CN114763628A - Antiviral nanofiber and preparation method thereof - Google Patents

Antiviral nanofiber and preparation method thereof Download PDF

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Publication number
CN114763628A
CN114763628A CN202110041928.4A CN202110041928A CN114763628A CN 114763628 A CN114763628 A CN 114763628A CN 202110041928 A CN202110041928 A CN 202110041928A CN 114763628 A CN114763628 A CN 114763628A
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antiviral
nanofiber
water
polyvinyl alcohol
solution
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戴伟民
刘险峰
段晓博
王春蕾
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Shengna Technology Shanghai Co ltd
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/50Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/0007Electro-spinning
    • D01D5/0015Electro-spinning characterised by the initial state of the material
    • D01D5/003Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • D01F1/103Agents inhibiting growth of microorganisms
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING 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
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282Addition polymers
    • D04H1/4309Polyvinyl alcohol
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING 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
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70Non-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
    • D04H1/72Non-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
    • D04H1/728Non-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
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/12Aldehydes; Ketones
    • D06M13/123Polyaldehydes; Polyketones
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16Synthetic fibres, other than mineral fibres
    • D06M2101/18Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/24Polymers or copolymers of alkenylalcohols or esters thereof; Polymers or copolymers of alkenylethers, acetals or ketones

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Artificial Filaments (AREA)

Abstract

The invention discloses an antiviral nanofiber and a preparation method thereof, wherein the antiviral nanofiber is a water-soluble polymer nanofiber loaded with an antiviral component, the antiviral component is a quaternary ammonium salt derivative, and the antiviral nanofiber is subjected to water-insoluble treatment; the preparation method comprises the following steps: (1) dispersing polyvinyl alcohol in water, and stirring and dissolving under a heating condition to obtain a polyvinyl alcohol solution; (2) adding an antiviral component into the polyvinyl alcohol solution, and uniformly stirring at room temperature to obtain a mixed spinning solution; (3) carrying out electrostatic spinning by using the mixed spinning solution to obtain the antiviral component-loaded nano-fiber; (4) and (4) carrying out water-insoluble treatment on the nanofiber obtained in the step (3) through a crosslinking reaction. The antiviral nanofiber can be used as a filtering layer of air filtering devices and equipment such as masks and air filters, and can efficiently adsorb and kill harmful substances such as viruses and bacteria in the air.

Description

Antiviral nanofiber and preparation method thereof
Technical Field
The invention belongs to the field of materials, and particularly relates to an antiviral nanofiber and a preparation method thereof.
Background
The nanofibers can be used as air filtration materials, generally, the filtration efficiency of the filtration materials increases with the decrease of the diameter of the filtration fibers, and the nanomaterials prepared by the electrospinning technology are generally distributed in the diameter range from a few nanometers to hundreds of nanometers. The electrostatic spinning is one of the most effective modes for preparing the nanofiber material at present, and has the advantages of simple operation, short preparation flow, wide material selection and the like.
The existing air filtering material only filters harmful substances such as viruses, bacteria and the like in the air through the physical properties of the material, and has limited effect.
Disclosure of Invention
The invention aims to provide an antiviral nanofiber and a preparation method thereof, provides a filtering material capable of killing harmful substances such as viruses, bacteria and the like in the air by a chemical method, and provides a dual filtering mechanism guarantee.
In order to achieve the above object, the present invention provides an antiviral nanofiber, wherein the nanofiber is a water-soluble polymer nanofiber loaded with an antiviral component, and the antiviral component is a quaternary ammonium salt derivative; the antiviral nanofiber is subjected to water-insoluble treatment to enhance the durability as an air filter material.
As a preferred example, the nanofibers are spun from a water-soluble high polymer PVA.
As a specific example, the water-insoluble treatment is a crosslinking reaction.
The invention also provides a preparation method of the antiviral nanofiber, which is characterized by comprising the following steps:
(1) dispersing polyvinyl alcohol in water, and stirring and dissolving under a heating condition to obtain a polyvinyl alcohol solution;
(2) adding an antiviral component quaternary ammonium salt derivative into the polyvinyl alcohol solution, and uniformly stirring at room temperature to obtain a mixed spinning solution;
(3) Carrying out electrostatic spinning by using the mixed spinning solution to obtain the antiviral component loaded nanofiber;
(4) and (3) carrying out water-insoluble treatment on the nanofibers obtained in the step (3) through a crosslinking reaction.
Wherein, the polymerization degree of the polyvinyl alcohol in the step (1) is 1700-2200, and the alcoholysis degree is not less than 95 percent;
wherein, the concentration of the polyvinyl alcohol solution in the step (1) is 8-15 wt%;
wherein the mass fraction of the antiviral component in the solution in the step (2) is 1-20 wt%, and the stirring time is 3-5 h;
wherein the electrostatic spinning parameters in the step (3) are as follows: the electrostatic spinning applied voltage is 12-20KV, the receiving distance is 12-22cm, and the solution flow rate is 0.4-1.2 mL/h;
wherein the temperature conditions of the electrostatic spinning in the step (3) are as follows: 20-25 ℃ and relative humidity of 30-50%;
wherein, the cross-linking agent of the cross-linking reaction in the step (4) is glutaraldehyde, and the solvent is acetone or absolute ethyl alcohol.
As a specific example, the quaternary ammonium salt derivative is dodecyltrimethylammonium chloride.
The nano material prepared by electrostatic spinning generally has higher porosity and excellent air permeability, is very suitable for being used as an air filtering material, has the excellent characteristics of high porosity, large specific surface area and the like of nano fibers, can better exert the drug effect, carries the drug by the nano fibers, can avoid the drug burst release in the release process of the drug, and can continuously and efficiently provide the drug effect.
The antiviral nanofiber can be used as a filter layer of air filtering devices and equipment such as a mask, an air filter, a breathing machine and the like, can efficiently adsorb and kill harmful substances such as viruses, bacteria and the like in the air, and further improves the filtering effect of the mask on the harmful substances in the air.
The anti-virus component of the invention is quaternary ammonium salt derivative which is a broad-spectrum anti-virus bacteriostatic agent, and the anti-virus component can attack the envelope composed of protein and polysaccharide in the virus to denature the envelope, so that the RNA of the virus can be accelerated to degrade until the RNA is finally inactivated to realize the anti-virus; the bacteria killing bacteria also has the function of sterilization, and the sterilization mechanism of the bacteria killing bacteria mainly effectively attaches cations with the sterilization function to the surface of the bacteria, so that bioactive enzymes and metabolic intermediates in the bacteria overflow by destroying cell membranes of the bacteria, thereby achieving the functions of sterilization and bacteriostasis.
The quaternary ammonium salt derivative is a water-soluble substance, has better compatibility with a polyvinyl alcohol solution, and enables the quaternary ammonium salt component to be uniformly distributed on the antiviral nano-fiber, thereby achieving better and more stable antiviral and antibacterial effects and having better biological safety.
The nanofiber is mainly prepared by spinning the water-soluble high polymer PVA, the problem of solvent residue is avoided, the selected material is green and environment-friendly, and the nanofiber has stronger durability in coping with humidity in the air, moisture discharged by breathing and the like through water-insoluble treatment such as crosslinking reaction; the invention is environment-friendly and nontoxic, kills harmful substances such as viruses, bacteria and the like in the air by a chemical method and provides a dual filtering mechanism guarantee.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example one
(1) Adding 10g of polyvinyl alcohol into 80g of water, and stirring for 8 hours under the heating condition of 80 ℃ to dissolve the polyvinyl alcohol to obtain a polyvinyl alcohol solution;
(2) adding 10g of dodecyl trimethyl ammonium chloride into the polyvinyl alcohol solution, and uniformly stirring for 3 hours at room temperature to obtain a mixed spinning solution;
(3) and (2) carrying out electrostatic spinning on the mixed spinning solution to obtain the nanofiber membrane loaded with the antiviral component, wherein the spinning conditions are as follows: the spinning voltage is 15KV, the receiving distance is 12cm, and the solution flow rate is 0.8 ml/h;
(4) Preparing a cross-linking agent solution: adding 5 wt% of glutaraldehyde (25% aqueous solution) into acetone, then adding 2ml of dilute hydrochloric acid, and uniformly mixing;
(5) and (4) flatly immersing the nanofiber membrane prepared in the step (3) into the cross-linking agent solution in the step (4), standing for 3 hours, taking out, washing for 5 times, and drying in a drying oven at 40 ℃.
The prepared nanofiber membrane is tested for antiviral effect, and the experimental result is shown in table one, so that the antiviral activity rate of the antiviral nanofiber provided by the embodiment of the invention on H1N1 influenza virus reaches more than 91%.
Table one:
Figure BDA0002895661390000031
example two
(1) Adding 10g of polyvinyl alcohol into 70g of water, and stirring for 8 hours under the heating condition of 80 ℃ to dissolve the polyvinyl alcohol to obtain a polyvinyl alcohol solution;
(2) adding 20g of dodecyl trimethyl ammonium chloride into the polyvinyl alcohol solution, and uniformly stirring for 3 hours at room temperature to obtain a mixed spinning solution;
(3) and (2) carrying out electrostatic spinning on the mixed spinning solution to obtain the antiviral component-loaded nanofiber, wherein the spinning conditions are as follows: the spinning voltage is 15KV, the receiving distance is 12cm, and the solution flow rate is 0.8 ml/h;
(4) preparing a cross-linking agent solution: adding 5 wt% glutaraldehyde (25% water solution) into acetone, adding 2ml dilute hydrochloric acid, and mixing;
(5) and (4) flatly immersing the nano-fibers prepared in the step (3) into the cross-linking agent solution in the step (4), standing for 3 hours, taking out and washing for 5 times, and drying in a drying oven at 40 ℃.
The prepared nanofiber membrane is subjected to antiviral effect test, and the experimental result is shown in table two, so that the antiviral activity rate of the nanofiber membrane prepared in the embodiment of the invention on H3N2 influenza virus reaches more than 99%.
Table two:
Figure BDA0002895661390000041
the parameters in the tests in the two above-described examples are explained below:
a) and (3) testing result validity judgment standard: when the following given 3 conditions are all satisfied, the test is determined to be valid, otherwise, the test is invalid, and the test needs to be performed again.
1) The virus titer measured by immediate recovery of the control sample after inoculation should be 1.0X 106PFU/cm2(or TCID50/cm2) To 1.0X 107PFU/cm2(or TCID50/cm2) In the presence of a surfactant.
2) The eluent does achieve effective inhibition of the antiviral agent in the sample.
3) The control sample had a log reduction in viral titer of less than or equal to 1.0.
The calculation is shown in formula (1):
M=lg(Va/Vb)=lg(Va)-lg(Vb) …………………(1)
wherein
M is a decreasing value;
lg (va) is the log mean of viral infectious titers eluting immediately after inoculation of 3 reference samples;
lg (vb) is the log mean value of the virus infection titer eluted 2h after 3 reference samples are inoculated;
b) calculation of antiviral Activity value
The antiviral activity value was calculated using formula (2).
Mv=lg(Va/Vc)=lg(Va)-lg(Vc)………………………(2)
Wherein:
mv — antiviral activity value;
lg (Va) -3 control samples are inoculated for 2 hours and then the recovered virus titer is the mean value of the logarithm;
log mean of virus titers recovered 2h after inoculation of lg (Vc) -3 samples.
c) Calculation of antiviral Activity Rate
The antiviral activity rate was calculated using formula (3).
Figure BDA0002895661390000051
Wherein:
r (%) — antiviral activity (%);
b-average titer value recovered 0h after inoculation of 3 control samples, in units of PFU/cm2(or TCID50/cm2);
C-average titer value recovered 2h after inoculation of 3 antiviral samples, in units of PFU/cm2(or TCID50/cm2)。
In summary, the above embodiments are merely preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. An antiviral nanofiber, characterized in that the antiviral nanofiber is a water-soluble polymer nanofiber loaded with an antiviral component, and the antiviral component is a quaternary ammonium salt derivative; the antiviral nanofibers are treated to be water insoluble.
2. The anti-viral nanofiber according to claim 1, wherein the nanofiber is spun from a water-soluble high polymer PVA.
3. The production method according to claim 1, wherein the water-insoluble treatment is a crosslinking reaction.
4. A method for preparing the antiviral nanofiber as set forth in claim 1, comprising the steps of:
(1) dispersing polyvinyl alcohol in water, and stirring and dissolving under a heating condition to obtain a polyvinyl alcohol solution;
(2) adding an antiviral component quaternary ammonium salt derivative into the polyvinyl alcohol solution, and uniformly stirring at room temperature to obtain a mixed spinning solution;
(3) carrying out electrostatic spinning by using the mixed spinning solution to obtain the antiviral component loaded nanofiber;
(4) and (3) carrying out water-insoluble treatment on the nanofibers obtained in the step (3) through a crosslinking reaction.
5. The preparation method according to claim 4, wherein the polymerization degree of the polyvinyl alcohol in step (1) is 1700-2200, and the alcoholysis degree is 95% or more; the concentration of the polyvinyl alcohol solution is 8-15 wt%.
6. The method according to claim 4, wherein in the step (2), the quaternary ammonium salt derivative is dodecyltrimethylammonium chloride.
7. The preparation method according to claim 4, wherein the mass fraction of the antiviral agent in the solution in the step (2) is 1-20 wt%, and the stirring time is 3-5 h.
8. The method according to claim 4, wherein the parameters of the electrospinning in the step (3) are as follows: the electrostatic spinning applied voltage is 12-20KV, the receiving distance is 12-22cm, and the solution flow rate is 0.4-1.2 mL/h; the temperature is 20-25 deg.C, and the relative humidity is 30-50%.
9. The method according to claim 4, wherein the crosslinking agent in the crosslinking reaction in step (4) is glutaraldehyde, and the solvent is acetone or absolute ethanol.
10. Use of the antiviral nanofibers of claim 1 as a filtration layer in air filtration devices and equipment.
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