis (phenylethynyl) tetracene, 16, 17-dideoxy violanthrone;
the luminol chemiluminescence system can be exemplified as follows, but the invention is not limited thereto:
Figure BDA0002376545090002092
the oxalate peroxide chemiluminescence system comprises an oxalate compound, a fluorescent agent and hydrogen peroxide, wherein the oxalate compound can be exemplified as follows, but the invention is not limited to the following:
Figure BDA0002376545090002093
among them, the fluorescent agent may be exemplified as follows, but the present invention is not limited thereto:
5, 12-bis (phenylethynyl) naphthalene, 9, 10-diphenylanthracene, 1-chloro-9, 10-diphenylanthracene, 1-methoxy-9, 10-diphenylanthracene, 1, 5-dichloro-9, 10-diphenylanthracene, 1, 8-dimethoxy-9, 10-diphenylanthracene, pyrene, 9, 10-bis (phenylethynyl) anthracene, 1-chloro-9, 10-bis (phenylethynyl) anthracene, 1-methoxy-9, 10-bis (phenylethynyl) anthracene, rubrene, 5, 12-bis (phenylethynyl) tetracene, 2-chloro-bis (phenylethynyl) tetracene, rhodamine B, 6-chloro-bis (phenylethynyl) tetracene, 16, 17-dideoxy violanthrone;
The chemiluminescence system of the acidic potassium permanganate consists of acidic potassium permanganate and a substance to be detected, and some adaptive compounds can be added to enhance the chemiluminescence intensity of the acidic potassium permanganate4Test substance or acidic KMnO4- (luminescence enhancer) -analyte, which may be exemplified as follows, but the present invention is not limited thereto:
acidic KMnO4Oxalate, acidic KMnO4Luminol, acidic KMnO4- (divalent lead ion) -luminol, acidic KMnO4-SO2Acidic KMnO4Sulfite, acidic KMnO4Glutamic acid, acidic KMnO4Aspartic acid, acidic KMnO4- (Formaldehyde) -L-Tryptophan, acidic KMnO4- (Formaldehyde) -methotrexate, acidic KMnO4- (Formaldehyde) -Dichloromethabenzuron, acidic KMnO4- (Formaldehyde) -Aminopyrine, acidic KMnO4- (Formaldehyde) -iodine, acidic KMnO4- (Formaldehyde) -tyrosine, acidic KMnO4- (glyoxal) -imipramine, acidic KMnO4- (glyoxal) -dipyridamole, acidic KMnO4- (glyoxal) -reserpine, acidic KMnO4- (sodium dithionite) -riboflavin, acidic KMnO4- (sodium dithionite) -tetrahydropalmatine, acidic KMnO4- (sodium dithionite) -vitamin B6Acidic KMnO4- (sodium dithionite) -pipemidic acid, acidic KMnO4Morphine, acidic KMnO 4-buprenorphine, acidic KMnO4-para-aminobenzoate, acidic KMnO4Codeine, acidic KMnO4Tryptophan, acidic KMnO4Dopamine, acidic KMnO4Levodopa, acidic KMnO4Adrenaline, acidic KMnO4-methoxybenzylaminopyridine, acidic KMnO4-DL-malic acid;
the tetravalent cerium chemiluminescence system is composed of tetravalent cerium and a test object, and some adaptive compounds can be added to enhance the chemiluminescence intensity, and in the invention, the tetravalent cerium chemiluminescence system is expressed as a tetravalent cerium-test object or a tetravalent cerium- (luminescence enhancer) -test object, which can be exemplified as follows, but the invention is not limited thereto:
tetravalent cerium-paracetamol, tetravalent cerium-naproxen, tetravalent cerium-phenacetin, tetravalent cerium-biphenyltriphenol, tetravalent cerium-sulfite, tetravalent cerium- (quinine) -penicillamine, tetravalent cerium- (quinine) -2-mercaptoethane sulfonate, tetravalent cerium- (quinine) -cysteine, tetravalent cerium- (quinine) -thiazole Schiff base, tetravalent cerium- (quinine) -sulfite, tetravalent cerium- (cinchonine) -sulfite, tetravalent cerium- (ciprofloxacin) -sulfite, tetravalent cerium- (oxfloxacin) -sulfite, tetravalent cerium- (norfloxacin) -sulfite, pentavalent cerium-and-bismuth-containing compound, and mixtures thereof, Tetravalent cerium- (sipafloxacin) -sulfite, tetravalent cerium- (roxofloxacin) -sulfite, tetravalent cerium- (Tb) 3++ enoxacin) -sulfite, tetravalent cerium- (Tb)3++ fleroxacin) -sulfite, tetravalent cerium- (Tb)3++ gatifloxacin-sulfite,Tetravalent cerium- (N-tetrahydrobenzothiazole imine Schiff base) -sulfite, tetravalent cerium-rhodamine 5G, tetravalent cerium- (rhodamine B) -folic acid, tetravalent cerium- (rhodamine B) -ascorbic acid;
among them, the acridinium ester chemiluminescence system can be exemplified as follows, but the invention is not limited thereto:
Figure BDA0002376545090002101
4- (2-succinimidylcarbonyl) phenyl-10-methylacridine-9-carboxylate fluorosulfonate;
the fluorescein chemiluminescence system can be exemplified as follows, but the invention is not limited to the following:
Figure BDA0002376545090002102
in the present invention, the biologically-activated luminophore, a precursor thereof, is referred to as a biologically-activatable luminophore, which refers to a chemical or biological group that is capable of undergoing a structural change by a biological reaction (e.g., catalysis by a biological enzyme) to produce a luminescence phenomenon. The bioactivated luminescence may be exemplified as follows, but the present invention is not limited thereto: marine animal luminescence, bacterial luminescence, firefly luminescence; wherein the marine animals are luminous, including but not limited to luminous marine animals such as noctiluca, dinoflagellate, radioworms, jellyfish, sea feathers, ctenopharyngodon idellus, multicastoma, krill, cerasus, cephalopods, echinoderm, tunicates, fish, clamworm, sea bamboo shoot, sea worm, copepods, schizothorax, Phillips longifolus, columna gigas and the like; the bacteria emit light, and the bacteria include but are not limited to luminescent heterobrevibacterium, luminous bacillus leiognathi, Shewanella villosa, alteromonas haiensis, Vibrio harveyi, Vibrio livialis biotype I, Vibrio fischeri, Vibrio paradoxus, Vibrio orientalis, Vibrio mediterranei, Vibrio arctica, Vibrio cholerae, Vibrio qinghai and the like; the firefly luminescence includes but is not limited to fluorescein bioluminescence and dioxetane bioluminescence.
In the present invention, the photo-activation generated/photo-luminescent luminophore and its precursor are called photo-activation luminophores, which refer to chemical groups that can undergo a structural change after a photo-reaction, thereby generating a luminescence phenomenon.
In the present invention, the thermally activated/thermoluminescable luminophore precursor thereof is referred to as a thermoactivatable luminophore, which refers to a chemical group that is capable of undergoing a structural change upon thermal reaction, thereby generating a luminescence phenomenon.
In the present invention, the electroactive produced/electroluminescent luminophore and its precursor are referred to as an electroactive luminophore, which means a chemical group that can generate a luminescence phenomenon by a structural change or charge/hole combination or electrical excitation after an electrochemical reaction. Examples thereof may be as follows, but the present invention is not limited thereto:
Figure BDA0002376545090002111
in the present invention, the electrically activatable luminophores further comprise organic light emitting diodes and inorganic light emitting diodes. Wherein, the organic light emitting diode includes, but not limited to, an organic small molecule light emitting diode and an organic polymer light emitting diode; wherein the electron transport layer material in the organic small molecule light emitting diode can be selected from fluorescent dye compounds such as Alq, Znq, Gaq, Bebq, Balq, DPVBi, ZnSPB, PBD, OXD, BBOT, etc.; the material of the hole transport layer is selected from, but not limited to, aromatic amine fluorescent compounds, such as organic materials like TPD, TDATA, etc. Organic polymer light emitting diodes include, but are not limited to: organic electroluminescent materials such as poly (p-phenylenes), poly (acetylenes), poly (carbazoles), polyfluorenes, and polythiophenes. Wherein, the inorganic light emitting diode material includes but not limited to: gallium arsenide light emitting diodes, gallium phosphide light emitting diodes, silicon carbide light emitting diodes, gallium nitride light emitting diodes, zinc selenide light emitting diodes, gallium phosphide light emitting diodes, aluminum arsenide light emitting diodes.
In the present invention, the magnetically activated/magnetoluminesceable luminophore and its precursor are referred to as magnetically activated luminophores, which refer to chemical groups capable of undergoing a structural change after a magnetic reaction, thereby generating a luminescence phenomenon.
In the present invention, the luminophore-generating precursor, which may also be a covalent and/or non-covalent complex of a suitable luminophore and a quencher, is in a quenched state before the action of a suitable chemical, biological, optical, thermal, electrical, magnetic, etc., and is activated by the action of a suitable chemical, biological, optical, thermal, electrical, magnetic, etc., to produce luminescence from the luminophore, which may be any suitable entity as described above that can produce luminescence upon excitation with light of a suitable wavelength.
It is noted that the same luminophore can exist simultaneously with one or more activated luminescence processes, such as dioxetane luminescence, oxalate peroxide luminescence, fluorescein luminescence, both chemically activated luminescence and biologically activated luminescence.
In the context of the present invention, the quencher refers to a non-fluorescent energy acceptor, which may also be selected from pre-existing or activated. Groups that can act as pre-existing quencher energy acceptors include, but are not limited to: quenching dyes having a basic skeleton such as NPI, NBD, DABCYL, BHQ, ATTO, Eclipse, MGB, QXL, QSY, Cy, Lowa Black, and IRDYE, and quenching dye derivatives thereof include, specifically, the following:
Figure BDA0002376545090002121
ATT0540Q (trade name), ATT0580Q (trade name), ATT0612Q (trade name), Eclipse (trade name), MGB (trade name), QXL490 (trade name), QXL520 (trade name), QXL570 (trade name), QXL610 (trade name), QXL670 (trade name), QXL680 (trade name), Cy5Q (trade name), Cy7Q (trade name), Lowa Black FQ (trade name), Lowa Black RQ (trade name), IRDYE QC-1 (trade name).
In the present invention, the fluorophore having an aggregate fluorescence quenching property includes, but is not limited to, triphenylamine-based fluorophore, fused ring-based fluorophore, rylimide-based fluorophore, rubrene-based fluorophore, porphyrin-based fluorophore, phthalocyanine-based fluorophore, and the like, and specifically, the following may be cited:
Figure BDA0002376545090002122
in the invention, the quenching group can also be selected from a structure with fluorescence quenching performance generated by activating a part of force-sensitive elements/force-sensitive groups with force-sensitive characteristics under other actions besides the mechanical force action.
In the present invention, suitable activatable fluorophores, luminophores, quenchers, which may have two or more activation methods, may be used independently, simultaneously or sequentially, and the different activation methods may even produce different activation effects.
In the present invention, the force-sensitive moiety/group having force-sensitive property capable of generating a fluorophore and/or a quencher by an activation action of one or more of chemical, biological, photothermal, thermal, electrical, magnetic, etc. other than mechanical force is mainly selected from a radical type structure, a five-membered ring structure, a six-membered ring structure, a cyclobutane structure, a monoacyclocyclobutane structure, a dioxetane structure, a cyclobutene structure, a DA structure, a hetero DA structure, a light-operated DA structure, a [4+4] cycloaddition structure, a metal-ligand structure. The force-sensitive element/group with force-sensitive property capable of generating a luminophore by other than mechanical force, such as activation by one or more of chemical, biological, photothermal, thermal, electrical, magnetic, etc., is selected from dioxetane structures. The structure can be connected to a polymer chain in a small molecule form, a single-chain connection form or a multi-chain connection form which cannot bear force of a basic unit structure, so that the structure cannot be stressed and activated; or even if it can be activated by a force, it cannot be activated by regulating the magnitude of the force so that the mechanical force is smaller than its activation force. Those skilled in the art may implement the present invention with reasonable benefit from the logic and concepts disclosed herein. These rich selectivities also represent advantages of the present invention.
In the present invention, in order to obtain the desired force-responsive properties, the non-covalent single force-sensitive groups of the energy transfer-based composition must be aligned in a suitable manner, preferably with nearly parallel transfer dipole orientation, in addition to satisfying the partial overlap of the emission spectrum of the energy donor and the absorption spectrum of the energy acceptor and the need for sufficient proximity of the energy donor and the energy acceptor.
The composite force-sensitive group is formed by tying and/or combining one or more of the covalent and/or non-covalent force-sensitive elements/single force-sensitive groups, and comprises but is not limited to a tying structure, a gating structure, a parallel structure, a serial structure, two or more of tying, gating, parallel and serial structures, and a multi-component composite structure formed by multi-component combination of the tying, gating, parallel and serial structures and the force-sensitive elements/single force-sensitive groups. The complex force sensitive groups may thus be covalent complex force sensitive groups, non-covalent complex force sensitive groups, covalent-non-covalent complex force sensitive groups. The flexibility and variety of the composite force sensing clusters provide the invention with flexible polymer design and rich force-induced responsiveness.
In the present invention, the tethered complex force-sensitive moiety is formed by any suitable one of the above-mentioned covalent or non-covalent force-sensitive moiety/single force-sensitive moiety modules being bound to any suitable linker or linkers, wherein the force-sensitive moiety/single force-sensitive moiety module is tethered by the linker, and after the force-sensitive moiety/single force-sensitive moiety is activated, the tethered linker can prevent (at least temporarily) the polymer chain from chain scission due to chain scission caused by the activation of the chain scission type force-sensitive moiety/single force-sensitive moiety or the activated non-chain scission type force-sensitive moiety/single force-sensitive moiety from continuing to be stressed to cause chain scission. The complex force sensitive groups of the tethered structure are particularly useful for preventing, at least temporarily, or slowing down the chain scission of the polymer chains due to activation of the force sensitive groups, which is extremely important for both achieving force-responsive responsiveness and protecting the polymer from chain scission damage. A typical tethering force sensitive moiety has the general structural formula shown below, but the invention is not limited thereto.
Figure BDA0002376545090002131
Wherein the content of the first and second substances,
Figure BDA0002376545090002132
is force sensitive element/single force sensitive group;
Figure BDA0002376545090002133
is a linker, which may be selected from small molecule and large molecule linkers;
Figure BDA0002376545090002134
is a link to any suitable polymer chain/group/atom.
In the present invention, the tethering linker may be formed by at least one of a common covalent bond, a dynamic covalent bond, and a supramolecular interaction. The force-sensitive module can be composed of chain-breaking type covalent force-sensitive element/single force-sensitive group with dynamic covalent characteristics, chain-breaking type non-dynamic covalent force-sensitive element/single force-sensitive group, chain-breaking type non-covalent force-sensitive element/single force-sensitive group. When the force-sensitive module is a chain-breaking non-dynamic covalent force-sensitive element/single force-sensitive group and the tethered connecting group is formed by common covalent bonds, the tethered structure is a non-dynamic non-chain-breaking tethered composite force-sensitive group. When only the force-sensitive module has dynamic covalent or non-covalent characteristics, and the tethered linker is formed by a common covalent bond, the tethered structure is a dynamic non-delinking tethered complex force-sensitive group. When the force-sensitive module has dynamic covalent character or non-covalent character and the tethering connection group is formed by dynamic covalent bond and/or supermolecular action, the tethering structure is a dynamic chain-breaking tethering composite force-sensitive group. When the force-sensitive module is a delinking non-dynamic covalent force-sensitive motif/single force-sensitive group and the tethered linker is formed by dynamic covalent bonds and/or supramolecular interactions, the tethered structure is a partially dynamic delinking tethered complex force-sensitive group. When the tethered linker is formed by only ordinary covalent bonds, the tethered linker is the most stable in structure and is most able to withstand complete chain scission of the polymer chain following activation by the tethered force-sensitive moiety/single force-sensitive group. Regardless of whether the force-sensitive module is dynamic or not, once the tethering linker contains dynamic covalent bonds and/or supramolecular interactions, the performance of the dynamic covalent bonds and/or supramolecular interactions can be realized by the dynamic covalent bonds and/or supramolecular interactions after final activation, and the force-sensitive module is dynamic.
In embodiments of the invention, the tethered complex force-sensitive groups preferably tether split homolytic, heterolytic, retrocyclic and non-covalent force-sensitive moieties/single force-sensitive groups of the split-chain type.
In an embodiment of the invention, the homolytic force sensing element/single force sensing group used for tethering is preferably a reversible free radical structure in the bis/polysulfide series, bis/polyselenium series, bis-aryl furanone series, bis-aryl cyclic ketone series, bis-aryl cyclopentenone series, bis-aryl chromene series, aryl biimidazole series, aryl ethane series, dicyano tetraaryl ethane series, aryl pinacol series, chain transfer series, cyclohexadienone series, tetracyanoethane series, cyanoacylethane series, adamantane substituted ethane series, bifluorene series, allyl sulfide series, thio/seleno ester series.
In embodiments of the invention, the heterolytic mechanism force sensitive element/single force sensitive group used for tethering is preferably a structure in the triarylsulfonium salt series.
In an embodiment of the invention, the reverse cyclization mechanism force-sensitive moiety/single force-sensitive group used for tethering is preferably a structure in the cyclobutane series, dioxetane series, DA series, heteroda series, [4+4] cycloaddition series.
In an embodiment of the invention, the non-covalent force-sensitive motif/single force-sensitive group used for tethering is preferably a platinum alkyne ligand, an azacarbene with silver/copper/gold/ruthenium ligand, a boron nitrogen ligand, a palladium phosphorus ligand, a ruthenium ligand, a ferrocene, a cobaltocene.
In the embodiment of the present invention, the linking group for tethering is preferably a hydrocarbon group, a hydrocarbon group containing a heteroatom, a polyester group, a polyethylene glycol group.
In the embodiment of the present invention, some preferred tethered complex force-sensitive groups have the following general structural formula, but the present invention is not limited thereto.
Figure BDA0002376545090002135
Wherein the content of the first and second substances,
Figure BDA0002376545090002141
selected from:
Figure BDA0002376545090002142
wherein the content of the first and second substances,
Figure BDA0002376545090002143
selected from:
Figure BDA0002376545090002144
Figure BDA0002376545090002145
wherein the content of the first and second substances,
Figure BDA0002376545090002146
to be connected with n
Figure BDA0002376545090002147
An aromatic ring of (2); wherein the ring structure of the aromatic ring is selected from a monocyclic structure, a polycyclic structure, a spiro structure, a fused ring structure, a bridged ring structure, and a nested ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, boron atoms, phosphine atoms, silicon atoms, and the hydrogen atoms attached to the ring-forming atoms are substituted or unsubstituted with any suitable substituent atom, substituent group; wherein, the substituent atom or substituent is not particularly limited, and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent. At different positions
Figure BDA0002376545090002148
Are the same or different; unless otherwise indicated, appear hereinafter
Figure BDA0002376545090002149
The same meanings are given, and description thereof will not be repeated; wherein the content of the first and second substances,
Figure BDA00023765450900021410
is a link to any suitable polymer chain/group/atom;
Figure BDA00023765450900021411
is a linker which may be selected from small molecule and large molecule linkers, and the linkers at different positions may be the same or different; n is
Figure BDA00023765450900021412
The number of the cells.
In the embodiments of the present invention, some preferred tethered complex force-sensitive groups are exemplified below, but the present invention is not limited thereto, and those skilled in the art can flexibly obtain more structures according to the teaching of the present invention.
Figure BDA00023765450900021413
Figure BDA0002376545090002151
Figure BDA0002376545090002161
Wherein the content of the first and second substances,
Figure BDA0002376545090002162
is linked to any suitable polymer chain/group/atom, preferably via an ether linkage, ester group, phenoxy group, amide linkage, urethane linkage, tertiary amine group, triazolyl group, double bond; r is selected from the group consisting of, but not limited to, hydrogenAtom, hydrocarbyl.
In the present invention, the gated complex force sensitive moiety, which is formed by binding any suitable two or more covalent or non-covalent force sensitive motif/single force sensitive moiety modules, can be sequentially activated, and only the module which is used as a substrate can be activated after the module which is used as the gated module is activated. In gated complex force sensors with only two modules combined, one module is gated and the other is gated as substrate. In a gated complex force sensor comprising three modules, one of the modules is gated by both a preceding and a subsequent activation module. When four or more modules are contained in the gated complex force-sensitive cluster, and n represents the total number of modules, the number of modules which are both substrates of the preceding activation module and gated of the subsequent activation module is n-2. When the activation force of the gate control module is higher than that of the substrate module, once the gate control module is activated by force, the substrate module is immediately activated, on one hand, the gate control module protects the substrate module, on the other hand, the gate control module indirectly improves the activation force of the substrate module, the substrate module is favorable for the substrate module to play a role under the action of higher external force on a polymer, and the functional significance of stress warning and the like is particularly outstanding. When the activation force of the gating module is lower than that of the substrate module, the substrate is not activated immediately after gating activation, and the substrate must be activated after the external force rises to reach the threshold of the activation force; on one hand, sequential force-induced responses can be obtained through stepwise activation, and different responses can give different effects, such as stress warning and the like; on the other hand, when a polymer chain contains a plurality of the gated complex force-sensitive groups, activation of the substrate is started only after activation of all the activatable gates, so that stepwise multiple activation is generated, which is beneficial to protect the polymer and improve the toughness of the polymer in multiple layers besides sequential force-induced response. When the activation force of the gating module is equal to that of the substrate module, the substrate is rapidly activated after gating activation, although gating cannot effectively protect the substrate and cannot generate step-type activation, sequential activation of a plurality of modules can generate multiple identical or different force-induced responses, and the method also has a positive effect on improving the toughness of the polymer. A typical gated complex force-sensitive moiety has a general structural formula as shown in the following formula, but the present invention is not limited thereto.
Figure BDA0002376545090002171
Wherein the content of the first and second substances,
Figure BDA0002376545090002172
is a force sensitive element/single force sensitive group, and p is the number of modules which are not only substrates of a preceding activation module but also gates of a following activation module;
Figure BDA0002376545090002173
is a linker which may be selected from small molecule and large molecule linkers, and the linkers at different positions may be the same or different;
Figure BDA0002376545090002174
is a link to any suitable polymer chain/group/atom.
In the present invention, the gating module may be selected from the group consisting of a chain-broken type and a non-chain-broken type. The substrate module may also be of the delicatessen or non-delicatessen type. Regardless of whether the gating module and the substrate module are of the broken-chain type, it must be ensured that the gating module is activated prior to the substrate module being subjected to force. The chain-breaking gating module comprises chain-breaking covalent force-sensitive elements/single force-sensitive groups with dynamic covalent characteristics, chain-breaking non-dynamic covalent force-sensitive elements/single force-sensitive groups and chain-breaking non-covalent force-sensitive elements/single force-sensitive groups. When the gating module and the substrate module are both selected from any one of a chain-breaking covalent force-sensitive element/single force-sensitive group and a chain-breaking non-covalent force-sensitive element/single force-sensitive group with dynamic covalent characteristics, the gating composite force-sensitive group has complete dynamic; however, if only one module is selected from any one of the chain-breaking covalent force-sensitive element/single force-sensitive group and the chain-breaking non-covalent force-sensitive element/single force-sensitive group with dynamic covalent character, the gated composite force-sensitive group has only partial dynamic property.
In the present invention, the linking group in the gated composite force sensitive group can be selected from small molecule or large molecule linking groups formed by one or more of common covalent bond, dynamic covalent bond and supermolecular action. Wherein the linker formed by the common covalent bond facilitates force activation of the substrate module. A linker formed by dynamic covalent bonds and/or supramolecular interactions, which is dynamic.
In an embodiment of the present invention, the preferred gating force-sensitive element/single force-sensitive group in the gating composite force-sensitive group is of a chain-breaking type, including but not limited to homolytic, heterolytic, reverse cyclic, and non-covalent force-sensitive element/single force-sensitive group; the substrate force-sensitive moiety/monodispersion may be any suitable force-sensitive moiety/monodispersion, preferably homolytic, heterolytic, reverse cyclization, electrocyclization, bending activation and non-covalent force-sensitive moiety/monodispersion.
In embodiments of the present invention, preferred gating moieties/groups include, but are not limited to, disulfide bonds, diselenide bonds, diarylfuranone groups, diarylcycloketo groups, diarylcyclopentenedione groups, diarylchromone groups, arylbiimidazolyl groups, arylethyl groups, dicyanotetraarylethyl groups, arylpinacol groups, alkoxyamino groups, alkylthioamino groups, cyclohexadienone groups, tetracyanoethyl groups, cyanoacylethyl groups, adamantane-substituted ethyl groups, dibenzoenyl groups, allylthioether groups, thioester groups, selenoate groups, cyclobutane groups, dioxethyl groups, DA cyclic groups, hetero DA cyclic groups, [4+4] cyclic groups, platyne ligands, azacarbene and silver/copper/gold/ruthenium ligands, boron nitrogen ligands, palladium phosphorus ligands, ruthenium ligands, ferrocene, cobaltocene.
In embodiments of the present invention, preferred substrate motifs/groups include, but are not limited to, disulfide bonds, bisseleno bonds, bisarylfuranones, bisarylcycloketones, bisarylcyclopentenediones, bisarylene-based, arylbiimidazoles, arylethanes, dicyanotetraarylethanes, arylpinacols, alkoxyamines, alkylthioamines, cyclohexadienones, tetracyanoethanes, cyanoacylethanes, adamantane-substituted ethanes, bifluorenes, allylthioether groups, thioesters, selenoates, cyclobutanes, dioxetanes, DA cyclics, hetero DA cyclics, [4+4] cyclics, platyne ligands, azacarbene and silver/copper/gold/ruthenium ligands, boron nitrogen ligands, palladium phosphorus ligands, ruthenium ligands, ferrocenes, cobaltocenes, six-membered rings, five-membered rings, Cyclopropane, oxirane.
Some preferred gated complex force sensors are exemplified below in the embodiments of the present invention, but the present invention is not limited thereto, and those skilled in the art can flexibly obtain more structures according to the teaching of the present invention.
Figure BDA0002376545090002181
Wherein the content of the first and second substances,
Figure BDA0002376545090002182
is linked to any suitable polymer chain/group/atom, preferably via an ether linkage, ester group, phenoxy group, amide linkage, urethane linkage, tertiary amine group, triazolyl group, double bond; r 1Is hydrogen, hydroxy, a protecting group, R2Is hydrogen, halogen, R3Hydrogen, a fluorophore.
In the present invention, a parallel composite force-sensitive cluster is formed by combining any suitable two or more suitable force-sensitive elementary/single force-sensitive cluster modules in a parallel connection manner, wherein all the force-sensitive elementary/single force-sensitive cluster modules can be stressed simultaneously. Wherein, the parallel force-sensitive elements/single force-sensitive mass modules can be the same or different; when the same, the activation force required by one parallel complex force-sensitive cluster is equivalent to the activation force required by two or more single force-sensitive clusters, and each force-sensitive element/single force-sensitive cluster module will typically be activated simultaneously; when not identical, different force-sensitive elements/single force-sensitive mass modules may not activate simultaneously if the activation force is different for each force-sensitive mass. A typical parallel complex force-sensitive group has a general structural formula shown in the following formula, but the invention is not limited thereto.
Figure BDA0002376545090002191
Wherein the content of the first and second substances,
Figure BDA0002376545090002192
the force-sensitive elements/single force-sensitive groups are arranged, m is the number of the force-sensitive elements/single force-sensitive groups connected in parallel, and the force-sensitive elements/single force-sensitive groups at different positions can be the same or different; r, R,
Figure BDA0002376545090002193
The linking group can be selected from small molecule linking groups and large molecule linking groups, and the linking groups at different positions can be the same or different;
Figure BDA0002376545090002194
Is a link to any suitable polymer chain/group/atom.
In the invention, the force-sensitive modules in the parallel composite force-sensitive clusters can be selected from a chain-breaking type and a non-chain-breaking type. When any one force sensitive module is in a dynamic chain-breaking structure, the dynamic property is conveniently provided. When all the parallel force-sensitive modules are selected from covalent force-sensitive group elements/single force-sensitive groups and non-covalent force-sensitive group elements/single force-sensitive groups with dynamic covalent characteristics, the parallel composite force-sensitive groups are dynamic chain-breaking composite force-sensitive groups. When any one force-sensitive module is a non-dynamic covalent force-sensitive element/single force-sensitive group and the connecting group is a common covalent bond structure, the parallel composite force-sensitive group is a non-chain-breaking composite force-sensitive group or a chain-breaking non-dynamic composite force-sensitive group.
In the present invention, the linking group in the parallel composite force sensitive group can be selected from small molecule or large molecule linking group formed by one or more of common covalent bond, dynamic covalent bond and supermolecular action. Wherein, the connecting base formed by common covalent bond is convenient for the force activation of the force sensitive module; a linker formed by dynamic covalent bonds and/or supramolecular interactions, which is dynamic.
Some preferred parallel complex force-sensitive clusters are exemplified below in the embodiments of the present invention, but the present invention is not limited thereto, and those skilled in the art can flexibly obtain more structures according to the teaching of the present invention.
Figure BDA0002376545090002195
Wherein the content of the first and second substances,
Figure BDA0002376545090002196
for attachment to any suitable polymer chain/group/atom, attachment to the polymer chain is preferably via an ether linkage, an ester group, a phenoxy group, an amide linkage, a urethane linkage, a tertiary amine group, a triazole group, a double bond. In the present invention, the activation force required by the parallel force sensing mass is the sum of the individual parallel units, but not the sum effect when the individual units are not activated simultaneously. The parallel force sensitive groups provide richer performance and selection for the force-induced response of the material, and particularly the comprehensive mechanical strength of the force sensitive groups can be improved.
In the invention, the tandem composite force-sensitive cluster is formed by combining any suitable two or more force-sensitive cells/single force-sensitive cluster modules in a tandem connection manner, the tandem connection group between any two adjacent force-sensitive cells/single force-sensitive cluster modules is part of any one of the two adjacent tandem force-sensitive cells/single force-sensitive cluster modules, and is an indispensable part for realizing force responsiveness/effect of any one of the tandem force-sensitive cells/single force-sensitive cluster modules, and each tandem force-sensitive cell/single force-sensitive cluster module can be activated under the action of a suitable mechanical force. A typical tandem complex force-sensitive group has a general structural formula shown in the following formula, but the present invention is not limited thereto.
Figure BDA0002376545090002201
Wherein the content of the first and second substances,
Figure BDA0002376545090002202
the force-sensitive elements/single force-sensitive groups at different positions can be the same or different; r, L is a linker group which may be selected from small molecule and large molecule linkers, linkers in different positionsMay be the same or different; n and m are the number of the force sensitive elements/single force sensitive groups connected in series;
Figure BDA0002376545090002203
is a link to any suitable polymer chain/group/atom.
In the present invention, the force-sensitive modules in the series-connected composite force-sensitive clusters can be selected from the group consisting of a chain-broken type and a non-chain-broken type. When any one of the force-sensitive modules is a covalent force-sensitive element/single force-sensitive group or a non-covalent force-sensitive element/single force-sensitive group with dynamic covalent characteristics, the tandem composite force-sensitive group is a dynamic chain-breaking composite force-sensitive group. When all the force-sensitive modules are non-dynamic covalent force-sensitive elements/single force-sensitive groups, the series-connection composite force-sensitive group is a non-chain-breaking composite force-sensitive group or a chain-breaking non-dynamic composite force-sensitive group.
In the invention, the linking group in the tandem composite force sensitive group can be selected from small molecule or macromolecule linking group formed by one or more of common covalent bond, dynamic covalent bond and supermolecule action. Preferably, the linker is formed by a common covalent bond to facilitate force activation of the force-sensitive module.
In the embodiment of the invention, the force sensitive element/single force sensitive group in the series composite force sensitive group is a non-chain-breaking module, preferably formed by combining a six-membered ring unit and a five-membered ring unit. Some preferred tandem composite force-sensitive groups are exemplified below in the embodiments of the present invention, but the present invention is not limited thereto, and those skilled in the art can flexibly obtain more structures according to the teaching of the present invention.
Figure BDA0002376545090002204
Figure BDA0002376545090002211
Wherein the content of the first and second substances,
Figure BDA0002376545090002212
is linked to any suitable polymer chain/group/atom, preferably via an ether linkage, ester group, phenoxy group, amide linkage, urethane linkage, tertiary amine group, triazolyl group, double bond; r1、R2Are any suitable groups/atoms, preferably hydrocarbon groups and hydrogen atoms. The series composite force sensitive group based on the six-membered ring and the five-membered ring is particularly suitable for obtaining multi-level force-induced color change/fluorescence response, can induce different stress effects and obtain synergistic effect through multi-level color change and mixed color/fluorescence, and has important significance for obtaining multifunctional force-induced response.
In the present invention, any one or more of the tethered, gated, parallel, and tandem modules can also be recombined with any suitable one or more force-sensitive motifs and/or single force-sensitive groups and/or linker modules, or any suitable two or more of the tethered, gated, parallel, and tandem modules, to obtain a multiplex composite force-sensitive group. For example, a gated multi-element force sensor group is obtained by tethering a gated composite force sensor group, a parallel multi-element composite force sensor group is obtained by combining the tethered composite force sensor group and a single force sensor group module, a multi-level gated multi-element composite force sensor group is obtained by combining the gated composite force sensor group and the single force sensor group module, two or more series composite force sensor groups are combined into a parallel multi-element composite force sensor group, a parallel multi-element composite force sensor group is obtained by combining the series composite force sensor group and the tethered composite force sensor group, a gated multi-element composite force sensor group is obtained by combining the gated composite force sensor group and the series composite force sensor group, a series multi-element force sensor group is obtained by combining the parallel composite force sensor group and the series composite force sensor group, and a multi-element force sensor group is obtained by continuously tethering the series multi-element force sensor group, and the like. The technical personnel in the field can carry out reasonable combination according to the guidance of the invention to prepare the multielement composite force sensitive groups with various structures and excellent performance. Some exemplary multi-element force-sensitive compound structures are shown below, but the invention is not limited thereto.
Figure BDA0002376545090002221
Wherein the content of the first and second substances,
Figure BDA0002376545090002222
the force-sensitive elements/single force-sensitive groups at different positions can be the same or different;
Figure BDA0002376545090002223
is a linker which may be selected from small molecule and large molecule linkers, and the linkers at different positions may be the same or different; n, m and q are the number of the force sensitive elements/single force sensitive groups/compound force sensitive groups/multi-element compound force sensitive groups connected in series/in parallel, and p is the number of gated modules which are not only substrates of the preceding activation modules but also the subsequent activation modules;
Figure BDA0002376545090002224
is a link to any suitable polymer chain/group/atom.
In the present invention, the force-sensitive modules in the multicomponent composite force-sensitive clusters can be selected from the group consisting of a chain-broken type and a non-chain-broken type. When all the force-sensitive modules are non-dynamic covalent force-sensitive elements/single force-sensitive groups, the multi-element composite force-sensitive group is a non-chain-breaking composite force-sensitive group or a chain-breaking non-dynamic composite force-sensitive group. When any one of the force-sensitive modules is a covalent force-sensitive element/single force-sensitive group or a non-covalent force-sensitive element/single force-sensitive group with dynamic covalent characteristics, the multi-element composite force-sensitive group is a dynamic chain-breaking composite force-sensitive group which has certain dynamic property and is convenient to provide the dynamic property.
In the invention, the linking group in the multi-element composite force sensitive group can be selected from small molecule or macromolecule linking group formed by one or more of common covalent bond, dynamic covalent bond and supermolecule action. Preferably, the linker is formed by a common covalent bond to facilitate force activation of the force-sensitive module.
In the invention, the dynamic chain-breaking type multi-component composite force sensitive group must meet the characteristics of dynamic and chain-breaking, and the non-dynamic chain-breaking type multi-component composite force sensitive group only needs to not meet one of the characteristics of dynamic or chain-breaking.
In the embodiment of the present invention, in the multi-element composite force-sensitive group, preferably, the tethered composite force-sensitive element/single force-sensitive group is of a chain-broken type, including but not limited to homolytic, heterolytic, and reverse cyclization force-sensitive elements/single force-sensitive groups; preferably, the gating force-sensitive element/single force-sensitive group in the gating composite force-sensitive group is of a chain breaking type, including but not limited to homolytic, heterolytic and reverse cyclization force-sensitive elements/single force-sensitive groups; preferably, the force-sensitive element/single force-sensitive group in the series-connection composite force-sensitive group is a non-chain-breaking module. Some preferred multi-element force-sensitive compounds are exemplified below in the embodiments of the present invention, but the present invention is not limited thereto, and those skilled in the art can flexibly obtain more structures according to the teaching of the present invention.
Figure BDA0002376545090002231
Wherein the content of the first and second substances,
Figure BDA0002376545090002232
is linked to any suitable polymer chain/group/atom, preferably via an ether linkage, ester group, phenoxy group, amide linkage, urethane linkage, tertiary amine group, triazolyl group, double bond; r is any suitable group/atom, preferably a hydrocarbyl group, a methoxy group and an ester group; r 1Is hydrogen, hydroxy, a protecting group, R2Is hydrogen, halogen, R3Hydrogen, a fluorophore. The multi-element composite force-sensitive group is beneficial to obtaining multi-level/multiple responses through one force-sensitive group by fusing multi-element/multi-level composite/single force-sensitive group/force-sensitive elements, and maximally utilizes force-induced responses.
In the present invention, the force-responsive component, which is not a polymer in itself, can generate force response by directly applying mechanical force to itself, and can generate force response by applying mechanical force after being blended with the slow rebound polymer, so that the slow rebound polymer has force responsiveness, including but not limited to force-responsive crystals, force-responsive assemblies, force-responsive aggregates, and force-responsive compositions. The responsive component is blended and dispersed in the slow rebound polymer or the composition thereof in a physical blending mode, and optionally generates force-induced response performance/effect in a synergistic and/or orthogonal mode with the force sensitive groups contained on the slow rebound polymer chain.
In the invention, the force-responsive crystal is generally a small molecular dye crystal, which is generally formed by crystallization/self-assembly followed by crystallization, and under the action of mechanical force, the crystalline state/assembly state of the force-responsive crystal changes to generate changes of color, fluorescence, luminescence and the like, so as to realize force response; typical structures of the compounds include small molecule crystals such as spiropyran, spirothiopyran, spirooxazine, spirothiazine, rhodamine, etc., crystalline small molecule assemblies, small molecule aggregates, and small molecule compositions.
In the present invention, the force-responsive assembly may be selected from a donor-receptor type, a diketopyrrolopyrrole type, a conjugated type, a platinum coordination type, a gold coordination type, a beryllium coordination type, a copper coordination type, an iridium coordination type, a boron coordination type, a phenothiazine type, a dioxaborolane type, and a dye molecule type; the typical structure of which can be referred to the structure described in the present invention in the previous paragraph based on non-covalent single force sensitive groups of supramolecular assemblies.
In the present invention, the force-responsive aggregate may be selected from the group consisting of a divinylanthracene type, a tetraarylethylene type, a cyanoethylene type, a berberine type, a maleimide type, a 4-hydropyran type; the typical structure of which can be referred to as the structure described in the invention above for the non-covalent aggregate-based force-sensitive groups.
In the present invention, energy transfer, in particular force-energy transfer, is also concerned.
In the present invention, the "energy transfer" refers specifically to the transfer of photon energy from an energy donor to an energy acceptor; in one case, when an energy donor absorbs a photon of a certain frequency, it is excited to a higher energy state of an electron, and energy transfer to an adjacent energy acceptor is achieved by dipole resonance interaction between the energy donor and the energy acceptor before the electron returns to the ground state; alternatively, when the emission from the energy donor comprises mechanoluminescence, energy transfer to the adjacent energy acceptor is achieved by dipole resonance interaction between the energy donor and the energy acceptor. Wherein, the energy donor can be selected from a fluorophore and/or a luminophore, and the energy acceptor can be selected from a fluorophore and/or a quencher. In order to achieve energy transfer, the following conditions must be satisfied: 1) the emission spectrum of the energy donor and the absorption spectrum of the energy acceptor are partially overlapped; 2) the energy donor and the energy acceptor need to be close enough together, preferably at a distance of no more than 10 nm; 3) the energy donor and the energy acceptor must also be aligned in a suitable manner, with the transfer dipole orientation preferably being approximately parallel.
In the present invention, at least one energy donor and/or at least one energy acceptor among the energy donors and energy acceptors for the energy transfer by force are directly and/or indirectly generated by the force-sensitive groups on the polymer chain and/or the force-sensitive components/components in the polymerization under force activation. In addition to at least one energy donor or acceptor being generated directly and/or indirectly by force-sensitive groups/components activated by force, one and the same polymer system may also contain one or more other donors and/or acceptors of non-force-inducing origin. That is, the combination of the energy donor and the energy acceptor in which the force-induced energy transfer is generated may include, but is not limited to, the following cases: the energy donor generated directly by force and the energy acceptor generated indirectly by force, the energy donor generated directly by force and the energy acceptor generated directly by force, the energy donor generated directly by force and the energy acceptor generated indirectly by force, the energy donor generated indirectly by force and the energy acceptor generated directly by force, the energy donor generated indirectly by other non-force and the energy acceptor generated directly by force, and the energy donor generated indirectly by force and the energy acceptor generated indirectly by force. Furthermore, the present invention does not exclude that activation of a suitable force sensitive moiety under suitable conditions may generate both an energy donor or an energy acceptor, directly and indirectly, or both. Moreover, when multiple energy donors and multiple energy acceptors are contained in the same polymer, more than one source of each energy donor and energy acceptor may be present. Wherein said other non-force-inducing source means that said energy donor/energy acceptor may be directly and/or indirectly generated in addition to said force-inducing activation, including but not limited to pre-existing, photo-activated, thermo-activated, electro-activated, chemically activated, bio-activated, magnetically activated; wherein other activation means may also generate the energy donor/energy acceptor directly and/or indirectly. Furthermore, in embodiments of the present invention, in addition to force-induced energy transfer, other forms of energy transfer may occur in the polymer, i.e., energy transfer between energy donors of other non-force-induced sources and energy acceptors of other sources.
In embodiments of the present invention, it is preferred that the energy donor and the energy acceptor generated directly by force-activated force-sensitive groups are outside the polymer chain, and the energy donor and the energy acceptor generated indirectly by force-activated force-sensitive groups/force-sensitive components/components and other non-force-induced sources may or may not be on the polymer chain, preferably on the polymer chain; preferably the distance between the energy donor and the energy acceptor is not more than 10nm, further preferably on the same polymer chain, even further preferably on the same polymer chain and the distance is not more than 10 nm; preferably, the energy donor and the energy acceptor are separated by no more than 20 atoms, more preferably no more than 10 atoms, and even more preferably no more than 5 atoms. The energy acceptor and donor may be linked covalently and/or non-covalently when they are on the same polymer chain. The non-covalent interaction for linking described herein may be any suitable non-covalent interaction including, but not limited to: hydrogen bonding, metal-ligand interaction, ionic interaction, ion-dipole interaction, host-guest interaction, metallophilic interaction, dipole-dipole interaction, halogen bonding, lewis acid-base pairing interaction, cation-pi interaction, anion-pi interaction, benzene-fluorobenzene interaction, pi-pi stacking interaction, ionic hydrogen bonding, radical cation dimerization, phase separation, crystallization; under the action of mechanical force, the non-covalent action is destroyed, so that the energy transfer process is changed, and force-induced responsiveness is obtained; furthermore, due to the reversible nature of the non-covalent interaction, a reversible, recyclable force-responsive effect may also be imparted to the force-sensitive groups. In the invention, the energy transfer including the energy transfer caused by force can be organically regulated and controlled by designing, selecting and regulating the type, the quantity, the combination, the connection mode and the like of the energy donor/energy donor from other non-force-caused sources, so that excellent and diversified energy transfer performance and wide application can be obtained.
In the present invention, the energy donor and the energy acceptor may be different or identical, preferably different. When the energy donor and acceptor are the same, at least one of the donor and acceptor must have multiple excitation and/or emission wavelengths.
In the present invention, the energy transfer may be only one stage or may be multi-stage. When the energy transfer polymer contains a plurality of fluorophores/luminophores (precursors), under appropriate energy transfer conditions, multi-stage energy transfer can be formed, namely, the fluorescence/cold luminescence wavelength emitted by the first-stage energy donor is used as the fluorescence excitation wavelength of the first-stage energy acceptor, the fluorescence wavelength emitted by the first-stage energy acceptor after being excited is used as the fluorescence excitation wavelength of the second-stage energy acceptor, the fluorescence wavelength emitted by the second-stage energy acceptor after being excited is used as the fluorescence excitation wavelength of the third-stage energy acceptor, and the like, thereby realizing the phenomenon of multi-stage energy transfer. Where only the first transfer is present, the energy transfer may be fluorescence quenching; in multiple transfer stages, the energy transfer of the last stage may be fluorescence quenching.
In the invention, the fluorescence refers to a photoluminescence cold luminescence phenomenon that when a fluorophore is irradiated by incident light with a certain wavelength, the fluorophore enters an excited state after absorbing light energy, and is immediately de-excited to emit emergent light with a wavelength longer or shorter than that of the incident light; the wavelength of the incident light is called the excitation wavelength and the wavelength of the outgoing light is called the emission wavelength. When the emission wavelength is longer than the excitation wavelength, it is called down-conversion fluorescence; when the emission wavelength is shorter than the excitation wavelength, it is called up-conversion fluorescence. In addition to photoluminescence, the fluorescence excitation wavelength that can be an energy acceptor or the cold luminescence that can be quenched by an energy acceptor can be any other suitable light that is not emitted by heat generation by a substance, including but not limited to chemiluminescence of a luminophore, bioluminescence of a luminophore. The fluorescence quenching refers to a phenomenon in which the fluorescence intensity and fluorescence lifetime of a fluorescent/luminescent substance are reduced due to the presence of a quencher or a change in the fluorescence environment, and includes static quenching, dynamic quenching, and aggregation-induced fluorescence quenching. The static quenching refers to a phenomenon that a complex is generated between a ground state fluorophore/luminophore and a quencher through weak combination, and the complex quenches fluorescence/luminescence; the dynamic quenching refers to that an excited state fluorophore/luminophore collides with a quenching group to quench the fluorescence/luminescence of the excited state fluorophore/luminophore; the aggregation-induced fluorescence quenching refers to the self-quenching phenomenon that some fluorophores/luminophores have the aggregation-induced fluorescence quenching property and are generated when the concentration of the fluorophores/luminophores is too large.
In the present invention, the fluorophore may be selected from the group consisting of organic fluorophores, organometallic fluorophores, organic elemental fluorophores, biological fluorophores, inorganic fluorophores, which may be selected from the group consisting of, but not limited to, covalent groups and non-covalent complexes, self-assemblies, compositions, aggregates and combinations thereof. The fluorophore may be selected from the group including, but not limited to, pre-existing, force-activated generated, chemical activation generated, biological activation generated, photo-activated generated, thermal activation generated, electro-activated generated, magnetic activation generated.
In the present invention, the pre-existing fluorophore refers to a substance that can absorb light energy and enter an excited state without any activation or intervention under the irradiation of incident light with a certain wavelength, and immediately de-excite and emit emergent light with a wavelength shorter or longer than that of the incident light, and includes, but is not limited to, organic fluorophores, organometallic fluorophores, organic elemental fluorophores, biological fluorophores, organic up-conversion fluorophores, inorganic up-conversion fluorophores, which may be selected from, but is not limited to, covalent structures and non-covalent complexes, self-assemblies, compositions, aggregates and combinations thereof.
In the present invention, fluorophores such as organic fluorophores, organic metal fluorophores, organic element fluorophores, biological fluorophores, organic upconversion fluorophores, inorganic fluorophores, and inorganic upconversion fluorophores can also form various noncovalent complexes, self-assemblies, aggregates, and combinations thereof, which can be the same or different.
In the present invention, the force-activated generated fluorophore refers to an entity having fluorescence, in which the excitation wavelength and/or emission wavelength of fluorescence generated by the precursor of the fluorophore is changed by the direct and/or indirect structural change of the precursor under the action of mechanical force, and the precursor of the fluorophore can be referred to as a fluorescence force-sensitive group. The fluorescent force sensitive moiety may or may not fluoresce prior to force activation, but may fluoresce after activation. Wherein, the fluorescence force-sensitive group contains force-sensitive elements, and the force-sensitive elements include but are not limited to covalent chemical groups, supramolecular complexes, supramolecular assemblies, compositions and aggregates.
In the invention, the fluorescence force sensitive group/force sensitive component/component comprises a fluorescence single force sensitive group and a fluorescence composite force sensitive group. Wherein the fluorescent single force sensitive group comprises only one force sensitive moiety or only one force sensitive moiety in its structure can be activated by force and is not tethered by a tethering structure, which is not an essential component for generating a force-induced response signal, comprising a covalent fluorescent single force sensitive group and a non-covalent fluorescent single force sensitive group. Wherein, the fluorescence composite force-sensitive group is formed by tying and/or combining one or more of the covalent and/or non-covalent fluorescence force-sensitive elements/single force-sensitive groups (including combining with non-fluorescence force-sensitive elements/single force-sensitive groups), and the fluorescence composite force-sensitive group comprises but not limited to a tying structure, a gating structure, a parallel structure, a serial structure, two or more of tying, gating, parallel and serial structures, and a multi-composite structure formed by multi-stage combination of the two or more of the tying, gating, parallel and serial structures and the fluorescence and/or non-fluorescence force-sensitive elements/single force-sensitive groups. The fluorescent complex force sensitive groups may thus be covalent complex force sensitive groups, non-covalent complex force sensitive groups, covalent-non-covalent complex force sensitive groups. The flexibility and variety of the composite force sensing clusters provide the invention with flexible polymer design and rich force-induced responsiveness.
One or more components of the upconversion fluorophore can be generated directly and/or indirectly through force-induced activation.
The organic up-converting fluorophore is preferably an organic composition which achieves up-conversion effect by triplet-triplet annihilation based, said organic composition mainly consisting of a sensitizer and an organic up-converting energy acceptor.
In the invention, the organic up-conversion sensitizer can be pre-existing, or can be directly and/or indirectly formed after activation, including but not limited to force activation, biological activation, chemical activation, and photoactivation, and under the action of the organic up-conversion sensitizer directly and/or indirectly formed after activation and an energy receptor, the effect of energy up-conversion is realized, the process of energy up-conversion can be more easily regulated, controlled and designed, and the effect of energy up-conversion is enriched.
In the present invention, the organic up-conversion energy acceptor can be exemplified as follows, but the present invention is not limited thereto:
Figure BDA0002376545090002261
Figure BDA0002376545090002271
in the invention, the organic up-conversion energy receptor can be pre-existing, or can be directly and/or indirectly formed after activation, including but not limited to force activation, biological activation, chemical activation, light activation, thermal activation, magnetic activation, and electric activation, and the organic up-conversion energy receptor directly and/or indirectly formed after activation is under the action of a sensitizer, so that the effect of energy up-conversion is realized, the process of energy up-conversion can be more easily regulated and designed, and the effect of energy up-conversion is enriched.
In the present invention, the fluorophore may function as an energy donor under suitable conditions and may function as an energy acceptor under otherwise suitable conditions. By rational utilization of the fluorophores, a desirable combination of energy donors and acceptors can be obtained, resulting in excellent energy transfer properties.
In the present invention, the luminophore may be selected from, but not limited to, force-activated, chemical-activated, photo-activated/photo-luminescent, thermal-activated/thermoluminescent, electro-activated/electroluminescent, magnetic-activated/magnetoluminescent.
In the present invention, the solid structure capable of force-activated to generate luminophore is called luminous force sensitive group/force sensitive component/component, which refers to a force sensitive group capable of undergoing a structural change directly and/or indirectly under the action of mechanical force to generate a luminescence phenomenon, and includes, but is not limited to, dioxetane-based luminescence single force sensitive groups and composite force sensitive groups.
In the context of the present invention, the quencher refers to a non-fluorescent energy acceptor, which may also be selected from pre-existing or activated.
In the present invention, the various pre-existing fluorophores, luminophores, quenchers can also be modified or derivatized as appropriate to generate structural precursors that can be activated by non-force-induced activation.
It is contemplated that the same fluorophore/luminophore/quencher may be activated in one or more ways, or that multiple activation ways may be used sequentially or simultaneously.
In the present invention, the moiety capable of acting as a force-sensitive moiety/group/component can also be capable of generating a fluorophore and/or a luminophore and/or a quencher by other actions than mechanical forces, such as activation by one or more of chemical, biological, photothermal, thermal, electrical, magnetic, and the like. The structure can be connected to a polymer chain in a small molecule form, a single-chain connection form or a multi-chain connection form which cannot bear force of a basic unit structure, so that the structure cannot be stressed and activated; or even if it can be activated by a force, it cannot be activated by regulating the magnitude of the force so that the mechanical force is smaller than its activation force. Those skilled in the art may implement the present invention with reasonable benefit from the logic and concepts disclosed herein. These rich selectivities also represent advantages of the present invention.
In the present invention, when the energy donor and the energy acceptor are indirectly generated by the force-sensitive element/force-sensitive group/force-sensitive component/component, it may be that the force-sensitive element/force-sensitive group/force-sensitive component/component is activated to generate the energy donor and/or the energy acceptor from other structures, or that the activated product is regenerated into the energy donor and/or the acceptor by other actions after the force-sensitive element/force-sensitive group/force-sensitive component/component is activated. Fluorophores, luminophores and quenchers can all be generated directly and/or by force. The up-converted fluorescence may also serve as excitation light, the fluorescence of the fluorophore may also serve as excitation light for the up-converted fluorescence, and the luminescence of the luminophore may also serve as excitation light for the up-converted fluorescence.
In the present invention, the matrix and/or dispersion may contain at least one dilatant mechanism/mode, at least one of dynamic covalent bond, supramolecule and force sensitivity, or multiple dynamic covalent bonds, multiple supramolecule actions and multiple force sensitivities. When the matrix or dispersion is free of dilatancy, it may also contain at least one of dynamic covalent bonds, supramolecules, force sensitivity, or simultaneously contain multiple dynamic covalent bonds, multiple supramolecular interactions, multiple force sensitivities. In embodiments of the invention, any suitable combination is facilitated to achieve optimal performance.
In the present invention, the energy absorbing compliance system includes, but is not limited to, the following embodiments:
according to a preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; wherein the matrix material of the open-cell walls contains an intrinsic dilatant polymer.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the base material of the pore wall of the open pore contains an intrinsic dilatant polymer, and the dilatant polymer is a vitreous dilatant polymer.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the base material of the pore wall of the open pore contains an intrinsic dilatancy polymer, and the dilatancy polymer is a dynamic dilatancy polymer.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the flexible energy absorption system comprises a flexible energy absorption system, wherein a matrix material of the pore walls of the open pores contains an intrinsic dilatancy polymer, and the flexible energy absorption system also contains a dispersive dilatancy polymer.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the flexible energy absorption system comprises a flexible energy absorption system, a flexible energy absorption system and a flexible energy absorption system, wherein the base material of the pore wall of the open pore contains an intrinsic dilatant polymer, and the flexible energy absorption system also contains an aerodynamic dilatant polymer.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; wherein the matrix material of the pore walls of the pores contains an intrinsic dilatant polymer, and wherein the matrix material is a thermoplastic polymer containing side hydrogen bonding.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; wherein the walls of the pores comprise a matrix material comprising an intrinsic dilatant polymer, and wherein the matrix material is a supramolecular polymer free of hydrogen bonds.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the flexible energy absorption system comprises a flexible energy absorption system, a flexible energy absorption system and a flexible energy absorption system, wherein a base material of the pore wall of the pore contains an intrinsic dilatant polymer, the base material contains a thermoplastic polymer with a side hydrogen bond effect, and the flexible energy absorption system also contains a dispersive dilatant polymer.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; wherein the matrix material of the walls of the open cells comprises an intrinsic dilatant polymer, and wherein the matrix material is a covalently cross-linked polymer.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; wherein the matrix material of the pore walls of the pores contains an intrinsic dilatant polymer, and wherein the matrix material is a dynamic covalent cross-linked polymer.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; wherein the matrix material of the pore walls of the open pores contains an intrinsic dilatant polymer, and wherein the matrix material is a hybrid covalently cross-linked polymer.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; wherein, the matrix material of the hole wall of the open hole contains intrinsic dilatant polymer, and the flexible energy absorption system also contains at least one force sensitive group.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the flexible energy absorption system comprises a flexible energy absorption system, a flexible energy absorption system and a flexible energy absorption system, wherein a base material of the pore wall of the pore contains an intrinsic dilatant polymer, the dilatant polymer is a vitreous dilatant polymer, and the flexible energy absorption system also contains at least one force sensitive group.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the flexible energy absorption system comprises a flexible energy absorption system, a flexible energy absorption system and a flexible energy absorption system, wherein a base material of the hole wall of the opening contains an intrinsic dilatancy polymer, the dilatancy polymer is a dynamic dilatancy polymer, and the flexible energy absorption system also contains at least one force sensitive group.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the flexible energy absorption system also comprises a dispersive dilatancy polymer and at least one force sensitive group.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the flexible energy absorption system also comprises an aerodynamic dilatancy polymer, and the flexible energy absorption system also comprises at least one force sensitive group.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the matrix material of the pore wall of the open pore contains an intrinsic dilatant polymer, the matrix material is a thermoplastic polymer containing a side hydrogen bond effect, and the flexible energy absorption system also contains at least one force sensitive group.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the flexible energy absorption system comprises a flexible energy absorption system, a flexible energy absorption system and a flexible energy absorption system, wherein the wall of the opening contains a matrix material containing an intrinsic dilatant polymer, the matrix material is a supramolecular polymer without hydrogen bonds, and the flexible energy absorption system also contains at least one force sensitive group.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the flexible energy absorption system also comprises a dispersive dilatant polymer, and the flexible energy absorption system also comprises at least one force sensitive group.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the flexible energy absorption system comprises a flexible energy absorption system, a flexible energy absorption system and a flexible energy absorption system, wherein a base material of the pore wall of the pore contains an intrinsic dilatant polymer, the base material is a covalent cross-linked polymer, and the flexible energy absorption system also contains at least one force sensitive group.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the flexible energy absorption system comprises a flexible energy absorption system, a flexible energy absorption system and a flexible energy absorption system, wherein a base material of the pore wall of the pore contains an intrinsic dilatant polymer, the base material is a dynamic covalent crosslinked polymer, and the flexible energy absorption system also contains at least one force sensitive group.
According to another preferred embodiment of the invention, the energy absorbing compliance system comprises adjacent apertures, at least one side of which is open to the surface along the thickness direction of the system and has an internal fillet structure; the flexible energy absorption system comprises a flexible energy absorption system, a flexible energy absorption system and a flexible energy absorption system, wherein a base material of the pore wall of the pore contains an intrinsic dilatant polymer, the base material is a hybrid covalent cross-linked polymer, and the flexible energy absorption system also contains at least one force sensitive group.
In the present invention, the polymer matrix material for preparing the fillet structure can be selectively added or used as a polymer formulation component by selectively adding or using additives, fillers and swelling agents according to the actual requirements of the preparation process, the forming process, the use performance requirements and the like, which can improve the processing performance of the material, improve the quality and the yield of the product, reduce the product cost or endow the product with certain specific application performance, but the additives or the used substances are not necessary.
The auxiliary agent can improve the preparation process of materials, improve the quality and the yield of products, reduce the cost of the products or endow the products with certain specific application performance. The auxiliary agent is selected from any one or more of the following components: auxiliary agents for synthesis, including catalysts; stabilizing aids including antioxidants, light stabilizers, heat stabilizers; the auxiliary agent for improving the mechanical property comprises a toughening agent and a compatilizer; the processing performance improving additives comprise a lubricant and a release agent; the auxiliary agents for softening and lightening comprise a plasticizer and a foaming agent; the auxiliary agents for changing the surface performance comprise an antistatic agent, an emulsifier and a dispersant; the color light changing auxiliary agent comprises a coloring agent, a fluorescent whitening agent and a delustering agent; flame retardant and smoke suppressant aids including flame retardants; other auxiliary agents include nucleating agents, rheological agents, thickening agents, leveling agents, antibacterial agents and dynamic adjusting agents.
The catalyst for synthesis is mainly used for the synthesis reaction of dynamic polymers, and can accelerate the reaction rate by catalyzing the reaction between reactive groups and reducing the reaction activation energy to realize the polymerization of the dynamic polymers, and the catalyst for synthesis comprises any one or more of the following catalysts for synthesis: catalyst for polyurethane synthesis: amine catalysts, such as triethylamine, triethylenediamine, bis (dimethylaminoethyl) ether, 2- (2-dimethylamino-ethoxy) ethanol, trimethylhydroxyethylpropylenediamine, N, N-bis (dimethylaminopropyl) isopropanolamine, N- (dimethylaminopropyl) diisopropanolamine, N, N, N '-trimethyl-N' -hydroxyethylbutylether, tetramethyldipropylenetriamine, N, N-dimethylcyclohexylamine, N, N, N ', N' -tetramethylalkylenediamine, N, N, N ', N', N '-pentamethyldiethylenetriamine, N, N-dimethylethanolamine, N-ethylmorpholine, 2,4,6- (dimethylaminomethyl) phenol, trimethyl-N-2-hydroxypropylhexanoic acid, 2- (2-dimethylamino-ethoxy) ethanol, trimethylhydroxyethylpropylenediamine, N, N-bis (dimethylaminopropyl) isopropanolamine, N- (dimethylaminopropyl) diisopropanolamine, N, N, N' -trimethyl-N '-hydroxyethylenediamine, N, N' -tetramethyldiethylenetriamine, N, N, N-dimethylethanolamine, N-2-ethylmorpholine, 4,6- (dimethylaminomethyl) phenol, trimethylhexanoic acid, and mixtures thereof, N, N-dimethylbenzylamine, N-dimethylhexadecylamine, or the like; organic metal catalysts such as stannous octoate, dibutyltin dilaurate, dioctyltin dilaurate, zinc isooctoate, lead isooctanoate, potassium oleate, zinc naphthenate, cobalt naphthenate, iron acetylacetonate, phenylmercuric acetate, phenylmercuric propionate, bismuth naphthenate, sodium methoxide, potassium octoate, potassium oleate, calcium carbonate, etc.; ② a catalyst for polyolefin synthesis: such as Ziegler-Natta catalysts, pi-allylnickel, alkyllithium catalysts, metallocene catalysts, diethylaluminum monochloride, titanium tetrachloride, titanium trichloride, boron trifluoride etherate, magnesium oxide, dimethylamine, cuprous chloride, triethylamine, sodium tetraphenylborate, antimony trioxide, aluminum sesquiethylate, vanadium oxychloride, triisobutylaluminum, nickel naphthenate, rare earth naphthenate, etc.; ③ CuAAC reaction catalyst: co-concerted catalysis by a monovalent copper compound and an amine ligand; the monovalent copper compound may be selected from Cu (I) salts, such as CuCl, CuBr, CuI, CuCN, CuOAc, and the like; can also be selected from Cu (I) complexes, such as [ Cu (CH3CN)4] PF6, [ Cu (CH3CN)4] OTf, CuBr (PPh3)3, etc.; the amine ligand may be selected from tris [ (1-benzyl-1H-1, 2, 3-triazol-4-yl) methyl ] amine (TBTA), tris [ (1-tert-butyl-1H-1, 2, 3-triazol-4-yl) methyl ] amine (TTTA), tris (2-benzimidazolemethyl) amine (TBIA), sodium bathophenanthroline disulfonate hydrate, and the like. The amount of the catalyst to be used is not particularly limited, but is usually 0.01 to 0.5% by weight.
The antioxidant can delay the oxidation process of a polymer sample, ensure that a material can be smoothly prepared and processed, and prolong the service life of the material, and comprises but is not limited to any one or more of the following antioxidants: hindered phenols such as 2, 6-di-t-butyl-4-methylphenol, 1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, pentaerythrityl tetrakis [ beta- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], 2' -methylenebis (4-methyl-6-t-butylphenol); sulfur-containing hindered phenols such as 4,4 '-thiobis- [ 3-methyl-6-t-butylphenol ], 2' -thiobis- [ 4-methyl-6-t-butylphenol ]; triazine-based hindered phenols such as 1,3, 5-bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] -hexahydro-s-triazine; blocked phenols of the trimeric isocyanates, such as tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -triisocyanate; amines, such as N, N ' -di (β -naphthyl) p-phenylenediamine, N ' -diphenyl-p-phenylenediamine, N-phenyl-N ' -cyclohexyl-p-phenylenediamine; sulfur-containing species such as dilauryl thiodipropionate, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole; phosphites such as triphenyl phosphite, trisnonylphenyl phosphite, tris [ 2.4-di-t-butylphenyl ] phosphite and the like; among them, preferred as the antioxidant are Tea Polyphenol (TP), Butyl Hydroxyanisole (BHA), dibutylhydroxytoluene (BHT), t-butylhydroquinone (TBHQ), tris [2, 4-di-t-butylphenyl ] phosphite (antioxidant 168), and tetrakis [ beta- (3, 5-di-t-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (antioxidant 1010). The amount of the antioxidant to be used is not particularly limited, but is usually 0.01 to 1% by weight.
The light stabilizer can prevent the polymer sample from photo-aging and prolong the service life of the polymer sample, and comprises but is not limited to any one or more of the following light stabilizers: light-shielding agents such as carbon black, titanium dioxide, zinc oxide, calcium sulfite; ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2,4, 6-tris (2-hydroxy-4-n-butoxyphenyl) -1,3, 5-s-triazine, 2-ethylhexyl 2-cyano-3, 3-diphenylacrylate; precursor type ultraviolet absorbers such as p-tert-butyl benzoate salicylate, bisphenol A disalicylate; ultraviolet light quenchers, such as bis (3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester), 2' -thiobis (4-tert-octylphenoloxy) nickel; hindered amine light stabilizers such as bis (2,2,6, 6-tetramethylpiperidine) sebacate, 2,2,6, 6-tetramethylpiperidine benzoate, tris (1,2,2,6, 6-pentamethylpiperidyl) phosphite; other light stabilizers, such as 2, 4-di-tert-butyl-4-hydroxybenzoic acid (2, 4-di-tert-butylphenyl) ester, alkylphosphoric acid amide, zinc N, N '-di-N-butyldithiocarbamate, nickel N, N' -di-N-butyldithiocarbamate, etc.; among them, carbon black and bis (2,2,6, 6-tetramethylpiperidine) sebacate (light stabilizer 770) are preferable as the light stabilizer. The amount of the light stabilizer to be used is not particularly limited, but is usually 0.01 to 0.5% by weight.
The heat stabilizer can prevent the polymer sample from being chemically changed due to heat during processing or use, or delay the change to achieve the purpose of prolonging the service life, and includes but is not limited to any one or more of the following heat stabilizers: lead salts, such as tribasic lead sulfate, dibasic lead phosphite, dibasic lead stearate, dibasic lead benzoate, tribasic lead maleate, basic lead silicate, lead stearate, lead salicylate, dibasic lead phthalate, basic lead carbonate, silica gel coprecipitated lead silicate; metal soaps: such as cadmium stearate, barium stearate, calcium stearate, lead stearate, zinc stearate; organotin compounds, such as di-n-butyltin dilaurate, di-n-octyltin dilaurate, di (n) -butyltin maleate, mono-octyl di-n-octyltin dimaleate, di-n-octyltin isooctyl dimercaptoacetate, tin C-102, isooctyl dimethyltin dimercaptoacetate; antimony stabilizers such as antimony mercaptide, antimony thioglycolate, antimony mercaptocarboxylate, antimony carboxylate; epoxy compounds, such as epoxidized oils, epoxidized fatty acid esters; phosphites, such as triaryl phosphites, trialkyl phosphites, triarylalkyl phosphites, alkyl-aryl mixed esters, polymeric phosphites; among them, barium stearate, calcium stearate, di-n-butyltin dilaurate, and di (n) -butyltin maleate are preferable as the heat stabilizer. The amount of the heat stabilizer to be used is not particularly limited, but is usually 0.1 to 0.5% by weight.
The toughening agent can reduce the brittleness of a polymer sample, increase the toughness and improve the bearing strength of a material, and comprises any one or more of the following toughening agents: methyl methacrylate-butadiene-styrene copolymer resin, chlorinated polyethylene resin, ethylene-vinyl acetate copolymer resin and its modified product, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene rubber, ethylene-propylene-diene monomer rubber, butadiene rubber, styrene-butadiene-styrene block copolymer, etc.; among them, the toughening agent is preferably ethylene-propylene rubber, acrylonitrile-butadiene-styrene copolymer (ABS), styrene-butadiene-styrene block copolymer (SBS), methyl methacrylate-butadiene-styrene copolymer resin (MBS) or chlorinated polyethylene resin (CPE). The amount of the toughening agent to be used is not particularly limited, but is generally 5 to 10% by weight.
The compatilizer can improve the interfacial properties between polymer samples or between the polymer samples and an inorganic filler or a reinforcing material by virtue of intermolecular bonding force, promote incompatible polymers or inorganic materials to be combined into a whole, further obtain a stable blend, reduce the viscosity of material melt in the plastic processing process, improve the dispersity of the filler to improve the processability, and further obtain good surface quality and mechanical, thermal and electrical properties of an article, and comprises any one or more of the following compatilizers: coupling agent type compatibilizing agents including organic acid chromium complexes, silane coupling agents, titanate coupling agents, sulfonyl azide coupling agents, aluminate coupling agents, zirconate coupling agents and the like, such as divinyltetramethyldisiloxane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (beta-methoxyethoxy) silane, gamma-glycidoxypropyl-trimethoxysilane, gamma-methacryloxypropyl-trimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl-methyl-trimethoxysilane, gamma-aminopropyltriethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, gamma-chloropropyl-trimethoxysilane, gamma-mercaptopropyl-trimethoxysilane, titanium oxide coupling agents, zirconium oxide coupling agents, gamma-methacryloxypropyl-trimethoxysilane, gamma-methyl-trimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl-methyl-trimethoxysilane, N- (beta-methyl-trimethoxysilane, gamma-propyl-methyl-propyl-trimethoxysilane, gamma-propyl-trimethoxysilane, gamma-propyl-trimethoxysilane, gamma-propyl-trimethoxysilane, gamma-propyl, N- (β -aminoethyl) - γ -aminopropyl-trimethoxysilane; copolymer-type compatibilizers including block copolymers, graft copolymers and random copolymers such as polyethylene glycol-polydimethylsiloxane copolymers, polyethylene-polystyrene copolymers, polypropylene-polystyrene copolymers, ABS-maleic anhydride copolymers, polyethylene-maleic anhydride copolymers, polypropylene-maleic anhydride copolymers, and the like; surfactant type compatilizers, including anionic surfactants such as stearic acid, sodium dodecylbenzene sulfonate and the like, cationic surfactants such as quaternaries and the like, nonionic surfactants such as alkyl glucosides (APG), polyglycidyl esters, fatty acid glycerides, fatty acid sorbitan (span), polysorbate (tween) and the like, amphoteric surfactants such as lecithin, amino acid types, betaine types and the like, and also including built surfactants, other surfactants and the like. Among them, the compatibilizer is preferably gamma-aminopropyltriethoxysilane (silane coupling agent KH550), gamma- (2, 3-glycidoxy) propyltrimethoxysilane (silane coupling agent KH560), polyethylene glycol-polydimethylsiloxane copolymer, polyethylene-maleic anhydride copolymer, polypropylene-maleic anhydride copolymer, stearic acid, sodium dodecylbenzenesulfonate, and glyceryl monostearate. The amount of the compatibilizer to be used is not particularly limited, and is generally 0.5 to 2 wt.%.
The lubricant can improve the lubricity, reduce the friction and reduce the interfacial adhesion performance of the polymer sample, and comprises but is not limited to any one or more of the following lubricants: saturated and halogenated hydrocarbons, such as paraffin wax, microcrystalline wax, liquid paraffin wax, low molecular weight polyethylene, oxidized polyethylene wax; fatty acids such as stearic acid, hydroxystearic acid; fatty acid esters such as fatty acid lower alcohol esters, fatty acid polyol esters, natural waxes, ester waxes and saponified waxes; aliphatic amides, such as stearamide or stearamide, oleamide or oleamide, erucamide, N' -ethylene bis stearamide; fatty alcohols, such as stearyl alcohol; metal soaps such as lead stearate, calcium stearate, barium stearate, magnesium stearate, zinc stearate, etc.; among them, the lubricant is preferably paraffin wax, liquid paraffin wax, stearic acid, low molecular weight polyethylene. The amount of the lubricant used is not particularly limited, but is generally 0.5 to 1% by weight.
The release agent, which allows easy release of the polymer sample, smooth and clean surface, includes but is not limited to any one or more of the following: paraffin, soaps, dimethyl silicone oil, ethyl silicone oil, methylphenyl silicone oil, castor oil, waste engine oil, mineral oil, molybdenum disulfide, vinyl chloride resin, polystyrene, silicone rubber and the like; among them, the release agent is preferably dimethyl silicone oil. The amount of the release agent to be used is not particularly limited, but is generally 0.5 to 2% by weight.
The plasticizer can increase the plasticity of a polymer sample, so that the hardness, modulus, softening temperature and brittle temperature of the polymer are reduced, and the elongation, flexibility and flexibility of the polymer are improved, and comprises any one or more of the following plasticizers: phthalic acid esters: dibutyl phthalate, dioctyl phthalate, diisooctyl phthalate, diheptyl phthalate, diisodecyl phthalate, diisononyl phthalate, butylbenzyl phthalate, butyl glycolate phthalate, dicyclohexyl phthalate, bis (tridecyl) phthalate, bis (2-ethyl) hexyl terephthalate; phosphoric acid esters such as tricresyl phosphate, diphenyl-2-ethyl hexyl phosphate; fatty acid esters such as di (2-ethyl) hexyl adipate, di (2-ethyl) hexyl sebacate; epoxy compounds, such as epoxyglycerides, epoxidized fatty acid monoesters, epoxidized tetrahydrophthalic acid esters, epoxidized soybean oil, epoxidized 2-ethylhexyl stearate, epoxidized 2-ethylhexyl soyate, 4, 5-epoxytetrahydrophthalic acid di (2-ethyl) hexyl ester, and methyl chrysene acetyl ricinoleate; glycol esters such as C5-9 ethylene glycol ester and C5-9 triethylene glycol ester; chlorine-containing compounds such as greening paraffin, chlorinated fatty acid ester; polyesters such as 1, 2-propanediol-series ethanedioic acid polyester, 1, 2-propanediol sebacic acid polyester, phenyl petroleum sulfonate, trimellitate ester, citrate ester and the like; among them, the plasticizer is preferably dioctyl phthalate (DOP), dibutyl phthalate (DBP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), or tricresyl phosphate (TCP). The amount of the plasticizer to be used is not particularly limited, but is generally 5 to 20% by weight.
The foaming agent can enable the polymer sample to be foamed into pores, and includes but is not limited to any one or any of the following foaming agents: physical blowing agents such as propane, methyl ether, pentane, neopentane, hexane, isopentane, heptane, isoheptane, petroleum ether, acetone, benzene, toluene, butane, diethyl ether, methyl chloride, methylene chloride, ethylene dichloride, dichlorodifluoromethane, chlorotrifluoromethane; inorganic foaming agents such as sodium bicarbonate, ammonium carbonate, ammonium bicarbonate; organic blowing agents, such as N, N ' -dinitropentamethylenetetramine, N ' -dimethyl-N, N ' -dinitrosoterephthalamide, azodicarbonamide, barium azodicarbonate, diisopropyl azodicarbonate, potassium azoformamide formate, azobisisobutyronitrile, 4 ' -oxybis-benzenesulfonylhydrazide, trihydrazinotriazine, p-toluenesulfonylaminourea, biphenyl-4, 4 ' -disulfonylazide; physical microsphere/particle blowing agents such as expandable microspheres manufactured by Acksonobel, et al; foaming promoters such as urea, stearic acid, lauric acid, salicylic acid, tribasic lead sulfate, dibasic lead phosphite, lead stearate, cadmium stearate, zinc oxide; foaming inhibitors such as maleic acid, fumaric acid, stearoyl chloride, phthaloyl chloride, maleic anhydride, phthalic anhydride, hydroquinone, naphthalenediol, aliphatic amines, amides, oximes, isocyanates, thiols, thiophenols, thioureas, sulfides, sulfones, cyclohexanone, acetylacetone, hexachlorocyclopentadiene, dibutyltin maleate, etc. Among them, sodium bicarbonate, ammonium carbonate, azodicarbonamide (foaming agent AC), N ' -dinitropentamethylenetetramine (foaming agent H), N ' -dimethyl-N, N ' -dinitrosoterephthalamide (foaming agent NTA), and physical microsphere foaming agents are preferable, and the amount of the foaming agent used is not particularly limited, but is usually 0.1 to 30 wt%.
The antistatic agent can guide or eliminate harmful charges accumulated in a polymer sample so as not to cause inconvenience or harm to production and life, and comprises any one or more of the following antistatic agents: anionic antistatic agents such as alkylsulfonates, sodium p-nonylphenoxypropane sulfonate, alkyl phosphate ester diethanolamine salts, potassium p-nonylphenyl ether sulfonates, phosphate ester derivatives, phosphates, phosphate ester derivatives, fatty amine sulfonates, sodium butyrate sulfonates; cationic antistatic agents, such as fatty ammonium hydrochloride, lauryl trimethyl ammonium chloride, lauryl trimethyl ammonium bromide, alkyl hydroxyethyl dimethyl ammonium perchlorate; zwitterionic antistatic agents, such as alkyl dicarboxymethylammonium ethyl inner salt, lauryl betaine, N, N, N-trialkylammonium acetyl (N' -alkyl) amine ethyl inner salt, N-lauryl-N, N-dipolyoxyethylene-N-ethylphosphonic acid sodium salt, N-alkyl amino acid salts; nonionic antistatic agents such as fatty acid ethylene oxide adducts, alkylphenol ethylene oxide adducts, polyoxyethylene ether phosphate esters, glycerin fatty acid esters; high molecular antistatic agents such as polyallylamine N-quaternary ammonium salt substitutes, poly-4-vinyl-1-acetonylpyridinophosphoric acid-p-butylbenzene ester salts, and the like; among them, lauryl trimethyl ammonium chloride and alkyl phosphate diethanol amine salt (antistatic agent P) are preferable as the antistatic agent. The amount of the antistatic agent to be used is not particularly limited, but is generally 0.3 to 3% by weight.
The emulsifier can improve the surface tension between various constituent phases in the polymer mixed solution containing the auxiliary agent to form a uniform and stable dispersion system or emulsion, and is preferably used for emulsion polymerization, and comprises any one or any several of the following emulsifiers: anionic type, such as higher fatty acid salts, alkylsulfonic acid salts, alkylbenzenesulfonic acid salts, sodium alkylnaphthalenesulfonate, succinic acid ester sulfonate, petroleum sulfonic acid salts, castor oil sulfate ester salts, sulfated ricinoleic acid butyl ester salts, phosphate ester salts, fatty acyl-peptide condensates; cationic, such as alkyl ammonium salts, alkyl quaternary ammonium salts, alkyl pyridinium salts; zwitterionic, such as carboxylate, sulfonate, sulfate, phosphate; nonionic types such as alkylphenol ethoxylates, polyoxyethylene fatty acid esters, glycerin fatty acid esters, pentaerythritol fatty acid esters, sorbitol and sorbitan fatty acid esters, sucrose fatty acid esters, alcohol amine fatty acid amides, and the like; the emulsifier is preferably sodium dodecyl benzene sulfonate, sorbitan fatty acid ester, and triethanolamine stearate (emulsifier FM). The amount of the emulsifier used is not particularly limited, but is generally 1 to 5% by weight.
The dispersant can disperse solid floccules in the polymer mixed solution into fine particles to be suspended in the liquid, uniformly disperse solid and liquid particles which are difficult to dissolve in the liquid, and simultaneously prevent the particles from settling and coagulating to form a stable suspension, and includes but is not limited to any one or more of the following dispersants: anionic type, such as sodium alkyl sulfate, sodium alkyl benzene sulfonate, sodium petroleum sulfonate; a cationic type; nonionic types, such as fatty alcohol polyoxyethylene ether, sorbitan fatty acid polyoxyethylene ether; inorganic types such as silicates, condensed phosphates, etc.; among them, sodium dodecylbenzene sulfonate, naphthalene methylene sulfonate (dispersant N) and fatty alcohol-polyoxyethylene ether are preferable as the dispersant. The amount of the dispersant used is not particularly limited, but is generally 0.3 to 0.8% by weight.
The colorant can make the polymer product present the required color and increase the surface color, and includes but is not limited to any one or more of the following colorants: inorganic pigments such as titanium white, chrome yellow, cadmium red, iron red, molybdenum chrome red, ultramarine, chrome green, carbon black; organic pigments, such as lithol rubine BK, lake red C, perylene red, galyl R red, phthalocyanine red, permanent carmine HF3C, plastic scarlet R and cromo red BR, permanent orange HL, fast yellow G, sparkle plastic yellow R, permanent yellow 3G, permanent yellow H2G, phthalocyanine blue B, phthalocyanine green, plastic violet RL, aniline black; organic dyes such as thioindigo red, vat yellow 4GF, Vaseline blue RSN, basic rose essence, oil-soluble yellow, etc.; the colorant is selected according to the color requirement of the sample, and is not particularly limited. The amount of the colorant to be used is not particularly limited, but is generally 0.3 to 0.8% by weight.
The fluorescent whitening agent can enable a stained substance to obtain a fluorite-like flash luminescence effect, and comprises but is not limited to any one or more of the following fluorescent whitening agents: stilbene type, coumarin type, pyrazoline type, benzoxazine type, phthalimide type, and the like; among the fluorescent whitening agents, sodium diphenylethylene disulfonate (fluorescent whitening agent CBS), 4-bis (5-methyl-2-benzoxazolyl) stilbene (fluorescent whitening agent KSN), 2- (4, 4' -distyryl) bisbenzoxazole (fluorescent whitening agent OB-1) are preferable. The amount of the fluorescent whitening agent to be used is not particularly limited, but is generally 0.002 to 0.03% by weight.
The matting agent, which is capable of causing diffuse reflection of incident light upon reaching the polymer surface, produces a low gloss matte and matte appearance, includes, but is not limited to, any one or any of the following matting agents: settling barium sulfate, silicon dioxide, hydrous gypsum powder, talcum powder, titanium dioxide, polymethyl urea resin and the like; among them, the matting agent is preferably silica. The amount of the matting agent to be used is not particularly limited, but is generally 2 to 5% by weight.
The flame retardant can increase the flame resistance of the material, and includes but is not limited to any one or any several of the following flame retardants: phosphorus series such as red phosphorus, tricresyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate; halogen-containing phosphates such as tris (2, 3-dibromopropyl) phosphate, tris (2, 3-dichloropropyl) phosphate; organic halides such as high chlorine content chlorinated paraffins, 1,2, 2-tetrabromoethane, decabromodiphenyl ether, perchlorocyclopentadecane; inorganic flame retardants such as antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate; reactive flame retardants such as chlorendic anhydride, bis (2, 3-dibromopropyl) fumarate, tetrabromobisphenol A, tetrabromophthalic anhydride, and the like; among them, decabromodiphenyl ether, triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, and antimony trioxide are preferable as the flame retardant. The amount of the flame retardant to be used is not particularly limited, but is generally 1 to 20% by weight.
The nucleating agent can accelerate the crystallization rate, increase the crystallization density and promote the grain size to be micronized by changing the crystallization behavior of the polymer, and achieves the purposes of shortening the molding cycle of the material, and improving the physical and mechanical properties of the product, such as transparency, surface gloss, tensile strength, rigidity, heat distortion temperature, impact resistance, creep resistance and the like, and the nucleating agent comprises any one or more of the following nucleating agents: benzoic acid, adipic acid, sodium benzoate, talcum powder, sodium p-phenolsulfonate, silicon dioxide, ethylene propylene rubber, ethylene propylene diene monomer and the like; wherein, the nucleating agent is preferably silicon dioxide and ethylene propylene diene monomer. The amount of the nucleating agent used is not particularly limited, but is generally 0.1 to 1% by weight.
The rheological agent can ensure that the polymer has good brushing property and proper coating thickness in the coating process, prevent the solid particles from settling during storage, and improve the redispersibility, and comprises any one or more of the following rheological agents: inorganic species such as barium sulfate, zinc oxide, alkaline earth metal oxides, calcium carbonate, lithium chloride, sodium sulfate, magnesium silicate, fumed silica, water glass, colloidal silica; organometallic compounds such as aluminum stearate, titanium chelates, aluminum chelates; organic compounds such as organobentonite, castor oil derivatives, isocyanate derivatives, acrylic emulsion, acrylic copolymer, polyethylene wax, etc.; among them, the rheological agent is preferably organic bentonite, polyethylene wax, hydrophobically modified alkaline expandable emulsion (HASE), and alkaline expandable emulsion (ASE). The amount of the rheology agent used is not particularly limited, but is generally 0.1 to 1% by weight.
The thickening agent can endow the polymer mixed solution with good thixotropy and proper consistency so as to meet the requirements of various aspects such as stability performance and application performance during production, storage and use, and the thickening agent comprises any one or more of the following thickening agents: low molecular substances such as fatty acid salts, alkyldimethylamine oxides, fatty acid isopropylamide, sorbitan tricarboxylates, glycerol trioleate, cocamidopropyl betaine; high molecular substances such as bentonite, artificial hectorite, micro-powder silica, colloidal aluminum, polymethacrylate, methacrylic acid copolymer, maleic anhydride copolymer, polyacrylamide, polyvinylpyrrolidone, polyether, and the like; among them, the thickener is preferably bentonite or an acrylic acid-methacrylic acid copolymer. The amount of the thickener to be used is not particularly limited, and is generally 0.1 to 1.5% by weight.
The leveling agent can ensure the smoothness and the evenness of a polymer coating, improve the surface quality of the coating and improve the decoration, and the leveling agent comprises any one or more of the following leveling agents: polyacrylates, silicone resins, and the like; among them, the leveling agent is preferably polyacrylate. The amount of the leveling agent to be used is not particularly limited, but is usually 0.5 to 1.5% by weight.
The antimicrobial agent can maintain the growth or reproduction of certain microorganisms (bacteria, fungi, yeasts, algae, viruses, etc.) below a necessary level within a certain period of time, and is generally classified into an inorganic antimicrobial agent, an organic antimicrobial agent, and a natural antimicrobial agent. Wherein, the inorganic antibacterial agent includes but not limited to silver, copper, zinc, nickel, cadmium, lead, mercury, zinc oxide, copper oxide, ammonium dihydrogen phosphate, lithium carbonate, etc.; the organic antibacterial agent includes but is not limited to organic compounds such as vanillin, ethyl vanillin, acylaniline, imidazole, thiazole, isothiazolone derivative, quaternary ammonium salt, biguanidine and phenol; natural antimicrobial agents include, but are not limited to, chitin, mustard, castor oil, horseradish, and the like. The antibacterial agent is preferably silver, zinc, vanillin compounds, and ethyl vanillin compounds, and the amount of the antibacterial agent used is not particularly limited, but is generally 0.05 to 0.5 wt%.
The dynamic regulator comprises dynamic regulators aiming at different dynamic covalent bonds and/or supermolecule actions, and can improve the dynamic property of dynamic polymers. Among these, the boron-containing dynamic covalent bond dynamic modifiers, which are typically compounds having a free hydroxyl group or a free carboxyl group, or capable of donating or accepting an electron pair, include, but are not limited to, water, sodium hydroxide, alcohols, carboxylic acids, lewis bases, lewis acids, and the like. The addition of such auxiliaries makes it possible to adjust the dynamic properties of the polymers in order to obtain optimum desired properties. The amount of the dynamic adjusting agent to be used is not particularly limited, but is usually 0.1 to 10% by weight.
In the present invention, the filler includes, but is not limited to, inorganic non-metallic fillers, organic fillers, and organometallic compound fillers.
The inorganic non-metal filler includes, but is not limited to, any one or more of the following: calcium carbonate, argil, barium sulfate, calcium sulfate and calcium sulfite, talcum powder, white carbon black, quartz, mica powder, clay, asbestos fiber, orthoclase, chalk, limestone, barite powder, gypsum, silica, graphite, carbon black, graphene oxide, fullerene, carbon nano tube, black phosphorus nano sheet, molybdenum disulfide, diatomite, red mud, wollastonite, silicon-aluminum carbon black, aluminum hydroxide, magnesium hydroxide, nano Fe3O4Particulate, nano gamma-Fe2O3Particulate, nano MgFe2O4Particulate, nano-MnFe2O4Granular, nano CoFe2O4Particles, quantum dots (including but not limited to silicon quantum dots, germanium quantum dots, cadmium sulfide quantum dots, cadmium selenide quantum dots, cadmium telluride quantum dots, zinc selenide quantum dots, lead sulfide quantum dots, lead selenide quantum dots, indium phosphide quantum dots, and indium arsenide quantum dots), upconversion crystal particles (including but not limited to NaYF)4:Er、CaF2:Er、Gd2(MoO4)3:Er、Y2O3:Er、Gd2O2S:Er、 BaYF8:Er、LiNbO3:Er,Yb,Ln、Gd2O2:Er,Yb、Y3Al5O12:Er,Yb、TiO2:Er,Yb、YF3:Er,Yb、Lu2O3:Yb,Tm、 NaYF4:Er,Yb、LaCl3:Pr、NaGdF4:Yb,Tm@NaGdF4Core-shell nanostructure of Ln, NaYF 4:Yb,Tm、Y2BaZnO5:Yb,Ho、 NaYF4:Yb,Er@NaYF4Core-shell nanostructures of Yb, Tm, NaYF4:Yb,Tm@NaGdF4Core-shell nanostructure of Yb), oil shale powder, expanded perlite powder, aluminum nitride powder, boron nitride powder, vermiculite, iron mud, white mud, alkali mud, boron mud, glass beads, resin beads, glass powder, glass fibers, carbon fibers, quartz fibers, carbon-core boron fibers, titanium diboride fibers, calcium titanate fibers, silicon carbide fibers, ceramic fibers, whiskers and the like. In one embodiment of the present invention, inorganic non-metallic fillers having electrical conductivity, including but not limited to graphite, carbon black, graphene, carbon nanotubes, carbon fibers, are preferred, which facilitate obtaining a composite material having electrical conductivity and/or electrothermal function. In another embodiment of the present invention, the non-metallic filler having the function of generating heat under the action of infrared and/or near-infrared light is preferable, and includes but is not limited to graphene, graphene oxide, carbon nanotube, black phosphorus nanosheet, nano-Fe3O4The composite material which can be heated by infrared and/or near infrared light is conveniently obtained. In another embodiment of the present invention, inorganic non-metallic fillers with thermal conductivity, including but not limited to graphite, graphene, carbon nanotubes, aluminum nitride, boron nitride, silicon carbide, are preferred, which facilitate obtaining composite materials with thermal conductivity.
The metal filler includes metal compounds, including but not limited to any one or any several of the following: metal powders, fibers including but not limited to powders, fibers of copper, silver, nickel, iron, gold, and the like, and alloys thereof; nano-metal particles including, but not limited to, nano-gold particles, nano-silver particles, nano-palladium particles, nano-iron particles, nano-cobalt particles, nano-nickel particles, nano-silver particles, nano-palladium particles, nano-iron particles, nano-cobalt particles, nano-nickel particles, nano-cobalt particles, nano-iron particles, nano-cobalt particles, nano-nickel particles, nano-cobalt particles, nano-nickel particles, nano-cobalt particles, nano-iron particles, nano-cobalt particles, nano-nickel particles, and nano-iron particles,Nano CoPt3Particles, nano FePt particles, nano FePd particles, nickel-iron bimetal magnetic nanoparticles and other nano metal particles capable of heating under at least one of infrared, near infrared, ultraviolet and electromagnetic action; liquid metals including, but not limited to, mercury, gallium indium liquid alloys, gallium indium tin liquid alloys, other gallium based liquid metal alloys. In one embodiment of the present invention, fillers that can be heated electromagnetically and/or near-infrared, including but not limited to nanogold, nanosilver, and nanopalladium, are preferred for remote heating. In another embodiment of the present invention, liquid metal fillers are preferred, which can enhance the thermal and electrical conductivity of the flexible substrate while maintaining the flexibility and ductility of the substrate.
The organic filler includes, but is not limited to, any one or any several of the following: natural organic filler; ② synthetic resin filler; ③ synthetic rubber filler; fourthly, synthetic fiber filler; foamable polymer particles; sixthly, conjugated polymer; organic functional dye/pigment. The organic filler with the properties of ultraviolet absorption, fluorescence, luminescence, photo-thermal and the like has important significance for the invention, and the properties can be fully utilized to obtain multifunctionality.
The organic metal compound filler contains a metal organic complex component, wherein a metal atom is directly connected with a carbon atom to form a bond (including a coordination bond, a sigma bond and the like), and the metal organic complex component can be a small molecule or a large molecule and can be in an amorphous or crystal structure. Metal organic compounds tend to have excellent properties including uv absorption, fluorescence, luminescence, magnetism, catalysis, photo-thermal, electromagnetic heat, and the like.
Wherein, the type of the filler is not limited, and is mainly determined according to the required material performance, and calcium carbonate, clay, carbon black, graphene, (hollow) glass microsphere and nano Fe are preferred3O4Particles, nano-silica, quantum dots, up-conversion metal particles, foamed microspheres, foamable particles, glass fibers, carbon fibers, metal powder, nano-metal particles, synthetic rubber, synthetic fibers, synthetic resin, resin microbeads, organometallic compounds, organic materials having photo-thermal properties. Used of The amount of the filler is not particularly limited, but is generally 1 to 30% by weight. In the embodiment of the invention, the filler can be selectively modified and then dispersed and compounded or directly connected into a polymer chain, so that the dispersibility, the compatibility, the filling amount and the like can be effectively improved, and the filler has important significance particularly on the action of photo-thermal, electromagnetic heat and the like.
Wherein, the swelling agent can include but is not limited to water, organic solvent, ionic liquid, oligomer and plasticizer. The oligomers can also be regarded as plasticizers.
Wherein the ionic liquid in the swelling agent is generally composed of an organic cation and an inorganic anion, and the cation is selected from, by way of example, but not limited to, alkyl quaternary ammonium ions, alkyl quaternary phosphine ions, 1, 3-dialkyl-substituted imidazolium ions, N-alkyl-substituted pyridinium ions, and the like; the anion is selected from the group including but not limited to halogen, tetrafluoroborate, hexafluorophosphate, and also CF3SO3-、(CF3SO2)2N-、C3F7COO-、 C4F9SO3-、CF3COO-、(CF3SO2)3C-、(C2F5SO2)3C-、(C2F5SO2)2N-、SbF6 -、AsF6 -And the like. In the ionic liquid used in the present invention, the cation is preferably an imidazolium cation, and the anion is preferably a hexafluorophosphate ion or a tetrafluoroborate ion.
In the preparation process of the polymer matrix material for preparing the fillet structure, the addition amount of the raw materials of each component of the polymer is not particularly limited, and can be adjusted by a person skilled in the art according to the actual preparation situation and the target polymer property.
The invention provides a flexible energy absorption system with an inner concave angle structure, which comprises adjacent holes, wherein at least one side of each hole is opened to the surface along the thickness direction of the system and is provided with the inner concave angle structure; comprising at least one polymer matrix material having dilatancy properties. The energy absorption performance of the polymer matrix material is adjustable in a large range by reasonably selecting the polymer matrix material; the energy absorption performance of the polymer can be adjusted by reasonably selecting the topological structure of the polymer molecules. The flexible energy absorption system of the concave angle structure can generate structural change or physical change under the stress condition to play a role in absorbing and dissipating energy, and other effects generated along with the flexible energy absorption system also expand the application range of the material. When a cross-linked network exists in the flexible energy absorption system with the concave corner structure, the characteristics of the material structure can be balanced and stabilized, and a proper topological structure can be selected according to requirements under different use environments, so that the required energy absorption performance is embodied. Through the introduction of various dynamic covalent bonds and supermolecule effects, the energy absorption structure can show excellent toughness under the action of external force, so that the energy absorption effect with excellent toughness can be obtained; through the dynamic equilibrium reaction in the polymer, the internal defects of the material caused by internal stress can be effectively reduced, so that the obtained energy-absorbing structure has better performance.
The flexible energy absorption system with the concave angle structure provided by the invention can also contain a force sensitive group, and the force sensitive group and the cross-linked network are combined according to requirements, so that the performances of damping, shock absorption, sound insulation, noise elimination, shock resistance protection, explosion prevention, buffering, shock absorption and the like of the force-induced response polymer composition can be greatly improved, and the characteristics of adjustability, visibility and the like of the energy absorption function can be realized, thereby having wider energy absorption application in the fields of life, production, movement, leisure, entertainment, military affairs, police affairs, security, medical care and the like. For example, the energy absorption structure can be applied to manufacturing a damping shock absorber for vibration isolation of various motor vehicles, mechanical equipment, bridges and buildings, and can dissipate a large amount of energy to play a damping effect when being vibrated, so that the vibration of a vibrator can be effectively alleviated, and a force sensitive group can be reasonably utilized to send out warning signals when being overloaded; the material can be prepared into elastomers, porous materials and gel materials, so that the material can be applied to the aspects of air-drop and air-drop protection, vehicle collision prevention, impact resistance and vibration reduction protection of electronic and electric appliances and precision mechanical instruments and the like, or can be prepared into sports protection products, impact protection products, protective clothing and the like for performing impact resistance protection on human bodies, animal bodies, articles and the like in daily life, production and sports, or can be used in the aspects of military and police protection materials and the like; in addition, an energy absorption structure with a shape memory function can be designed, and the energy absorption structure is applied to specific occasions to prepare personalized and customized energy absorption articles.
The energy absorbing compliance system of the present invention is further described below in conjunction with certain embodiments. The specific examples are intended to illustrate the present invention in further detail, and are not intended to limit the scope of the present invention.
Example 1
Figure BDA0002376545090002351
Using dicumyl peroxide as an initiator, and grafting and modifying low molecular weight polypropylene by maleic anhydride through a melt grafting reaction to obtain graft modified polypropylene, wherein the mass ratio of the dicumyl peroxide to the maleic anhydride is 1: 10; then, the boric acid graft modified polymer (a) is prepared by using 1-aminoethylboric acid through a melt grafting reaction by using p-toluenesulfonic acid as a catalyst. Taking 50g of boric acid grafted modified polyethylene (a), 15g of ethylene-vinyl alcohol copolymer, 9g of dioctyl phthalate, 6.2g of stearic acid, 5.4g of tribasic basic lead sulfate, 1.6g of di-n-butyltin dilaurate and 1.2g of dimethyl silicone oil, uniformly mixing, adding into a small internal mixer, mixing for 10min, adding 10g of carbon fiber, continuously mixing, taking out the mixed material, cooling, placing in a double-roller machine at 150 ℃ to prepare a sheet, cooling and cutting the sheet at room temperature, placing a sample in a proper mold, placing on a flat plate vulcanizing machine, heating at 160 ℃ for 10min, taking out, filling into a mold with an inward concave angle structure shown in figure 1a in the specification, placing in a vacuum oven at 80 ℃ for 12h for further reaction, and finally obtaining the carbon fiber reinforced polyethylene polymer material. Taking a part of flexible energy absorption system material, preparing the material into a sample with the thickness of 1cm, and performing an impact test according to an EN1621-2012 standard method to obtain a penetrating impact force of 9.3 kN. The obtained flexible energy absorption system has good flexibility, and can be used as a buffer material for buffering in the automobile field or the aerospace field.
Example 2
Figure BDA0002376545090002361
Taking 0.5 molar equivalent of the compound (a) and 0.75 molar equivalent of 1, 6-hexanediol, putting the mixture into a reaction vessel, recording the mass of the reaction materials as 100 wt%, adding 0.02 wt% of tetra-n-butyl titanate catalyst, stirring and reacting for 4 hours at 170 ℃ under the protection of nitrogen, heating to 220 ℃, controlling the pressure to be 0.4kpa, and continuing to react for 10 hours to obtain the hydroxyl-terminated liquid crystal prepolymer.
Taking 1 molar equivalent carboxyl-terminated four-arm polyethylene glycol (molecular weight is 2000Da) and 2 molar equivalents of compound (b), placing the mixture into a reaction vessel, recording the mass of the reactants as 100 wt%, dissolving the reactants with a proper amount of tetrahydrofuran, adding 2 molar equivalents of 4-dimethylaminopyridine and 8 molar equivalents of dicyclohexylcarbodiimide, stirring the mixture at room temperature for reaction for 24 hours, and removing the tetrahydrofuran under reduced pressure after the reaction is finished to obtain the inorganic boron anhydride bond crosslinked dynamic polymer. Taking 1 molar equivalent carboxyl-terminated four-arm polyethylene glycol (molecular weight is 2000Da) and 2 molar equivalent hydroxyl-terminated liquid crystal prepolymer, placing the four-arm polyethylene glycol and the hydroxyl-terminated liquid crystal prepolymer in a reaction vessel, recording the mass of the reactants as 100 wt%, dissolving the reactants with a proper amount of tetrahydrofuran, adding 80 wt% of inorganic boron anhydride bond crosslinked dynamic polymer, stirring and swelling for 30min, adding 2 molar equivalent 4-dimethylaminopyridine and 8 molar equivalent dicyclohexylcarbodiimide, stirring and reacting for 24h at room temperature, reducing pressure after the reaction is finished, removing tetrahydrofuran, and filling the mixture into a die with an inward concave angle structure shown in figure 1b of the specification to obtain the dilatant polymer flexible energy absorption system. The glass transition temperature of the flexible energy absorption system is-35 ℃, and the flexible energy absorption system shows good low-temperature dilatancy. In the embodiment, the dynamic covalent bond cross-linked network with strong dynamic property is dispersed in the common covalent bond cross-linked network, so that the toughness can be increased while the good mechanical strength is kept, and the tensile strength of the elastomer is 4.6MPa and the elongation at break is 545 percent; a part of flexible energy absorption system material is prepared into a sample with the thickness of 1cm, and an impact test is carried out according to the EN1621-2012 standard method, and the transmitted impact force is measured to be 11.4 kN. The dilatant elastomer in this embodiment can be used as a sealing material to cushion and also to seal.
Example 3
Figure BDA0002376545090002362
25g of MDI and 100g of polyether polyol were reacted to give an isocyanate-terminated prepolymer. Mixing 1 molar equivalent of the compound (a) and 1 molar equivalent of the compound (b) and dissolving in toluene, adding 0.01 molar equivalent of triethylamine, stirring and heating to 80 ℃, slowly adding 2 molar equivalents of isocyanate-terminated prepolymer, continuing to react for 2 hours, then adding methanol for termination, and removing the solvent after the reaction is completed to obtain the product 1. Fully mixing 1 molar equivalent of hydrogen-containing silicone oil (the average molecular weight is about 10000Da, the molar ratio of the repeating unit containing the silicon and the repeating unit without the silicon and the hydrogen is about 1:2), 0.2 molar equivalent of the product 1, 0.5 molar equivalent of cross-linking agent divinyl terminated silicone oil and 7% of the total mass of the silicone oil of quaternary ammonium base, adding 1 part by mass of glass fiber, stirring for 6 hours at 50 ℃, taking out and filling into a die with an inward concave angle structure shown in the attached figure 1e of the specification to obtain the force-induced response dilatant polymer flexible energy absorption system. Taking part of the flexible energy absorption system material, preparing the material into a sample with the thickness of 1cm, and performing an impact test according to an EN1621-2012 standard method to obtain a transmitted impact force of 7.8 kN. The stress protection device has good strength and plasticity, and the color of the stress protection device can be changed into orange red in a stress action area by utilizing the force-induced response characteristic of the stress protection device, and the depth of the color is in direct proportion to the magnitude of the acting force, so that the stress protection device can be applied to body protection and can judge the strength of the external force applied to the body.
Example 4
Figure BDA0002376545090002363
Taking 2-aminoethyl acrylate as a polymerization monomer, taking azobisisobutyronitrile as a free radical initiator, taking dimethyl sulfoxide as a solvent, and preparing a homopolymer with amino groups on side groups through free radical polymerization; and then taking dichloromethane as a solvent, and carrying out graft modification on the homopolymer by using acryloyl chloride, wherein the molar ratio of amino to the acryloyl chloride is 3:1, so as to prepare the homopolymer with the side group containing amino and acrylate group. Triethylamine is used as a catalyst, dichloromethane is used as a solvent, polytetrahydrofuran diol (with the molecular weight of 1500Da) and succinic anhydride are stirred and react for 4 hours at room temperature under nitrogen atmosphere, and then reflux reaction is carried out for 1 hour to prepare carboxyl double-terminated polytetrahydrofuran; taking 3 molar equivalents of carboxyl double-terminated polytetrahydrofuran, 1 molar equivalent of the compound (a) and 1 molar equivalent of pentaerythritol, placing the mixture in a reaction vessel, recording the mass of the reactants as 100 wt%, dissolving the reactants with a proper amount of tetrahydrofuran, then adding 5 molar equivalents of 4-dimethylaminopyridine and 20 molar equivalents of dicyclohexylcarbodiimide, stirring the mixture at room temperature for reaction for 24 hours, and removing impurities and solvent after the reaction is finished to obtain a purified product. 15g of homopolymer with amino and acrylate groups on side groups, 85g of purified product, 20g of submicron silicon dioxide and 120mL of 1-hydroxyethyl-3-methylimidazole tetrafluoroborate ionic liquid are taken, the materials are filled into a mold with an inward concave angle structure shown in figure 1j of the specification, and the dilatant polymer gel flexible energy absorption system is obtained after full swelling. The glass transition temperature of the gel flexible energy absorption system is 43 ℃, and a dynamic polymer containing a dentate hydrogen bond and submicron silicon dioxide are dispersed in the gel flexible energy absorption system to obtain vitrification dilatancy, dynamic dilatancy and dispersive dilatancy. The gel had a tensile strength of 3.1MPa and an elongation at break of 725%. When the gel has damages such as cracks, reversible breakage of dynamic covalent bonds based on reversible free radicals can be realized by heating to 120 ℃ or ultraviolet irradiation, active free radicals are generated, free radical polymerization of acrylate groups dispersed in the gel is initiated, a new covalent cross-linked network is obtained, and damage repair and rapid recovery of mechanical strength are realized. Taking part of the flexible energy absorption system material, preparing the material into a sample with the thickness of 1cm, and performing an impact test according to an EN1621-2012 standard method to obtain a transmitted impact force of 8.9 kN. The gel flexible energy absorption system in the embodiment can be used as an interlayer material of body armor, and can keep the flexibility of gel and the wearing comfort and the action convenience when the body armor is normally worn; in the impact process of bullets, sharp cutters and the like, energy absorption and puncture resistance are realized through the dilatancy of gel, and the instant high temperature generated by friction can excite the free radical polymerization of the acrylate side group to form a new covalent crosslinking network, so that the bulletproof and puncture-resistant effects are improved, and the bullet-resistant and puncture-resistant protective film has strong practicability.
Example 5
Figure BDA0002376545090002371
Taking 60 molar equivalents of 1- (2-methoxyethoxy) -4-vinylbenzene, 10 molar equivalents of compound (a), 10 molar equivalents of compound (b), 4 molar equivalents of N- (2- (4-vinylphenoxy) ethyl) acrylamide and 1.2 molar equivalents of divinylbenzene, putting the mass of the reaction materials in a reaction vessel, recording that the mass of the reaction materials is 100 wt%, adding 120 wt% of deionized water, 0.3 wt% of sodium dodecyl benzene sulfonate, 0.5 wt% of active calcium phosphate, 0.25 wt% of tributyl phosphate, 3 wt% of hexabromocyclododecane, 0.25 wt% of benzoyl peroxide, 0.05 wt% of tert-butyl peroxybenzoate, 0.05 wt% of 1, 1-bis (tert-butyl peroxide) -3,3, 5-trimethylcyclohexane, starting stirring, raising the temperature to 85 ℃ for reaction for 1h after the phase transition of a suspension polymerization system is normal, adding 0.2 wt% of calcium carbonate, continuing to react for 6 hours, adding 0.05 wt% of active calcium phosphate and 0.01 wt% of sodium dodecyl benzene sulfonate, sealing the reaction vessel, pressing 30L of pentane into the reaction kettle by using an air compressor, pressurizing by using nitrogen, sequentially reacting for 6 hours at 110 ℃, cooling to room temperature after the reaction is finished, washing by water, extracting, and drying to obtain the expandable copolymer beads. Taking 240g of the copolymer beads, 25g of decabromodiphenyl ether, 3 wt% of antioxidant BHT and 4g of barium stearate, putting the materials into a container, stirring and mixing uniformly, adding the materials into a pre-foaming machine, introducing steam, heating and pre-foaming, wherein the pre-foaming temperature is 100 ℃, then curing for 8 hours at 25 ℃, then adding the cured expandable copolymer beads into a mold with an inward concave angle structure shown in the attached figure 1n of the specification, introducing steam, carrying out mold pressing, foaming and forming, wherein the foaming temperature is 120 ℃, and the foaming time is 20 minutes, so as to obtain the dilatant polymer foam flexible energy absorption system. A part of flexible energy absorption system material is prepared into a sample with the thickness of 1cm, and an impact test is carried out according to the EN1621-2012 standard method, and the transmitted impact force is measured to be 12.4 kN. The glass transition temperature of the flexible energy absorption system is 58 ℃, so that the flexible energy absorption system has better support property at room temperature, and can provide energy absorption performance through aerodynamic dilatancy and dynamic dilatancy when being impacted by energy. After the foam material has local crack damage, local damage repair can be realized through heating, and the service life of the material can be prolonged. The dilatant foam material in the embodiment also has the characteristics of light weight, high specific strength and the like, and can be used for commodity packaging, shock resistance and collision resistance, and damage to articles is avoided.
Example 6
Figure BDA0002376545090002372
Taking 160 molar equivalent of benzyl acrylate, 40 molar equivalent of compound (a), 3 molar equivalent of methylene bis acrylate and 0.4 molar equivalent of azobisisobutyronitrile, placing the materials in a reaction vessel, stirring and reacting for 24 hours at 70 ℃ under nitrogen atmosphere, and removing impurities and solvent after the reaction is finished to obtain single-network polyacrylate; taking 100 molar equivalents of benzyl acrylate, 12 molar equivalents of 2-isocyanoethyl acrylate and 0.8 molar equivalents of azobisisobutyronitrile, placing the materials in a reaction vessel, recording the mass of the reaction materials as 100 wt%, adding a proper amount of tetrahydrofuran solvent, adding 40 wt% of single-network polyacrylate, stirring and swelling for 30min, reacting for 24h at 70 ℃ under nitrogen atmosphere, adding dimethylglyoxime dissolved with 6 molar equivalents, continuing to react for 12h, and removing impurities and solvent after the reaction is finished to obtain the double-network polymer. Taking 50g of double-network polymer, 10g of nano silicon dioxide and 80mL of 1-ethyl-3-methylimidazole tetrafluoroborate ionic liquid, placing the materials in a mold with an inward concave angle structure shown in figure 1s of the specification, and swelling for 6 hours in a vacuum oven at the constant temperature of 60 ℃ to obtain the dilatant ionic liquid swollen gel flexible energy absorption system. One glass transition process of the gel occurs at 4-40 ℃, and the polymer contains strong dynamic bidentate hydrogen bond action and shows good room temperature dilatancy and room temperature slow resilience. The gel had a tensile strength of 12.7MPa and an elongation at break of 350%. Taking part of the flexible energy absorption system material, preparing the material into a sample with the thickness of 1cm, and performing an impact test according to an EN1621-2012 standard method to obtain a transmitted impact force of 9.2 kN. The dilatant gel flexible energy absorption system in the embodiment also has self-adhesiveness and puncture resistance, and can be attached to corners, sharp objects and the like for buffering and puncture resistance, so that the injury of personnel is reduced.
Example 7
Figure BDA0002376545090002381
And (2) taking cyclohexane as a solvent, taking potassium carbonate and tetrabutylammonium bromide as catalysts, and carrying out graft modification on the polyvinyl chloride by using 3-mercaptopropionic acid to prepare the carboxyl graft-modified polyvinyl chloride. 80g of carboxyl graft modified polyvinyl chloride and 4.8g of compound (a) are taken, dissolved by using a proper amount of tetrahydrofuran, then a proper amount of dicyclohexylcarbodiimide and 4-dimethylaminopyridine are added, then the mixture is stirred and reacted for 24 hours at room temperature in a nitrogen atmosphere, and after the reaction is finished, impurities and solvents are removed, so that the azobenzene group graft modified polyvinyl chloride is obtained. Taking 100 parts by mass of azobenzene group graft modified polyvinyl chloride and 4 parts by mass of column [6 ]]Aromatic hydrocarbon, 10 parts by mass of kaolin, 3 parts by mass of tribasic lead sulfate, 1 part by mass of nano titanium dioxide, 30 parts by mass of dibasic lead stearate, 10 parts by mass of tricresyl phosphate, 3 parts by mass of azodicarbonamide, 3 parts by mass of sodium bicarbonate, 2.5 parts by mass of diisopropylbenzene hydroperoxide, 10 parts by mass of antimony trioxide, 10 parts by mass of aluminum hydroxide and 600 parts by mass of toluene, and placing the materials in a kneader to be mixed for 60min, wherein the toluene is added for 2 times to obtain a mixed material; placing the obtained mixed material in a mould with an inward concave angle structure shown in figure 1t of the specification, foaming for 30min at the temperature of 170 ℃ under the pressure of 12MPa, cooling the mould after foaming is finished, and taking out a sample after pressure release; the taken out sample is placed in a hot air circulation oven at 110 ℃ for heat preservation and drying, so as to remove And removing residual solvent to finally obtain the dilatant polymer foam flexible energy absorption system. The density of the foam was measured to be 136g/cm3And the compressive strength is 3.5 MPa. A part of flexible energy absorption system material is prepared into a sample with the thickness of 1cm, and the impact test is carried out according to the EN1621-2012 standard method, and the transmitted impact force is measured to be 13.7 kN. The flexible energy absorption system has two glass transition temperatures of 60 ℃ and 85 ℃, and the polymer also has the functions of a subject and an object with strong dynamic property, so that multiple dilatancy is obtained, and the flexible energy absorption system has high specific strength, is antibacterial and insulating, and can be used for sound insulation and noise reduction of mechanical equipment, large-scale machine tools and the like.
Example 8
Figure BDA0002376545090002382
Taking 70g of natural rubber to dissolve in toluene, adding 0.2g of benzoyl peroxide, 7g of compound (a) and 5.2g of compound (b), after the raw materials are completely dissolved, introducing nitrogen for 3min to remove oxygen, then stirring and reacting for 12h at 70 ℃ under nitrogen atmosphere, and thermally initiating a sulfydryl-olefin click reaction to prepare the supermolecule crosslinked natural rubber. Plasticating 100 parts by mass of supramolecular crosslinked natural rubber, 5 parts by mass of carbon black and 5 parts by mass of stearic acid on an open mill, then adding 20 parts by mass of diatomite, 4 parts by mass of tetramethyl thiuram disulfide, 4 parts by mass of 4, 4-oxo-diphenyl sulfonyl hydrazide, 5 parts by mass of stearic acid, 0.5 part by mass of dicumyl peroxide, 3 parts by mass of sulfur and 12 parts by mass of naphthenic oil, passing through for 6 times, adjusting the roller distance to be 1mm and the temperature to be 70 ℃, then adjusting the roller distance to be 5mm, discharging after passing through for 3 times, and cutting to obtain a mixed rubber sheet; and then placing the mixed rubber sheet into a die with an inward concave angle structure shown in the attached figure 2a of the specification, and performing hot-pressing foaming molding by a flat vulcanizing machine, wherein the hot-pressing temperature is 150 ℃, the vulcanizing time is 10min, and the pressure is 10MPa, so as to finally prepare the dilatant polymer foam flexible energy absorption system. A part of flexible energy absorption system material is prepared into a sample with the thickness of 1cm, and an impact test is carried out according to the EN1621-2012 standard method, and the transmitted impact force is measured to be 12.6 kN. Cells of the resulting compliant energy absorbing system The average size is 168 μm, the size distribution is relatively uniform, and the foam density is 0.43kg/m3When the foam cracks, the crack can be repaired by local heating. The dilatant polymer foam energy absorbing compliance system of the present embodiment may be used as a shock absorbing material.
Example 9
And (2) taking benzoyl peroxide as an initiator and maleic anhydride as a grafting modifier, and carrying out grafting modification on the low-molecular-weight ethylene propylene diene monomer to obtain the maleic anhydride grafted ethylene propylene diene monomer, wherein the mass ratio of the benzoyl peroxide to the maleic anhydride is 1: 30. Placing 40g of maleic anhydride grafted ethylene propylene rubber into a reaction vessel, adding 80mL of xylene solvent, heating and stirring for 30min, adding 0.6g of hexanediol, heating to 80 ℃, stirring and mixing, adding 0.7g of p-toluenesulfonic acid, 0.3g of polyethylene wax, 0.15g of dibutyltin maleate, 0.8g of aluminum nitride and 0.12g of antioxidant BHT, stirring and reacting for 6h at 80 ℃ under nitrogen atmosphere, placing the obtained product into a mold with an inward concave angle structure shown in figure 2c of the specification, and drying for 12h in a vacuum oven at 80 ℃ to obtain the dilatant polymer elastomer flexible energy absorption system. The elastomer contains common covalent crosslinking, so that the elastomer has good dilatancy and tensile toughness at a low temperature of-30 ℃ and good support property at a high temperature. A part of flexible energy absorption system material is prepared into a sample with the thickness of 1cm, and the impact test is carried out according to the EN1621-2012 standard method, and the transmitted impact force is measured to be 8.7 kN. The flexible energy absorption system is used as an automobile accessory, such as an engine damping sheet, for damping and vibration, and can better adapt to energy absorption requirements in different climates and temperature environments.
Example 10
Figure BDA0002376545090002391
Reacting 1 molar equivalent of the compound (a) with 1.1 molar equivalent of TDI to produce an isocyanate-terminated compound (a); compound (b) is prepared by reacting 1 molar equivalent of dimethylglyoxime with 1.1 molar equivalent of TDI. Dispersing 5 parts by mass of an isocyanate-terminated compound (a), 1 part by mass of diethyltoluenediamine (DETDA), 0.5 part by mass of dibutyltin dilaurate (DY-12), 5 parts by mass of TDI, and 10 parts by mass of polyether polyol DEP-5631D (hydroxyl value 54-58) by ultrasonic waves, putting the mixture into a proper mold, uniformly mixing the mixture by a special stirrer, and heating to 80 ℃ for reaction; after the reaction is completed, 10 parts by mass of polyether polyol EP-330N (hydroxyl value is 32-36), 2 parts by mass of compound (b) and 1 part by mass of TDI are added, the mixture is placed in a die with an inward concave angle structure shown in figure 3a of the specification, the reaction is continued for 2 hours, and after the reaction is finished, the polyurethane elastomer flexible energy absorption system is obtained. Taking part of the flexible energy absorption system material, preparing the material into a sample with the thickness of 1cm, and performing an impact test according to an EN1621-2012 standard method to obtain a transmitted impact force of 9.2 kN. In the embodiment, the manufactured flexible energy absorption system can be used as an aircraft bracket cushion, the color of the polymer can gradually change into green after compression, the compression degree can be judged according to the color, and the self-repairing of the flexible energy absorption system can be realized under different light wavelengths or different pH conditions.
Example 11
Figure BDA0002376545090002392
Taking 40 molar equivalents of a mesogen-like compound (a), 1 molar equivalent of tetramethylpiperidine oxynitride and 0.4 molar equivalent of benzoyl peroxide, placing the reactants in a reaction vessel, dissolving the reactants with a proper amount of dimethylbenzene, then reacting at 90 ℃ for 3 hours under a nitrogen atmosphere, heating to 120 ℃ for reacting for 15 hours, and purifying to obtain a liquid crystal homopolymer after the reaction is finished; and then taking a liquid crystal homopolymer as a macromolecular chain transfer agent, taking p-xylene as a solvent, taking n-octyl acrylate as a soft segment monomer, wherein the molar ratio of the chain transfer agent to the soft segment monomer is 1:160, and reacting for 18 hours at 120 ℃ under a nitrogen atmosphere to obtain the block copolymer. Taking 60 molar equivalent of n-octyl acrylate, 12 molar equivalent of 2- (isopropylamino) ethyl acrylate and 0.4 molar equivalent of benzoyl peroxide, putting the materials into a reaction vessel, dissolving the materials by using a proper amount of tetrahydrofuran, then reacting for 16h at 70 ℃ under a nitrogen atmosphere, and purifying to obtain the acrylate copolymer containing a dentate hydrogen bond group after the reaction is finished. Taking 120 molar equivalent of n-octyl acrylate, 5 molar equivalent of a compound (b), 1 molar equivalent of methylene bisacrylamide and 0.8 molar equivalent of benzoyl peroxide, placing the materials in a reaction container, recording that the mass of the reaction materials is 100 wt%, dissolving the materials in proper amount of toluene, adding 60 wt% of block copolymer and 15 wt% of acrylate copolymer containing a dentate hydrogen bond group, stirring and mixing for 30min, reacting for 24h at 70 ℃ under nitrogen atmosphere, placing the product in a mold with an inward concave angle structure shown in figure 3b of the specification after the reaction is finished, and drying for 12h in a vacuum oven at 60 ℃ to obtain the dilatant polymer elastomer flexible energy absorption system. Taking part of the flexible energy absorption system material, preparing the material into a sample with the thickness of 1cm, and performing an impact test according to an EN1621-2012 standard method to obtain a transmitted impact force of 15.4 kN. The flexible energy absorption system has two glass transition temperatures of-15 ℃ and 40 ℃, and the polymer contains strong dynamic covalent cross-linking and is dispersed with strong dynamic polymer, and has dilatancy in a relatively wide temperature range. When the flexible energy absorption system has local cracks, local repair can be realized based on the reversible characteristic of the contained dynamic structure, and the service life of the material is prolonged. The dilatant polymer elastomer flexible energy absorption system in the embodiment can be used as a shock absorption sealing material, such as a sealing rubber strip in a deep sea detector and a spacecraft, and can effectively absorb shock and seal within a wider temperature range.
Example 12
The stannous octoate is used as a catalyst, and the aminopropyl methyl siloxane-dimethyl siloxane copolymer reacts with excessive isopropyl isocyanate to prepare the polysiloxane containing the carbamido hydrogen bond group. Placing 60 parts by mass of brominated butyl rubber, 40 parts by mass of fluororubber raw rubber and 25 parts by mass of polysiloxane containing urea-based hydrogen bond groups in a two-roll open mill for mixing, then sequentially adding 15 parts by mass of carbon black, 4.5 parts by mass of mica, 4 parts by mass of carbon nano tube, 5 parts by mass of sulfur, 5 parts by mass of zinc oxide, 2 parts by mass of 2,2' -dithiodibenzothiazole, 0.8 part by mass of tetramethyl thiuram disulfide, 2 parts by mass of terpene resin and 2 parts by mass of liquid paraffin, and continuously mixing to obtain a mixed rubber sheet; placing the mixed rubber sheet on a molding press for hot press molding, cutting and cutting, and realizing pre-vulcanization in the hot press molding process to obtain a plate-shaped rubber blank with the size of 100 multiplied by 6 mm; placing the rubber blank into a foaming mould of mould pressing foaming equipment, wherein the volume ratio of a cavity of the foaming mould to the volume of the rubber blank is 3:1, filling carbon dioxide into the foaming mould after hydraulic mould closing, controlling the temperature in the foaming mould to be 75 ℃ and the pressure to be 15MPa, keeping the temperature and the pressure for 30min, fully swelling the rubber blank, then releasing the pressure, foaming the swollen rubber blank in a mould with an inward concave angle structure shown in the specification and attached figure 3c, opening the mould after complete foaming, and taking out the obtained pre-vulcanized rubber foaming material; and (3) placing the pre-vulcanized rubber foaming material in a hot drying tunnel at 168 ℃ for 4h for post-vulcanization, then taking out and cooling to room temperature to obtain the dilatant polymer foam flexible energy absorption system. A part of flexible energy absorption system material is prepared into a sample with the thickness of 1cm, and the impact test is carried out according to the EN1621-2012 standard method, and the transmitted impact force is measured to be 10.6 kN. The prepared flexible energy absorption system has a uniform cell structure, the average cell size is 158 micrometers, and the cell structure contains small-sized open pores, so that under the energy impact, the energy absorption system can absorb energy based on the vitrification dilatancy and dynamic dilatancy and can also obtain an additional energy absorption effect based on the aerodynamic dilatancy. The dilatant polymer foam energy absorbing system of this embodiment can be used as a bumper material to provide impact resistance.
Example 13
Figure BDA0002376545090002401
Pyridine is used as a catalyst, dichloromethane is used as a solvent, and the compound (a) and excessive 5-norbornene-2-acyl chloride react in ice bath for 16 hours to prepare the bisnorbornene crosslinking agent. Dissolving 10 molar equivalents of a bisnorbornene crosslinking agent and 150 molar equivalents of 5-norbornene-2-carboxylic acid 2' -ethoxyethyl ester in appropriate amount of chlorobenzene, introducing nitrogen, carrying out bubbling to remove oxygen for 30min, and adding appropriate amount of ReCl5Chlorobenzene as catalystThe solution is stirred and reacted for 3 hours under nitrogen atmosphere to prepare the dynamic covalent crosslinking polynorbornene. Taking 150 molar equivalents of 5-norbornene-2-carboxylic acid 2' -ethoxyethyl ester and 10 molar equivalents of dicyclopentadiene, placing the reactants in a reaction container, recording the mass of the reactants as 100 wt%, adding 100 wt% of dynamic covalent crosslinked polynorbornene, adding a proper amount of chlorobenzene solvent, fully swelling, introducing nitrogen, carrying out bubbling for deoxygenation for 30min, adding a proper amount of Recl5Stirring and reacting chlorobenzene solution of the catalyst for 3h under nitrogen atmosphere, placing the solution in a mould with an inward concave angle structure shown in figure 3d of the specification for forming, and removing impurities such as the catalyst, the solvent and the like after the reaction is finished to obtain the dilatant polymer elastomer. Taking part of the flexible energy absorption system material, preparing the material into a sample with the thickness of 1cm, and performing an impact test according to an EN1621-2012 standard method to obtain a transmitted impact force of 15.2 kN. The elastomer has a glass transition temperature of-30 deg.C, and has vitrification dilatancy. The flexible energy absorption system has thermal response, ultraviolet response, redox responsiveness and the like, and after the flexible energy absorption system is damaged, local repair of the damaged part can be realized through heating, ultraviolet illumination and the action of reducing substances. Based on the orthogonality of the two network crosslinking forms, multiple shape memory functions are shown. The flexible energy absorption system of the embodiment can be used as a sports protective tool material with a shape memory function, and can effectively resist impact even in low-temperature sports scenes such as skiing and the like.
Example 14
Figure BDA0002376545090002411
Taking 1 molar equivalent of ethyl hydrogen-containing silicone oil, 8 molar equivalents of compound (a) and 2 molar equivalents of dimethyl divinyl silane, placing the mixture in a reaction vessel, dissolving the mixture with a proper amount of toluene, adding a small amount of a dimethylbenzene solution of a platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyl disiloxane complex (wherein the platinum content is 0.003 wt%), stirring the mixture for reaction for 48 hours at 60 ℃ in an argon atmosphere, and removing impurities and a solvent after the reaction is finished to obtain a purified product; swelling the obtained purified product in chloroform, dropwise adding an acetonitrile solution dissolved with 4 molar equivalent of zinc trifluoromethanesulfonate under stirring, continuing stirring for 1h after dropwise adding is finished, then placing the obtained product in a mould with an inward concave angle structure shown in the attached figure 3d of the specification for molding, naturally drying for 24h, and then drying in vacuum for 12h to obtain the dilatant polymer elastomer flexible energy absorption system. The glass transition temperature of the flexible energy absorption system is-40 ℃, and the polymer contains a dentate metal-ligand effect, so that the flexible energy absorption system has excellent low-temperature dilatancy and low-temperature tensile toughness. A part of flexible energy absorption system material is prepared into a sample with the thickness of 1cm, and an impact test is carried out according to the EN1621-2012 standard method, and the transmitted impact force is measured to be 12.8 kN. The flexible energy absorption system also has good corrosion resistance, tear resistance and rebound resilience. The dilatant elastomer flexible energy absorption system in the embodiment can be used as a sealing element in a deep sea detector and a ship and warship to perform shock absorption and sealing.
Example 15
Figure BDA0002376545090002412
Adding 200 parts by mass of toluene solvent into a dry and clean reaction bottle, adding 15 parts by mass of brominated butyl rubber (b) containing side double bonds, 20 parts by mass of compound (a), 3 parts by mass of ethanedithiol and 0.05 part by mass of antioxidant 1010, and preparing a first network by using DMPA as a photoinitiator and thiol-olefin under the condition of ultraviolet irradiation. 200 parts by mass of toluene solvent is measured in a dry and clean reaction bottle, 15 parts by mass of brominated butyl rubber (b) is added, after complete dissolution and stirring, 3 parts by mass of ethanedithiol and 0.05 part by mass of antioxidant 1010 are reacted for 2 hours under the condition of ultraviolet light irradiation by using DMPA as a photoinitiator, then 0.09 part by mass of ruthenium-based catalyst (c) is added, and the reaction is continued for 24 hours under the condition of 65 ℃ to prepare a second network. Preparing brominated butyl rubber (d) containing lateral hydroxyl by taking brominated butyl rubber and 3-mercapto-1-propanol as raw materials and DMPA as a photoinitiator through mercaptan-olefin click addition reaction under the condition of ultraviolet irradiation; 200 parts by mass of toluene solvent is measured in a dry and clean reaction bottle, 15 parts by mass of brominated butyl rubber (d) containing lateral hydroxyl is added, after complete dissolution and stirring, nitrogen is introduced to remove water and remove oxygen for 1h, 2.68 parts by mass of terephthalaldehyde and a proper amount of p-toluenesulfonic acid are added, after stirring and mixing, the mixture reacts at 65 ℃ for 3h under the protection of nitrogen, then a first network, a second network and 3 parts by mass of compound (e) are added, after uniform mixing, the reaction solution is poured into a die with an inward concave angle structure shown in the specification and attached figure 3e, and the die is placed in a vacuum oven at 80 ℃ for reaction and drying for 24h, so that a flexible energy absorption system with good resilience is finally prepared, and the flexible energy absorption system can be stretched and extended in a large range under the action of external force. Taking part of the flexible energy absorption system material, preparing the material into a sample with the thickness of 1cm, and performing an impact test according to an EN1621-2012 standard method to obtain a transmitted impact force of 6.8 kN. The force sensitive groups after force activation can catalyze the reaction of olefin to form a new cross-linked network fixed shape, when the shape is changed, the flexible energy absorption system is cut off by a blade and then is heated at 50 ℃ for 3h, the sample can be bonded again for stretching, the obtained flexible energy absorption system can be used as a shoelace material, and the shoelace cannot be loosened easily due to the existence of the inward concave angle structure.
Example 16
Figure BDA0002376545090002413
Adding a certain amount of dichloroethane solvent into a dry and clean reaction bottle, adding 1, 10-bis (2-oxocyclohexyl) -1, 10-decanedione, 1, 4-butanediamine, 1,3, 5-tris (aminomethyl) -2,4, 6-triethylbenzene into the reaction bottle according to the molar ratio of 10:6:3, fully mixing, adding 6 mol% of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene and 5 mol% of zinc acetate as catalysts, heating to 100 ℃ for 24 hours, and reacting to obtain the 1 st network polymer. 0.02mol of the amino-terminated compound (c) and 0.05mol of 1, 8-octanediamine are added into a reaction bottle, stirred and dissolved, then 2ml of triethylamine is added, mixed evenly, 0.11mol of octanedioyl chloride is added dropwise, and stirring, mixing and reacting are continued for 6 hours. Then 100 parts by mass of polyether polyol MN-3050DF (hydroxyl value is 54-57), 4 parts by mass of triethylamine, 10 parts by mass of compound (b), 10 parts by mass of epoxidized soybean oil, 0.5 part by mass of KH550, 60 parts by mass of kaolin, 3 parts by mass of UV-531, 10 parts by mass of pentachlorophenol and 35 parts by mass of MDI are added into a reactor, the mixture is uniformly stirred, the mixture is placed into a mold with an inward concave angle structure shown in figure 3e of the specification, and is kept stand in a baking oven at 50 ℃ for 4 hours, and the elastic body flexible energy absorption system is prepared after being taken out and cooled. Taking part of the flexible energy absorption system material, preparing the material into a sample with the thickness of 1cm, and performing an impact test according to an EN1621-2012 standard method to obtain a transmitted impact force of 9.1 kN. The flexible energy absorption system can be prepared into an elastic gasket with good damping and buffering performance for damping, the effect of automatic repair can be realized when the elastic gasket is damaged and cracked, and meanwhile, the color of the elastic gasket can be changed when the elastic gasket is subjected to impact force, so that the effect of warning or attractiveness is achieved.
Example 17
Figure BDA0002376545090002421
1.1 molar equivalent of polyethylene glycol (with the molecular weight of 800Da) and 1 molar equivalent of a compound (a) are taken and placed in a reaction container, a proper amount of tetrahydrofuran is used for dissolving, then 1 molar equivalent of 4-dimethylaminopyridine and 4 molar equivalents of dicyclohexylcarbodiimide are added, stirring reaction is carried out at room temperature for 24 hours, then 0.5 molar equivalent of n-butyric acid is added, reaction is continued for 12 hours, and impurities and solvents are removed after the reaction is finished, so that a dynamic polymer containing a dynamic covalent bond based on a reversible free radical is obtained; taking 100 molar equivalents of 2-methoxyethyl methacrylate, 40 molar equivalents of a compound (b), 20 molar equivalents of 2-naphthyl acrylate, 3.5 molar equivalents of methylene bisacrylate and 0.25 molar equivalents of azobisisobutyronitrile, placing the materials in a reaction vessel, recording the mass of the reaction materials as 100 wt%, dissolving the materials in a proper amount of tetrahydrofuran, adding 100 wt% of the prepared dynamic polymer, stirring and dissolving the materials, reacting the materials at 70 ℃ for 24 hours under a nitrogen atmosphere, placing the product in a mold with an inward concave angle structure shown in the figure 3h of the specification after the reaction is finished, and carrying out heat preservation and drying for 6 hours in a vacuum oven at 110 ℃ to obtain the dilatant polymer elastomer flexible energy-absorbing system after cooling. A part of flexible energy absorption system material is prepared into a sample with the thickness of 1cm, and the impact test is carried out according to the EN1621-2012 standard method, and the transmitted impact force is measured to be 16.3 kN. The flexible energy absorption system has the advantages that the flexible energy absorption system has common covalent crosslinking, crystallization caused by hydrogen bond action and strong dynamic pi-pi stacking action, and can provide better mechanical strength and toughness for the flexible energy absorption system. The flexible energy absorption system in the embodiment has a glass transition temperature of 20 ℃, and dynamic polymers containing strong dynamic covalent bonds are dispersed in the flexible energy absorption system, so that the flexible energy absorption system shows stable dilatancy and slow rebound resilience from 0 ℃ to room temperature. The material can be used as an industrial protective material for shock absorption and noise reduction.
Example 18
Figure BDA0002376545090002422
Taking azobisisobutyronitrile as an initiator, taking a compound (a) as a polymerization monomer, taking tetrahydrofuran as a solvent, and preparing the bidentate hydrogen bond crosslinked dynamic polymer through free radical polymerization. Dissolving 180 molar equivalents of 2- (2-phenoxyethoxy) ethyl acrylate, 0.12 molar equivalent of the compound (a) and 1 molar equivalent of pentamethyldiethylenetriamine with a proper amount of tetrahydrofuran, introducing nitrogen, bubbling, deoxidizing for 30min, adding 1 molar equivalent of cuprous bromide, stirring and reacting for 48h at 80 ℃ in an argon atmosphere, and purifying to obtain a bromine-terminated multi-arm acrylate homopolymer after the reaction is finished; taking a bromine-terminated multi-arm acrylate homopolymer with 4 molar equivalents, a compound (c) with 2 molar equivalents and pentaerythritol tetrakis (3-mercaptopropionate) with 2 molar equivalents, putting the materials into a reaction vessel, recording the mass of the reactants as 100 wt%, dissolving the reactants with a proper amount of dimethylformamide, adding 40 wt% of bidentate hydrogen bond crosslinked dynamic polymer and 36 molar equivalents of pyridine catalyst, stirring and reacting for 12 hours under a nitrogen atmosphere, and removing impurities and solvents after the reaction is finished to obtain a purified product; and putting 45g of the purified product, 1.5g of zinc acetate and 25g of PMMA particles (the particle size is 2.5 microns) into a reaction container, adding 70g of glycerol, and putting the reactants into a mold with an inward concave angle structure shown in figure 3k of the specification for full swelling to obtain the dilatant polymer organogel flexible energy absorption system. Taking part of the flexible energy absorption system material, preparing the material into a sample with the thickness of 1cm, and performing an impact test according to an EN1621-2012 standard method to obtain a transmitted impact force of 7.3 kN. The glass transition temperature of the flexible energy absorption system is 10 ℃, and the dynamic cross-linked state polymer with strong dynamic property is dispersed in the flexible energy absorption system, so that the flexible energy absorption system can well maintain the dilatancy at the low temperature of 0 ℃. When the gel cracks, the crack can be repaired through the dynamic reversibility of hydrogen bonds contained in the gel and exchangeable acyl bonds with binding property. The flexible energy absorption system in the embodiment can be used as an automobile damping material, and can effectively damp and absorb shock based on the wavy dilatancy, dynamic dilatancy and dispersive dilatancy of gel, so that the automobile can run stably and is comfortable to ride.
Example 19
Figure BDA0002376545090002431
Taking 40 molar equivalents of a mesogen-like compound (a), 1 molar equivalent of tetramethylpiperidine oxynitride and 0.4 molar equivalent of benzoyl peroxide, placing the reactants in a reaction vessel, dissolving the reactants with a proper amount of dimethylbenzene, then reacting at 90 ℃ for 3 hours under a nitrogen atmosphere, heating to 120 ℃ for reacting for 15 hours, and purifying to obtain a liquid crystal homopolymer after the reaction is finished; and then taking a liquid crystal homopolymer as a macromolecular chain transfer agent, taking p-xylene as a solvent, taking n-octyl acrylate as a soft segment monomer, wherein the molar ratio of the chain transfer agent to the soft segment monomer is 1:160, and reacting for 18 hours at 120 ℃ under a nitrogen atmosphere to obtain the block copolymer. Taking 60 molar equivalent of n-octyl acrylate, 12 molar equivalent of 2- (isopropylamino) ethyl acrylate and 0.4 molar equivalent of benzoyl peroxide, putting the materials into a reaction vessel, dissolving the materials by using a proper amount of tetrahydrofuran, then reacting for 16h at 70 ℃ under a nitrogen atmosphere, and purifying to obtain the acrylate copolymer containing a dentate hydrogen bond group after the reaction is finished. Taking 120 molar equivalent of n-octyl acrylate, 5 molar equivalent of a compound (b), 1 molar equivalent of methylene bisacrylamide and 0.8 molar equivalent of benzoyl peroxide, placing the materials in a reaction container, recording that the mass of the reaction materials is 100 wt%, dissolving the materials in proper amount of toluene, adding 60 wt% of block copolymer and 15 wt% of acrylate copolymer containing a dentate hydrogen bond group, stirring and mixing for 30min, reacting for 24h at 70 ℃ under nitrogen atmosphere, placing the product in a mold with an inward concave angle structure shown in figure 3k of the specification after the reaction is finished, and drying for 12h in a vacuum oven at 60 ℃ to obtain the dilatant polymer elastomer flexible energy absorption system. Taking part of the flexible energy absorption system material, preparing the material into a sample with the thickness of 1cm, and performing an impact test according to an EN1621-2012 standard method to obtain a transmitted impact force of 8.5 kN. The flexible energy absorption system has two glass transition temperatures of-15 ℃ and 40 ℃, and the polymer contains strong dynamic covalent cross-linking and is dispersed with strong dynamic polymer, and has dilatancy in a relatively wide temperature range. When the flexible energy absorption system has local cracks, local repair can be realized based on the reversible characteristic of the contained dynamic structure, and the service life of the material is prolonged. The flexible energy absorption system in the embodiment can be used as a shock absorption sealing material, such as a sealing rubber strip in a deep sea detector and a spacecraft, and can effectively absorb shock and seal within a wider temperature range.
Example 20
Figure BDA0002376545090002432
Taking 160 molar equivalent of hexyl methacrylate, 2 molar equivalent of methylene diacrylates, 1 molar equivalent of the compound (a) and 1.2 molar equivalent of azodiisobutyronitrile, placing the materials in a reaction vessel, dissolving the materials with a proper amount of dimethylformamide, placing reactants in a mold with an inward concave angle structure shown in the attached figure 3o of the specification, and then reacting for 36 hours at 70 ℃ under a nitrogen atmosphere to prepare the dilatant polymer organogel flexible energy absorption system. A part of flexible energy absorption system material is prepared into a sample with the thickness of 1cm, and the impact test is carried out according to the EN1621-2012 standard method, and the transmitted impact force is measured to be 9.7 kN. The glass transition temperature of the flexible energy absorption system is-5 ℃, when the temperature is reduced to 0 ℃, the flexible energy absorption system still cannot be hardened, good low-temperature dilatancy is kept, the flexible energy absorption system can be used as a protective tool for energy absorption and shock absorption, and the flexible energy absorption system can also play an energy absorption and protection role even in cold use scenes such as winter in the north.
Example 21
Figure BDA0002376545090002441
20 molar equivalents of the compound (b), 1 molar equivalent of the compound (c) and 0.5 molar equivalent of polyethylene glycol (molecular weight 2000Da) were placed in a reactor, and stirred uniformly with methylene chloride as a solvent, and then 0.01 molar equivalent of N, N-diisopropylcarbodiimide and 0.01 molar equivalent of diphenyl-4-phenylthiophenylthionium salt were added, and stirred at room temperature for 24 hours. After the reaction is finished, pouring the reaction liquid into a mould, and removing the solvent to obtain the polysiloxane crosslinked particles. Taking 1 molar equivalent of a compound (a), 10 molar equivalents of a compound (b), 0.5 molar equivalent of a compound (c) and 5 molar equivalents of polysiloxane crosslinked particles, putting the mixture into a reactor, taking dichloromethane as a solvent, stirring and mixing the mixture uniformly, adding 0.01 molar equivalent of bis (acetylacetone) di-N-butyltin, 0.01 molar equivalent of N, N-diisopropylcarbodiimide, 0.01 molar equivalent of diphenyl-4-thiophenyl phenyl sulfonium salt and 0.5 molar equivalent of dimethyl siloxane into the reactor, continuing to react for 12 hours at 50 ℃, pouring the reaction liquid into a mold with an inward concave angle structure shown in the attached figure 3t of the specification, and removing the solvent to obtain the polysiloxane elastomer flexible energy-absorbing system. Taking part of the flexible energy absorption system material, preparing the material into a sample with the thickness of 1cm, and performing an impact test according to an EN1621-2012 standard method to obtain a transmitted impact force of 5.9 kN. When the flexible energy absorption system is stretched or compressed, the color of a deformation area can be changed into red, the flexible energy absorption system has a sensitive stress response effect, and also has good toughness and elasticity, the damaged and cracked area can automatically recover within 2 hours at 80 ℃, and the flexible energy absorption system has certain self-repairing capability; the energy-absorbing and shock-absorbing material with the stress warning effect can be made into a material for absorbing shock.
Example 22
Figure BDA0002376545090002442
In N2Adding 1 molar equivalent of hexanediol, 8 molar equivalent of MDI, 1 molar equivalent of compound (e) and 0.1 molar equivalent of DABCO into a reaction bottle under the atmosphere, stirring for 10 minutes by taking tetrahydrofuran as a solvent, adding 5 molar equivalent of polyethylene glycol (with the molecular weight of 700Da) and 0.1 molar equivalent of tris (hydroxymethyl) ethane, continuing to react for 2 hours, adding 1 molar equivalent of compound (c) and 1 molar equivalent of compound (d), uniformly stirring, pouring the reaction liquid into a mold with an inward concave angle structure shown in the attached figure 1a of the specification, continuing to react for 48 hours, and observing that the reaction liquid is gradually gelatinized to prepare the flexible energy-absorbing system for the polyurethane elastomer. A part of flexible energy absorption system material is prepared into a sample with the thickness of 1cm, and an impact test is carried out according to the EN1621-2012 standard method, and the transmitted impact force is measured to be 11.4 kN. Scratches on the surface of the flexible energy absorption system can be automatically recovered after a period of time; when the flexible energy-absorbing system is stressed and compressed, the polymer can release furan micromolecules, the self-degradation of a polymer material can be promoted, the flexible energy-absorbing system can be made into an energy-absorbing material with a force-induced catalytic degradation effect for use, and the flexible energy-absorbing system can be used for environment-friendly materials.
Example 23
Figure BDA0002376545090002443
Dissolving 1 molar equivalent polycaprolactone diol (molecular weight of 1200Da), 1 molar equivalent polycaprolactone diol (molecular weight of 830Da), 2 molar equivalent 1, 4-butanediol and 2 molar equivalent compound (a) in a proper amount of toluene, adding 7.5 molar equivalent diphenylmethane diisocyanate, uniformly mixing, adding a small amount of stannous octoate catalyst, stirring and reacting at 35 ℃ for 8 hours under a nitrogen atmosphere, adding 1 molar equivalent tri (2-hydroxyethyl) amine, continuously reacting for 12 hours, adding 5 wt% of talcum powder and 10 wt% of recycled rubber particles, uniformly mixing, placing a product into a mold with an inward concave angle structure shown in the specification attached figure 1a, and drying in a vacuum oven at 80 ℃ to finally obtain the flexible energy absorption system for the dilatant polymer elastomer. The flexible energy absorption system has two glass transition temperatures of-40 ℃ and 25 ℃ respectively, and shows low-temperature dilatancy. Taking part of the flexible energy absorption system material, preparing the material into a sample with the thickness of 1cm, and performing an impact test according to an EN1621-2012 standard method to obtain a transmitted impact force of 7.1 kN. The flexible energy absorption system has good slow rebound resilience and good tactile texture at room temperature. The saturated five-membered ring inorganic borate ester bond with strong dynamic property in the flexible energy absorption system can enhance dilatancy, slow resilience and quick self-repairing performance, can be used as a shoe material, can buffer while providing comfort, and avoids ankle and knee injuries.
Example 24
In a torque rheometer, natural rubber is used as a matrix, benzoyl peroxide is used as an initiator, N-vinyl imidazole and styrene are used as grafting monomers, and a double-monomer melt grafting technology is adopted to prepare the modified ethylene propylene diene monomer, wherein the mass ratio of the natural rubber to the benzoyl peroxide to the N-vinyl imidazole to the styrene is 100:0.8:15:10, the reaction temperature is 135 ℃, the reaction time is 30min, and the rotor rotation speed is 45 r/min. Taking 75 parts by mass of modified natural rubber, 25 parts by mass of butadiene rubber, 5 parts by mass of zinc chloride, 10 parts by mass of white carbon black, 7.5 parts by mass of antimony trioxide, 15 parts by mass of decabromodiphenyl ether and 4 parts by mass of triallyl cyanurate, mixing for 15min at 100 ℃ on a double-roll open mill, standing the mixed rubber material for 24h, then returning to the same temperature for 5min, then placing the obtained material piece in a transparent mould with an inward-concave angle structure shown in figure 1c of the specification at 130 ℃, and placing the transparent mould in a 60Co gamma radiation field for 6h at room temperature to obtain the dilatant polymer elastomer flexible energy absorption system. Taking part of the flexible energy absorption system material, preparing the material into a sample with the thickness of 1cm, and performing an impact test according to an EN1621-2012 standard method to obtain a transmitted impact force of 5.8 kN. The flexible energy absorption system has low glass transition temperature and also has a tooth metal-ligand effect, so that the flexible energy absorption system has good low-temperature dilatancy and rebound resilience, and can be used as a damping and energy-absorbing part for damping and shock absorption.
Example 25
The stannous octoate is used as a catalyst, and the aminopropyl methyl siloxane-dimethyl siloxane copolymer reacts with excessive isopropyl isocyanate to prepare the polysiloxane containing the carbamido hydrogen bond group. Placing 60 parts by mass of brominated butyl rubber, 40 parts by mass of fluororubber raw rubber and 25 parts by mass of polysiloxane containing urea-based hydrogen bond groups in a two-roll open mill for mixing, then sequentially adding 15 parts by mass of carbon black, 4.5 parts by mass of mica, 4 parts by mass of carbon nano tube, 5 parts by mass of sulfur, 5 parts by mass of zinc oxide, 2 parts by mass of 2,2' -dithiodibenzothiazole, 0.8 part by mass of tetramethyl thiuram disulfide, 2 parts by mass of terpene resin and 2 parts by mass of liquid paraffin, and continuously mixing to obtain a mixed rubber sheet; placing the mixed rubber sheet on a molding press for hot press molding, cutting and cutting, and realizing pre-vulcanization in the hot press molding process to obtain a plate-shaped rubber blank with the size of 100 multiplied by 6 mm; placing the rubber blank into a foaming mould of mould pressing foaming equipment, wherein the volume ratio of a cavity of the foaming mould to the volume of the rubber blank is 3:1, filling carbon dioxide into the foaming mould after hydraulic mould closing, controlling the temperature in the foaming mould to be 75 ℃ and the pressure to be 15MPa, keeping the temperature and the pressure for 30min, fully swelling the rubber blank, then releasing the pressure, foaming the swollen rubber blank in a mould with an inward concave angle structure shown in the attached figure 1p of the specification, opening the mould after complete foaming, and taking out the obtained pre-vulcanized rubber foaming material; and (3) placing the pre-vulcanized rubber foaming material in a hot drying tunnel at 168 ℃ for 4h for post-vulcanization, then taking out and cooling to room temperature to obtain the dilatant polymer foam flexible energy absorption system. Taking part of the flexible energy absorption system material, preparing the material into a sample with the thickness of 1cm, and performing an impact test according to an EN1621-2012 standard method to obtain a penetrating impact force of 12.2 kN. The flexible energy absorption system is small in molding shrinkage and free of buckling deformation. The prepared flexible energy absorption system has a uniform cell structure, the average cell size is 158 micrometers, and the cell structure contains small-sized open pores, so that under the energy impact, the energy absorption system can absorb energy based on the vitrification dilatancy and dynamic dilatancy and can also obtain an additional energy absorption effect based on the aerodynamic dilatancy. The flexible energy absorption system of the embodiment can be used as a bumper material to resist impact.
Example 26
Figure BDA0002376545090002451
Using triethylamine as a catalyst, and carrying out condensation reaction on equimolar [ (1E) -6-hydroxy-1-hexene-1-yl ] boric acid and 3- (2-hydroxyethoxy) propane-1, 2-diol at 50 ℃ to prepare the borate compound (b). Weighing 5mmol of polyetheramine D2000 in a dry clean flask, heating to 100 ℃, introducing nitrogen to remove water and remove oxygen for 1h, then adding 0.02mol of diphenylmethane diisocyanate, reacting for 2 hours under the protection of nitrogen at the temperature of 80 ℃, then cooling to 60 ℃, adding 8mmol of N- (2, 3-dihydroxypropyl) maleimide, a proper amount of triethylamine and 0.5 wt% of stannous octoate, continuing to react for 4 hours, then adding 5mmol of cyclobutane compound (a), 8mmol of borate compound (b), 5 wt% of carbon fiber, 5 wt% of graphene nanosheet and 5 wt% of talcum powder, continuing to react for 1h, after the reaction is finished, the polymer sample is placed in a mould with an open-pore inner corner structure as shown in the specification, figure 2b, is placed in a vacuum oven to be dried for 24h, and then cooling to room temperature to finally obtain the polyurethane-based elastomer flexible energy absorption system with high elasticity. Taking part of the flexible energy absorption system material, preparing the material into a sample with the thickness of 1cm, and performing an impact test according to an EN1621-2012 standard method to obtain a transmitted impact force of 6.3 kN. In the embodiment, because the flexible energy absorption system polymer has force sensitive groups, dynamic covalent bonds and skeleton supramolecular hydrogen bonds, a stress-strain curve fluctuates along with the increase of the elongation rate in the stretching process, because the force-induced crosslinking is spontaneously generated in the polymer during stretching, the mechanical property of the material is improved, and different stretching effects and self-repairing capabilities can be expressed under the conditions of normal temperature and heating. The anti-collision energy-absorbing component with self-repairing performance can be made into the anti-collision energy-absorbing component for use, and the service life of the material is prolonged.
Example 27
Figure BDA0002376545090002461
The linear polyurethane containing bidentate ligand groups is prepared by taking stannous octoate as a catalyst and reacting polyoxypropylene diol, 4 '-bis (hydroxymethyl) -2,2' -bipyridyl and isophorone diisocyanate in a molar ratio of 0.8:1.2: 2. Adding 100 parts by mass of ethylene-vinyl acetate copolymer, 50 parts by mass of linear polyurethane containing bidentate ligand groups, 10 parts by mass of compound (a), 8 parts by mass of solid paraffin, 4 parts by mass of stearic acid, 5 parts by mass of zinc chloride, 1.2 parts by mass of dicumyl peroxide, 6 parts by mass of melamine, 3 parts by mass of aluminum nitride, 1.6 parts by mass of nano titanium dioxide, 0.5 part by mass of antioxidant TBHQ and 0.5 part by mass of light stabilizer 770 into an extruder, and uniformly mixing at 90 ℃ to obtain a rubber compound; molding the rubber compound through an extruder die, placing the rubber compound sheet on a molding press for hot press molding, cutting and cutting, and realizing pre-vulcanization in the hot press molding process to obtain a plate-shaped rubber blank with the size of 400 multiplied by 100 multiplied by 12 mm; placing the rubber blank into a foaming mold of a mold pressing foaming device with an open-pore inward-concave angle structure shown in the attached figure 2d of the specification, wherein the volume ratio of a cavity of the foaming mold to the rubber blank is 4:1, filling butane into the foaming mold after hydraulic mold closing, controlling the temperature in the foaming mold to be 55 ℃ and the pressure to be 6MPa, keeping the temperature and the pressure for 60min, fully swelling the rubber blank, then releasing the pressure and opening the mold, ejecting and foaming the swollen rubber blank to obtain pre-vulcanized rubber foam; and finally, preserving the heat in a vacuum oven at 90 ℃ for 60min, and vulcanizing and crosslinking to obtain the dilatant polymer foam flexible energy absorption system. A part of flexible energy absorption system material is prepared into a sample with the thickness of 1cm, and the impact test is carried out according to the EN1621-2012 standard method, and the transmitted impact force is measured to be 7.6 kN. The flexible energy absorption system is dispersed with a crosslinked dynamic polymer under the actions of bidentate metal-coordination and bidentate hydrogen bonds, so that the flexible energy absorption system is endowed with better room-temperature dilatancy and room-temperature slow resilience. The prepared flexible energy absorption system has a uniform cell structure, the average cell size is 155 mu m, and the cell structure contains small-sized open pores, so that under the energy impact, the energy absorption system can absorb energy based on the vitrification dilatancy and the dynamic dilatancy and can also obtain an additional energy absorption effect based on the aerodynamic dilatancy. The flexible energy absorption system in the embodiment also has the advantages of light weight, wear resistance, oil resistance, bacteria resistance, low permanent deformation rate and the like, and can be used as a high-grade shoe material with self-repairing performance for buffering and damping.
Example 28
Figure BDA0002376545090002462
1 molar equivalent of the compound (a) and 10 molar equivalents of the compound (c) are placed in a reactor, dichloromethane is used as a solvent, the mixture is stirred uniformly, 0.01 molar equivalent of N, N-diisopropylcarbodiimide and 0.01 molar equivalent of diphenyl-4-thiophenyl phenyl sulfonium salt are added, and the mixture is stirred and reacted for 24 hours at room temperature to prepare a product 1. And (3) adding 10 molar equivalents of the compound (c), 1 molar equivalent of the compound (b) and 1 molar equivalent of the compound (d) into another reactor, taking dichloromethane as a solvent, uniformly stirring, adding 0.01 molar equivalent of N, N-diisopropylcarbodiimide, 0.01 molar equivalent of diphenyl-4-phenylthiophenyl sulfonium salt and tri-N-propylphosphine, uniformly stirring, adding the product 1, continuously stirring at room temperature for reacting for 24 hours, pouring the reaction liquid into a die with an open-hole inward concave angle structure shown in figure 2g of the specification, and removing the solvent to obtain the polysiloxane elastomer flexible energy absorption system. A part of flexible energy absorption system material is prepared into a sample with the thickness of 1cm, and the impact test is carried out according to the EN1621-2012 standard method, and the transmitted impact force is measured to be 13.4 kN. After the flexible energy absorption system is pulled to a certain elongation, the color of the polymer gradually turns into red, the polymer is heated, the shape of the polymer is fixed, the flexible energy absorption system is stretched again, then the stress is released quickly, the original shape is recovered, and the flexible energy absorption system has a shape memory effect; meanwhile, when the tensile strength is measured, the stress-strain curve fluctuates, which shows that a force-induced crosslinking reaction occurs inside the flexible energy absorption system, and scratches on the surface of the flexible energy absorption system can be automatically compounded after the flexible energy absorption system is heated to 80 ℃ for a period of time, so that the flexible energy absorption system has self-repairing performance. Based on the above-mentioned diversity of properties, the energy-absorbing compliance system can be cushioned as an elastomeric gasket, which has good sealing and durability properties.
Example 29
Figure BDA0002376545090002471
Dissolving 120 molar equivalent of ethyl acrylate, 20 molar equivalent of hydroxyethyl acrylate, 0.12 molar equivalent of compound (a) and 1 molar equivalent of pentamethyldiethylenetriamine with a proper amount of tetrahydrofuran, introducing nitrogen, bubbling, deoxidizing for 30min, adding 1 molar equivalent of cuprous bromide, stirring and reacting for 48h at 80 ℃ in an argon atmosphere, and purifying to obtain the bromine-terminated multi-arm acrylate homopolymer after the reaction is finished; taking 1 molar equivalent of bromine-terminated multi-arm acrylate homopolymer and 4 molar equivalents of compound (b), dissolving the materials in a proper amount of dimethylformamide, adding 12 molar equivalents of pyridine catalyst, stirring and reacting for 12 hours under a nitrogen atmosphere, and preparing a modified homopolymer 1 after the reaction is finished; taking 1 molar equivalent of bromine-terminated multi-arm acrylate homopolymer and 4 molar equivalents of compound (C), dissolving the materials in a proper amount of dimethylformamide, adding 12 molar equivalents of pyridine catalyst, stirring and reacting for 12 hours under a nitrogen atmosphere, and preparing a modified homopolymer 2 after the reaction is finished; and then 1 molar equivalent of bromine-terminated multi-arm acrylate homopolymer, 0.5 molar equivalent of modified homopolymer 1, 0.5 molar equivalent of modified homopolymer 2 and 1 molar equivalent of pentaerythritol tetrakis (3-mercaptopropionate) are taken, the materials are dissolved in a proper amount of dimethylformamide, then 36 molar equivalent of pyridine catalyst is added, the mixture is stirred and reacts for 12 hours under a nitrogen atmosphere, after the reaction is finished, the obtained product is placed in a mold with an open-hole inner concave angle structure shown in figure 2g of the specification, and is dried for 48 hours in a vacuum oven at 60 ℃, so that the dilatant polymer elastomer flexible energy-absorbing system with an interpenetrating network structure is obtained. A part of flexible energy absorption system material is prepared into a sample with the thickness of 1cm, and the impact test is carried out according to the EN1621-2012 standard method, and the transmitted impact force is measured to be 17.5 kN. The glass transition temperature of the flexible energy absorption system is-23 ℃, the low-temperature dilatancy can be well maintained, and no obvious hardening is needed even in the low temperature range of-20 ℃ to-5 ℃. The flexible energy absorption system also has a good thermotropic shape memory function, and can better meet the requirements of individual users. The flexible energy absorption system in the embodiment can be used as an automobile impact-resistant part, so that the safety of personnel and articles is guaranteed.
Example 30
Figure BDA0002376545090002472
Weighing 1 molar equivalent of the compound (a) and 1 molar equivalent of the compound (b), putting the compound (a) and the compound (b) into a reaction bottle, adding 1 molar equivalent of 1, 2-dibromoethane and 10 molar equivalents of potassium carbonate into DMF (dimethyl formamide) serving as a solvent, stirring the mixture for reaction for 24 hours, and removing the solvent to obtain a product 1. Adding 50 parts by mass of polytetramethylene glycol with the molecular weight of 2500Da, 7 parts by mass of product 1, 0.05 part by mass of diethyl toluene diamine (DETDA), 0.02 part by mass of organic silicone oil, 3 parts by mass of glass fiber, 3 parts by mass of nano talcum powder, 2 parts by mass of hollow glass microsphere, 0.5 part by mass of N-ethyl morpholine, 3 parts by mass of 1, 2-dibromoethane and 10 parts by mass of potassium carbonate into a reactor, stirring, dissolving and mixing uniformly by taking DMF as a solvent, continuing stirring and reacting for 24 hours, placing reaction liquid into a mold with an inward concave angle structure shown in figure 3a of the specification, and drying for 24 hours in a vacuum oven at 50 ℃ to obtain the flexible expansion system of the energy-absorbing fluid polymer. Taking part of the flexible energy absorption system material, preparing the material into a sample with the thickness of 1cm, and performing an impact test according to an EN1621-2012 standard method to obtain a transmitted impact force of 13.2 kN. Under different states of stress and relaxation, the polymer has different fluorescent colors, can be used for bearing indication glue, and warns through color change and fluorescent change when a certain energy load is exceeded.
Example 31
Figure BDA0002376545090002481
Weighing 1 molar equivalent of the compound (b) and 2 molar equivalents of the compound (d), putting the mixture into a reactor, taking dichloromethane as a solvent, adding 0.02 molar equivalent of N, N-diisopropylcarbodiimide and 0.02 molar equivalent of diphenyl-4-thiophenyl phenyl sulfonium salt, stirring the reaction system at room temperature for 24 hours, and removing the solvent to obtain a product 1. An aqueous solution of 0.2 molar equivalents of sodium ascorbate and 0.2 molar equivalents of copper sulfate pentahydrate was added to a solution of 2 molar equivalents of product 1 and 1 molar equivalent of compound (c) in dichloromethane. The mixture was stirred at room temperature overnight under nitrogen. Then, methylene chloride and water were added to the above solution, and a methylene chloride layer was separated, washed twice with water, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain product 2. Adding 0.1 molar equivalent of the product 2, 0.05 molar equivalent of 1, 4-butanediol, 0.01 molar equivalent of triethylamine and 0.2 molar equivalent of a sensitizer compound (a) into a reactor, uniformly mixing, adding 0.1 molar equivalent of polyethylene glycol with single-ended isocyanate with the molecular weight of 1200Da, heating to 60 ℃, reacting for 2 hours, placing reactants into a mold with an inward concave angle structure shown in the attached figure 3b of the specification, and drying in a vacuum oven at 50 ℃ for 24 hours to obtain the dilatant polymer flexible energy absorption system. A part of flexible energy absorption system material is prepared into a sample with the thickness of 1cm, and an impact test is carried out according to the EN1621-2012 standard method, and the transmitted impact force is measured to be 11.5 kN. In the relaxed state, it emits yellow fluorescence at 580nm when irradiated with 550nm light, and emits red fluorescence at 660nm when pressed by force, when irradiated with 550nm light. It can be used as an impact stress detection material.
Example 32
Figure BDA0002376545090002482
NaYF coated with 1 molar equivalent of silica4:Yb,Er@CaF2Up-conversion nanopowder (120mg) and 4 molar equivalents of the spiropyran compound (a)Disperse in sufficient ethyl acetate and stir the resulting pale purple solution at room temperature for 24 h. After centrifugation and washing, product 1 was obtained. Adding 1 molar equivalent of the product 1, 0.5 molar equivalent of 1, 4-butanediol and 0.1 molar equivalent of triethylamine into a reactor, uniformly mixing, adding MDI prepolymer with molecular weight of 3500Da of 0.1 molar equivalent, heating to 60 ℃, reacting for 2h, placing reactants into a mold with an inward concave angle structure shown in figure 3h of the specification, and drying in a vacuum oven at 50 ℃ for 24h to obtain the flexible energy absorption system with the dilatant polymer. Taking a part of flexible energy absorption system material, preparing the material into a sample with the thickness of 1cm, and performing an impact test according to an EN1621-2012 standard method to obtain a penetrating impact force of 9.3 kN. In a relaxed state, 980nm infrared light irradiates the flexible energy absorption system to emit yellow fluorescence, when the flexible energy absorption system is stressed and extruded, 980nm infrared light irradiates the flexible energy absorption system to emit red fluorescence, different up-conversion fluorescence colors are realized in different stress states, and the flexible energy absorption system can be used as a logic control material of impact stress.
Example 33
Figure BDA0002376545090002483
Reacting 1 molar equivalent of the compound (a) with 1 molar equivalent of methyl acrylate to prepare a product 1; reacting 1 molar equivalent of 5-hydroxy-beta-cyclodextrin with 1 molar equivalent of methyl acrylate to prepare a product 2; dissolving the product 1 and the product 2 in a toluene solution, enabling cyclodextrin in the product 2 to form a host-guest action with spirothiopyran in the product 1, then using propanetrithiol as a cross-linking agent to carry out cross-linking, simultaneously adding a proper amount of zinc chloride, placing the pre-cross-linked polymer in a mould with an inward concave angle structure shown in the attached figure 3k of the specification, and swelling for 12 hours to obtain the dilatant polymer elastomer flexible energy absorption system. Taking part of the flexible energy absorption system material, preparing the material into a sample with the thickness of 1cm, and performing an impact test according to an EN1621-2012 standard method to obtain a transmitted impact force of 9.2 kN. When the energy absorption system is not impacted, the energy absorption system is in a common transparent gel state, when the energy absorption system is stressed, the energy absorption system firstly shows the characteristic of dilatancy, after the energy absorption system is continuously stressed, the system starts to change color and gradually becomes red, meanwhile, the mechanical property of the system is obviously improved, and based on the stage force response characteristic, the energy absorption system can be used for a cushion pad to play a role in energy absorption and warning.
Example 34
Figure BDA0002376545090002491
The dihydroxy compound (b) is prepared by dissolving the compound (a) and N- (2-hydroxyethyl) maleimide as raw materials in a toluene solvent, heating to 80 ℃, and stirring for 24 hours.
Adding 100 parts by mass of polyether polyol ED-28 (hydroxyl value is 26.5-29.5) into a reactor, heating to 80 ℃, then adding 5 parts by mass of 3-amino-1, 2-propylene glycol, 15 parts by mass of epoxidized soybean oil, 1 part by mass of KH550, 70 parts by mass of kaolin, 2 parts by mass of glass fiber, 1 part by mass of fumed silica, 4 parts by mass of UV-531, 10 parts by mass of pentachlorophenol and 2 parts by mass of dibutyltin dilaurate, sequentially adding 11 parts by mass of the compound (b), 10 parts by mass of MDI, 4 parts by mass of the compound (c), 20 parts by mass of MDI, 7 parts by mass of the compound (d) and 20 parts by mass of MDI at a time interval of 3min, uniformly mixing, placing the mixed solution in a mold with an inward concave angle structure shown in figure 3o of the specification, standing for 4 hours in a baking oven at 50 ℃, taking out and cooling to obtain the dilatant polymer elastomer flexible energy absorption system. A part of flexible energy absorption system material is prepared into a sample with the thickness of 1cm, and the impact test is carried out according to the EN1621-2012 standard method, and the transmitted impact force is measured to be 10.3 kN. When the flexible energy absorption system is impacted, the stressed area of the flexible energy absorption system turns red, the shape of the flexible energy absorption system is memorized into a stressed shape, the shape of the flexible energy absorption system can be recovered by releasing pressure after being stressed again, the flexible energy absorption system has good energy absorption effect and shape memory function, and the flexible energy absorption system can be used in the fields of buffering, warning and the like.
Example 35
Figure BDA0002376545090002492
Weighing 1 molar equivalent of polyacrylic acid (molecular weight is 1000) in a dry clean flask, heating to 100 ℃, introducing nitrogen to remove water and remove oxygen for 1h, adding 0.01 molar equivalent of N, N-diisopropylcarbodiimide and 0.01 molar equivalent of diphenyl-4-thiophenyl phenyl sulfonium salt, then adding 0.1 molar equivalent of 1, 10-decanediol, 0.1 molar equivalent of compound (a), 0.2 molar equivalent of methanol, 5 wt% of vegetable fiber, 5 wt% of barium sulfate and 5 wt% of talcum powder, continuing to react for 1h, after the reaction is finished, placing a polymer sample in a mold with an inward concave angle structure shown in figure 3k of the specification, placing the polymer sample in a vacuum oven to dry for 24h, and then cooling to room temperature to finally obtain the flexible energy absorption system for the fluid polymer elastomer. Taking part of the flexible energy absorption system material, preparing the material into a sample with the thickness of 1cm, and performing an impact test according to an EN1621-2012 standard method to obtain a transmitted impact force of 12.1 kN. In general, when the flexible energy absorption system is irradiated by a light source with the wavelength of 470nm, red fluorescence is emitted; and after the stress is applied, the 470nm light source is used for irradiating the flexible energy absorption system, the fluorescence disappears, and the phenomenon of energy transfer occurs. By utilizing this phenomenon, the flexible energy absorbing system can be used for stress absorption and detection.

Claims (6)

1. A flexible energy absorbing system having a reentrant corner structure, comprising adjacent apertures having at least one side open to a surface along a thickness direction of the system and having a reentrant corner structure; comprising at least one polymer matrix material having dilatancy properties.
2. The energy absorbing system according to claim 1, wherein the energy absorbing system has one of the following configurations:
the flexible energy absorption system comprises adjacent holes, at least one side of each hole is open to the surface along the thickness direction of the system, and the hole is provided with an inner concave angle structure; wherein the matrix material of the open-cell walls contains an intrinsic dilatant polymer;
the flexible energy absorption system comprises adjacent holes, at least one side of each hole is open to the surface along the thickness direction of the system, and the hole is provided with an inner concave angle structure; the base material of the pore wall of the open pore contains an intrinsic dilatant polymer, and the dilatant polymer is a vitreous dilatant polymer;
the flexible energy absorption system comprises adjacent holes, at least one side of each hole is open to the surface along the thickness direction of the system, and the hole is provided with an inner concave angle structure; the base material of the pore wall of the open pore contains an intrinsic dilatancy polymer, and the dilatancy polymer is a dynamic dilatancy polymer;
The flexible energy absorption system comprises adjacent holes, at least one side of each hole is open to the surface along the thickness direction of the system, and the hole is provided with an inner concave angle structure; wherein the matrix material of the open pore wall contains an intrinsic dilatancy polymer, and the flexible energy absorption system also contains a dispersive dilatancy polymer;
the flexible energy absorption system comprises adjacent holes, at least one side of each hole is open to the surface along the thickness direction of the system, and the hole is provided with an inner concave angle structure; the flexible energy absorption system comprises a flexible energy absorption system, a flexible energy absorption system and a flexible energy absorption system, wherein a base material of the pore wall of the pore contains an intrinsic dilatant polymer;
the flexible energy absorption system comprises adjacent holes, at least one side of each hole is open to the surface along the thickness direction of the system, and the hole is provided with an inner concave angle structure; wherein the matrix material of the pore wall of the open pore contains an intrinsic dilatant polymer, and the matrix material is a thermoplastic polymer containing a side hydrogen bond function;
the flexible energy absorption system comprises adjacent holes, at least one side of each hole is open to the surface along the thickness direction of the system, and the hole is provided with an inner concave angle structure; wherein the walls of the pores and the matrix material of the walls of the pores contain an intrinsic dilatant polymer, and wherein the matrix material is a hydrogen bond-free supramolecular polymer;
The flexible energy absorption system comprises adjacent holes, at least one side of each hole is open to the surface along the thickness direction of the system, and the hole is provided with an inner concave angle structure; the flexible energy absorption system comprises a flexible energy absorption system, a flexible energy absorption system and a flexible energy absorption system, wherein a base material of the pore wall of the pore contains an intrinsic dilatant polymer, the base material is a thermoplastic polymer containing a side hydrogen bond effect, and the flexible energy absorption system also contains a dispersive dilatant polymer;
the flexible energy absorption system comprises adjacent holes, at least one side of each hole is open to the surface along the thickness direction of the system, and the hole is provided with an inner concave angle structure; wherein the matrix material of the walls of the open pores contains an intrinsic dilatant polymer, and wherein the matrix material is a covalently cross-linked polymer;
the flexible energy absorption system comprises adjacent holes, at least one side of each hole is open to the surface along the thickness direction of the system, and the hole is provided with an inner concave angle structure; wherein the matrix material of the pore walls of the pores contains an intrinsic dilatant polymer, and wherein the matrix material is a dynamic covalent cross-linked polymer;
the flexible energy absorption system comprises adjacent holes, at least one side of each hole is open to the surface along the thickness direction of the system, and the hole is provided with an inner concave angle structure; wherein the matrix material of the pore walls of the pores contains an intrinsic dilatant polymer, and wherein the matrix material is a hybrid covalent cross-linked polymer;
The flexible energy absorption system comprises adjacent holes, at least one side of each hole is open to the surface along the thickness direction of the system, and the hole is provided with an inner concave angle structure; wherein, the matrix material of the hole wall of the open hole contains intrinsic dilatant polymer, and the flexible energy absorption system also contains at least one force sensitive group;
the flexible energy absorption system comprises adjacent holes, at least one side of each hole is open to the surface along the thickness direction of the system, and the hole is provided with an inner concave angle structure; the base material of the pore wall of the open pore contains an intrinsic dilatancy polymer, the dilatancy polymer is a vitreous dilatancy polymer, and the flexible energy absorption system also contains at least one force sensitive group;
the flexible energy absorption system comprises adjacent holes, at least one side of each hole is open to the surface along the thickness direction of the system, and the hole is provided with an inner concave angle structure; the flexible energy absorption system comprises a flexible energy absorption system, a flexible energy absorption system and a flexible energy absorption system, wherein a base material of the pore wall of the pore contains an intrinsic dilatancy polymer, the dilatancy polymer is a dynamic dilatancy polymer, and the flexible energy absorption system also contains at least one force sensitive group;
the flexible energy absorption system comprises adjacent holes, at least one side of each hole is open to the surface along the thickness direction of the system, and the hole is provided with an inner concave angle structure; the flexible energy absorption system also comprises a dispersive dilatancy polymer and at least one force-sensitive group;
The flexible energy absorption system comprises adjacent holes, at least one side of each hole is open to the surface along the thickness direction of the system, and the hole is provided with an inner concave angle structure; the flexible energy absorption system also comprises an aerodynamic dilatancy polymer, and the flexible energy absorption system also comprises at least one force sensitive group;
the flexible energy absorption system comprises adjacent holes, at least one side of each hole is open to the surface along the thickness direction of the system, and the hole is provided with an inner concave angle structure; wherein, the matrix material of the pore wall of the open pore contains an intrinsic dilatant polymer, the matrix material is a thermoplastic polymer containing a side hydrogen bond function, and the flexible energy absorption system also contains at least one force sensitive group;
the flexible energy absorption system comprises adjacent holes, at least one side of each hole is open to the surface along the thickness direction of the system, and the hole is provided with an inner concave angle structure; wherein, the matrix material of the pore walls of the pores contains an intrinsic dilatant polymer, the matrix material is a supramolecular polymer without hydrogen bonds, and the flexible energy absorption system also contains at least one force sensitive group;
The flexible energy absorption system comprises adjacent holes, at least one side of each hole is open to the surface along the thickness direction of the system, and the hole is provided with an inner concave angle structure; the flexible energy absorption system also comprises a dispersive dilatant polymer and at least one force sensitive group;
the flexible energy absorption system comprises adjacent holes, at least one side of each hole is open to the surface along the thickness direction of the system, and the hole is provided with an inner concave angle structure; wherein, the matrix material of the pore wall of the open pore contains an intrinsic dilatant polymer, the matrix material is a covalent cross-linked polymer, and the flexible energy absorption system also contains at least one force sensitive group;
the flexible energy absorption system comprises adjacent holes, at least one side of each hole is open to the surface along the thickness direction of the system, and the hole is provided with an inner concave angle structure; wherein, the matrix material of the pore wall of the open pore contains an intrinsic dilatant polymer, the matrix material is a dynamic covalent cross-linked polymer, and the flexible energy absorption system also contains at least one force sensitive group;
The flexible energy absorption system comprises adjacent holes, at least one side of each hole is open to the surface along the thickness direction of the system, and the hole is provided with an inner concave angle structure; the flexible energy absorption system comprises a flexible energy absorption system, a flexible energy absorption system and a flexible energy absorption system, wherein a base material of the pore wall of the pore contains an intrinsic dilatant polymer, the base material is a hybrid covalent cross-linked polymer, and the flexible energy absorption system also contains at least one force sensitive group.
3. A flexible energy absorbing system with an inward recessed corner structure according to any one of claims 1-2, wherein the energy absorbing structure further comprises a force sensitive component, and the force sensitive component undergoes a chemical and/or physical change under the action of a mechanical force to realize a force-induced response.
4. Energy-absorbing compliant system with fillet structure according to any of claims 1 to 2, characterized in that the formulation components constituting the energy-absorbing compliant system comprise any or any of the following additions/utilizations: auxiliary agent and filler;
wherein, the additive can be selected from any one or more of the following: catalysts, antioxidants, light stabilizers, heat stabilizers, toughening agents, compatilizers, lubricants, mold release agents, plasticizers, foaming agents, antistatic agents, emulsifiers, dispersing agents, colorants, fluorescent whitening agents, delustering agents, flame retardants, nucleating agents, rheological agents, thickeners, leveling agents, antibacterial agents, dynamic modifiers;
Wherein, the filler which can be added is selected from any one or more of the following materials: inorganic non-metallic fillers, organic fillers, organometallic compound fillers.
5. Energy-absorbing compliant system with fillet structure according to any of claims 1 to 2, characterized in that the energy-absorbing compliant system is capable of forming solid structures, layered structures, gradient structures, woven structures and combinations thereof.
6. Energy-absorbing compliant system with fillet structure according to any of claims 1 to 2, characterized in that it is applied for shock protection, cushioning, shock absorption, sound insulation, sound attenuation, explosion protection, shock absorption, damping.
CN202010068049.6A 2020-01-21 2020-01-21 Flexible energy absorption system with concave corner structure Pending CN114001114A (en)

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