CN109675450B - Antibacterial composite nanofiber membrane and preparation method and application thereof - Google Patents

Antibacterial composite nanofiber membrane and preparation method and application thereof Download PDF

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CN109675450B
CN109675450B CN201811599162.6A CN201811599162A CN109675450B CN 109675450 B CN109675450 B CN 109675450B CN 201811599162 A CN201811599162 A CN 201811599162A CN 109675450 B CN109675450 B CN 109675450B
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nanofiber membrane
membrane
antibacterial
nano
antibacterial composite
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CN109675450A (en
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高明
李佳
黄逸凡
喻学锋
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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Priority to PCT/CN2019/121561 priority patent/WO2020134835A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
    • 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
    • A61L15/18—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing inorganic materials
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    • 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
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    • 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
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    • 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
    • A61L15/32—Proteins, polypeptides; Degradation products or derivatives thereof, e.g. albumin, collagen, fibrin, gelatin
    • 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
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    • 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
    • A61L15/46—Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/26—Polyalkenes
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/48—Polyesters
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    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/74—Natural macromolecular material or derivatives thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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    • D01F4/00—Monocomponent artificial filaments or the like of proteins; Manufacture thereof
    • D01F4/02—Monocomponent artificial filaments or the like of proteins; Manufacture thereof from fibroin
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/34—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated alcohols, acetals or ketals as the major constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
    • 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
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D—TEXTILES; PAPER
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
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    • 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
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/48—Antimicrobial properties

Abstract

The invention discloses an antibacterial composite nanofiber membrane and a preparation method and application thereof. An antibacterial composite nano-fibre membrane is composed of a nano-fibre membrane and g-C particles distributed on the surface and in said nano-fibre membrane3N4Nanosheets. Also discloses a preparation method of the antibacterial composite nanofiber membrane and application of the antibacterial composite nanofiber membrane. Compared with the prior art, the invention can prepare the nanofiber membrane with antibacterial and filtering functions only by utilizing the plasma technology and the graphite-phase carbon nitride particle material, and the membrane material has low resistance and high efficiency. Meanwhile, the preparation process of the antibacterial composite nanofiber membrane is safe and environment-friendly, and the preparation method is simple and feasible.

Description

Antibacterial composite nanofiber membrane and preparation method and application thereof
Technical Field
The invention relates to a nanofiber material, in particular to an antibacterial composite nanofiber membrane and a preparation method and application thereof.
Background
In recent years, regional atmospheric environmental problems with respirable particulate matter (PM10) and fine particulate matter (PM2.5) as characteristic pollutants have become prominent, and these particulate pollutants not only reduce the visibility of air, but also seriously affect people's health. Meanwhile, in some internal environments for human activities, besides dust particles, a large amount of pathogenic bacteria exist in the air, and the harmful bacteria also cause great harm to human health. Compared with the traditional filter material, the electrostatic spinning nanofiber membrane has the most excellent performance in a plurality of filter materials due to the sparse and porous structure and the relatively high specific surface area. However, since it is generally spun from high polymer, most of them can only intercept and electrostatically adsorb suspended particles in the air, and cannot remove bacteria, viruses and organic pollutants in the air. Under the guidance of the background and the application requirement, the preparation of the nanofiber filtering material with the antibacterial function has important practical significance.
In the prior art, chinese patent document CN102302875A discloses a preparation method of an antibacterial air filtration membrane, comprising: blending inorganic antibacterial agent containing metal or organic antibacterial agent containing sulfur and bromine, polymer, additive and solvent into solution; or the antibacterial agent and the polymer are melted and blended to obtain a uniform melt; and then spinning the nano-fiber on the surface of the non-woven fabric by using the blended solution or the melt through electrostatic spinning to obtain the antibacterial air filtering membrane.
CN103446803A discloses an antibacterial air filter felt and a preparation method and application thereof, wherein an electrostatic spinning polymer nano fiber felt is used as a carrier, a nano silver antibacterial agent is loaded by electrostatic spraying, a nano silver antibacterial agent suspension and a polymer spinning solution are prepared firstly, then the nano fiber felt is prepared by electrostatic spinning, the nano antibacterial agent is loaded by synchronous electrostatic spraying, and finally vacuum drying is carried out.
CN103520999A discloses an antibacterial composite nanofiber high-efficiency air filter material and a preparation method thereof, wherein the material sequentially comprises a non-woven fabric support layer, an antibacterial fiber and micron fiber blended filter layer and a nanofiber filter layer. In the antimicrobial fibers disclosed in this document, the antimicrobial agent is an inorganic particle containing silver, copper or zinc ions.
CN104070751A discloses an antibacterial composite fiber membrane for removing haze particles and formaldehyde and a preparation method thereof. The membrane is composed of a polymer nanofiber layer and a polymer-metal oxide composite ultrafine fiber layer. The metal oxide is prepared from MgO, CaO, ZnO and TiO2、MnO2、CuO、SnO、Fe2O3And AgO.
CN104213202A discloses a spinning solution and a method for preparing an antibacterial air filtering membrane by using the same, which comprises the following steps: (1) preparing a spinning solution; (2) the nanofiber antibacterial air filtering membrane is prepared through an electrostatic spinning process. The inorganic antibacterial agent is one or two of titanate and titanium dioxide; the organic antibacterial agent is one or more of sorbic acid, benzoic acid, dehydroacetic acid and sodium diacetate.
CN104524866A discloses a composite antibacterial air filtering material and its preparation method, comprising: the composite material comprises at least one layer of non-woven fabric base material, cellulose nano-fibers which are adhered among fibers of the non-woven fabric base material to form a network structure, and chitosan loaded on the surfaces of the fibers and/or the cellulose nano-fibers of the non-woven fabric base material.
CN104815483A discloses a composite antibacterial air filter material, a preparation method and application thereof, comprising: an electret fabric layer, an electrostatic spinning fiber membrane layer and a base material non-woven fabric layer which are sequentially bonded, wherein chitosan and nano TiO are loaded on the surfaces of the electrostatic spinning fiber membrane layer and the base material non-woven fabric layer2A photocatalyst.
CN105544091A discloses an antibacterial nanofiber composite material and a preparation method thereof, wherein the surface of the PLA fiber is provided with nano holes and TiO2Nanoparticles are deposited on the surface and nano holes of the PLA fiber to form a hybrid structure PLA/TiO with nano holes on the whole fiber and nano projections on the surface of the fiber2A fibrous membrane.
CN106039839A discloses a but cyclic utilization, high-efficient low resistance, antibiotic antifog air filtration material of haze, this air filtration material includes substrate layer and filter layer, and the filter layer is the nanofiber layer of load nanometer silver antibacterial agent, and this filter layer is made through the normal position growth method to the non-woven fabrics is the substrate layer.
CN107051232A discloses a sterilizing and aldehyde-removing air filtering membrane which is of a three-layer nanofiber membrane composite structure, wherein the upper layer is an active carbon nanofiber membrane, and the middle layer is pure TiO2A nano-fiber film, a lower nano-silver antibacterial fiber film, the pure TiO2The nano-fiber membrane is a high polymer material/TiO prepared by an electrostatic spinning method2Pure TiO obtained by heat treatment of precursor composite nanofiber membrane2The nano-fiber membrane is an electrospun nano-active carbon particle/high polymer material composite nano-fiber membrane, and the nano-silver antibacterial fiber membrane is an electrospun nano-silver particle/high polymer material composite nano-fiber membrane.
CN107051221A discloses an antibacterial air filtering membrane and a manufacturing process thereof, wherein the antibacterial air filtering membrane comprises the following raw materials in parts by weight: 20-35 parts of a composite antibacterial agent; 10-20 parts of a polymer; 1-2 parts of an additive; 200-250 parts of a solvent; 1-2 parts of tourmaline nano particles; 150-200 parts of adhesive suspension; 1-2 parts of nano titanium dioxide; the composite antibacterial agent is one or more of silver oxide, zinc oxide, silver-loaded zirconium phosphate, methylene bis-thiocyanate, chitin, mustard and castor oil.
CN107261865A discloses a functional air filter material, which is formed by compounding a base material and an antibacterial electrospun nanofiber layer, wherein the antibacterial agent in the antibacterial electrospun nanofiber layer is a biological antibacterial agent.
CN107497179A discloses a nano-antibacterial air-filtering nonwoven material and a preparation method thereof, the nano-antibacterial air-filtering nonwoven material comprises a nano-fiber antibacterial layer made of a polypropylene nonwoven material and an air-filtering layer formed on the surface of the nano-fiber antibacterial layer, a plurality of viscose dots are arranged between the nano-fiber antibacterial layer and the air-filtering layer, and the nano-fiber antibacterial layer and the air-filtering layer are bonded through the viscose dots. The nano-fiber antibacterial layer is a metal nano-antibacterial layer formed by loading a metal nano-antibacterial material on polypropylene.
CN108660611A discloses a nanofiber membrane for air sterilization and purification and a preparation method thereof, nylon and nano zeolite powder are added into N, N-dimethylformamide to prepare a shell material spinning solution; dispersing graphene oxide, ascorbic acid and water to obtain a core material spinning solution; and (3) obtaining the nanofiber membrane with nylon at the outside and graphene at the inside through coaxial electrostatic spinning.
CN108560145A discloses a preparation method of a bactericidal nanofiber membrane, which comprises the steps of proportioning deionized water, polyvinyl alcohol, boric acid, hydrochloric acid, polyhexamethylene biguanide salt and undecylenic acid amidopropyl betaine according to corresponding mass parts, adding polyvinyl alcohol and distilled water into a beaker, stirring and heating until the polyvinyl alcohol and the distilled water are dissolved to obtain a polyvinyl alcohol aqueous solution, adding boric acid into the solution, and stirring and reacting to obtain a polyvinyl alcohol-boric acid aqueous solution; adding polyhexamethylene biguanide salt and undecylenamidopropyl betaine respectively, stirring uniformly, adding hydrochloric acid, pouring the prepared electrostatic spinning solution into a syringe, using a stainless steel needle as a spray needle, connecting a high-voltage electric field at the needle to provide high voltage, and obtaining the nanofiber membranes with different thicknesses according to the spinning time.
The methods disclosed in the above documents all achieve good effects, but the antibacterial effect is based on an antibacterial agent with complex chemical components, and the filtering material is complex, and the preparation steps are complicated.
Recently, a simple and low-cost nano antibacterial material, namely graphite phase carbon nitride (g-C)3N4) Attracting attention, the material has the characteristics of high chemical stability, thermal stability, excellent conductivity, mechanical property and the like. Above all, the bactericidal composition has good bactericidal performance, is safe and green, and has no toxic or side effect. CN107034585A discloses a g-C3N4A nano-fibre antibacterial film with loose and porous structure g-C and its preparing process and application3N4The nano particles are added into a polyethylene oxide solution to prepare the nano fiber membrane. Subsequently, g-C is reacted3N4And drying the nanofiber antibacterial film in an oven for 4 hours, placing the dried nanofiber antibacterial film under an ultraviolet lamp for sterilization treatment for 2 hours, and treating the nanofiber antibacterial film with cold plasma of 500W for 2 minutes for later use to obtain the nanofiber film capable of resisting escherichia coli and staphylococcus aureus. CN107158969A also discloses a functionalized nano-fiber filter material, a preparation method and an application thereof, namely C is added3N4Dispersing the nanosheets into a solvent uniformly by ultrasonic oscillation, adding polymer powder, and dissolving uniformly to obtain the C-containing nanoparticles3N4The nano-sheet polymer spinning solution is prepared on a substrate by an electrostatic spinning technology to obtain the filter material capable of removing organic pollutants such as formaldehyde and the like. However, in these filter materials, C3N4The nano material is present in the interior of the filter material, and the air is first in contact with the surface of the filter material, and the filtering effect is still to be further improved. Therefore, how to provide a more efficient and low-resistance antibacterial filtration nanofiber membrane is a hot issue of attention by researchers in the industry.
Disclosure of Invention
The antibacterial nanofiber filtering membrane in the prior art generally uses an antibacterial agent containing metal or organic matters, and the structure of the fiber membrane is complex and the preparation steps are complicated. In order to overcome the defects of the prior art and solve the technical problem of how to prepare an antibacterial filtering nanofiber material with high efficiency and low resistance by using a material which is simple, easy to implement, low in cost, environment-friendly and safe, the invention aims to provide an antibacterial composite nanofiber membrane, the invention aims to provide a preparation method of the antibacterial composite nanofiber membrane, and the invention aims to provide application of the antibacterial composite nanofiber membrane.
The technical scheme adopted by the invention is as follows:
an antibacterial composite nano-fibre membrane is composed of a nano-fibre membrane and g-C particles distributed on the surface and in said nano-fibre membrane3N4Nanosheets.
Further, in the antibacterial composite nanofiber membrane, g-C3N4The nano-sheet is two-dimensional g-C3N4Nanosheets, g-C3N4The nano sheet exists on the surface and inside of the nano fiber membrane at the same time, and is in gridding distribution.
Preferably, in the antibacterial composite nanofiber membrane, etched pore channels with the pore diameter of 20 nm-100 nm exist on the surface of the nanofiber membrane.
Preferably, in the antibacterial composite nanofiber membrane, the thickness of the nanofiber membrane is more than 100 μm; more preferably, the thickness of the nanofiber membrane is 120 to 800 μm; still more preferably, the nanofiber membrane has a thickness of 150 to 500 μm
Preferably, in the antibacterial composite nanofiber membrane, the nanofiber membrane is made of at least one of polyacrylonitrile, polyamide, polylactic acid, polyurethane, polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, polycaprolactone, polyethylene oxide, polystyrene, polyester, polyimide, chitosan, silk fibroin, and collagen.
Preferably, in the antibacterial composite nanofiber membrane, g-C3N4The size of the nano sheet is 10 nm-100 nm.
The preparation method of the antibacterial composite nanofiber membrane comprises the following steps:
1) g to C3N4Mixing the nanoparticles with a solvent to obtain a mixture, and treating the mixture in a plasma atmosphere to obtain a mixture containing g-C3N4Of nanosheetsA dispersion liquid;
2) will contain g-C3N4Mixing and stirring the dispersion liquid of the nano sheets and the polymer capable of electrostatic spinning to obtain a polymer spinning solution;
3) performing electrostatic spinning on the polymer spinning solution to obtain a nanofiber membrane;
4) placing the nanofiber membrane in a plasma atmosphere for treatment, and coating the nanofiber membrane containing g-C obtained in the step 1)3N4Dispersing the nano sheets to obtain the antibacterial composite nanofiber membrane with the composition.
Preferably, in the step 1) of the preparation method of the antibacterial composite nanofiber membrane, g-C3N4The dosage ratio of the nanoparticles to the solvent is (1-8) g: 1L of the compound.
Preferably, in the step 1) of the preparation method of the antibacterial composite nanofiber membrane, g-C3N4The nano-particles are prepared by a high-temperature calcination method.
Preferably, in step 1) of the preparation method of the antibacterial composite nanofiber membrane, the solvent is at least one of water, acetone, halogenated methane, halogenated acetic acid, formic acid, N-dimethylformamide, tetrahydrofuran and dimethyl sulfoxide; further preferably, in the step 1), the solvent is at least one of water, acetone, dichloromethane, trifluoroacetic acid, formic acid, N-dimethylformamide, tetrahydrofuran and dimethyl sulfoxide; still further preferably, in step 1) of the preparation method, the solvent is at least one of water, formic acid and N, N-dimethylformamide.
Preferably, the preparation method of the antibacterial composite nanofiber membrane comprises the step 1) of g-C3N4g-C in Dispersion of nanosheets3N4The particle size of the nano-sheet is 10 nm-100 nm.
Preferably, the preparation method of the antibacterial composite nanofiber membrane comprises the steps 1), 2) and 4) of g-C3N4g-C in Dispersion of nanosheets3N4The mass percent of the nano-sheet is optionally 0.05-5%.
Preferably, the preparation method of the antibacterial composite nanofiber membrane comprises the step 2) In (b) contains g-C3N4The mass ratio of the dispersion liquid of the nanosheets to the polymer capable of being electrospun is 1: (5-30).
Preferably, in step 2) of the preparation method of the antibacterial composite nanofiber membrane, the polymer capable of being electrospun is at least one of polyacrylonitrile, polyamide, polylactic acid, polyurethane, polyvinyl alcohol, polyvinyl butyral, polyvinylpyrrolidone, polycaprolactone, polyethylene oxide, polystyrene, polyester, polyimide, chitosan, silk fibroin and collagen; further preferably, in the step 2) of the preparation method, the polymer capable of being electrospun is at least one of polyacrylonitrile, polyamide, polylactic acid, polyurethane, polyvinyl alcohol, polyethylene oxide, polystyrene, polyester, polyimide, chitosan, silk fibroin and collagen; still further preferably, in step 2), the polymer capable of being electrospun is at least one of polyacrylonitrile, polyamide, polyvinyl alcohol and silk fibroin.
Preferably, in step 3) of the preparation method of the antibacterial composite nanofiber membrane, the thickness of the obtained nanofiber membrane is more than 100 μm; further preferably, in the step 3) of the preparation method, the thickness of the nanofiber membrane is 120 to 800 μm; still more preferably, in the step 3) of the production method, the thickness of the nanofiber membrane is 150 to 500 μm.
Preferably, in step 4), the coating method is any one or more of spraying, curtain coating, roller coating and dip coating; further preferably, the preparation method step 4) is to spray; still further, the preparation method step 4) has the spraying time of 10-60 s.
Preferably, the preparation method of the antibacterial composite nanofiber membrane comprises the step 4) of g-C3N4g-C in Dispersion of nanosheets3N4The mass percent of the nano-sheets is 0.05-2%; even more preferably, in step 4) of the preparation process, contains g-C3N4g-C in Dispersion of nanosheets3N4The mass percentage of the nano-sheets is 0.1-1%.
Preferably, the preparation method of the antibacterial composite nanofiber membrane comprises the step 4) of g-C3N4g-C in Dispersion of nanosheets3N4The particle size of the nano-sheet is 10 nm-100 nm.
Preferably, in step 1) of the preparation method of the antibacterial composite nanofiber membrane, plasma is generated by at least one gas of nitrogen, air, oxygen, argon and helium, and the treatment time of the plasma atmosphere is more than 60 s; further preferably, in the step 1) of the production method, the time for the plasma atmosphere treatment is 90 to 300 seconds.
Preferably, in step 4) of the preparation method of the antibacterial composite nanofiber membrane, the plasma is generated by uniformly glow-discharging discharge gas, the discharge gas is at least one of nitrogen, argon, helium and air, and the treatment time of the plasma atmosphere is not more than 300 s; further preferably, in the step 4) of the preparation method, the time for the plasma atmosphere treatment is 20s to 300 s; still more preferably, in the step 4) of the production method, the time for the plasma atmosphere treatment is 30 to 200 seconds.
The antibacterial composite nanofiber membrane is applied to an air filtration membrane and/or a food preservative film and/or a medical dressing.
Further preferably, the antibacterial composite nanofiber membrane is applied as an air filtration membrane.
The invention has the beneficial effects that:
compared with the prior art, the invention only utilizes the plasma technology and the graphite phase carbon nitride (g-C)3N4) The nano-fiber membrane with antibacterial and filtering functions can be prepared by the particle material, and the membrane material has low resistance and high efficiency. Meanwhile, the preparation process of the antibacterial composite nanofiber membrane is safe and environment-friendly, no wastewater or waste chemical reagent is generated, and the preparation method is simple and easy to implement.
Drawings
FIG. 1 is a surface topography of nanofibers on the outer layer of the antimicrobial composite nanofiber membrane of example 1;
FIG. 2 is a surface topography of nanofibers on the outer layer of the nanofiber membrane of comparative example 3.
Detailed Description
The invention discloses an antibacterial composite nanofiber air filtering membrane which is composed of nanofibers and two-dimensional g-C3N4Nano-sheet, and nano-pore channel g-C is existed on the surface of nano-fiber of membrane outer layer3N4The nano-sheet exists on the surface and in the interior of the nano-fiber membrane. The invention is realized by the pair g-C3N4The design of the composite mode and structure of the nano-sheets and the nano-fibers enables the g-C3N4The nano sheets exist on the surface and in the nano fiber membrane simultaneously, so that the grid-shaped dense distribution is formed. In use, the surface coated with the nanosheets is placed on the side in contact with the contaminated air containing bacteria, and when the bacteria-laden particulate contacts the nanofiber web, g-C in the nanopores on the surface of the outer layer of nanofibers3N4The nano-sheets and the nano-sheets inside the nano-sheets can act on bacteria together to inhibit the bacteria from surviving. The preparation method adopts a plasma technology, and firstly prepares the g-C by a high-temperature calcination method3N4The method comprises the steps of adding nanoparticles into a solvent required by spinning, and then placing the solution in a plasma atmosphere for treatment, so that the nanoparticles are stripped into nanosheets with certain sizes, and meanwhile, active groups are introduced to the surfaces of the nanosheets. The polymer to be spun is then added and stirred until uniformly dispersed. And spinning the obtained polymer spinning solution by a conventional electrostatic spinning technology to obtain the nanofiber membrane with a thickness larger than a certain thickness. The obtained nanofiber membrane is put in a plasma atmosphere for treatment, and then the g-C content is sprayed3N4A dispersion of nanoplatelets.
The present invention will be described in further detail with reference to specific examples. The starting materials used in the examples are, unless otherwise specified, commercially available from conventional sources. The calcination at elevated temperature mentioned in the examples gives g-C3N4Nanoparticles, and electrospinning are common techniques.
Example 1
0.1g of the raw materials are calcined at high temperature to prepare g-C3N4The nanoparticles were added to 50ml of N, N-Dimethylformamide (DMF) solvent and then treated in an air plasma atmosphere for 120s, so that the nanoparticles were exfoliated into nanosheets having a particle size of 15 nm. Adding polyacrylonitrile polymer to be spun, and stirring until the polyacrylonitrile polymer is uniformly dispersed; spinning the obtained polymer spinning solution by an electrostatic spinning method to obtain a nanofiber membrane with the thickness of 300 microns; placing the obtained nanofiber membrane in helium uniform glow discharge plasma atmosphere for processing for 180s, and then spraying the nanofiber membrane containing g-C3N4Spraying 0.1 wt.% dispersion liquid of the nano sheets for 20s, and drying at room temperature to obtain the antibacterial composite nano fiber membrane product.
Fig. 1 is a surface topography of outer layer nanofibers in the antibacterial composite nanofiber membrane obtained in this example. It can be seen from fig. 1 that the surface of the nanofiber has etched pore channels and is loaded with nanosheets.
The general cigarette smoke filtration test method is used for testing the filtration effect of the nanofiber membrane, the pressure gauge is used for measuring the airflow pressure difference of the filter membrane, and the result shows that the filtration efficiency of the prepared fiber membrane on PM (particulate matter) in the air is up to more than 97.8%, and the filtration pressure drop is 10-50 Pa. According to the test of the antibacterial performance of the fiber membrane in accordance with the national standard GB/T20944.3-2008, the antibacterial rate of the fiber membrane to staphylococcus aureus reaches 98.6%, and the antibacterial rate to escherichia coli reaches 97.5%.
Example 2
0.15g of the raw materials are calcined at high temperature to prepare g-C3N4And adding the nanoparticles into 60ml of formic acid solvent, and then placing the mixture in an argon plasma atmosphere for treatment for 90s, so that the nanoparticles are stripped into nanosheets with the particle size of 20 nm. Then adding the polyamide polymer to be spun, and stirring until the polyamide polymer is uniformly dispersed; spinning the obtained polymer spinning solution by an electrostatic spinning method to obtain a nanofiber membrane with the thickness of 450 microns; placing the obtained nanofiber membrane in an argon uniform glow discharge plasma atmosphere for treating for 150s, and then spraying the nanofiber membrane containing g-C3N4Spraying 0.2 wt.% dispersion liquid of the nano-sheets for 30s, and drying at room temperature to obtain the antibacterial compoundAnd synthesizing the nanofiber membrane product.
The general cigarette smoke filtration test method is used for testing the filtration effect of the nanofiber membrane, the pressure gauge is used for measuring the airflow pressure difference of the filter membrane, and the result shows that the filtration efficiency of the prepared fiber membrane on PM in the air is up to more than 96.9%, and the filtration pressure drop is between 20 and 50 Pa. According to the test of the antibacterial performance of the fiber membrane in accordance with the national standard GB/T20944.3-2008, the antibacterial rate of the fiber membrane to staphylococcus aureus reaches 97.8%, and the antibacterial rate to escherichia coli reaches 96.5%.
Example 3
0.4g of the raw materials are calcined at high temperature to prepare g-C3N4And adding the nano particles into 100ml of deionized water solvent, and then placing the solvent in an oxygen plasma atmosphere for treatment for 300s, so that the nano particles are stripped into nano sheets with the particle size of 30 nm. Then adding a polyvinyl alcohol polymer to be spun, and stirring until the polyvinyl alcohol polymer is uniformly dispersed; spinning the obtained polymer spinning solution by an electrostatic spinning method to obtain a nanofiber membrane with the thickness of 500 microns; placing the obtained nanofiber membrane in nitrogen uniform glow discharge plasma atmosphere for treatment for 200s, and then spraying the solution containing g-C3N4Spraying 0.5 wt.% dispersion liquid of the nano sheets for 15s, and drying at room temperature to obtain the antibacterial composite nano fiber membrane product.
The general cigarette smoke filtration test method is used for testing the filtration effect of the nanofiber membrane, the pressure gauge is used for measuring the airflow pressure difference of the filter membrane, and the result shows that the filtration efficiency of the prepared fiber membrane on PM in the air is up to more than 98.9%, and the filtration pressure drop is between 20 and 60 Pa. According to the test of the antibacterial performance of the fiber membrane in accordance with the national standard GB/T20944.3-2008, the antibacterial rate of the fiber membrane to staphylococcus aureus reaches 98.8%, and the antibacterial rate to escherichia coli reaches 98.1%.
Example 4
0.2g of the raw materials are calcined at high temperature to prepare g-C3N4Adding the nanoparticles into 80ml of formic acid solvent, and then placing the mixture in a nitrogen plasma atmosphere for processing for 180s to strip the nanoparticles into nanoparticles with the particle size of 10nmAnd (5) rice flakes. Then adding the silk fibroin polymer to be spun, and stirring until the silk fibroin polymer is uniformly dispersed; spinning the obtained polymer spinning solution by an electrostatic spinning method to obtain a nanofiber membrane with the thickness of 150 microns; placing the obtained nanofiber membrane in an air uniform glow discharge plasma atmosphere for treatment for 30s, and then spraying the nanofiber membrane containing g-C3N4Spraying 1 wt.% dispersion liquid of the nanosheets for 45s, and drying at room temperature to obtain the antibacterial composite nanofiber membrane product.
The general cigarette smoke filtration test method is used for testing the filtration effect of the nanofiber membrane, the pressure gauge is used for measuring the airflow pressure difference of the filter membrane, and the result shows that the filtration efficiency of the prepared fiber membrane on PM in the air is up to more than 99.1%, and the filtration pressure drop is 30-70 Pa. According to the test of the antibacterial performance of the fiber membrane in accordance with the national standard GB/T20944.3-2008, the antibacterial rate of the fiber membrane to staphylococcus aureus reaches 98.2%, and the antibacterial rate to escherichia coli reaches 99.0%.
Comparative example 1
0.2g of g-C prepared by a high-temperature calcination method3N4The nano particles are added into a formic acid solvent, the plasma treatment is not carried out, then the silk fibroin polymer to be spun is directly added, and the stirring is carried out to find that the nano particles have an agglomeration phenomenon and can not be uniformly dissolved, so that the conventional electrostatic spinning can not be carried out.
Comparative example 2
0.2g of the raw materials are calcined at high temperature to prepare g-C3N4And adding the nanoparticles into 80ml of formic acid solvent, and then placing the mixture in a nitrogen plasma atmosphere for processing for 180s, so that the nanoparticles are stripped into nanosheets with the particle size of 10 nm. Then adding the silk fibroin polymer to be spun, and stirring until the silk fibroin polymer is uniformly dispersed; spinning the obtained polymer spinning solution by a conventional electrostatic spinning technology to obtain a nanofiber membrane with the thickness of 150 microns; placing the obtained nanofiber membrane in an air uniform glow discharge plasma atmosphere for treatment for 30s, and then spraying g-C3N4And (5) nanosheet, namely obtaining the final product.
Comparative example 3
The same polyacrylonitrile polymer as in example 1 was used to spin by the same electrospinning method, and a nanofiber membrane 300 μm thick was obtained. FIG. 2 is a surface topography of nanofibers on the outer layer of the nanofiber membrane obtained in this comparative example.
The general cigarette smoke filtration test method is used for testing the filtration effect of the nanofiber membrane, the pressure gauge is used for measuring the airflow pressure difference of the filter membrane, and the result shows that the filtration efficiency of the filter membrane prepared in the comparative example 2 on PM in air is reduced to more than 89.1%, and the filtration pressure drop is 40-70 Pa. According to the test of the antibacterial performance of the fiber membrane in accordance with the national standard GB/T20944.3-2008, the antibacterial rate of the fiber membrane to staphylococcus aureus is only 87.2 percent and the antibacterial rate to escherichia coli is only 88.0 percent.
As can be seen from comparative examples 1 and 2, the absence of plasma treatment causes the nanoparticles to agglomerate, and conventional spinning cannot be performed. And spraying the nanosheets without post-treatment, such that g-C is obtained3N4The nano sheet only exists in the nano fiber film, so that the antibacterial and bacteriostatic effects of the nano fiber film are obviously reduced.
Comparing the surface topography of the nanofiber membrane outer layer nanofiber of example 1 and comparative example 3, that is, as can be seen from fig. 1 and fig. 2, the surface of the nanofiber is obviously rough and nano sheets are supported by the etched pore channels formed by plasma treatment in example 1.
From the above examples it can be seen that: the nanofiber membrane disclosed by the invention is simple in structure, does not contain an antibacterial agent of metal or organic matters, is safe and efficient, and is green and environment-friendly. The preparation method of the nanofiber membrane provided by the invention is simple and feasible, and does not generate chemical residue and wastewater.

Claims (10)

1. An antibacterial composite nanofiber membrane, which is characterized in that: comprises a nanofiber membrane and g-C distributed on the surface and inside the nanofiber membrane3N4Nanosheets;
the antibacterial composite nanofiber membrane is prepared by the following method, and comprises the following steps:
1) g to C3N4Mixing the nanoparticles with a solvent to obtainTreating the obtained mixed solution in a plasma atmosphere to obtain a mixture containing g-C3N4A dispersion of nanoplatelets;
2) will contain g-C3N4Mixing and stirring the dispersion liquid of the nano sheets and the polymer capable of electrostatic spinning to obtain a polymer spinning solution;
3) performing electrostatic spinning on the polymer spinning solution to obtain a nanofiber membrane;
4) placing the nanofiber membrane in a plasma atmosphere for treatment, and coating the nanofiber membrane containing g-C obtained in the step 1)3N4Dispersing the nano sheets to obtain the antibacterial composite nanofiber membrane.
2. The antibacterial composite nanofiber membrane as claimed in claim 1, wherein: the surface of the nanofiber membrane has an etching pore channel with the pore diameter of 20 nm-100 nm.
3. The antibacterial composite nanofiber membrane as claimed in claim 1 or 2, wherein: the thickness of the nanofiber membrane is greater than 100 μm.
4. The antibacterial composite nanofiber membrane as claimed in claim 1, wherein: g-C3N4The size of the nano sheet is 10 nm-100 nm.
5. A preparation method of an antibacterial composite nanofiber membrane is characterized by comprising the following steps: the method comprises the following steps:
1) g to C3N4Mixing the nanoparticles with a solvent to obtain a mixture, and treating the mixture in a plasma atmosphere to obtain a mixture containing g-C3N4A dispersion of nanoplatelets;
2) will contain g-C3N4Mixing and stirring the dispersion liquid of the nano sheets and the polymer capable of electrostatic spinning to obtain a polymer spinning solution;
3) performing electrostatic spinning on the polymer spinning solution to obtain a nanofiber membrane;
4) placing the nanofiber membrane in a plasma atmosphere for treatment, and coating the nanofiber membrane obtained in the step 1)Containing g-C3N4A dispersion of nanosheets to provide the antibacterial composite nanofiber membrane of any one of claims 1 to 4.
6. The method for preparing an antibacterial composite nanofiber membrane as claimed in claim 5, wherein the method comprises the following steps: in step 1), step 2) and step 4), contains g-C3N4g-C in Dispersion of nanosheets3N4The mass percent of the nano-sheet is optionally 0.05-5%.
7. The method for preparing an antibacterial composite nanofiber membrane as claimed in claim 5 or 6, wherein: in step 2), contains g-C3N4The mass ratio of the dispersion liquid of the nanosheets to the polymer capable of being electrospun is 1: (5-30).
8. The method for preparing an antibacterial composite nanofiber membrane as claimed in claim 5 or 6, wherein: in the step 1), the plasma is generated by at least one gas of nitrogen, air, oxygen, argon and helium, and the treatment time of the plasma atmosphere is more than 60 s.
9. The method for preparing an antibacterial composite nanofiber membrane as claimed in claim 5 or 6, wherein: in the step 4), the plasma is generated by uniformly glow discharging discharge gas, the discharge gas is at least one of nitrogen, argon, helium and air, and the plasma atmosphere treatment time is not more than 300 s.
10. The use of the antibacterial composite nanofiber membrane as claimed in any one of claims 1 to 4 as an air filtration membrane and/or a food preservative film and/or a medical dressing.
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