CN110253984A - A kind of electrostatic spinning nano fiber film-fabric composite coating material and preparation method - Google Patents

A kind of electrostatic spinning nano fiber film-fabric composite coating material and preparation method Download PDF

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Publication number
CN110253984A
CN110253984A CN201910533122.XA CN201910533122A CN110253984A CN 110253984 A CN110253984 A CN 110253984A CN 201910533122 A CN201910533122 A CN 201910533122A CN 110253984 A CN110253984 A CN 110253984A
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fabric
electrostatic spinning
coating material
fiber film
composite coating
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CN201910533122.XA
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CN110253984B (en
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王迎
杨云
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Dalian Polytechnic University
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Dalian Polytechnic University
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    • A61F13/01017—
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/00051—Accessories for dressings
    • A61F13/00063—Accessories for dressings comprising medicaments or additives, e.g. odor control, PH control, debriding, antimicrobic
    • A61F13/01029—
    • A61F13/01046—
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/02—Adhesive plasters or dressings
    • A61F13/0203—Adhesive plasters or dressings having a fluid handling member
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/0038—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding involving application of liquid to the layers prior to lamination, e.g. wet laminating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
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    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/08—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer the fibres or filaments of a layer being of different substances, e.g. conjugate fibres, mixture of different fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12H—PASTEURISATION, STERILISATION, PRESERVATION, PURIFICATION, CLARIFICATION OR AGEING OF ALCOHOLIC BEVERAGES; METHODS FOR ALTERING THE ALCOHOL CONTENT OF FERMENTED SOLUTIONS OR ALCOHOLIC BEVERAGES
    • C12H1/00—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages
    • C12H1/02—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages combined with removal of precipitate or added materials, e.g. adsorption material
    • C12H1/04—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages combined with removal of precipitate or added materials, e.g. adsorption material with the aid of ion-exchange material or inert clarification material, e.g. adsorption material
    • C12H1/0416—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages combined with removal of precipitate or added materials, e.g. adsorption material with the aid of ion-exchange material or inert clarification material, e.g. adsorption material with the aid of organic added material
    • C12H1/0424—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages combined with removal of precipitate or added materials, e.g. adsorption material with the aid of ion-exchange material or inert clarification material, e.g. adsorption material with the aid of organic added material with the aid of a polymer
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12H—PASTEURISATION, STERILISATION, PRESERVATION, PURIFICATION, CLARIFICATION OR AGEING OF ALCOHOLIC BEVERAGES; METHODS FOR ALTERING THE ALCOHOL CONTENT OF FERMENTED SOLUTIONS OR ALCOHOLIC BEVERAGES
    • C12H1/00—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages
    • C12H1/02—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages combined with removal of precipitate or added materials, e.g. adsorption material
    • C12H1/06—Precipitation by physical means, e.g. by irradiation, vibrations
    • C12H1/063—Separation by filtration
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3562—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0223—Vinyl resin fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0253—Polyolefin fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0276—Polyester fibres
    • B32B2262/0284—Polyethylene terephthalate [PET] or polybutylene terephthalate [PBT]
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/14—Mixture of at least two fibres made of different materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/22—Polymers or copolymers of halogenated mono-olefins

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Abstract

The invention discloses a kind of electrostatic spinning nano fiber film-fabric composite coating material and preparation methods.Composite coating material is made of three-decker.Surface layer is the cross-linked pvp P that PVP persulfate free radical polymerization obtains；Middle layer is Kynoar-hexafluoropropene (PVDF-HFP)/polyvinylpyrrolidone (PVP) needleless electrostatic spinning nano fiber film；Bottom is fabric.Surface layer is that functional layer, middle layer and bottom are combined with each other by PVP self-crosslinking in PVP cross-linking process and with being mutually crosslinked for PVDF-HFP, collectively constitutes the supporting layer of composite coating material.Composite material prepared by the present invention can be used for functional medical dressing, it may also be used for Beer stabilizer has polyphenol substance absorption and filters the double-deck function.

Description

A kind of electrostatic spinning nano fiber film-fabric composite coating material and preparation method
Technical field
The invention belongs to field of composite material preparation, and in particular to a kind of to process a kind of Static Spinning/fabric binary composite wood The preparation method of material.It can be applied to nano material analytical technology and membrane material applied technical field.
Background technique
It is multi-functional multiple with the continuous promotion that the continuous development and people of textile industry require textile comprehensive performance Closing fabric undoubtedly will occupy one seat in fabric development.Wherein, the electrostatic spinning of domestic and international common concern is received in recent years Application of the rice fiber in weaving is also being increasing, and is especially combined nanofiber with conventional fabrics and is applied to extraordinary produce The report of industry material is commonplace.
By vinyl-pyrrolidone monomers, cross-linked polymeric forms PVPP under given conditions, is a kind of macromolecule of good properties Fine chemical product, and a kind of new type medicinal stuff risen in recent years.PVPP is mainly used as the disintegrating agent of tablet, has permitted Stabilizer, clarifying agent etc. as food compound, as brewing industries such as beer, fruit juice.
PVPP at home and abroad beer field extensive utilization, as beer colloid stabilizer.It is no matter how refrigerant after filtering Beer still contains the classification compound and protein of dissolution, these polyphenol substances and protein are formed under conditions of aerobic can not Inverse permanent polymerization object is the main reason for causing beer chaos.PVPP can effectively remove polyphenol substance in beer, improve The clarity of beer extends the shelf life of beer.
Currently, in Beer Brewage, need being quantitatively adding in beer after diatomite and PVPP mixing, after filtering PVPP and Diatomite is to form filter cake, as waste processing.The technique does not need individual PVPP filter plant, but production cost is higher.
Summary of the invention
In order to solve the problems, such as the above PVPP as the effective use in Beer stabilizer, the present invention breaks conventional PVPP in beer The application method for being adsorbed and being filtered in the form of filter cake removal in wine stabilizer by powdered intermediate, prepares one kind with Static Spinning Nano fibrous membrane-woven filter materials are support layer, and PVPP coating is the composite material of functional layer.
A kind of electrostatic spinning nano fiber film-fabric composite coating material, forms three-decker by surface layer, middle layer, bottom, The surface layer is the polyvinylpyrrolidone of crosslinking, is the cross-linked pvp P coating obtained by PVP persulfate free radical polymerization, in Interbed is Kynoar-hexafluoropropene (PVDF-HFP)/polyvinylpyrrolidone (PVP) electrostatic spinning nano fiber film, preferably Kynoar-the hexafluoropropene (PVDF-HFP) obtained for needleless Static Spinning/polyvinylpyrrolidone (PVP) needleless Static Spinning Nano fibrous membrane, bottom are fabric, and the fabric is woven fabric or non-woven fabrics.
Kynoar-the hexafluoropropene/polyvinylpyrrolidone Static Spinning Nanowire as a preferred technical solution, Tie up film with a thickness of 0.054-0.114mm；The fabric is the woven fabric or non-woven fabrics of terylene, polypropylene fibre or polyamide fibre.
The present invention also provides a kind of preparation method of electrostatic spinning nano fiber film-fabric composite coating material, including it is as follows Step:
(1) Kynoar-hexafluoropropene (PVDF-HFP) solution and polyvinylpyrrolidone (PVP) solution are pressed into volume Than mixing for (9:1-7:3), composite spinning solution is obtained, then Kynoar-hexafluoropropene is prepared by electrospinning process (PVDF-HFP)/polyvinylpyrrolidone (PVP) electrostatic spinning nano fiber film；
The concentration of Kynoar-hexafluoropropene (PVDF-HFP) solution is 14-20wt%, the polyvinyl pyrrole The concentration of alkanone solution is 6-8wt%；
(2) step (1) is obtained into Kynoar-hexafluoropropene (PVDF-HFP)/polyvinylpyrrolidone (PVP) electrostatic Spinning nanometer fiber membrane, fabric are placed in parallel, and are mutually fitted, and are immersed in containing polyvinylpyrrolidone (PVP), initiator, water In initiation system, polymerization (crosslinking) reaction occurs, it is dry after crosslinking, obtain nano fibrous membrane-fabric composite coating material Material；
Initiator in the initiation system is ammonium persulfate, and the concentration of polyvinylpyrrolidone (PVP) is 5-10wt%, The concentration of ammonium persulfate is 0.5-1wt%, and the temperature of reaction is 90-95 DEG C, and the time of reaction is 6-8h.
Kynoar-hexafluoropropene (PVDF-HFP) solution described in step (1) and poly- as a preferred technical solution, The solvent of vinylpyrrolidone (PVP) solution is N-N- dimethyl acetamide (DMAC)；Step as a preferred technical solution, (1) electrospinning process described in is needleless electrostatic spinning.
Needleless electrospinning conditions described in step (1) as a preferred technical solution, are as follows: voltage 60-80kV, solution box Speed 80-150mm/s, spinning time 40-120min.
Kynoar-hexafluoropropene (PVDF-HFP)/polyethylene described in step (1) as a preferred technical solution, Pyrrolidones (PVP) electrostatic spinning nano fiber film with a thickness of 0.054-0.114mm.
Condition dry described in step (2) as a preferred technical solution, are as follows: 40-60 DEG C, dry 2-4h.
Fabric described in step (2) is the woven fabric or nonwoven of terylene, polypropylene fibre or polyamide fibre as a preferred technical solution, Cloth.
The present invention also provides nano fibrous membrane described above-fabric composite coating materials in pharmaceutical carrier, functional doctor With the application in dressing, the absorption of beer polyphenol.Due to having polyphenol substance absorption and filtering the double-deck function, it can be used for beer and stablize Agent.
As a preferred technical solution, when the electrostatic spinning nano fiber film-fabric composite coating material is in beer polyphenol In application, the fabric is the woven fabric or non-woven fabrics of polypropylene fibre in absorption.
The surface layer of electrostatic spinning nano fiber film-fabric composite coating material of the present invention is functional layer, middle layer and bottom Layer is combined with each other by PVP self-crosslinking in PVP cross-linking process and with being mutually crosslinked for PVDF-HFP, collectively constitutes composite coating The supporting layer of material.Fiber surface adsorbs in the PVPP and fabric that surface covering, the nanofiber of composite coating material are mutually crosslinked PVPP increase the contact area of PVPP and adsorbent material, play the role of stabilizer, it is effective to remove polyphenol object in beer Matter, and play the role of reinforcing composite coating material and connect.Middle layer has been compounded to form second level with bottom binary fabric Filter condition.Nano fibrous membrane middle layer is nanofiltration, and tissue layer is micron filter.The composite coating material has both more The absorption of phenol substance and the double-deck function of filtering, shorten process flow, have saved cost.
The invention has the advantages that:
1, for composite coating material by up of three-layer, surface is PVPP coating, and centre is PVDF-HFP/PVP nano fibrous membrane, Bottom is fabric.Under the conditions of existing for the persulfate, PVDF-HFP can also generate corresponding free radical, and PVP and PFDF- occurs The mutual cross-linking reaction of HFP, forms stable structure.Using PVP self-crosslinking and with the mutual cross-linking reaction of PVDF-HFP, can make PVPP firmly links together coating and layers of nanofibers, layers of nanofibers and fabric, improves material interface intensity, solves Film easily peelable problem.
2, in the absorption of beer polyphenol, the PVPP of composite material surface coating and fiber surface fixation improves connecing for material Contacting surface product, plays the role of stabilizer, effective to remove polyphenol substance in beer.The complex of middle layer and bottom binary fabric At secondary filtration condition.Layers of nanofibers is nanofiltration, and tissue layer is micron filter.The composite material has filtering And the function of polyphenol substance absorption, shorten process flow, save the cost.
3, due to needing caustic dip in PVPP recycling use process, polypropylene fabric is selected in the absorption of beer polyphenol.Polypropylene fibre Fabric, the resistance to acid and alkali of PVDF-HFP nano fibrous membrane be good, water-tolerant.The composite material can under acid, alkaline condition work Make, working life is longer.
4, PVPP due to its with physiological security, absorb liquid ability, can carry and discharge drug, water-insoluble, The characteristics such as complexing, composite material prepared by the present invention may also be fabricated which adhesive tape that is soft and having some strength, as ideal medicine Object carrier or wound wrap up dressing.Functional layer provides the ability for carrying medicine and absorbing liquid, intermediate nanometer layer acid and alkali-resistance, hydrophobicity It is good, product venting capability, bottom are provided as support layer, and strength and flexibility are provided.
Detailed description of the invention
Fig. 1 is the SEM figure of 7:3PVDF-HFP/PVP nano composite membrane in embodiment 1；
Fig. 2 is the SEM figure of 9:1PVDF-HFP/PVP nano composite membrane in embodiment 2；
Fig. 3 is nano fibrous membrane in embodiment 2-fabric composite coating material SEM figure, wherein (a) is face-coating, (b) It (c) is nano fibrous membrane and fabric interface for reverse side fabric.
Specific embodiment
Following nonlimiting examples can with a person of ordinary skill in the art will more fully understand the present invention, but not with Any mode limits the present invention.
The embodiment of the present invention selects following material and facility:
Scanning electron microscope (SEM): super-resolution thermal field emission scanning electron microscope JSM-780DF, Japan Electronics JEDL；
Needleless electrostatic spinning equipment: nanometer spider silk electrostatic spinning machine, ELMARCO company, Czech；
Strength test equipment: LLY-06E type electronic mono-fiber strong force instrument, Laizhou Electron Instrument Co., Ltd..Test specimens Product manufacturing process: long 5cm, the sample of wide 0.6cm are cut out.It is 20 DEG C in temperature, humidity is tested under the conditions of being 65%；
Thickness test equipment: YG141LA type digital textile thickness gauge, Laizhou Electron Instrument Co., Ltd..
Embodiment 1
PVDF-HFP is dissolved in DMAC, the PVDF-HFP solution of 20wt% is obtained.PVP is dissolved in DMAC, is obtained To the PVP solution of 6wt%.It is again that 7:3 is mixed with volume ratio with PVP solution by PVDF-HFP solution, prepares PVDF-HFP/PVP Composite spinning liquid.By PVDF-HFP/PVP composite spinning liquid in voltage 80kV, solution box speed 80mm/s, spinning time 40min Under the conditions of carry out needleless electrostatic spinning, obtain PVDF-HFP/PVP nano composite membrane.PVDF-HFP/PVP nano composite membrane breaks Resistance to spalling is 4.6202MPa, and nanofiber average diameter is 113nm, and with a thickness of 0.054mm, SEM is as shown in Figure 1.By PVDF- HFP/PVP nano composite membrane and Woven Polyester Fabrics (terylene: polyester filament 300DX5, weft yarn: polyester filament, 300DX4；Through close: 307/10cm, filling density: 122/10cm, 2/2 twill), it is placed in parallel up and down, and be bonded to each other, edge is pressed from both sides with mold Cause polymerization (crosslinking) reaction in next immersion initiation system, the concentration 0.5wt%'s, PVP of ammonium persulfate is dense in initiation system 5wt%, 90 DEG C of the temperature of reaction are spent, the time 6h of reaction reacts after terminating in 40 DEG C of dry 4h, obtains nano fibrous membrane- Fabric composite coating material.
Embodiment 2
PVDF-HFP is dissolved in the PVDF-HFP solution that 20wt% is obtained in DMAC.The PVP of 6wt% is dissolved in DMAC In, obtain PVP solution.It is again that 9:1 is mixed with volume ratio with PVP solution by PVDF-HFP solution, preparation PVDF-HFP/PVP is multiple Close spinning solution.PVDF-HFP/PVP composite spinning liquid is in voltage 80kV, solution box speed 80mm/s, spinning time 40min condition Lower progress needleless electrostatic spinning, obtains PVDF-HFP/PVP nano composite membrane.The fracture of PVDF-HFP/PVP nano composite membrane is strong Degree is 9.1565MPa, and nanofiber average diameter is 156nm, and with a thickness of 0.114mm, SEM is as shown in Figure 2.By PVDF-HFP/ PVP nano composite membrane and Woven Polyester Fabrics (warp thread: polyester filament 300DX5, weft yarn: polyester filament, 300DX4；Through close: 307 Root/10cm, filling density: 122/10cm, 2/2 twill), it is placed in parallel up and down, and be bonded to each other, after the mold cramping of edge It immerses in initiation system and causes polymerization (crosslinking) reaction, the concentration of the concentration 1wt%, PVP of ammonium persulfate in initiation system 10wt%, 95 DEG C of the temperature of reaction, the time 8h of reaction react after terminating in 40 DEG C of dry 4h, obtain nano fibrous membrane-and knit Object composite coating material, SEM as shown in figure 3, wherein (a) be face-coating, (b) be reverse side fabric, (c) be nano fibrous membrane With fabric interface.

Claims (10)

1. a kind of electrostatic spinning nano fiber film-fabric composite coating material, which is characterized in that be made of surface layer, middle layer, bottom Three-decker, the surface layer are the polyvinylpyrrolidone of crosslinking, and the middle layer is Kynoar-hexafluoropropene/poly- second Alkene pyrrolidone electrostatic spinning nano fiber film, the bottom are fabric, and the fabric is woven fabric or non-woven fabrics.
2. nano fibrous membrane according to claim 1-fabric composite coating material, which is characterized in that the polyvinylidene fluoride Alkene-hexafluoropropene/polyvinylpyrrolidone electrostatic spinning nano fiber film is with a thickness of 0.054-0.114mm；The fabric is to wash The woven fabric or non-woven fabrics of synthetic fibre, polypropylene fibre or polyamide fibre.
3. a kind of preparation method of electrostatic spinning nano fiber film-fabric composite coating material, which is characterized in that including walking as follows It is rapid:
(1) by volume it is that 9:1-7:3 is mixed with polyvinylpyrrolidonesolution solution by Kynoar-hexafluoropropene solution, obtains Kynoar-hexafluoropropene/polyvinylpyrrolidone Static Spinning is prepared to composite spinning solution, then by electrospinning process Nano fibrous membrane；
The Kynoar-hexafluoropropene solution concentration is 14-20wt%, the concentration of the polyvinylpyrrolidonesolution solution For 6-8wt%；
(2) Kynoar-hexafluoropropene/polyvinylpyrrolidone electrostatic spinning nano fiber film, fabric for preparing step (1) It is placed in parallel, and mutually fits, be immersed in initiation system, it is dry after polymerization reaction, it obtains electrostatic spinning nano fiber film-and knits Object composite coating material；
The fabric is woven fabric or non-woven fabrics；
The initiation system is the initiation system containing polyvinylpyrrolidone, initiator, water, and initiator is ammonium persulfate, poly- second The concentration of alkene pyrrolidone is 5-10wt%, and the concentration of ammonium persulfate is 0.5-1wt%, and the temperature of reaction is 90-95 DEG C, reaction Time be 6-8h.
4. according to the method described in claim 3, it is characterized in that, electrospinning process described in step (1) is needleless electrostatic Spinning.
5. according to the method described in claim 4, it is characterized in that, needleless electrospinning conditions described in step (1) are as follows: voltage 60-80kV, solution box speed 80-150mm/s, spinning time 40-120min.
6. preparation method according to claim 3, which is characterized in that fabric described in step (2) is terylene, polypropylene fibre or brocade The woven fabric or non-woven fabrics of synthetic fibre.
7. according to the method described in claim 3, it is characterized in that, the condition of drying described in step (2) are as follows: 40-60 DEG C Dry 2-4h.
8. according to the method described in claim 3, it is characterized in that, Kynoar described in step (1)-hexafluoropropene solution Solvent with polyvinylpyrrolidonesolution solution is N-N- dimethyl acetamide.
9. electrostatic spinning nano fiber film-fabric composite coating material or claim described in any one of claim 1-2 Electrostatic spinning nano fiber film-fabric composite coating material that any one of 2-8 the method obtains is in pharmaceutical carrier, Medical coating Application in material, the absorption of beer polyphenol.
10. application according to claim 9, when the electrostatic spinning nano fiber film-fabric composite coating material is in beer In application, the fabric is the woven fabric or non-woven fabrics of polypropylene fibre in polyphenol absorption.
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