CN114086390A

CN114086390A - Epoxidized soybean oil modified collagen fiber and preparation method and application thereof

Info

Publication number: CN114086390A
Application number: CN202111493301.9A
Authority: CN
Inventors: 曾运航; 雷超; 许维星; 石碧; 周继博
Original assignee: Sichuan University
Current assignee: Sichuan University
Priority date: 2021-12-08
Filing date: 2021-12-08
Publication date: 2022-02-25
Anticipated expiration: 2041-12-08
Also published as: CN114086390B

Abstract

The invention relates to the technical field of composite materials, and provides epoxidized soybean oil modified collagen fibers and a preparation method and application thereof. The preparation method comprises the following steps: and carrying out ring-opening grafting reaction on the pretreated collagen fibers and a solution containing epoxidized soybean oil and a catalyst for 4-12 h at the temperature of 80-140 ℃. The invention also provides a modified composite material, which comprises the epoxy soybean oil modified collagen fiber and a high polymer, wherein the high polymer is a high polymer material with the molding processing temperature not higher than the dry heat denaturation temperature of the collagen fiber. According to the invention, epoxidized soybean oil is used for modifying collagen fibers, so that the surface free energy of the collagen fibers is reduced, and the surfaces of the collagen fibers have hydrophobicity. The prepared epoxidized soybean oil modified collagen fiber is mixed with a high polymer matrix, so that the difference of surface free energy and surface polarity between the collagen fiber and the high polymer matrix is reduced, and the obtained modified composite material has excellent mechanical property and heat resistance.

Description

Epoxidized soybean oil modified collagen fiber and preparation method and application thereof

Technical Field

The invention relates to the technical field of composite materials, in particular to an epoxidized soybean oil modified collagen fiber and a preparation method and application thereof.

Background

The high polymer composite material is a novel structural material formed by compounding a reinforcing material and a high polymer matrix through different compounding processes, has the advantages of excellent physical properties, high strength and modulus, light weight and the like, and is widely applied to the fields of high-performance automobiles, aerospace, building materials, chemical industry and the like.

The reinforcing material is a high-strength material which is combined in a matrix and used for improving the mechanical property of the matrix, and is divided into zero-dimensional (granular reinforcing material), one-dimensional (fibrous reinforcing material and whisker-shaped reinforcing material), two-dimensional (sheet or plane fabric reinforcing material) and three-dimensional (plant fiber, three-dimensional fabric reinforcing material and the like) according to the shape. The zero-dimensional and one-dimensional reinforcing materials are weak in-plane and interlayer properties of reinforced high polymers and have the risk of migration. The interlayer performance of the two-dimensional reinforced material reinforced high polymer is weak, and the modification effect of the material is influenced by the interlayer stripping phenomenon easily generated in the actual use process. The three-dimensional reinforced material is distributed in a three-dimensional space in a multidirectional way, so that the expansion of cracks between layers of the composite material under the action of mechanical load can be prevented or slowed down, and the three-dimensional reinforced material has excellent comprehensive performance and stronger complex shape adaptability. In the reinforced materials, the collagen fibers have a more complex multi-level structure, multi-directional crack propagation can be effectively prevented or slowed down under the action of mechanical load, the composite material has more integrity and uniformity through matrix distribution, the movement of polymer molecular chains is further limited, and therefore the mechanical property of the composite material is improved. Due to the existence of the multi-level structure, the collagen fibers are not easy to deform and move, so that the application of high polymer substrate molecules can be limited at higher use temperature, and the heat resistance of the high polymer material is improved. However, the side chains of the collagen fibers contain abundant active hydrophilic functional groups, and the presence of the functional groups can cause poor compatibility of the collagen fibers and the hydrophobic polymer, thereby affecting the effect of the collagen fiber modified polymer.

In view of the above phenomena, in the conventional polymer modification, materials such as silane, titanate, aluminate and other coupling agents, acrylic copolymers, maleic anhydride graft copolymers and other materials are generally adopted to improve the compatibility between the reinforcing material and the polymer, thereby improving the performance of the polymer composite material. Similarly, for the composite material added with the collagen fiber, Chinese patent CN110258111A discloses a method for modifying the collagen fiber by using a fluorine-containing silane coupling agent, which improves the compatibility between the collagen fiber and rubber, so that the rubber composite material has excellent mechanical property and self-cleaning property, but the silane coupling agent has the defects of high cost and non-environmental-friendly preparation process. Based on the above analysis, there is a need to find a modified material and a modification method that are environmentally friendly, low in cost and capable of improving the mechanical properties of the composite material.

Disclosure of Invention

In order to solve the problems in the background art, a first object of the present invention is to provide a method for preparing epoxidized soybean oil-modified collagen fibers.

The second purpose of the invention is to provide epoxidized soybean oil modified collagen fibers which can be used for modified composite materials and can improve the mechanical properties and heat resistance of the modified composite materials.

A third object of the present invention is to provide a modified composite material having excellent mechanical properties and heat resistance.

In order to achieve the above purpose, the first technical solution adopted by the present invention is:

the preparation method of the epoxidized soybean oil modified collagen fiber comprises the following steps:

carrying out ring-opening grafting reaction on the pretreated collagen fibers and a solution containing epoxidized soybean oil and a catalyst at the temperature of 80-140 ℃ for 4-12 h;

preferably, the ring-opening grafting reaction is carried out at 90-120 ℃ for 6-8 h.

Preferably, the pretreatment of the collagen fibers comprises: washing collagen fiber with water, adjusting pH, drying, and pulverizing; preferably, the pH is adjusted to 2-12; more preferably, the pH is adjusted to 3-5 and 7-9; preferably, the crushed materials are 10 to 500 meshes in particle size; more preferably, the pulverization is to a particle size of 20 to 200 mesh.

Preferably, the raw material of the collagen fiber is selected from any one or more of waste leather scraps and tanned leather; the waste leather scraps are leather making corner wastes generated in the leather making process; the tanned leather is selected from any one or more of chrome tanned leather, aldehyde tanned leather, vegetable tanned leather, non-chrome metal tanned leather, organic tanned leather, composite tanned leather and the like.

Preferably, the catalyst is a protic acid, a lewis acid, a protic base, and a lewis base; more preferably, the catalyst comprises, but is not limited to, any one or more of boron trifluoride diethyl etherate, tin tetrachloride, tetrabutylammonium bromide, zinc chloride, magnesium chloride, triethylene diamine, N-dimethylbenzylamine; more preferably, the catalyst is any one or more of tetrabutylammonium bromide, triethylenediamine, zinc chloride and stannic chloride. More preferably, the catalyst is selected to match the charge state of the collagen fibers, and when the pretreated collagen fibers have positive charges, Lewis bases are preferred, and tetrabutylammonium bromide and triethylene diamine are more preferred; when the collagen fibers after pretreatment exhibit a negative charge, Lewis acids are preferred, and zinc chloride and tin tetrachloride are more preferred.

Preferably, the mass ratio of the collagen fibers, the epoxidized soybean oil and the catalyst is 1: (0.1-3): (0.02-1.5); the mass of the solution is 5-20 times of that of the collagen fiber.

More preferably, the mass ratio of the collagen fibers, the epoxidized soybean oil and the catalyst is 1: (0.5-2): (0.2-0.8); the mass of the solution is 8-12 times of that of the collagen fiber.

Preferably, the solution includes, but is not limited to, hydrocarbon, ketone, ester, alcohol organic solvents; more preferably, the solution is isopropanol or n-butanol.

Preferably, the method further comprises the steps of filtering, heating, washing, drying and crushing the reacted collagen fibers after the ring-opening grafting reaction; the heating temperature is 50-105 ℃ and the time is 6-36 h; more preferably, the heating temperature is 70-90 ℃ and the time is 12-24 h; the drying conditions include: drying at 80-140 deg.C for 4-12 h by any one of heating drying and vacuum drying; the crushed granularity is 10-500 meshes; more preferably, the pulverized particle size is 20 to 200 mesh.

The second technical scheme adopted by the invention is that the epoxidized soybean oil modified collagen fiber prepared by adopting the method in any one of the first technical scheme is adopted.

The third technical scheme adopted by the invention is a modified composite material, which comprises the epoxidized soybean oil modified collagen fiber and a high polymer, wherein the high polymer is a high polymer material with the molding processing temperature not higher than the dry heat denaturation temperature of the collagen fiber; preferably, the high polymer includes, but is not limited to, polyvinyl chloride, thermoplastic polyester, phenolic resin, nitrile rubber, and neoprene rubber.

The collagen fiber is used in an amount of 1-150 wt.%, preferably 3-80 wt.% of the polymer.

Compared with the prior art, the invention has the following beneficial effects:

the invention carries out activation pretreatment on the collagen fibers, so that more-NH is exposed out of the collagen fibers₂The epoxy group on the flexible long chain of the epoxy soybean oil molecule is utilized at the same time (OH, COOH and the like) ((

) The characteristic of ring opening under the catalytic condition of 80-140 ℃ to enable the collagen fibers to be in contact with-NH on the side chains of the collagen fibers₂Reaction of-OH-COOH groups to form

、

、

The grafting structure is effectively covered on the surface of the collagen fiber, the surface free energy of the collagen fiber is reduced, and the hydrophobic modification of the collagen fiber is realized.

The surface of the modified collagen fiber is grafted and coated with a large number of ester groups, so that the difference of the surface free energy between the collagen fiber and a high polymer matrix is reduced, and the compatibility of the collagen fiber and the high polymer matrix is improved. The complex multi-level structure of the collagen fiber and the performance of the collagen fiber are not changed and reduced by the modification process, and the modified collagen fiber is compounded with the high polymer base material to realize the enhancement and modification of the high polymer material.

In addition, epoxy groups which are not completely reacted in the collagen fiber modification process can continuously react under the influence of heat and pressure in the material forming process, so that the interaction between the collagen fibers and high polymer molecules and the interaction between the high polymer molecules and the high polymer molecules are further enhanced. In addition, epoxy groups of collagen and epoxidized soybean oil in the collagen fiber have the ability to capture free radicals. Free radicals generated in the thermal-oxidative degradation process of the high polymer composite material prepared by the method can be captured and inactivated, and chain reaction can not be initiated to cause the reduction of the mechanical property of the material. The composite material obtained by the method can keep better mechanical property at higher temperature.

The traditional method for the collagen fiber compatibilization modification generally uses silane coupling agent materials, such as patent CN 110258111A. Compared with silane coupling agent materials, the modifier epoxidized soybean oil used in the patent has the advantages of low price, better heat resistance and mutual permeability, and more environment-friendly preparation process. The technical route of the invention is used for preparing the high polymer composite material, and the scorching phenomenon which is easy to occur in the preparation process of modifying the high polymer by using the silane coupling agent can not occur. The interpenetration of the epoxidized soybean oil can be reserved on the modified collagen fiber, so that the interaction between the collagen fiber and the high polymer substrate is expected to be further enhanced in the material compounding process, and the material has better universality. Besides being suitable for modifying non-polar high polymer materials (such as natural rubber), the modifier can also be used for modifying polar high polymer materials (such as polyvinyl chloride).

Drawings

FIG. 1 is a schematic diagram of a epoxidized soybean oil modified collagen fiber reinforced polyvinyl chloride composite material;

FIG. 2 is a graph showing the rate of change in tensile strength with temperature for each sample in Experimental example 2;

FIG. 3 is a graph showing the change in elongation at break with temperature for each sample in Experimental example 2;

FIG. 4 is a graph showing the rate of change in flexural strength with temperature of each sample in Experimental example 2.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings in conjunction with the following detailed description. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The first embodiment of the invention provides a preparation method of epoxidized soybean oil modified collagen fibers, which comprises the following steps:

and (3) carrying out ring-opening grafting reaction on the pretreated collagen fibers and a solution containing epoxidized soybean oil and a catalyst for 4-12 h at the temperature of 80-140 ℃.

The collagen fiber after activation pretreatment can expose more-NH₂Groups of-OH, -COOH, etc., part of epoxy groups on flexible long chain of epoxy soybean oil molecule(s) ((

) Can be atRing opening at 80-140 ℃ in the presence of a catalyst and reacting with-NH on the side chain of collagen fibres₂Reaction of-OH, -COOH, etc. groups to form

、

、

It should be noted that the epoxidized soybean oil can also modify the plant fiber, but compared with the plant fiber, the collagen fiber has a more complex multi-level structure and more abundant active functional groups, so that the collagen fiber has greater advantages in structure and grafting ratio, and the effect of applying the modified plant fiber to the enhancement modification of the high polymer is not as good as that of the present invention. In an alternative embodiment, the ring-opening grafting reaction is carried out at 90-120 ℃ for 6-8 h.

As in various embodiments, the temperature of the ring-opening grafting reaction can be 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, etc.; the ring-opening reaction time can be 4h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, 11 h, 12 h and the like; the specific reaction time and reaction temperature are determined according to-NH on the surface of the collagen fiber₂The groups of-OH, -COOH and the like and the epoxy group of epoxidized soybean oil

The reaction requirements for ring-opening grafting to occur are determined. The purpose of controlling the temperature and the time is that as the epoxidized soybean oil usually contains 3-4 epoxy groups in each molecule, but some epoxy groups are in ortho positions, a steric hindrance structure is formed after the ring opening of one epoxy group to prevent the ring opening reaction of the ortho epoxy groups, so that the epoxidized soybean oil can be grafted on the collagen fibers more effectively only by reacting for 4-12 hours at 80-140 ℃, and the effect of the invention is achieved.

The collagen fibre raw material used in the present invention is selected from any one or more of waste leather scraps and tanned leather. The waste leather scraps refer to leather making leftover wastes generated by operations of chipping, grinding, cutting and the like in the leather making process. The tanned leather is a semi-finished product in the leather production process. Preferably, the tanned leather is selected from any one or more of chrome tanned leather, aldehyde tanned leather, vegetable tanned leather, non-chrome metal tanned leather, organic tanned leather, composite tanned leather and the like.

In some embodiments, the pretreatment of the collagen fibers comprises: washing collagen fiber with water, adjusting pH, drying, and pulverizing.

In the washing, the collagen fiber raw material is washed with an aqueous solution containing a surfactant, and impurities such as fats and oils and inorganic salts in the raw material are removed by washing with water.

The pH value of the collagen fiber is adjusted to 2-12 by adopting alkaline substances, sodium bicarbonate, sodium carbonate and the like; more preferably, the pH is adjusted to 3-5 and 7-9. The purpose of controlling the pH value of the invention is that the collagen fibers can expose more-NH only under the condition of pH 2-12₂OH, COOH and the like so as to be convenient for later reaction with the epoxidized soybean oil and achieve the effect of the invention.

It should be noted that, for the adjustment of pH in the pretreatment, the pH may not be adjusted first in the pretreatment process, and the collagen fibers and the epoxidized soybean oil may be directly reacted at the above pH value. But because the pH value of the collagen fiber is adjusted for a long time (24 h) in the pretreatment, the groups on the collagen fiber are exposed more fully, and the subsequent reaction is facilitated; if the pH is adjusted in the reaction process of the collagen fibers and the epoxidized soybean oil, groups on the collagen fibers may not be exposed in time due to short reaction time, so that the final effect is not as good as the pH adjustment in the pretreatment step.

The pulverization is mechanochemical activation, and the collagen fiber is treated by using pulverization equipment with the functions of opening, defibering and grinding, so that hydrogen bonds and covalent bonds of the collagen fiber are broken, more active functional groups are exposed, and the collagen fiber is pulverized into particles with the particle size of 10-500 meshes; preferably, the pulverization is to a particle size of 20-200 mesh.

Preferably, the catalyst is a protic acid, a lewis acid, a protic base, and a lewis base; more preferably, the catalyst comprises, but is not limited to, any one or more of boron trifluoride diethyl etherate, tin tetrachloride, tetrabutylammonium bromide, zinc chloride, magnesium chloride, triethylene diamine, N-dimethylbenzylamine; more preferably, the catalyst is any one or more of tetrabutylammonium bromide, triethylenediamine, zinc chloride and stannic chloride.

In other preferred embodiments, the catalyst is selected to match the charge state of the collagen fibrils, and when the pretreated collagen fibrils exhibit a positive charge, lewis bases are preferred, and tetrabutylammonium bromide, triethylenediamine are more preferred; when the collagen fibers after pretreatment exhibit a negative charge, Lewis acids are preferred, and zinc chloride and tin tetrachloride are more preferred.

Under the action of the catalyst, the epoxy group in the structure of the epoxidized soybean oil can open the ring according to the course of ionic chain polymerization. The ternary cyclic ether group has stronger tension and higher ring opening tendency in thermodynamics. Therefore, ring-opening reaction can be carried out only by strengthening electron delocalization through acid and alkali, so that the epoxidized soybean oil is grafted with groups corresponding to charges on the collagen fibers. It should be noted that, in this case, the charge property of the selected catalyst needs to be matched with the charge property of the pretreated collagen fiber raw material.

In some embodiments, the mass ratio of the collagen fibers, the epoxidized soybean oil, and the catalyst is: 1: (0.1-3): (0.02-1.5); the mass of the solution is 5-20 times of that of the collagen fiber.

It should be noted that, in the mass ratio of the collagen fibers, the epoxidized soybean oil and the catalyst, if the usage amount of the epoxidized soybean oil and the catalyst is less than the range of the present invention, the grafting ratio of the epoxidized soybean oil on the collagen fibers is extremely low, which is not enough to achieve the effect of the present invention; if the dosage of the epoxidized soybean oil and the catalyst is higher than the range of the invention, the epoxidized soybean oil and the catalyst are wasted while the effect of the invention cannot be effectively improved, so that the cost of the epoxidized soybean oil modified collagen fiber is increased. The mass of the solvent in the solution is related to the mass of the collagen fibers, and generally the mass of the solvent is about 10 times of the mass of the collagen fibers.

In some embodiments, the ring-opening grafting reaction further comprises the steps of filtering, heating, washing, drying and crushing the reacted collagen fibers.

Wherein the heating temperature is 50-105 ℃ and the time is 6-36 h; preferably, the heating temperature is 70-90 ℃ and the time is 12-24 h; the drying conditions include: drying at 80-140 deg.C for 4-12 h by either heating drying or vacuum drying.

The washing refers to alcohol washing, namely, the collagen fibers are stirred and washed by using an alcohol organic solvent so as to ensure that the unreacted excessive epoxidized soybean oil is removed. As in the different embodiments, it is possible to carry out a plurality of alcohol washes, for example 1 to 3, each wash with stirring for 0.5 to 5 h, preferably l to 3 h.

The pulverization is mechanochemical activation, and the collagen fiber is treated by using pulverization equipment with the functions of opening, defibering and grinding, so that hydrogen bonds and covalent bonds of the collagen fiber are broken, more active functional groups are exposed, and the collagen fiber is pulverized to have the granularity of 10-1500 meshes; more preferably, the pulverized particle size is 20 to 800 mesh.

The second embodiment of the present invention is the epoxidized soybean oil-modified collagen fiber obtained by the first embodiment.

A third embodiment of the present invention provides a modified composite comprising the epoxidized soybean oil-modified collagen fibers of the second embodiment and a high polymer.

The high polymer can be formed by conventional melting or mixing of prepolymers, and the forming temperature is not higher than the dry thermal denaturation temperature of the collagen fibers. The part of the self-processing temperature is higher than the dry heat denaturation temperature of the collagen fibers, but the processing temperature can be reduced to be below the dry heat denaturation temperature by using a proper plasticizing method, and the part of the self-processing temperature is also attributed to the high polymer of the invention.

Preferably, the high polymer includes, but is not limited to, polyvinyl chloride, thermoplastic polyester, phenolic resin, nitrile rubber, and neoprene rubber.

The epoxy soybean oil modified collagen fiber prepared by the method is combined with the high polymer to obtain the modified composite material, so that the surface free energy and the surface polarity difference between the collagen fiber and the high polymer matrix are reduced, and other long chains with epoxy groups in the epoxy soybean oil molecule have certain compatibility with the high polymer, thereby effectively improving the mechanical property of the modified composite material. In addition, the collagen in the collagen fibers has the ability to capture radicals, and the heat resistance of the modified composite material can be improved. The mechanism of the epoxidized soybean oil modified collagen fiber reinforced polyvinyl chloride composite material is shown in figure 1.

In order to better understand the technical scheme provided by the invention, the following specific examples respectively illustrate the epoxidized soybean oil modified collagen fiber, the modified composite material, the preparation method thereof and the performance test thereof, which are provided by applying the above embodiments of the invention.

Some of the material information used in the embodiments of the present invention may be as follows:

leather scraps from the hide company, heinin, ruixing, inc;

epoxidized soybean oil, model EBSO-6.6, manufactured by: shandong Youso chemical science and technology, Inc.;

tetrabutylammonium bromide, technical grade, manufacturer: chemical products limited of Henan Ming Hui;

triethylene diamine, technical grade, manufacturer: shandong Cheng Teng chemical Co., Ltd;

zinc chloride, technical grade, manufacturer: shandong Polymer chemistry, Inc.;

tin tetrachloride, technical grade, manufacturer: shandong Polymer chemistry, Inc.;

polyvinyl chloride, model number FG-5, manufacturer: xinjiang Tianye (group) Co., Ltd;

polylactic acid, model 3051D, manufactured by manufacturer: NatureWorks, USA;

the phenolic aldehyde linear prepolymer is self-synthesized by using phenol, formaldehyde and sodium hydroxide as raw materials, reagents are analytically pure, and a manufacturer is a metropolis Kolon chemical Co., Ltd;

the chloroprene rubber has the model of S-40V and is manufactured by the following manufacturers: japan electrical corporation;

nitrile rubber, type XL 33.61, manufacturer: shandong Youso chemical science and technology, Inc.;

glass fiber, model is alkali-free short cut 6 mm, and the producer is: changzhou Zhuwei building materials, Inc.;

carbon black, type N330, manufacturer: shanghai Kayin chemical Co., Ltd;

lignocellulosic fiber, model a04401116, manufactured by: shandong Youso chemical technology, Inc.

Example 1

The embodiment provides a preparation method of epoxidized soybean oil modified collagen fibers, which comprises the following steps:

(1) adding the washed waste leather scraps into deionized water, adjusting the pH value to 8 by using sodium bicarbonate powder, filtering after washing, dehydrating by using ethanol, grinding by using an ultracentrifugal pulverizer with cooling equipment or air dispersing equipment after the ethanol is volatilized, and sieving by using a 40-mesh screen to obtain collagen fibers;

(2) taking 10 parts by weight of the crushed collagen fibers obtained in the step (1), adding the crushed collagen fibers into 100 parts by weight of isopropanol solvent containing 10 parts by weight of epoxidized soybean oil and 4 parts by weight of tetrabutylammonium bromide serving as a catalyst in advance, and stirring for 6 hours at 90 ℃; filtering, discharging, and placing in an oven at 80 ℃ for 12 h; because the isopropanol and the epoxy soybean oil form an azeotrope, the boiling point is increased, so the stirring temperature can be higher than the boiling point of the solvent isopropanol under experimental conditions;

(3) stirring and washing the solid fiber obtained in the step (2) with isopropanol for l h times to remove unreacted excessive epoxidized soybean oil;

(4) and (4) drying the solid fiber obtained in the step (3) in a 90 ℃ oven for 8 h, grinding by using an ultracentrifugal pulverizer with a cooling device or an air dispersing device, and sieving by using a 40-mesh sieve to obtain the epoxidized soybean oil modified collagen fiber.

Example 2

(1) adding the washed waste leather scraps into deionized water, adjusting the pH value to 5 by using sodium bicarbonate powder, filtering after washing, dehydrating by using ethanol, grinding by using an ultracentrifugal pulverizer with cooling equipment or air dispersing equipment after the ethanol is volatilized, and sieving by using a 100-mesh screen to obtain collagen fibers;

(2) the pulverized 10 parts by weight of collagen fibers obtained in step (1) were taken, added to 120 parts by weight of an isopropyl alcohol solvent previously containing 10 parts by weight of epoxidized soybean oil and 4 parts by weight of anhydrous tin tetrachloride as a catalyst, and stirred at 95 ℃ for 5 hours. Filtering, discharging, and placing in a 90 ℃ oven for 10 h;

(3) stirring and washing the solid fiber obtained in the step (2) with isopropanol for l.5 h, and repeating stirring and washing for 2 times to remove unreacted excessive epoxidized soybean oil;

(4) and (3) drying the solid fiber obtained in the step (3) in a 100 ℃ oven for 5 h, grinding by using an ultracentrifugal pulverizer with a cooling device or an air dispersing device, and sieving by using a 100-mesh sieve to obtain the epoxidized soybean oil modified collagen fiber.

Example 3

This example refers to the preparation of example 1, with the only difference that: in step (1), the pH was adjusted to 2 with sodium bicarbonate powder.

Example 4

This example refers to the preparation of example 1, with the only difference that: in step (1), the pH was adjusted to 3 with sodium carbonate powder.

Example 5

This example refers to the preparation of example 1, with the only difference that: in step (1), the pH was adjusted to 7 with sodium carbonate powder.

Example 6

This example refers to the preparation of example 1, with the only difference that: in step (1), the pH is adjusted to 10 with sodium carbonate powder.

Example 7

This example refers to the preparation of example 1, with the only difference that: in step (1), the pH was adjusted to 12 with sodium carbonate powder.

Example 8

This example refers to the preparation of example 1, with the only difference that: in the step (2), 1 part by weight of epoxidized soybean oil and 0.2 part by weight of catalyst triethylenediamine were added to 80 parts by weight of an isopropyl alcohol solution.

Example 9

This example refers to the preparation of example 2, with the only difference that: in step (2), 20 parts by weight of epoxidized soybean oil and 8 parts by weight of zinc chloride as a catalyst were added to 100 parts by weight of an isopropyl alcohol solution.

Example 10

This example refers to the preparation of example 1, with the only difference that: in step (2), stirring was carried out at 110 ℃ for 3.5 h. Filtering, discharging, and drying in an oven at 105 ℃ for 6 h.

Example 11

This example refers to the preparation of example 1, with the only difference that: in step (2), stirring was carried out at 120 ℃ for 3 h. Filtering, discharging, and placing in a 60 ℃ oven for 18 h.

Example 12

This example refers to the preparation of example 1, with the only difference that: in step (2), stirring was carried out at 140 ℃ for 2 h. Filtering, discharging, and placing in a 50 ℃ oven for 36 h.

Example 13

This example refers to the preparation of example 1, with the only difference that: in the step (3), stirring and washing the solid fiber obtained in the step (2) by using isopropanol for 5 hours, and repeating stirring and washing for 1 time to remove the unreacted excessive epoxidized soybean oil; in the step (4), the solid fiber obtained in the step (3) is dried in an oven at 80 ℃ for 12 hours.

Example 14

This example refers to the preparation of example 1, with the only difference that: in the step (3), stirring and washing the solid fiber obtained in the step (2) by using isopropanol for 3 hours, and repeating stirring and washing for 2 times to remove the unreacted excessive epoxidized soybean oil; and (4) drying the solid fiber obtained in the step (3) in an oven at 120 ℃ for 10 hours.

Example 15

This example refers to the preparation of example 1, with the only difference that: in the step (3), the solid fiber obtained in the step (2) is stirred and washed by isopropanol for 0.5 h, and the stirring and washing are repeated for 3 times to remove the unreacted excessive epoxidized soybean oil; in the step (4), the solid fiber obtained in the step (3) is placed in an oven at 140 ℃ for drying for 4 hours.

Example 16

This example refers to the preparation of example 1, with the only difference that: in the steps (1) and (3), grinding by using an ultracentrifugal pulverizer with a cooling device or an air dispersing device, and sieving by using a 10-mesh sieve.

Example 17

This example refers to the preparation of example 1, with the only difference that: in the steps (1) and (3), the mixture is ground by using an ultracentrifugal pulverizer with a cooling device or an air dispersing device, and is sieved by a 50-mesh screen.

Example 18

This example refers to the preparation of example 1, with the only difference that: in the steps (1) and (3), grinding by using an ultracentrifugal pulverizer with a cooling device or an air dispersing device, and sieving by using a 200-mesh sieve.

Example 19

This example refers to the preparation of example 1, with the only difference that: in the steps (1) and (3), grinding by using an ultracentrifugal pulverizer with a cooling device or an air dispersing device, and sieving by using a 500-mesh sieve.

Examples 20 to 38

Examples 20-38 provide various modified composites and methods for their preparation, the raw material formulations of the modified composites are shown in table 1 below.

TABLE 1 raw material ratios of different composites

。

The method for preparing the composite material containing modified collagen fibers of examples 20, 25, 27 and 28, comprising the steps of:

mixing the epoxidized soybean oil modified collagen fibers, the high polymer and a processing aid (Ca-Zn heat stabilizer and plasticizer dioctyl phthalate) in a high-speed mixer according to the proportion in the table 1 for 10 min, then banburying at 140 ℃ in a torque rheometer and carrying out compression molding to obtain the high polymer composite material containing the modified collagen fibers.

The method for preparing the polymer composite containing modified collagen fibers of examples 21, 22 and 23, comprising the steps of:

mixing the epoxidized soybean oil modified collagen fibers and the high polymer in a high-speed mixer according to the proportion in the table 1 for 10 min, then banburying at 175 ℃ in a torque rheometer and carrying out compression molding to obtain the high polymer composite material containing the modified collagen fibers.

The method for preparing the polymer composite containing modified collagen fibers of examples 29, 30, 37 and 38, comprising the steps of:

mixing the epoxidized soybean oil modified collagen fibers and the high polymer prepolymer solution according to the proportion in the table 1 for 1 h, and then pouring and forming at 60 ℃ to obtain the high polymer composite material containing the modified collagen fibers.

The method for preparing the polymer composite containing modified collagen fibers of examples 24, 26 and 31 to 36, comprising the steps of:

mixing epoxidized soybean oil modified collagen fibers, high polymer and rubber accelerator (2-mercaptobenzothiazole) in a torque rheometer at 140 ℃ according to the proportion in the table 1, and then carrying out compression molding to obtain the high polymer composite material containing the modified collagen fibers.

Comparative example 1

Comparative example 1 provides a blank polyvinyl chloride:

mixing 100 parts by weight of polyvinyl chloride and a processing aid (6 parts by weight of Ca-Zn heat stabilizer and 20 parts by weight of plasticizer dioctyl phthalate) in a high-speed mixer, then banburying at 140 ℃ in a torque rheometer and carrying out compression molding to obtain a blank polyvinyl chloride material.

Comparative example 2

Comparative example 2 provides a blank polylactic acid:

and (3) banburying 100 parts by weight of polylactic acid in a torque rheometer at 140 ℃ and carrying out compression molding to obtain a blank polylactic acid material.

Comparative example 3

Comparative example 3 provides a blank phenolic resin:

pouring and forming 100 parts by weight of phenolic resin prepolymer solution at 60 ℃ to obtain blank phenolic resin.

Comparative example 4

Comparative example 4 provides a blank neoprene:

100 parts by weight of chloroprene rubber and 1 part by weight of rubber accelerator (2-mercaptobenzothiazole) were banburied at 140 ℃ in a torque rheometer, followed by compression molding to obtain a blank chloroprene rubber.

Comparative example 5

Comparative example 5 provides a blank nitrile rubber:

100 parts by weight of nitrile rubber and 1 part by weight of rubber accelerator (2-mercaptobenzothiazole) are subjected to banburying at 140 ℃ in a torque rheometer, and then compression molding is carried out to obtain blank nitrile rubber.

Comparative example 6

Comparative example 6 the preparation of example 20 was referenced, with the following differences: referring to step (1) of example 1, the collagen fibers were washed with water, dried, and pulverized to a particle size of 40 mesh to obtain unmodified collagen fibers; the modified waste collagen fibers are replaced with an equal amount of the unmodified collagen fibers.

Comparative example 7

Comparative example 7 the preparation of example 20 was referenced, with the following differences: the modified collagen fiber was replaced with an equivalent amount of glass fiber (manufacturer: Changzhou Zhunwei building materials Co., Ltd., model: alkali-free chopped 6 mm).

Comparative example 8

Comparative example 8 the preparation of example 20 was referenced, with the following differences: the modified collagen fiber was replaced with an equal amount of carbon black (manufacturer: Shanghai Kahn chemical Co., Ltd., model: N330).

Comparative example 9

Comparative example 9 the preparation of reference example 20 was carried out with the following differences: the modified collagen fiber was replaced with an equivalent amount of lignocellulose (manufacturer: Shandong Youso chemical science and technology Co., Ltd., model: A04401116).

Experimental example 1

In order to comparatively illustrate the mechanical properties of the resin materials obtained in different examples 20-38 and comparative examples 1-9 of the present invention, the composite materials obtained in different examples and comparative examples were tested, and the test standards refer to GB/T1040.2-2006, GB/T9341-.

TABLE 2 mechanical Property test results for different composites

。

According to the test results, the modified collagen fiber-polymer composite material prepared from the modified collagen fiber and the polymer (polyvinyl chloride, polylactic acid, phenolic resin, nitrile rubber, chloroprene rubber and the like) composite material has the advantages that the mechanical properties such as tensile strength, elongation at break, tensile modulus, flexural strength, flexural modulus and the like are remarkably improved within the proper mass ratio range of the epoxidized soybean oil, the collagen fiber and the polymer.

Experimental example 2

In order to comparatively illustrate the heat resistance of the resin materials obtained in the different embodiments and comparative examples of the present invention, the composite materials obtained in the different embodiments 20, 21, 29, 32, 34 and comparative examples 1 to 5 were tested, the mechanical properties of the materials were measured at 25 °, 30 °, 35 °, 40 °, 45 °, 50 ° and 60 °, respectively, and the graph of the change in tensile strength with temperature, the change in elongation at break with temperature, and the change in bending strength with temperature of each sample are respectively shown in fig. 2 to fig. 4.

As can be seen from fig. 2-4, the mechanical properties of the modified collagen fiber-polymer composite material prepared by compounding the modified collagen fiber obtained by the present invention and a polymer (polyvinyl chloride, polylactic acid, phenolic resin, nitrile rubber, chloroprene rubber, etc.) are less changed with the temperature rise within a certain temperature range, which indicates that the polymer composite material has better heat resistance.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. The preparation method of the epoxidized soybean oil modified collagen fiber is characterized by comprising the following steps:

2. The method of preparing epoxidized soybean oil-modified collagen fibers according to claim 1, wherein the pretreatment of the collagen fibers comprises: washing collagen fiber with water, adjusting pH, drying, and pulverizing;

preferably, the pH is adjusted to 2-12;

more preferably, the pH is adjusted to 3-5 and 7-9;

preferably, the crushing particle size is 10-500 meshes;

more preferably, the pulverized particle size is 20 to 200 mesh.

3. The method for preparing epoxidized soybean oil-modified collagen fibers according to claim 1 or 2, wherein the raw material of the collagen fibers is selected from any one or more of waste leather scraps and tanned leather;

preferably, the waste leather scraps are leather making leftover wastes generated in the leather making process;

preferably, the tanned leather is selected from any one or more of chrome tanned leather, aldehyde tanned leather, vegetable tanned leather, non-chrome metal tanned leather, organic tanned leather, combination tanned leather and the like tanned leather.

4. The method for preparing epoxidized soybean oil-modified collagen fibers according to claim 1, wherein the catalyst is a protonic acid, a Lewis acid, a protonic base, or a Lewis base;

preferably, the catalyst comprises, but is not limited to, any one or more of boron trifluoride diethyl ether, tin tetrachloride, tetrabutylammonium bromide, zinc chloride, magnesium chloride, triethylene diamine, N-dimethylbenzylamine;

more preferably, the catalyst is any one or more of tetrabutylammonium bromide, triethylenediamine, zinc chloride and stannic chloride.

5. The method for preparing epoxidized soybean oil modified collagen fibers according to claim 1 or 4, wherein the mass ratio of the collagen fibers, epoxidized soybean oil and the catalyst is 1: (0.1-3): (0.02-1.5); the mass of the solution is 5-20 times of that of the collagen fiber;

preferably, the mass ratio of the collagen fibers, the epoxidized soybean oil and the catalyst is 1: (0.5-2): (0.2-0.8);

the mass of the solution is 8-12 times of that of the collagen fiber.

6. The method of claim 1, wherein the solution comprises but is not limited to hydrocarbon, ketone, ester, alcohol organic solvents;

preferably, the solution is isopropanol or n-butanol.

7. The method for preparing epoxidized soybean oil-modified collagen fibers according to claim 1, further comprising the steps of filtering, heating, washing, drying and pulverizing the reacted collagen fibers after the ring-opening grafting reaction;

the heating temperature is 50-105 ℃ and the time is 6-36 h;

preferably, the heating temperature is 70-90 ℃ and the time is 12-24 h;

the drying conditions include: drying at 80-140 deg.C for 4-12 h by any one of heating drying and vacuum drying;

the crushing granularity is 10-1500 meshes;

preferably, the crushed particle size is 20-800 meshes.

8. Epoxidized soybean oil-modified collagen fibers obtained by the process for producing epoxidized soybean oil-modified collagen fibers according to any one of claims 1 to 7.

9. A modified composite material comprising epoxidized soybean oil-modified collagen fibers according to claim 8 and a high polymer, wherein the high polymer is a high polymer material having a molding processing temperature not higher than the dry heat denaturation temperature of the collagen fibers;

10. The modified composite material according to claim 9, wherein the collagen fibers are present in an amount of 1 to 150 wt.%, preferably 3 to 80 wt.%, of the polymer.