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CN110253984B - Electrospinning nanofiber membrane-fabric composite coating material and preparation method - Google Patents

Electrospinning nanofiber membrane-fabric composite coating material and preparation method Download PDF

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Publication number
CN110253984B
CN110253984B CN201910533122.XA CN201910533122A CN110253984B CN 110253984 B CN110253984 B CN 110253984B CN 201910533122 A CN201910533122 A CN 201910533122A CN 110253984 B CN110253984 B CN 110253984B
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China
Prior art keywords
fabric
nanofiber membrane
coating material
composite coating
polyvinylpyrrolidone
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CN201910533122.XA
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CN110253984A (en
Inventor
王迎
杨云
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New Oriental Zhiyi Dandong Technology Co ltd
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Dalian Polytechnic University
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    • 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
    • A61F13/01—Non-adhesive bandages or dressings
    • A61F13/01008—Non-adhesive bandages or dressings characterised by the material
    • A61F13/01017—Non-adhesive bandages or dressings characterised by the material synthetic, e.g. polymer based
    • 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
    • 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
    • A61F13/01—Non-adhesive bandages or dressings
    • A61F13/01021—Non-adhesive bandages or dressings characterised by the structure of the dressing
    • A61F13/01029—Non-adhesive bandages or dressings characterised by the structure of the dressing made of multiple layers
    • 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
    • A61F13/01—Non-adhesive bandages or dressings
    • A61F13/01034—Non-adhesive bandages or dressings characterised by a property
    • A61F13/01046—Air-vapor permeability
    • 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 bandages or dressings
    • A61F13/0203—Adhesive bandages or dressings with fluid retention members
    • 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
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    • 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
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    • 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
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    • 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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    • B32B5/02—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
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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
    • 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
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    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
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    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
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    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
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Abstract

The invention discloses an electrostatic spinning nanofiber membrane-fabric composite coating material and a preparation method thereof. The composite coating material is composed of a three-layer structure. The surface layer is cross-linked PVPP obtained by PVP persulfate free radical polymerization; the middle layer is a polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP)/polyvinylpyrrolidone (PVP) needle-free electrostatic spinning nanofiber membrane; the bottom layer is a fabric. The surface layer is a functional layer, and the middle layer and the bottom layer are compounded together through PVP self-crosslinking and the cross-linking with PVDF-HFP in the PVP crosslinking process to jointly form a supporting layer of the composite coating material. The composite material prepared by the invention can be used for functional medical dressings and beer stabilizers, and has the double-layer functions of polyphenol substance adsorption and filtration.

Description

Electrostatic spinning nanofiber membrane-fabric composite coating material and preparation method thereof
Technical Field
The invention belongs to the field of composite material preparation, and particularly relates to a preparation method for processing an electrostatic spinning/fabric binary composite material. Can be applied to the technical field of nano material analysis technology and membrane material application.
Background
With the continuous development of the textile industry and the continuous improvement of the requirements of people on the comprehensive performance of textiles, the multifunctional composite fabric undoubtedly occupies a place in the development of the fabric. In recent years, the application of electrostatic spinning nanofibers which are generally concerned at home and abroad in spinning is increasing, and particularly reports that nanofibers are combined with traditional fabrics and applied to special industrial materials are frequent.
PVPP is formed by cross-linking polymerization of a vinylpyrrolidone monomer under specific conditions, is a high-molecular fine chemical product with excellent properties, and is a novel pharmaceutic adjuvant which is popular in recent years. PVPP is mainly used as a disintegrant for tablets, and has been approved as a food additive, a stabilizer, a clarifier, and the like in the brewing industry of beer, fruit juice, and the like.
PVPP is widely applied in the field of domestic and foreign beer and is used as a beer colloid stabilizer. No matter how cool the beer is after filtration, the dissolved classified compounds and proteins are still contained, and the irreversible permanent polymers formed by the polyphenol substances and the proteins under the condition of oxygen are the main reasons for beer chaos. The PVPP can effectively remove polyphenol substances in the beer, improve the clarity of the beer and prolong the shelf life of the beer.
At present, in beer production, kieselguhr and PVPP are mixed and then quantitatively added into beer, and after filtration, the PVPP and the kieselguhr form a filter cake which is treated as waste. The process does not need separate PVPP filtering equipment, but has higher production cost.
Disclosure of Invention
In order to solve the problem of high-efficiency use of the PVPP as the beer stabilizer, the invention breaks through the use method that the conventional PVPP is adsorbed by a powdery intermediate in the beer stabilizer and is filtered and removed in the form of a filter cake, and prepares the composite material which takes the electrostatic spinning nanofiber membrane-fabric filter material as a supporting layer and the PVPP coating as a functional layer.
The electrostatic spinning nanofiber membrane-fabric composite coating material is of a three-layer structure consisting of a surface layer, a middle layer and a bottom layer, wherein the surface layer is a crosslinked polyvinyl pyrrolidone (PVPP) coating obtained by PVP persulfate free radical polymerization, the middle layer is a polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP)/polyvinyl pyrrolidone (PVP) electrostatic spinning nanofiber membrane, preferably a polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP)/polyvinyl pyrrolidone (PVP) needle-free electrostatic spinning nanofiber membrane obtained by needle-free electrostatic spinning, and the bottom layer is a fabric which is a woven fabric or a non-woven fabric.
As a preferable technical scheme, the thickness of the polyvinylidene fluoride-hexafluoropropylene/polyvinylpyrrolidone electrostatic spinning nanofiber membrane is 0.054-0.114 mm; the fabric is a woven fabric or a non-woven fabric of terylene, polypropylene or chinlon.
The invention also provides a preparation method of the electrostatic spinning nanofiber membrane-fabric composite coating material, which comprises the following steps:
(1) mixing polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) solution and polyvinylpyrrolidone (PVP) solution according to a volume ratio of (9:1-7:3) to obtain a composite spinning solution, and preparing a polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP)/polyvinylpyrrolidone (PVP) electrospun nanofiber membrane by an electrostatic spinning method;
the concentration of the polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) solution is 14-20wt%, and the concentration of the polyvinylpyrrolidone solution is 6-8 wt%;
(2) placing the polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP)/polyvinylpyrrolidone (PVP) electrostatic spinning nanofiber membrane and fabric obtained in the step (1) in parallel, mutually attaching, immersing the membrane and the fabric into an initiation system containing PVP, an initiator and water to perform polymerization (crosslinking) reaction, and drying after crosslinking to obtain a nanofiber membrane-fabric composite coating material;
the initiator in the initiation system is ammonium persulfate, the concentration of polyvinylpyrrolidone (PVP) is 5-10wt%, the concentration of ammonium persulfate is 0.5-1wt%, the reaction temperature is 90-95 ℃, and the reaction time is 6-8 h.
As a preferable technical scheme, a solvent of the polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) solution and the polyvinylpyrrolidone (PVP) solution in the step (1) is N-Dimethylacetamide (DMAC); as a preferred technical scheme, the electrostatic spinning method in the step (1) is needle-free electrostatic spinning.
As a preferred technical scheme, the needleless electrospinning conditions in the step (1) are as follows: the voltage is 60-80kV, the solution box speed is 80-150mm/s, and the spinning time is 40-120 min.
Preferably, the thickness of the polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP)/polyvinylpyrrolidone (PVP) electrospun nanofiber membrane in the step (1) is 0.054-0.114 mm.
As a preferable technical scheme, the drying conditions in the step (2) are as follows: drying at 40-60 deg.C for 2-4 h.
As a preferable technical scheme, the fabric in the step (2) is a woven fabric or a non-woven fabric of terylene, polypropylene or chinlon.
The invention also provides application of the nanofiber membrane-fabric composite coating material in drug carriers, functional medical dressings and beer polyphenol adsorption. The product has double-layer functions of polyphenol adsorption and filtration, and can be used as beer stabilizer.
As a preferable technical scheme, when the electrostatic spinning nanofiber membrane-fabric composite coating material is applied to beer polyphenol adsorption, the fabric is a woven fabric or a non-woven fabric of polypropylene fibers.
The surface layer of the electrostatic spinning nanofiber membrane-fabric composite coating material is a functional layer, and the middle layer and the bottom layer are compounded together through PVP self-crosslinking and crosslinking with PVDF-HFP in the PVP crosslinking process to jointly form a supporting layer of the composite coating material. The surface coating of the composite coating material, the PVPP mutually crosslinked by the nano fibers and the PVPP adsorbed on the surfaces of the fibers in the fabric increase the contact area between the PVPP and the adsorbing material, play a role of a stabilizer, effectively remove polyphenol substances in beer and play a role in reinforcing and connecting the composite coating material. The intermediate layer and the bottom layer of the binary fabric are compounded to form a secondary filtering condition. The middle layer of the nano-fiber membrane is nano-grade filtration, and the fabric layer is micro-grade filtration. The composite coating material has the double-layer functions of polyphenol substance adsorption and filtration, shortens the process flow and saves the cost.
The invention has the beneficial effects that:
1. the composite coating material consists of three layers, wherein the surface is a PVPP coating, the middle is a PVDF-HFP/PVP nano fiber membrane, and the bottom layer is a fabric. In the presence of persulfate, PVDF-HFP can generate corresponding free radicals, and the cross-linking reaction of PVP and PFDF-HFP occurs to form a stable structure. By utilizing the self-crosslinking reaction of PVP and the cross-linking reaction of PVDF-HFP, the PVPP can firmly connect the coating with the nanofiber layer and the nanofiber layer with the fabric, the interface strength of the material is improved, and the problem that the membrane is easy to peel is solved.
2. In the beer polyphenol adsorption, the PVPP fixed on the surface coating of the composite material and the surface of the fiber improves the contact area of the material, plays a role of a stabilizer and effectively removes polyphenol substances in beer. The intermediate layer and the bottom layer of the binary fabric are compounded to form a secondary filtering condition. The nano-fiber layer is nano-filtration, and the fabric layer is micro-filtration. The composite material has the functions of filtering and adsorbing polyphenol substances, shortens the process flow and saves the cost.
3. Because the PVPP needs to be washed by alkali liquor in the recycling process, polypropylene fabrics are selected in the adsorption of the beer polyphenol. The polypropylene fabric and the PVDF-HFP nanofiber membrane have good acid and alkali resistance and water resistance. The composite material can work under acidic and alkaline conditions, and has a long service life.
4. The PVPP has the characteristics of physiological safety, liquid absorption capacity, drug carrying and releasing, water insolubility, complexation and the like, and the composite material prepared by the invention can also be prepared into a soft adhesive tape with certain strength and used as an ideal drug carrier or an ideal wound dressing. The functional layer provides drug loading and liquid absorption capacity, the middle nano layer is acid and alkali resistant and has good hydrophobicity, the product ventilation capacity is provided, and the bottom layer is a supporting layer and provides strength and flexibility.
Drawings
FIG. 1 is an SEM photograph of a 7:3PVDF-HFP/PVP nano-composite membrane in example 1;
FIG. 2 is an SEM photograph of a 9:1PVDF-HFP/PVP nano-composite membrane in example 2;
fig. 3 is SEM image of the nanofiber membrane-fabric composite coating material of example 2, wherein (a) is front side coating, (b) is back side fabric, and (c) is interface between nanofiber membrane and fabric.
Detailed Description
The following non-limiting examples will allow one of ordinary skill in the art to more fully understand the present invention, but are not intended to limit the invention in any way.
The embodiment of the invention selects the following materials and devices:
scanning Electron Microscope (SEM): a super-high resolution thermal field emission scanning electron microscope JSM-780DF, Japanese Electron JEDL;
needle-free electrospinning apparatus: nano spider silk electrostatic spinning machine, czech ELMARCO company;
and (3) a strength test device: LLY-06E model electronic single fiber strength tester, Leizhou electronic instruments, Inc. The test sample manufacturing process comprises the following steps: the specimens were cut out to a length of 5cm and a width of 0.6 cm. Testing at 20 deg.C and 65% humidity;
thickness test equipment: model YG141LA digital textile thickness meter, electronics ltd, lazhou.
Example 1
PVDF-HFP was dissolved in DMAC to give a 20wt% PVDF-HFP solution. PVP was dissolved in DMAC to give a 6 wt% PVP solution. And mixing the PVDF-HFP solution with the PVP solution according to the volume ratio of 7:3 to prepare the PVDF-HFP/PVP composite spinning solution. And (3) carrying out needleless electrostatic spinning on the PVDF-HFP/PVP composite spinning solution under the conditions of voltage of 80kV, solution box speed of 80mm/s and spinning time of 40min to obtain the PVDF-HFP/PVP nano composite membrane. The PVDF-HFP/PVP nano composite membrane has the breaking strength of 4.6202MPa, the average diameter of the nano fiber is 113nm, the thickness is 0.054mm, and SEM is shown in figure 1. The PVDF-HFP/PVP nano composite membrane and polyester woven fabric (polyester: polyester filament 300DX5, weft: polyester filament 300DX4, warp density: 307 pieces/10 cm, weft density: 122 pieces/10 cm, 2/2 twill) are placed in parallel up and down and are mutually attached, the peripheral edges are clamped by a mould and then immersed into an initiation system to initiate polymerization (crosslinking) reaction, the concentration of ammonium persulfate in the initiation system is 0.5 wt%, the concentration of PVP is 5 wt%, the reaction temperature is 90 ℃, the reaction time is 6 hours, and after the reaction is finished, the nano fiber membrane-fabric composite coating material is obtained after drying at 40 ℃ for 4 hours.
Example 2
PVDF-HFP was dissolved in DMAC to give a 20wt% solution of PVDF-HFP. 6 wt% of PVP was dissolved in DMAC to obtain a PVP solution. And mixing the PVDF-HFP solution with the PVP solution according to the volume ratio of 9:1 to prepare the PVDF-HFP/PVP composite spinning solution. And (3) carrying out needleless electrostatic spinning on the PVDF-HFP/PVP composite spinning solution under the conditions of voltage 80kV, solution box speed 80mm/s and spinning time 40min to obtain the PVDF-HFP/PVP nano composite membrane. The PVDF-HFP/PVP nano composite membrane has the breaking strength of 9.1565MPa, the average diameter of the nano fiber is 156nm, the thickness is 0.114mm, and SEM is shown in figure 2. The PVDF-HFP/PVP nano composite membrane and a polyester woven fabric (warp yarn: polyester filament 300DX5, weft yarn: polyester filament 300DX4, warp density: 307 pieces/10 cm, weft density: 122 pieces/10 cm, 2/2 twill) are placed in parallel up and down and are mutually attached, the peripheral edge is clamped by a mould and then is immersed into an initiation system to initiate polymerization (crosslinking) reaction, the concentration of ammonium persulfate in the initiation system is 1wt%, the concentration of PVP is 10wt%, the reaction temperature is 95 ℃, the reaction time is 8 hours, and after the reaction is finished, the nano fiber membrane-fabric composite coating material is dried at 40 ℃ for 4 hours to obtain the nano fiber membrane-fabric composite coating material, wherein SEM of the nano fiber membrane-fabric composite coating material is shown in figure 3, wherein (a) is a front side coating, (b) is a fabric, and (c) is an interface of the nano.

Claims (8)

1.一种用于啤酒多酚吸附的静电纺纳米纤维膜-织物复合涂层材料，其特征在于，制备方法，包括如下步骤：1. an electrospinning nanofiber membrane-fabric composite coating material for beer polyphenol adsorption, is characterized in that, preparation method, comprises the steps: （1）将聚偏氟乙烯-六氟丙烯溶液与聚乙烯吡咯烷酮溶液按体积比为9:1-7:3混合，得到复合纺丝溶液，再通过静电纺丝方法制备聚偏氟乙烯-六氟丙烯/聚乙烯吡咯烷酮静电纺纳米纤维膜；(1) Mix the polyvinylidene fluoride-hexafluoropropylene solution with the polyvinylpyrrolidone solution in a volume ratio of 9:1-7:3 to obtain a composite spinning solution, and then prepare the polyvinylidene fluoride-hexafluoroethylene by electrospinning. Fluoropropylene/polyvinylpyrrolidone electrospun nanofiber membrane; 所述聚偏氟乙烯-六氟丙烯溶液的浓度为14-20wt%，所述聚乙烯吡咯烷酮溶液的浓度为6-8wt%；The concentration of the polyvinylidene fluoride-hexafluoropropylene solution is 14-20wt%, and the concentration of the polyvinylpyrrolidone solution is 6-8wt%; （2）将步骤（1）制备的聚偏氟乙烯-六氟丙烯/聚乙烯吡咯烷酮静电纺纳米纤维膜、织物平行放置，且互相贴合，浸入到引发体系中，聚合反应后，干燥，得到静电纺纳米纤维膜-织物复合涂层材料；(2) The polyvinylidene fluoride-hexafluoropropylene/polyvinylpyrrolidone electrospinning nanofiber membrane and fabric prepared in step (1) are placed in parallel, and attached to each other, immersed in the initiation system, and after the polymerization reaction, drying is obtained to obtain Electrospinning nanofiber membrane-fabric composite coating material; 所述织物为机织物；The fabric is a woven fabric; 所述引发体系为含聚乙烯吡咯烷酮、引发剂、水的引发体系，引发剂为过硫酸铵，聚乙烯吡咯烷酮的浓度为5-10wt%，过硫酸铵的浓度为0.5-1wt%，反应的温度为90-95℃，反应的时间为6-8h。The initiating system is an initiating system containing polyvinylpyrrolidone, an initiator and water, the initiator is ammonium persulfate, the concentration of polyvinylpyrrolidone is 5-10wt%, the concentration of ammonium persulfate is 0.5-1wt%, and the reaction temperature It is 90-95 ℃, and the reaction time is 6-8h. 2.根据权利要求1所述的纳米纤维膜-织物复合涂层材料，其特征在于，所述聚偏氟乙烯-六氟丙烯/聚乙烯吡咯烷酮静电纺纳米纤维膜的厚度为0.054-0.114 mm；所述织物为涤纶、丙纶或锦纶的机织物。2. The nanofiber membrane-fabric composite coating material according to claim 1, wherein the polyvinylidene fluoride-hexafluoropropylene/polyvinylpyrrolidone electrospinning nanofiber membrane has a thickness of 0.054-0.114 mm; The fabric is a woven fabric of polyester, polypropylene or nylon. 3.根据权利要求1所述的纳米纤维膜-织物复合涂层材料，其特征在于，步骤（1）中所述静电纺丝方法为无针静电纺丝。3 . The nanofiber membrane-fabric composite coating material according to claim 1 , wherein the electrospinning method in step (1) is needle-free electrospinning. 4 . 4.根据权利要求3所述的纳米纤维膜-织物复合涂层材料，其特征在于，步骤（1）中所述无针静电纺丝条件为：电压60-80kV，溶液盒速度80-150mm/s，纺丝时间40-120min。The nanofiber membrane-fabric composite coating material according to claim 3, wherein the needle-free electrospinning conditions in step (1) are: voltage 60-80kV, solution box speed 80-150mm/ s, spinning time 40-120min. 5.根据权利要求1所述的纳米纤维膜-织物复合涂层材料，其特征在于，步骤（2）中所述的干燥的条件为：40-60℃干燥2-4h。5 . The nanofiber membrane-fabric composite coating material according to claim 1 , wherein the drying conditions in step (2) are: drying at 40-60° C. for 2-4 hours. 6 . 6.根据权利要求1所述的纳米纤维膜-织物复合涂层材料，其特征在于，步骤（1）中所述聚偏氟乙烯-六氟丙烯溶液和聚乙烯吡咯烷酮溶液的溶剂为N,N-二甲基乙酰胺。6 . The nanofiber membrane-fabric composite coating material according to claim 1 , wherein the solvents of the polyvinylidene fluoride-hexafluoropropylene solution and the polyvinylpyrrolidone solution in step (1) are N,N - Dimethylacetamide. 7.权利要求1-6中任意一项所述的静电纺纳米纤维膜-织物复合涂层材料在药物载体、医用敷料、啤酒多酚吸附中的应用。7. Application of the electrospun nanofiber membrane-fabric composite coating material according to any one of claims 1 to 6 in drug carrier, medical dressing, and beer polyphenol adsorption. 8.根据权利要求7所述的应用，当所述静电纺纳米纤维膜-织物复合涂层材料在啤酒多酚吸附中应用时，所述织物为丙纶的机织物。The application according to claim 7, when the electrospun nanofiber membrane-fabric composite coating material is applied in the adsorption of beer polyphenols, the fabric is a polypropylene woven fabric.
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