CN114875667A - Broad-spectrum antibacterial and antiviral textile based on double-long-chain ionic liquid structural monomer graft copolymerization and preparation method thereof - Google Patents
Broad-spectrum antibacterial and antiviral textile based on double-long-chain ionic liquid structural monomer graft copolymerization and preparation method thereof Download PDFInfo
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- CN114875667A CN114875667A CN202210392031.0A CN202210392031A CN114875667A CN 114875667 A CN114875667 A CN 114875667A CN 202210392031 A CN202210392031 A CN 202210392031A CN 114875667 A CN114875667 A CN 114875667A
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- textile
- antiviral
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- ionic liquid
- antibacterial
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- 239000004753 textile Substances 0.000 title claims abstract description 84
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 74
- 239000000178 monomer Substances 0.000 title claims abstract description 69
- 230000000840 anti-viral effect Effects 0.000 title claims abstract description 53
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 13
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 7
- 125000000962 organic group Chemical group 0.000 claims abstract description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 5
- 125000000129 anionic group Chemical group 0.000 claims abstract description 3
- 125000002091 cationic group Chemical group 0.000 claims abstract description 3
- -1 methacryloyloxyethyl didecyl methyl ammonium chloride Chemical group 0.000 claims description 68
- 238000000034 method Methods 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
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Classifications
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- 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
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
- D06M14/20—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of natural origin
- D06M14/22—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of natural origin of vegetal origin, e.g. cellulose or derivatives thereof
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- 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
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
- D06M14/20—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of natural origin
- D06M14/24—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of natural origin of animal origin, e.g. wool or silk
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- 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
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
- D06M14/26—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin
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Abstract
The invention relates to a broad-spectrum antibacterial and antiviral textile based on double-long-chain ionic liquid structural monomer graft copolymerization, which comprises a textile and at least one organic monomer, wherein the organic monomer is grafted and copolymerized on the textile, is an organic monomer containing a double-long-chain ionic liquid structure, and is represented by the general formulaWherein A is an organic group containing a carbon-carbon double bond, C is a cationic group of an ionic liquid, X is an organic group or an organic chain segment which covalently links A and C, B 1 And B 2 Respectively a hydrophobic chain segment connected with C by a covalent bond, and D is an anionic group of the ionic liquid. The invention also relates to a preparation method of the broad-spectrum antibacterial and antiviral textile. According to the broad-spectrum antibacterial and antiviral textile, the functional groups with antibacterial and antiviral effects are firmly combined on the textile in a covalent bond mode, and the textile has excellent washing resistance and abrasion resistance and has a lasting function.
Description
Technical Field
The invention relates to a textile, in particular to a broad-spectrum antibacterial and antiviral textile based on double-long-chain ionic liquid structural monomer graft copolymerization and a preparation method thereof.
Background
Infectious diseases caused by pathogenic microorganisms (such as pathogenic bacteria or viruses) have long been a major threat to human health. With the improvement of living standard and the progress of transportation technology, the range of human activities is wider, the contact is more frequent, the transmission and outbreak of serious infectious diseases occur at times, and the transmission of diseases such as pneumonia caused by influenza and coronavirus causes huge damage to human health, public health and social and economic lives.
The most effective method to prevent the spread of infectious diseases is isolation. Preventing pathogenic bacteria or viruses from contacting human bodies is an important measure for preventing the occurrence and prevalence of infectious diseases. The common textile has no inhibition effect on pathogenic microorganisms, and the pathogenic microorganisms are easy to grow and propagate on the common textile and have chances to contact and invade human bodies. The antibacterial and antiviral textile can cut off the way of transferring germs or viruses and prevent the germs and the viruses from living and propagating on the textile, thereby effectively isolating the germs or the viruses from contacting the human body, reducing the risk of the human body being invaded by the germs or the viruses and reducing the cross infection rate of the public environment. In addition, the antibacterial and antiviral textile can also prevent the textile from being damaged due to the erosion of pathogenic microorganisms, inhibit peculiar smell generated by decomposing and polluting the pathogenic microorganisms on the textile, and ensure the health and comfort of human bodies.
Currently, antibacterial and antiviral textiles are produced by mainly bonding an antibacterial agent or an antiviral functional finishing agent to the textiles in a physical adsorption manner through a post-finishing method (padding, heating, drying, and the like). The antibacterial agent and the antiviral function finishing agent comprise nano metal particles (such as nano silver, nano copper and the like, wherein the nano silver is forbidden in the United states due to the toxicity of the nano silver to human bodies), nano inorganic particles (such as nano zinc oxide and the like), metal salts (copper series and silver series salts, such as copper sulfate and the like) and some natural polymers with antibacterial and antiviral functions, such as chitosan and the like. However, the conventional production method has the disadvantages that the antibacterial component is mainly combined with the textile through physical adsorption and the like, the binding force is weak, the antibacterial and antiviral active ingredients are quickly lost after the antibacterial and antiviral active ingredients are used and washed, the antibacterial and antiviral effects of the textile are not durable, the lost antibacterial and antiviral components have potential harm to human bodies and the environment, and the types of applicable pathogenic bacteria and viruses are limited.
Disclosure of Invention
In order to solve the problems of narrow range of antibacterial and antiviral property, weak bonding fastness of antibacterial and antiviral functional groups/particles and textiles, non-lasting antibacterial and antiviral functions and the like in the prior art, the invention provides a broad-spectrum antibacterial and antiviral textile based on double-long-chain ionic liquid structural monomer graft copolymerization and a preparation method thereof.
The broad-spectrum antibacterial and antiviral textile based on the double-long-chain ionic liquid structural monomer graft copolymerization comprises a textile and at least one organic monomer, wherein the organic monomer is graft copolymerized on the textile, is an organic monomer containing a double-long-chain ionic liquid structure and has a general formulaWherein A is an organic group containing a carbon-carbon double bond, C is a cationic group of an ionic liquid, X is an organic group or an organic chain segment which covalently links A and C, B 1 And B 2 Respectively a hydrophobic chain segment connected with C by a covalent bond, and D is an anionic group of the ionic liquid.
The main components of the cell membrane of bacteria and the envelope of enveloped viruses (such as influenza virus and coronavirus) are phosphate layers, the surfaces of the phosphate layers are negatively charged, so the phosphate layers are attracted by positive charges of structural groups of ionic liquid, and the phosphate layers are easily inserted into hydrophobic molecular chains to be broken, so the bacteria and the viruses die. Therefore, the group containing the hydrophobic chain segment and the ionic liquid structure has good broad-spectrum antibacterial and antiviral effects. However, the cell membranes of different kinds of bacteria and envelopes of different kinds of viruses are different in thickness, and thus, the hydrophobic chain length has a direct influence on the antibacterial and antiviral effects, and if the hydrophobic chain length is shorter, the penetration ability to the thicker cell membrane and viral envelope is weak. The invention uses the ionic liquid structure organic monomer with two long chains as the antibacterial and antiviral functional group, and the double long chain structure can more effectively destroy the cell membrane of the germ and the envelope of the virus, thereby achieving the effect of more broad-spectrum antibacterial and antiviral. Graft polymerization can firmly fix specific functional groups on the textile through covalent bonds. According to the invention, through graft polymerization, the monomer containing the double-long-chain ionic liquid structure is connected to the textile through a covalent bond, so that the textile has broad-spectrum antibacterial and antiviral functions, the durability of the functions can be ensured, and potential harm to human health and environment caused by loss of antibacterial and antiviral groups in the using process is avoided.
Preferably of the formulaA in (A) is vinyl, allyl, acrylate, methacrylate, styrene, or methylstyrene.
Preferably of the formulaWherein C is imidazole, pyridine, pyrrole, quaternary ammonium, quaternary phosphonium, or sulfonate.
Preferably of the formulaB in (1) 1 And B 2 The alkyl chain is an alkyl chain, an alkyl halide, an alkyl chain substituted by terminal olefin, an alkyl chain substituted by a terminal benzene ring, an alkyl chain substituted by a terminal ester group or an alkyl chain substituted by terminal ether, and the length of the carbon chain is 2-20.
Preferably of the formulaB in (1) 1 And B 2 The chain length and chemical group of (a) are the same or different.
Preferably of the formulaD in (A) is an inorganic anion (e.g. halide, OH) - 、NO 3 - 、HSO 4 - 、BF 4 - 、PF 6 - 、SbF 6 - 、AsF 6 - ) Or organic anions (e.g. CF) 3 SO 3 - 、(CF 3 SO 2 ) 2 N - 、C 3 F 7 COO - 、C 4 F 9 SO 3 - 、CF 3 COO - 、(CF 3 SO 2 ) 3 C - 、(C 2 F 5 SO 2 ) 3 C - 、(C 2 F 5 SO 2 ) 2 N - )。
Preferably, the organic monomer is methacryloyloxyethyl didecyl methyl ammonium chloride, 1-perfluorohexyl-2-dodecyl-3-vinylimidazole tetrafluoroborate, 1-hexyl-2-octyl-3-vinylpyridine chloride, methacryloyloxyethyl didecyl methyl ammonium chloride, [ 1-vinyl-3-methylbutyldecylimidazole ] bis (trifluoromethyl) amide, hydroxyethyl acrylate, 1-styrene-3-butylimidazole peroxytrifluoroacetate, acryloyloxyethyl methylbutyl eicosyl phosphonium chloride, 1-allyl-2, 3-dihexylpyridine hexafluoroarsenate, or methacryloyloxyethyl didecyl methyl bis (perfluoroethylsulfonyl) imide phosphonium salt.
Preferably, the textile is a woven cloth, a non-woven fabric, a yarn or a fiber.
Preferably, the material of the textile is natural polymer or artificial synthetic polymer or a mixture of the two. More preferably, the natural polymer is one or more of cotton, wool, silk and hemp. More preferably, the synthetic polymer is one or more of nylon, terylene, polypropylene, acrylic fiber, vinylon, spandex, polyethylene, polyvinyl chloride, aromatic polyamide, aromatic polyester, polysulfone, polyethersulfone, polyetherketone, polyetheretherketone, polyvinylidene fluoride, polystyrene, polycarbonate and cellulose. Obviously, the range of materials for the textile product according to the invention is wide. In a preferred embodiment, the material of the textile is cotton/chinlon or cotton/spandex blend fabric. More preferably, the content ratio of the materials of the different textiles is between 60/40-90/10.
According to the preparation method of the broad-spectrum antibacterial and antiviral textile based on the double-long-chain ionic liquid structural monomer graft copolymerization, the active free radicals are formed on the textile through initiation, and the addition polymerization reaction is carried out by utilizing the carbon-carbon double bond of the organic monomer and the active free radicals, so that at least one organic monomer is co-grafted on the textile.
Preferably, the textile is initiated by chemical initiator initiation, ionizing radiation initiation, ultraviolet light initiation, plasma initiation, and/or ozone treatment to form reactive free radicals on the textile. In a preferred embodiment, the textile is initiated by gamma radiation from a cobalt 60 source. More preferably, the irradiation dose is from 20kGy to 50 kGy. More preferably, the irradiation dose is 30 kGy. In a preferred embodiment, the textile is initiated by irradiation under an ultraviolet lamp having a wavelength of 256 nm. In a preferred embodiment, the textile is initiated by potassium persulfate. In a preferred embodiment, the textile is initiated by an electron beam emitted by an electron accelerator having an energy of 200 keV.
Preferably, the addition polymerization is carried out in bulk monomer, solution monomer, suspension monomer, or emulsion monomer. It should be understood that bulk of the monomers herein refers to pure monomers, and bulk polymerization is a basic form of high molecular weight polymerization. In a preferred embodiment, the solution addition polymerization is carried out in an aqueous solution of an organic monomer. More preferably, the addition polymerization reaction is carried out in a mixed aqueous solution of at least two organic monomers. In a preferred embodiment, the emulsion addition polymerization is carried out in an emulsion of an organic monomer, an emulsifier and an organic solvent. In particular, the organic solvent is N, N-dimethylformamide, or toluene. More preferably, the addition polymerization is carried out in a mixed emulsion of at least two organic monomers. In a preferred embodiment, the suspension addition polymerization is carried out in a suspension of a mixture of an organic monomer and an organic solvent, in particular N, N-dimethylformamide, or toluene. More preferably, the suspension addition polymerization is carried out in a mixed suspension of at least two organic monomers.
Preferably, the mass ratio of the two organic monomers is between 1:100 and 100: 1. More preferably, the mass ratio of the two organic monomers is from 1:3 to 5: 1. More preferably, the mass ratio of the two organic monomers is 3: 1. It will be appreciated that when two organic monomers are used for built co-grafting, both organic monomers may be of the general formulaThe organic monomer represented by the general formula (I) may beThe organic monomers represented and conventional organic monomers not having the above general formula.
Preferably, the total grafting of the organic monomers on the textile is between 0.1% and 200%. In a preferred embodiment, the total grafting of the organic monomer onto the textile is from 0.9% to 199.2%. More preferably, the total grafting of the organic monomer on the textile is from 6.9% to 155.2%. More preferably, the total grafting of the organic monomer on the textile is from 33.5% to 53.5%. More preferably, the total grafting of the organic monomer onto the textile is 36.9%.
According to the broad-spectrum antibacterial and antiviral textile based on the double-long-chain ionic liquid structural monomer graft copolymerization, the functional group with the antibacterial and antiviral effects is firmly combined on the textile in a covalent bond mode, the combination fastness is strong, and the textile has excellent washing resistance and abrasion resistance and has lasting functions. The broad-spectrum antibacterial and antiviral textile based on the double-long-chain ionic liquid structural monomer graft copolymerization has a broad-spectrum antibacterial effect, and has a very good killing effect on various bacteria, fungi (including various drug-resistant bacteria) and enveloped viruses (such as influenza viruses and coronavirus). The preparation method of the broad-spectrum antibacterial and antiviral textile based on the double-long-chain ionic liquid structural monomer graft copolymerization is simple and easy to implement, has lower cost, can be seamlessly connected with the conventional textile finishing process, is suitable for batch production, and is beneficial to large-scale production. According to the preparation method of the broad-spectrum antibacterial and antiviral textile based on the double-long-chain ionic liquid structural monomer graft copolymerization, no adhesive, resin or cross-linking agent is needed to be added, the properties of hand feeling, air permeability, moisture permeability and the like of the original textile are maintained to the greatest extent, and the preparation method is suitable for application in the aspects of clothing, household, industry and the like.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1 preparation of cotton cloth radiation solution grafting of methacryloyloxyethyl didecylmethyl ammonium chloride
Corresponding to the general structural formulaThe formula of methacryloyloxyethyl didecylmethyl ammonium chloride of this example is:
preparing an aqueous solution of methacryloyloxyethyl didecylmethyl ammonium chloride with the mass percentage concentration of 40%. Shearing pure cotton cloth into a proper size, uniformly rolling the water solution of the methacryloyloxyethyl didecylmethyl ammonium chloride on the surface of the cotton cloth in a padding mode, then placing the cotton cloth in an irradiation tube, introducing nitrogen to remove oxygen for 20 minutes, sealing the opening, and irradiating 50kGy by using a cobalt 60 source gamma ray at room temperature. The irradiated cotton cloth is extracted for 48 hours in a Soxhlet extractor by using water as a solvent, unreacted monomers and homopolymers are removed, and the cotton cloth is dried and weighed.
The grafting rate of methacryloyloxyethyl didecylmethyl ammonium chloride was measured by a gravimetric method to be 33.5%.
The antibacterial performance and broad spectrum of antibacterial activity of materials are currently assessed in the antibacterial research literature and representative species of different species of bacteria used in the mainstream standards of antibacterial testing, usually escherichia coli as a representative for gram-negative bacteria, staphylococcus aureus as a representative for gram-positive bacteria, and candida albicans as a representative for fungi.
Accordingly, according to the evaluation part 2 of the antibacterial performance of the textile in the national standard GB/T20944.2-2007: the absorption method tests the antibacterial effect of escherichia coli, staphylococcus aureus and candida on modified cotton cloth to evaluate the antibacterial performance and the antibacterial broad spectrum.
At present, the textile antiviral test mainly uses influenza virus as a model to evaluate the antiviral effect, and the invention tests the antiviral performance of the modified cotton cloth to the influenza virus H3N2 according to the ISO 18184-2014 standard.
Results of the antibacterial and antiviral tests are shown in effect example 1.
Example 2 preparation of chemically initiated emulsion for Silk broadcloth the binary cografting of 1-perfluorohexyl-2-dodecyl-3-vinylimidazole tetrafluoroborate and hydroxyethyl acrylate
In order to enhance the hydrophilicity and the flexibility of the graft modified antibacterial and antiviral textile, a hydrophilic monomer hydroxyethyl acrylate and an antibacterial and antiviral functional monomer 1-perfluorohexyl-2-dodecyl-3-vinylimidazole tetrafluoroborate are subjected to binary co-grafting. Toluene is used as a disperse phase, sorbitan stearate is used as an emulsifier, and water-in-oil type emulsion of hydroxyethyl acrylate and 1-perfluorohexyl-2-dodecyl-3-vinyl imidazole tetrafluoroborate (the mass ratio of the two is 1:3) in the toluene is prepared under high-shear stirring. Soaking silk fabric of 5 × 5cm in the emulsion, adding potassium persulfate as initiator, introducing nitrogen to remove oxygen for 20 min, sealing the container, heating to 60 deg.C to initiate graft polymerization reaction, and introducing oxygen to terminate the reaction after 5 hr.
The grafting sample is characterized by a weighing method and fluorine content analysis, and the grafting rate of hydroxyethyl acrylate on the pure silk fabric is 11.2 percent, the grafting rate of 1-perfluorohexyl-2-dodecyl-3-vinyl imidazole tetrafluoroborate on the pure silk fabric is 25.7 percent, and the total grafting rate of the hydroxyethyl acrylate and the 1-perfluorohexyl-2-dodecyl-3-vinyl imidazole tetrafluoroborate is 36.9 percent.
Refer to the national standard GB/T20944.2-2007 evaluation part 2 of antibacterial properties of textiles: the absorption method aims at the representative strains of drug-resistant bacteria (super bacteria), namely methicillin-resistant staphylococcus and vancomycin-resistant enterococcus in the current literature and mainstream antibacterial detection standards, and tests the antibacterial effect of the modified non-woven fabric.
In order to test the durability of the antibacterial effect of the sample, after accelerated washing for 30 cycles (equivalent to 150 domestic daily washes) according to ATCC 61-2006, 2A standard, the antibacterial effect test of the drug-resistant bacteria was performed in the same manner as described above.
The antibacterial effect is shown in effect example 2.
EXAMPLE 3 preparation of polyester Fabric UV-initiated solution grafting of 1-hexyl-2-octyl-3-vinylpyridine chloride salt
Cutting the polyester fabric into a proper size, soaking the polyester fabric in acetone solution of benzophenone for 20 minutes, then taking out the polyester fabric, and volatilizing the acetone at a ventilation position to uniformly disperse the benzophenone on the surface of the polyester fabric. Then 10% of 1-hexyl-2-octyl-3-vinyl pyridine chloride salt water solution is sprayed on the surface of the polyester fabric. Transferring the polyester fabric into a sealable quartz container, introducing nitrogen to remove oxygen for 20 minutes, sealing, irradiating under an ultraviolet lamp with the wavelength of 256nm to initiate graft polymerization, and introducing oxygen to terminate the reaction after 30 minutes.
The graft ratio of 1-hexyl-2-octyl-3-vinylpyridine chloride salt, determined by weighing, was 6.9%.
Example 4 preparation of ozone-initiated suspension grafting of spandex yarn with 1-perfluorohexyl-2-dodecyl-3-vinylimidazole tetrafluoroborate
1-perfluorohexyl-2-dodecyl-3-vinylimidazole tetrafluoroborate is poured into N, N-dimethylformamide and stirred at high speed by a high-shear cutter to prepare 10 percent suspension. Coiling the spandex yarn on a roller, and generating ozone by an ozone generator to perform surface treatment on the spandex yarn. Putting the suspension into a triangular flask, immersing the spandex yarn treated by ozone into the suspension, introducing nitrogen to remove oxygen for 20 minutes, sealing the triangular flask, heating to 70 ℃, initiating a graft polymerization reaction, cooling after 3 hours, introducing oxygen to terminate the reaction.
The grafting rate of 1-perfluorohexyl-2-dodecyl-3-vinylimidazole tetrafluoroborate was determined by weight method to be 0.9%.
EXAMPLE 5 preparation of Polyethylene (PE) nonwoven Pre-irradiated solution binary Co-grafting of methacryloyloxyethyl didecylmethyl ammonium chloride and [ 1-vinyl-3-methylbutyldecylimidazole ] bis (trifluoromethyl) amide
Preparing aqueous solution with the mass ratio of methacryloyloxyethyl didecylmethyl ammonium chloride to [ 1-vinyl-3-methylbutyldecylimidazole ] bis (trifluoromethyl) amide being 5:1 and the total mass percentage concentration being 10%. 10g of PE non-woven fabric is weighed, placed in an irradiation tube and irradiated to 30kGy by gamma rays of a cobalt 60 source in an air atmosphere. 100mL of aqueous solution of the methacryloyloxyethyl didecylmethyl ammonium chloride and the [ 1-vinyl-3-methylbutyldecylimidazole ] bis (trifluoromethyl) amide is placed into a triangular flask, the irradiated PE non-woven fabric is immersed in the solution, nitrogen is introduced to remove oxygen for 20 minutes, the flask is sealed, the PE non-woven fabric is heated to 70 ℃ in a water bath to initiate graft polymerization, and the temperature is reduced after 6 hours, and the oxygen is introduced to terminate the reaction.
The total grafting rate of methacryloyloxyethyl didecylmethyl ammonium chloride and [ 1-vinyl-3-methylbutyldecylimidazole ] bis (trifluoromethyl) amide on the PE nonwoven fabric was determined by a weighing method to be 155.2%, and the grafting rate of [ 1-vinyl-3-methylbutyldecylimidazole ] bis (trifluoromethyl) amide on the PE nonwoven fabric was calculated to be 20.1% by measuring the fluorine element content, and the grafting rate of methacryloyloxyethyl didecylmethyl ammonium chloride was 155.2% -20.1% ═ 135.1%.
Example 6 preparation of radiation-ternary co-grafted hydroxyethyl acrylate, methacryloyloxyethyl didecylmethylammonium chloride, 1-perfluorohexyl-2-dodecyl-3-vinylimidazolium tetrafluoroborate on cotton/nylon blend Fabric
Cutting the cotton/nylon blended fabric (the content ratio of cotton/nylon is 60/40) into a proper size. Preparing a solution by the mass ratio of the hydroxyethyl acrylate, the methacryloyloxyethyl didecyl methyl ammonium chloride, the 1-perfluorohexyl-2-dodecyl-3-vinyl imidazole tetrafluoroborate to the water of 1/5/20/100. Placing 100mL of the solution in an irradiation tube, immersing the cut cotton/nylon blended fabric in the solution, introducing nitrogen to remove oxygen for 20 minutes, sealing, and irradiating 20kGy by using cobalt 60 gamma rays at room temperature. The resulting product was extracted in a soxhlet extractor with water as solvent for 48 hours to remove unreacted monomers and homopolymers, and the modified fabric was then oven-dried and weighed.
The total grafting rate of the three monomers is 199.2% by weight, the grafting rate of methacryloyloxyethyl didecylmethylammonium chloride is 46.1% by bromine content test, the grafting rate of 1-perfluorohexyl-2-dodecyl-3-vinylimidazole tetrafluoroborate is 127.5% by fluorine content test, and the grafting rate of 1-butyl-3-vinylimidazole chloride is (199.2-127.5-46.1)% 100% ═ 24.6%.
EXAMPLE 7 plasma initiated Co-grafting of 1-styrene-3-butylimidazole Perfluorotrifluoroacetate and Acryloxyethylmethylbutyldicosylphosphonium chloride solutions to a Cotton/Spandex blended Fabric
Cutting the cotton/spandex blended fabric (the content ratio of cotton/chinlon is 90/10) into a proper size. Preparing an aqueous solution of 1-styrene-3-butyl imidazole peroxytrifluoroacetate and acryloyloxyethyl methyl butyl eicosyl phosphonium chloride, wherein the weight ratio of the 1-styrene-3-butyl imidazole peroxytrifluoroacetate to the acryloyloxyethyl methyl butyl eicosyl phosphonium chloride is 1:100, and the total mass percentage concentration of the two is 50%. The cotton/spandex blended fabric was padded in this solution at a pressure of 5 atm, the padded fabric had a wet pick-up of 75%, irradiated under a vacuum plasma generator with a power of 50kW for 0.5h, the product obtained was extracted with water as solvent in a soxhlet extractor for 48 h to remove unreacted monomers and homopolymers, and the modified fabric was then oven-dried and weighed.
The total grafting rate of the two monomers is 53.3 percent by weight method, and the grafting rate of the acryloyloxyethyltrimethyl phosphonium chloride is 52.2 percent by phosphorus element content test, and the grafting rate of the acryloyloxyethyltributyleicosyl phosphonium chloride is (53.3 to 52.2 percent) 100 percent to 1.1 percent.
EXAMPLE 8 preparation of reverse emulsion Co-grafting of 1-allyl-2, 3-dihexylpyridine hexafluoroarsenate and methacryloyloxyethyl didecyl methyl bis (perfluoroethylsulfonyl) imide phosphonium salt by Electron Beam Pre-irradiation of acrylic staple fiber nonwoven Fabric
The acrylic staple fiber non-woven fabric is cut into a proper size, and is irradiated to 20kGy by using an electron accelerator with 200keV in an air atmosphere. 5g of mixed monomer, 5g of emulsifier span-800.05 g and 94.95g of cyclohexane, which are weighed according to the mass ratio of 100:1, of 1-allyl-2, 3-dihexylpyridine hexafluoroarsenate to methacryloyloxyethyl didecyl methyl di (perfluoroethylsulfonyl) imide phosphonium salt, are prepared into mixed liquid, and then the mixed liquid is sheared for 10min by a high shearing machine at 2000rpm to prepare the reverse emulsion. Soaking the irradiated acrylic staple fiber non-woven fabric in the reverse emulsion, placing the emulsion into a triangular flask, introducing nitrogen to remove oxygen for 15min, sealing, heating to 60 ℃ to initiate grafting reaction, and cooling after 0.5h, introducing oxygen to terminate the reaction. The resulting product was extracted in a soxhlet extractor with water as solvent for 48 hours to remove unreacted monomers and homopolymers, and the modified fabric was then oven-dried and weighed.
The total grafting ratio of the two monomers is 0.1% by weight, and the grafting ratio of the 1-allyl-2, 3-dihexylpyridine hexafluoroarsenate is 0.91% by element content test, so that the grafting ratio of the methacryloyloxyethyl didecyl methyl di (perfluoroethylsulfonyl) imide phosphonium salt is (0.1% -0.82%) and is 100% ═ 0.09%.
Effect example 1
Experiment of antibacterial and antiviral effects of cotton cloth radiation solution grafted methacryloyloxyethyl didecyl methyl ammonium chloride
For the product obtained in example 1 with a grafting ratio of methacryloyloxyethyl didecylmethylammonium chloride of 33.5% (wt), reference is made to the national standard GB/T20944.2-2007 evaluation of antibacterial properties of textiles section 2: absorption method, which tests the effect against Escherichia coli, Staphylococcus aureus, Candida albicans, see Table 1. The table shows that the sterilization value is more than 99.9%, which indicates that the antibacterial cotton cloth prepared by the invention has good antibacterial effect, escherichia coli, staphylococcus aureus and candida albicans are typical representatives of gram-negative bacteria, gram-positive bacteria and fungi respectively, and the antibacterial test effect also indicates that the antibacterial textile prepared by the invention has good antibacterial broad-spectrum property.
TABLE 1 degerming efficiency of graft-modified antibacterial and antiviral cotton cloth to different kinds of bacteria
Test strains | Bacteria removal rate |
Escherichia coli (gram-negative bacteria) | >99.9% |
Staphylococcus aureus (gram-positive bacterium) | >99.9% |
Candida albicans (fungus) | >99.9% |
The modified cotton cloth is tested for the antiviral performance of influenza virus H3N2 according to the standard ISO 18184-2014. The test result shows that the antiviral coefficient is 2.52, and the percent is 99.7 percent of the killing rate of the virus, which indicates that the modified cotton cloth has good antiviral performance.
Effect example 2 test of the Effect of the drug-resistant bacteria on samples of chemically initiated emulsion dually cografted 1-perfluorohexyl-2-dodecyl-3-vinylimidazole tetrafluoroborate and hydroxyethyl acrylate after 150 washes at home
For the product obtained in example 2, in which the total grafting ratio of 1-perfluorohexyl-2-dodecyl-3-vinylimidazole tetrafluoroborate and hydroxyethyl acrylate is 36.9% (wt), by means of the evaluation part 2 of the antibacterial performance of textiles in the national standard GB/T20944.2-2007: absorption method for testing the effects of resisting methicillin-resistant staphylococcus, vancomycin-resistant enterococcus and carbapenem-resistant acinetobacter baumannii. To test the durability of the antibacterial effect of the samples, after 30 cycles of accelerated washing (equivalent to 150 household daily washes) according to ATCC 61-2006, 2A standard, reference is made to the national standard GB/T20944.2-2007 evaluation part 2 of the antibacterial properties of textiles: absorption method, the antibacterial effect test for drug-resistant bacteria was carried out in the same manner.
The antimicrobial effect of the samples before and after washing is shown in table 2. It can be seen from the table that the sterilization value of the samples before and after washing to the drug-resistant bacteria such as methicillin-resistant staphylococcus, vancomycin-resistant enterococcus and carbapenem acinetobacter baumannii is more than 99%. Methicillin-resistant staphylococcus aureus and vancomycin-resistant enterococci are gram-positive bacteria and gram-negative bacteria respectively, methicillin is a typical representative of a first-generation antibiotic, and vancomycin is a typical representative of a new-generation antibiotic (called as a last-line drug, if bacteria have strong resistance to vancomycin, the bacteria become super bacteria in which the antibiotics are not effective to the restraint at present). The extremely strong killing performance of the modified textile prepared by the invention on the two strains proves that the modified textile can resist not only common bacteria but also super bacteria, and the antibacterial effect has excellent broad spectrum.
After accelerated washing (equivalent to 150 times of household washing) according to AATCC standard, the antibacterial effect of the modified fabric is unchanged, which shows that the antibacterial effect of the modified fabric obtained by using the method of the invention has excellent durability.
TABLE 2 degerming rate of graft-modified antibacterial antiviral silk broadcloth before and after washing against drug-resistant bacteria
Test strains | Sterilization rate of samples before washing | Degerming rate of sample after washing |
Methicillin-resistant staphylococcus | >99.9% | >99.9% |
Vancomycin-resistant enterococcus | >99.9% | >99.9% |
Carbapenem-resistant acinetobacter baumannii | >99.9% | >99.9% |
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and various modifications may be made to the above-described embodiment of the present invention. All simple and equivalent changes and modifications made according to the claims and the content of the specification of the present application fall within the scope of the claims of the present patent application. The invention has not been described in detail in order to avoid obscuring the invention.
Claims (10)
1. The broad-spectrum antibacterial and antiviral textile based on double-long-chain ionic liquid structural monomer graft copolymerization is characterized by comprising a textile and at least one organic monomer, wherein the organic monomer is grafted and copolymerized on the textile, the organic monomer is an organic monomer containing a double-long-chain ionic liquid structure, and the organic monomer is represented by the general formulaWherein A is an organic group containing a carbon-carbon double bond, and C is a cationic group of an ionic liquidX is an organic group or an organic chain segment covalently linking A and C, B 1 And B 2 Respectively a hydrophobic chain segment connected with C by a covalent bond, and D is an anionic group of the ionic liquid.
4. The broad spectrum antibacterial and antiviral textile of claim 1, wherein the textile is of the formulaB in (1) 1 And B 2 The alkyl chain is an alkyl chain, an alkyl halide, an alkyl chain substituted by terminal olefin, an alkyl chain substituted by a terminal benzene ring, an alkyl chain substituted by a terminal ester group or an alkyl chain substituted by terminal ether, and the length of the carbon chain is 2-20.
6. The broad spectrum antibacterial and antiviral textile of claim 1, the organic monomer is methacryloyloxyethyl didecyl methyl ammonium chloride, 1-perfluorohexyl-2-dodecyl-3-vinylimidazole tetrafluoroborate, 1-hexyl-2-octyl-3-vinylpyridine chloride salt, methacryloyloxyethyl didecyl methyl ammonium chloride, [ 1-vinyl-3-methylbutyl decylimidazole ] bis (trifluoromethyl) amide, hydroxyethyl acrylate, 1-styrene-3-butylimidazole peroxytrifluoroacetate, acryloyloxyethyl methylbutyl eicosyl phosphonium chloride, 1-allyl-2, 3-dihexylpyridine hexafluoroarsenate, or methacryloyloxyethyl didecyl methyl bis (perfluoroethylsulfonyl) imide phosphonium salt.
7. A method for preparing broad-spectrum antibacterial and antiviral textile based on double-long-chain ionic liquid structural monomer graft copolymerization according to any one of claims 1 to 6, wherein the preparation method comprises the step of carrying out addition polymerization reaction by using carbon-carbon double bonds of organic monomers and active free radicals by initiating the formation of active free radicals on the textile, so as to co-graft at least one organic monomer onto the textile.
8. The method of claim 7, wherein the textile is initiated by chemical initiator initiation, ionizing radiation initiation, ultraviolet light initiation, plasma initiation, and/or ozone treatment to form reactive free radicals on the textile.
9. The method of claim 7, wherein the mass ratio of the two organic monomers is between 1:100 and 100: 1.
10. The method of claim 7, wherein the grafting of the organic monomer onto the textile is between 0.1% and 200%.
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CN107044053A (en) * | 2016-02-05 | 2017-08-15 | 中国科学院上海应用物理研究所 | A kind of antibacterial fabric and preparation method thereof |
CN109577000A (en) * | 2018-12-27 | 2019-04-05 | 中广核达胜加速器技术有限公司 | A kind of preparation method and antibacterial fabric of quaternary ammonium salt-modified antibacterial fabric |
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US5945514A (en) * | 1996-08-08 | 1999-08-31 | Mitsuru Akashi | Antiviral raw materials |
CN102174737A (en) * | 2010-12-30 | 2011-09-07 | 中国科学院上海应用物理研究所 | Superhydrophobic fabric or superhydrophobic non-woven fabric and preparation method thereof |
CN107044053A (en) * | 2016-02-05 | 2017-08-15 | 中国科学院上海应用物理研究所 | A kind of antibacterial fabric and preparation method thereof |
CN109577000A (en) * | 2018-12-27 | 2019-04-05 | 中广核达胜加速器技术有限公司 | A kind of preparation method and antibacterial fabric of quaternary ammonium salt-modified antibacterial fabric |
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