CN1166831C - Preparation method of high-molecular anti-bacterial fibre with high grafting rate in surface - Google Patents
Preparation method of high-molecular anti-bacterial fibre with high grafting rate in surface Download PDFInfo
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- CN1166831C CN1166831C CNB021289492A CN02128949A CN1166831C CN 1166831 C CN1166831 C CN 1166831C CN B021289492 A CNB021289492 A CN B021289492A CN 02128949 A CN02128949 A CN 02128949A CN 1166831 C CN1166831 C CN 1166831C
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Abstract
The present invention relates to a preparation method of a high-molecular anti-bacterial fibre with high surface grafting rates, which belongs to the technical field of macromolecular materials. The method comprises the following steps: firstly, acyl chloride containing C=C unsaturation double keys and a trialkylamine monomeric substance with an OH group react, and triethylamine is added as auxiliary agents to obtain trialkylamine with C=C keys; benzyl chloride is added, back flow reaction is carried out, and macromolecule fibres and initiating agents are added; After the reaction ends, solution agitation and wash, suction filtration, and dryness are carried out to the objects of the reaction 1. Infrared spectral analysis, TGA analysis, weighing analysis, etc. are carried out to the antibacterial fibres prepared by the preparation method of the high-molecular anti-bacterial fibre with high surface grafting rates provided by the present invention to prove that monomers are grafted and polymerized on the surfaces of the fibres, and the grafting ratio measured by a weight method is within the range of 50% to 150%.
Description
Technical field
The present invention relates to a kind of preparation method of high-molecular anti-bacterial fibre with high grafting rate in surface, belong to technical field of polymer materials.
Background technology
In use generally there is the problem of excess residual in the micromolecule bactericidal agent, can cause the secondary pollution of water and to the harm of health.Compare with low molecule bactericide, that the macromolecule bactericide has is non-volatile, chemically stable good, generally can not infiltrate advantages such as human or animal's skin, toxicity is little, thereby has good application prospects.Because fiber has very big specific area, be filled into easily in the various bactericidal units simultaneously and go, so fiber product is one of most important kind of macromolecule sterilization material.Sterilization fibre can or adopt the method for surface graft modification to obtain by bactericide and polyblend spinning.Obviously, latter's economic and reliable more.Its major advantage has: (1) bactericide utilization ratio height.And the bactericide of the fibrous inside that co-blended spinning obtains can not contact with bacterium, and a large amount of bactericide do not have sterilization functions.(2) bactericide is connected with covalent bond with base material, stable performance.The mode of co-blended spinning then exists problems such as bactericide migration, can lose efficacy after use a period of time.(3) surface grafting can be selected different monomers and base material, structure that can be different according to Application Design.
Quaternary ammonium salt is one of the most frequently used micromolecule antiseptic, with the method for polymerisable quaternary ammonium salt monomer by surface grafting, is linked at the macromolecular fibre surface, can be used for application fields such as water treatment.Present existing technology has
Use the monomer of hydrophilic radicals such as hydroxyl, alkoxyl, amido, pyrrolidinyl among the United States Patent (USP) U.S.5506188, contain the monomer of CATION dissociation groups such as carboxyl, carboxymethyl, sulfonic group, sulfoethyl, phosphate, phosphorus methyl and contain the monomer of anion dissociation groups such as primary amine, secondary amine, tertiary amine and quaternary ammonium salt, radiation polymerization becomes the macromonomer of degree of polymerization 10-100, and add monose (as glucose), base material is carried out radiation grafting.Radiation ray has ultraviolet light, α-ray, β-ray, γ-ray, eletron beam, and base material comprises cellulose, polyolefin, animal hair, leather and the synthetic leather etc. of various forms such as fiber, diaphragm, powder.Monose can quicken the speed that macromonomer is impregnated into base material, thereby can obviously improve the grafting efficiency of macromonomer.The sorbing material that makes is used for removing stink from gas, liquid.
The fibrous filter media of European patent E.P.433661A3, surface grafting one deck overlie polymer is by the unsaturated vinyl monomer that contains quaternary ammonium or amido.Filter medium has positive ξDian Wei when pH=7, strengthen adsorption capacity.
But in above-mentioned two patented technologies, the high-molecular anti-bacteria material of grafting quaternary ammonium salt all is to utilize its surperficial positive charge, and absorption has the bacterium of negative electricity.And the bacterium of handling through anti-biotic material, its physiologically active and metamorphosis are not observed variation.Just ineffective after anti-bacterial fibre adsorbs a certain amount of bacterium, even because the anti-bacterial fibre surface aggregation a large amount of bacteriums and become pollution sources.
Summary of the invention
The objective of the invention is to propose a kind of preparation method of high-molecular anti-bacterial fibre with high grafting rate in surface, prepare a series of high percent grafting quaternary ammonium salt grafting polymer anti-bacterial fibres.The fiber that obtains not only has quick absorption bacterium from water, thereby reaches the function of removing the middle bacterium of anhydrating, also really has the inhibition bacterial activity, further the effect of kill bacteria.Macromolecular sterilization fibre through surface grafting preparation is a kind of portable above, does not need specific operation condition, cheap macromolecule water treatment agent.Processing target mainly concentrates on the removal to pathogenetic bacteria.This sterilization fibre can also be used as hospital gauze, artificial skin and take lining.
The preparation method of the high-molecular anti-bacterial fibre with high grafting rate in surface that the present invention proposes may further comprise the steps:
(1) acyl chlorides that contains the C=C unsaturated double-bond and the reaction that has the tertiary amine monomers material of OH group: with toluene, benzene, carrene or oxolane is solvent, the adding triethylamine is an auxiliary agent, the mol ratio of hydroxyl and acyl chlorides and auxiliary agent is 1: 1～8: 1～1.2, the molar concentration that has the tertiary amine monomers material of OH group is 0.5～2mol/L, reaction temperature is 0～20 ℃, and the reaction time is 8～24 hours.Acyl chlorides can be third rare acyl chlorides, the rare acyl chlorides of methyl-prop; Tertiary amine can have one or two-OH, can be N, N-dimethylethanolamine, N, and N-diethyl ethylene diamine, N methyldiethanol amine, N-ethyldiethanolamine, reaction makes the tertiary amine that has the C=C key.
(2) above-mentioned product is a solvent with acetone, carrene, and concentration is 0.5～2mol/L, adds benzyl chloride, and containing the tertiary amine of C=C unsaturated double-bond and the mol ratio of benzyl chloride is 1: 1, back flow reaction, and the reaction time is 6～18 hours.
(3) add above-mentioned second step product and the macromolecular fibre in reactor, macromolecular fibre can be cellulose fibre, chitin fiber etc.Add solvent, the molar concentration of the second step product in solvent is 0.6～1.4mol/L, and the weight ratio of macromolecular fibre and solvent is 1: 10～1: 25.Solvent can be water and rare nitric acid, dilute sulfuric acid, watery hydrochloric acid.
(4) inflated with nitrogen adds initator to drain air in reactor, and making the concentration of initator in above-mentioned solution is 0.01～0.03mol/L, and initator can be ammonium ceric nitrate, Cericammoniumsulfate.Under agitation continue to fill nitrogen, reaction temperature is 20 ℃～60 ℃, reacts 0.5～4 hour.
(5) after reaction finished, with solution stirring, flushing reactant, suction filtration, the aqueous solution with acetone carried out extracting about 6～24 hours to the good fiber of grafting then, and was dry under being lower than 60 ℃ then.
The preparation method of the high-molecular anti-bacterial fibre with high grafting rate in surface that the present invention proposes, anti-bacterial fibre prepared therefrom, by infrared spectrum analysis, TGA analysis and the analysis etc. of weighing, the proof monomer is by the surface of glycerol polymerization to fiber, by weight between the percent grafting scope 50%～150% that method is measured.
Escherichia coli E.coli and staphylococcus aureus were cultivated through 18 hours, with the mixed of sterilized water with 1: 4.The anti-bacterial fibre of above-mentioned bacterium liquid 100ml and the present invention preparation is mixed in shaking bottle, under 37 ℃, 150rpm, cultivate, regularly take out certain amount of mixed solution, survey viable count with dull and stereotyped progression dilution method.The order of magnitude of number of bacteria decline 3～8 in the bacterium liquid.To mix the anti-bacterial fibre of certain hour in bacterium liquid directly observes under environmental scanning electron microscope, can observe the metamorphosis of bacterium under the anti-bacterial fibre effect of the present invention's preparation, bacterium on the high percent grafting anti-bacterial fibre over time, form generation distortion breaks until thalline.And the morphosis that the bacterium on the low percent grafting anti-bacterial fibre of prior art still is kept perfectly.
The specific embodiment
Embodiment 1
(1) N of rare acyl chlorides of methyl-prop and 0.1mol, the reaction of N-dimethylethanolamine is a solvent with 100ml benzene, the adding triethylamine is an auxiliary agent, N, the mol ratio of N-dimethylethanolamine and acyl chlorides and auxiliary agent is 1: 2: 1,0 ℃ of reaction temperature, the reaction time is 16 hours.Obtaining product is methacrylic acid 2-(N, N dimethyl amido) ethyl ester.
(2) above-mentioned product is a solvent with the 100ml carrene, adds benzyl chloride, and the mol ratio of methacrylic acid 2-(N, N dimethyl amido) ethyl ester and benzyl chloride is 1: 1, back flow reaction, and the reaction time is 6 hours.Obtaining product is the rare acyl-oxygen ethyl-benzyl of methyl-prop-alkyl dimethyl ammonium chloride.
(3) in reactor, add the rare acyl-oxygen ethyl-benzyl of 1g cellulose fiber peacekeeping 0.02mol methyl-prop-alkyl dimethyl ammonium chloride, add deionized water 25ml as solvent.
(4) inflated with nitrogen adds initator 0.000376mol ammonium ceric nitrate to drain air in reactor, under agitation continues to fill nitrogen, and reaction temperature is 30 ℃, reacts 1 hour.
(5) after reaction finished, with stirring solvent flushing, suction filtration, the mixed solvent with water and acetone carried out extracting 6 hours to the good fiber of grafting then, and was dry down at 60 ℃ then.Weigh percent grafting 67%.
Embodiment 2
The reaction of the N methyldiethanol amine of (1) third rare acyl chlorides and 0.1mol is a solvent with 200ml benzene, and the adding triethylamine is an auxiliary agent, and the mol ratio of N methyldiethanol amine and acyl chlorides and auxiliary agent is 1: 8: 1,5 ℃ of reaction temperatures, and the reaction time is 24 hours.Obtaining product is acrylic acid 2-(N methyl amido) diethylester.
(2) above-mentioned product is a solvent with the 100ml carrene, adds benzyl chloride, and the mol ratio of acrylic acid 2-(N methyl amido) diethylester and benzyl chloride is 1: 1, back flow reaction, and the reaction time is 6 hours.Obtaining product is the rare acyl-oxygen ethyl-benzyl of dipropyl-ammonio methacrylate.
(3) add the 1.5g cellulose fibre in reactor, the rare acyl-oxygen ethyl-benzyl of 0.02mol methyl-prop-alkyl dimethyl ammonium chloride and the rare acyl-oxygen ethyl-benzyl of 0.002mol dipropyl-ammonio methacrylate add deionized water 25ml as solvent.
(4) inflated with nitrogen adds initator 0.000376mol ammonium ceric nitrate to drain air in reactor, under agitation continues to fill nitrogen, and reaction temperature is 40 ℃, reacts 0.5 hour.
(5) after reaction finished, with stirring solvent flushing, suction filtration, the mixed solvent with water and acetone carried out extracting 6 hours to the good fiber of grafting then, and was dry down at 50 ℃ then.Weigh percent grafting 79%.
Embodiment 3
(1) reaction of the N-ethyldiethanolamine of rare acyl chlorides of methyl-prop and 0.1mol is a solvent with 200ml benzene, and the adding triethylamine is an auxiliary agent, and the mol ratio of N-ethyldiethanolamine and acyl chlorides and auxiliary agent is 1: 16: 1,5 ℃ of reaction temperatures, and the reaction time is 24 hours.Obtaining product is methacrylic acid 2-(N ethyl amido) diethylester.
(2) above-mentioned product is a solvent with the 100ml carrene, adds benzyl chloride, and the mol ratio of methacrylic acid 2-(N ethyl amido) diethylester and benzyl chloride is 1: 1, back flow reaction, and the reaction time is 6 hours.Obtaining product is the rare acyl-oxygen ethyl-benzyl of dipropyl-ammonio methacrylate.
(3) add the 1.5g cellulose fibre in reactor, the rare acyl-oxygen ethyl-benzyl of 0.02mol methyl-prop-alkyl dimethyl ammonium chloride and 0.004mol dimethyl propylene acyl-oxygen ethyl-benzyl-ethyl ammonium chloride add deionized water 25ml as solvent.
(4) inflated with nitrogen adds initator 0.000376mol ammonium ceric nitrate to drain air in reactor, under agitation continues to fill nitrogen, and reaction temperature is 40 ℃, reacts 0.5 hour.
(5) after reaction finished, with stirring solvent flushing, suction filtration, the mixed solvent with water and acetone carried out extracting 6 hours to the good fiber of grafting then, and was dry down at 60 ℃ then.Weigh percent grafting 89%.
Embodiment 4
The N of (1) third rare acyl chlorides and 0.1mol, the reaction of N-dimethylethanolamine is a solvent with the 50ml carrene, the adding triethylamine is an auxiliary agent, N, the mol ratio of N-dimethylethanolamine and acyl chlorides and auxiliary agent is 1: 4: 1.2,10 ℃ of reaction temperatures, and the reaction time is 16 hours.Obtaining product is acrylic acid 2-(N methyl amido) diethylester.
(2) above-mentioned product is a solvent with the 50ml carrene, adds benzyl chloride, and the mol ratio of acrylic acid 2-(N methyl amido) diethylester and benzyl chloride is 1: 1, back flow reaction, and the reaction time is 8 hours.Obtaining product is third rare acyl-oxygen ethyl-benzyl-alkyl dimethyl ammonium chloride
(3) add 2g chitin fiber and the rare acyl-oxygen ethyl-benzyl of 0.015mol methyl-prop-alkyl dimethyl ammonium chloride in reactor, the rare nitric acid acid 25ml that adds 0.05M is as solvent.
(4) inflated with nitrogen adds initator 0.000251mol Cericammoniumsulfate to drain air in reactor, under agitation continues to fill nitrogen, and reaction temperature is 50 ℃, reacts 1 hour.
(5) after reaction finished, with stirring solvent flushing, suction filtration, the mixed solvent with water and acetone carried out extracting 12 hours to the good fiber of grafting then, and was dry down at 60 ℃ then.Weigh percent grafting 62%.
Embodiment 5
The N of (1) third rare acyl chlorides and 0.1mol, the reaction of N-diethyl ethylene diamine is a solvent with the 50ml oxolane, the adding triethylamine is an auxiliary agent, N, the mol ratio of N-diethyl ethylene diamine and acyl chlorides and auxiliary agent is 1: 4: 1.1,10 ℃ of reaction temperatures, and the reaction time is 16 hours.Obtaining product is acrylic acid 2-(N, N diethyl amido) ethyl ester.
(2) above-mentioned product is a solvent with 50ml acetone, adds benzyl chloride, and the mol ratio of acrylic acid 2-(N, N diethyl amido) ethyl ester and benzyl chloride is 1: 1, back flow reaction, and the reaction time is 8 hours.Obtaining product is third rare acyl-oxygen ethyl-benzyl-diethyl ammonium chloride
(3) add 1g cellulose fiber peacekeeping 0.025mol third rare acyl-oxygen ethyl-benzyl-diethyl ammonium chloride in reactor, the dilute sulfuric acid acid 25ml that adds 0.05M is as solvent.
(4) inflated with nitrogen is to drain air in reactor, and adding the 0.000501mol ammonium ceric nitrate is initator, under agitation continues to fill nitrogen, and reaction temperature is 50 ℃, reacts 2 hours.
(5) after reaction finished, with stirring solvent flushing, suction filtration, the mixed solvent with water and acetone carried out extracting 18 hours to the good fiber of grafting then, and was dry down at 60 ℃ then.Weigh percent grafting 69%.
Embodiment 6
The N of (1) third rare acyl chlorides and 0.1mol, the reaction of N-diethyl ethylene diamine is a solvent with 50ml toluene, the adding triethylamine is an auxiliary agent, N, the mol ratio of N-diethyl ethylene diamine and acyl chlorides and auxiliary agent is 1: 4: 1.2,10 ℃ of reaction temperatures, the reaction time is 16 hours.Obtaining product is acrylic acid 2-(N, N diethyl amido) ethyl ester.
(2) above-mentioned product is a solvent with the 50ml carrene, adds benzyl chloride, and the mol ratio of acrylic acid 2-(N, N diethyl amido) ethyl ester and benzyl chloride is 1: 1, back flow reaction, and the reaction time is 8 hours.Obtaining product is third rare acyl-oxygen ethyl-benzyl-diethyl ammonium chloride
(3) add 1g cellulose fiber peacekeeping 0.035mol third rare acyl-oxygen ethyl-benzyl-diethyl ammonium chloride in reactor, the watery hydrochloric acid acid 25ml that adds 0.05M is as solvent.
(4) inflated with nitrogen is to drain air in reactor, and adding the 0.000752mol ammonium ceric nitrate is initator, under agitation continues to fill nitrogen, and reaction temperature is 60 ℃, reacts 4 hours.
(5) after reaction finished, with stirring solvent flushing, suction filtration, the mixed solvent with water and acetone carried out extracting 24 hours to the good fiber of grafting then, and was dry down at 60 ℃ then.Weigh percent grafting 71%.
Claims (7)
1, a kind of preparation method of high-molecular anti-bacterial fibre with high grafting rate in surface is characterized in that this method may further comprise the steps:
(1) making the molar concentration of the tertiary amine monomers material that has the OH group with solvent is 0.5～2mol/L, in having the tertiary amine monomers material of OH group, add acyl chlorides and the triethylamine auxiliary agent that contains the C=C unsaturated double-bond, wherein the mol ratio of tertiary amine monomers material, acyl chlorides, auxiliary agent is 1: 1～8: 1～1.2, reaction temperature is 0～20 ℃, reaction time is 8～24 hours, and reaction makes the tertiary amine that has the C=C key;
(2) adding benzyl chloride in above-mentioned product, is solvent with acetone, carrene, and the concentration that makes the tertiary amine of the above-mentioned C=C of having key is 0.5～2mol/L, and the mol ratio of tertiary amine and benzyl chloride is 1: 1, back flow reaction, and the reaction time is 6～18 hours;
(3) in the above-mentioned second step product, add macromolecular fibre, add solvent, making the molar concentration of above-mentioned product in solvent is 0.6～1.4mol/L, and the weight ratio of macromolecular fibre and solvent is 1: 10～25, and macromolecular fibre wherein is cellulose fibre or chitin fiber;
(4) add initator in above-mentioned solution, making the concentration of initator in above-mentioned solution is 0.01～0.03mol/L, and inflated with nitrogen under agitation continues to fill nitrogen to drain air, and reaction temperature is 20 ℃～60 ℃, reacts 0.5～4 hour;
(5) after reaction finishes, stir, wash reactant with reactant liquor, suction filtration, the aqueous solution with acetone carried out extracting about 6～24 hours to the good fiber of grafting then, and is dry under being lower than 60 ℃ then.
2, the method for claim 1 is characterized in that used solvent in the first step wherein is any in toluene, benzene, carrene or the oxolane.
3, the method for claim 1 is characterized in that wherein acyl chlorides is third rare acyl chlorides or the rare acyl chlorides of methyl-prop in the first step.
4, the method for claim 1 is characterized in that the tertiary amine in the first step wherein has one or two OH group, is N, N-dimethylethanolamine, N, any in N-diethyl ethylene diamine, N methyldiethanol amine or the N-ethyldiethanolamine.
5, the method for claim 1 is characterized in that wherein the macromolecular fibre in the 3rd step is cellulose fibre or chitin fiber.
6, the method for claim 1 is characterized in that wherein solvent in the 3rd step is any in water, rare nitric acid, dilute sulfuric acid or the watery hydrochloric acid.
7, the method for claim 1 is characterized in that wherein the initator in the 4th step is ammonium ceric nitrate or Cericammoniumsulfate.
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| CNB021289492A CN1166831C (en) | 2002-08-23 | 2002-08-23 | Preparation method of high-molecular anti-bacterial fibre with high grafting rate in surface |
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| CNB021289492A CN1166831C (en) | 2002-08-23 | 2002-08-23 | Preparation method of high-molecular anti-bacterial fibre with high grafting rate in surface |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US7358223B2 (en) * | 2004-10-04 | 2008-04-15 | Nitto Denko Corporation | Biodegradable cationic polymers |
| CN100465215C (en) * | 2006-12-15 | 2009-03-04 | 清华大学 | Process of optically grafting long fatty carbon chain pyridine salt to the surface of polymer |
| EP2317007B1 (en) * | 2008-08-11 | 2015-09-30 | Kurashiki Boseki Kabushiki Kaisha | Sliver for spinning, process for producing same, and spun yarn and textile product both using same |
| CN103015160B (en) * | 2012-12-18 | 2015-06-03 | 武汉纺织大学 | Method for producing bacteriostatic sole, lining or insole by using bacteriostatic agent |
| CN104892842A (en) * | 2015-05-15 | 2015-09-09 | 深圳先进技术研究院 | Antimicrobial bacterial cellulose, preparation method and application thereof |
| CN111519432B (en) * | 2020-05-12 | 2022-09-27 | 北京福田戴姆勒汽车有限公司 | Non-woven fabric material and preparation method and application thereof |
| CN114232336A (en) * | 2021-12-27 | 2022-03-25 | 罗莱生活科技股份有限公司 | Hemp diphenol modified viscose fiber and preparation method thereof |
| CN114686733B (en) * | 2022-04-12 | 2022-11-18 | 江苏中基复合材料有限公司 | Cast-rolling aluminum foil for aseptic packaging and preparation method thereof |
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