CN1456576A - Bactericidal chitin and its preparation and method for making cellulose solvent weaving liquid - Google Patents
Bactericidal chitin and its preparation and method for making cellulose solvent weaving liquid Download PDFInfo
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- CN1456576A CN1456576A CN 03119103 CN03119103A CN1456576A CN 1456576 A CN1456576 A CN 1456576A CN 03119103 CN03119103 CN 03119103 CN 03119103 A CN03119103 A CN 03119103A CN 1456576 A CN1456576 A CN 1456576A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 23
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- 239000001913 cellulose Substances 0.000 title claims abstract description 21
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 19
- 239000002904 solvent Substances 0.000 title claims abstract description 10
- 239000007788 liquid Substances 0.000 title claims description 10
- 238000009941 weaving Methods 0.000 title description 2
- 229920002101 Chitin Polymers 0.000 title 1
- 229920001661 Chitosan Polymers 0.000 claims abstract description 107
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 42
- 239000000243 solution Substances 0.000 claims abstract description 41
- 238000009987 spinning Methods 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims abstract description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000015556 catabolic process Effects 0.000 claims abstract description 6
- 238000006731 degradation reaction Methods 0.000 claims abstract description 6
- NEQZXUBZTZDVAF-UHFFFAOYSA-M trimethyl(2-methylprop-2-enoyloxy)azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)O[N+](C)(C)C NEQZXUBZTZDVAF-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000003242 anti bacterial agent Substances 0.000 claims abstract 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000000835 fiber Substances 0.000 claims description 34
- 239000000725 suspension Substances 0.000 claims description 23
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000004599 antimicrobial Substances 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 230000005855 radiation Effects 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 230000006196 deacetylation Effects 0.000 claims description 4
- 238000003381 deacetylation reaction Methods 0.000 claims description 4
- 230000000845 anti-microbial effect Effects 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 claims 1
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 claims 1
- 230000005251 gamma ray Effects 0.000 claims 1
- 238000005979 thermal decomposition reaction Methods 0.000 claims 1
- VVEPKWSPMLXNKZ-UHFFFAOYSA-M trimethyl(prop-2-enoyloxy)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)OC(=O)C=C VVEPKWSPMLXNKZ-UHFFFAOYSA-M 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- XPPODKQKBFSUCU-UHFFFAOYSA-M (3-chloro-3-hydroxypropyl)-trimethylazanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCC(O)Cl XPPODKQKBFSUCU-UHFFFAOYSA-M 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 229920001282 polysaccharide Polymers 0.000 abstract description 2
- 239000005017 polysaccharide Substances 0.000 abstract description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000003115 biocidal effect Effects 0.000 description 7
- 229920000297 Rayon Polymers 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- -1 phenyl aldehyde Chemical class 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- OOKXXQLOVUDNCD-UHFFFAOYSA-M [Cl-].C(C=C)(=O)O[N+](C)(C)C.CCl Chemical compound [Cl-].C(C=C)(=O)O[N+](C)(C)C.CCl OOKXXQLOVUDNCD-UHFFFAOYSA-M 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
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- 241000894006 Bacteria Species 0.000 description 1
- 241000222122 Candida albicans Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
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- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
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- 230000000843 anti-fungal effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 229920005615 natural polymer Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 230000001376 precipitating effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 235000019633 pungent taste Nutrition 0.000 description 1
- 125000003132 pyranosyl group Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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Abstract
本发明公开了一种抗菌剂壳聚糖及其制备和配制抗菌性壳聚糖/纤维素纤维溶剂纺丝溶液的方法，属于壳聚糖抗菌剂及应用于纤维素纤维的纺制技术。该壳聚糖抗菌剂是O－2’－羟丙基三甲基氯化铵壳聚糖和O－甲基丙烯酰氧基三甲基氯化铵壳聚糖；其制备是降解后壳聚糖与苯甲醛反应生成的产物与3－氯－羟丙基三甲基氯化铵和氯化甲基丙烯酰氧基三甲基氯化铵在异丙醇介质中反应，得到的O－壳聚糖季铵衍生物。将此壳聚糖抗菌剂的水溶液或DMAc分散体加入到纤维素NMMO/H2O/水溶液或LiCl/DMAc溶液，配制成抗菌性壳聚糖/纤维素纤维纺丝液。本发明的优点在于配制纺丝液方法工艺简单，易于操作，利用本身纺丝设备即可生产。The invention discloses an antibacterial agent chitosan and a method for preparing and preparing an antibacterial chitosan/cellulose fiber solvent spinning solution, belonging to chitosan antibacterial agent and the spinning technology applied to cellulose fiber. The chitosan antibacterial agent is O-2'-hydroxypropyltrimethylammonium chloride chitosan and O-methacryloyloxytrimethylammonium chloride chitosan; its preparation is chitosan after degradation The product produced by the reaction of sugar and benzaldehyde reacts with 3-chloro-hydroxypropyltrimethylammonium chloride and methacryloyloxytrimethylammonium chloride in isopropanol medium to obtain the O-shell Polysaccharide quaternary ammonium derivatives. The aqueous solution or DMAc dispersion of the chitosan antibacterial agent is added to the cellulose NMMO/H 2 O/water solution or LiCl/DMAc solution to prepare the antibacterial chitosan/cellulose fiber spinning solution. The invention has the advantages that the method for preparing the spinning solution is simple in process, easy to operate, and can be produced by using its own spinning equipment.
Description
Technical field
The present invention relates to the method for a kind of antiseptic-germicide chitosan and preparation thereof and preparation germ resistance chitosan/cellulosic fibre solvent spinning solution.Belong to chitosan antimicrobial agent and be applied to the spinning technology of cellulosic fibre.
Background technology
The quaternary ammonium derivative of chitosan has stronger germ resistance, and (Dean is strong, the special collection of polymer natural polymer (day), 1998,47 (6): 386) in application existing certain aspect the antibacterial fabric hygienic finishing.But, there is the preparation feedback of the chitosan quaternary ammonium salt of application report all to occur on the amino of chitosan pyranose ring at present, its result has influenced the unique natural alkaline polysaccharide of occurring in nature---some characteristics of chitosan.We have developed grafted chitosan quaternary ammonium salt on 6 hydroxyls of chitosan ring carbon for this reason, and this derivative has good water-soluble and germ resistance.And the chitosan basal body of this derivative has similar molecular structure and good consistency with Mierocrystalline cellulose, can be used for developing the natural antibacterial cellulosic fibre.
At present, the current fine production method of cellulosic one-tenth of textile industry has two kinds of viscose process and solvent methods in the world.Based on cellulosic viscose glue production technique, Japanese fuji weaving is gone into viscose glue and is developed antibiotic odourproof fiber Chitopoly the chitosan powder is mixing, this fiber can use separately, also can with blending such as synthon, cotton fibre, be used for the preparation (Japanese kokai publication hei 4-289211,6-308109,10-37018) of garment for children.Applicant is (number of patent application: 00100636.3 in last applying for a patent, publication number: CN1266922A), with fine chitosan water dispersion and derivative thereof is antiseptic-germicide, with N, the O-cm-chitosan is an expanding material, join in the viscose rayon filament yarn spinning solution, spin out the chitosan/viscose glue antibacterial fiber of appearance, anti-microbial property excellence.
But cellulosic viscose process spinning complex manufacturing, serious waste of resources, and have the serious environmental pollution problem in process of production.And cellulosic solvent method spinning has production technique cleaning, pollution-free, the characteristics such as cellulosic fibre performance excellence that make, is the focus of present cellulose fiber spinning technical study.The solvent that more sophisticated cellosolve method spinning technique uses mainly contains two kinds of lithium chloride/N,N-dimethylacetamide (LiCl/DMAc) and N-methyl beautiful jades-N-oxide compound/water (NMMO/H2O).The solvent method spinning method for genuine of germ resistance chitosan (derivative)/cellulosic fibre that patent of the present invention relates to is not seen any report as yet.
Summary of the invention
The object of the present invention is to provide the method for a kind of antiseptic-germicide chitosan and preparation thereof and preparation cellosolve spinning solution.Described chitosan antimicrobial agent is to be starting material with the chitosan, 6 the O-quaternary ammonium derivatives of serial chitosan ring carbon that synthesize, and this derivative is than chitosan, and it is good to have germ resistance, has a broad antifungal spectrum, advantage such as water soluble characteristic is good.This O-chitosan quaternary ammonium derivative is mixed with solution or solvent borne suspension, with the cellulose spinning fluid blend, spin out that quality softness, height are preserved moisture, nontoxic, no skin irritation, produce free of contamination germ resistance chitosan/cellulosic fibre by solvent method.
For achieving the above object, the present invention's design has also been developed following technical proposals:
The chitosan that a kind of anti-microbial property is good, it is 6 O-quaternary ammonium derivatives of chitosan ring carbon, comprising: O-2 '-HACC and its constitutional features of O-methacryloxy trimethyl ammonium chloride chitosan are:
This chitosan derivatives viscosity-average molecular weight is 10-60 ten thousand, and degree of deacetylation is greater than 80%, and 6 O substitution values of carbon are 0.5-0.8, and heat decomposition temperature is 250 ℃, solubleness 〉=10g/100ml water.
The preparation method of above-mentioned chitosan derivatives: the chitosan of molecular weight between 10-60 ten thousand that adopts the gamma-rays radiation degradation to obtain, in 10% acetum, carry out the building-up reactions of N-Ben Yajiaji chitosan with the phenyl aldehyde of 3 times of weight; (chitosan pyranoid ring equivalent: 3-chloro-hydroxypropyl-trimethyl ammonium chloride substituted reactant) and methyl chloride acryloxy trimethyl ammonium chloride reacted at isopropanol medium reaction product than 1: 1.5 with molar equivalent again, in the HCl of 0.25mol/L ethanolic soln the N-Ben Yajiaji is removed, product obtains serial O-chitosan quaternary ammonium derivative through the acetone precipitating, after refining.
With the 10%-15% aqueous solution of this O-chitosan quaternary ammonium derivative, content (being the weight ratio of chitosan antimicrobial agent and the cellulosic fibre) 0.5-3% by chitosan antimicrobial agent in the prepared antibacterial fiber under agitation joins Mierocrystalline cellulose NMMO/H
2In the O aqueous solution, be mixed with the germ resistance chitosan/cellulose fiber spinning liquid of N-methyl beautiful jade-N-oxide compound/aqueous systems.
Also available 10%NaOH solution transfers to alkalescence with the 8%-10% aqueous solution of chitosan quaternary ammonium derivative, the chitosan quaternary ammonium derivative is separated out obtain 4%-10% suspension, in 100ml suspension, add the DMAc solution of 100ml, stir, staticly settle, remove supernatant liquid, add the DMAc solution of 100ml again, stir, staticly settle, remove supernatant liquid, with 200ml LiCl/DMAc the water in the suspension is replaced at last, make the O-chitosan derivatives LiCl/DMAc suspension of 4%-10%.This suspension is carried out pulverization process with ultrasonic wave, the median size of suspended particle is dropped to about 2 microns, content (being the weight ratio of chitosan antimicrobial agent and regenerated cellulose) 0.5-3% by chitosan antimicrobial agent in the prepared antibacterial fiber, under agitation join in the cellulosic LiCl/DMAc solution, be mixed with the germ resistance chitosan/cellulose fiber spinning liquid of lithium chloride/N,N-dimethylacetamide system.
Pass through with streptococcus aureus, intestinal bacteria, bacterial classifications such as Candida albicans are the germ resistance test of experimental strain, the antibiotic fiber cellulose fiber of the present invention's preparation shows very strong germ resistance.The addition of chitosan quaternary ammonium derivative in fiber is 0.5～3.0% of fibre weight among the present invention.
The chitosan antimicrobial agent modified cellulose fibre of the present invention's preparation is a natural matter---the matrix material of Mierocrystalline cellulose and chitosan or derivatives thereof, cellulosic fibre is through human life-time service, its security and comfortableness are well-known, and chitosan and derivative thereof, especially chitosan, its pungency, acute malicious domestic animal, subacute toxicity, chronic toxicity and supersensitivity prove qualified by experiment, thereby this antibacterial fiber can be used suitable fiber as the most comfortable in the ecology safely.This matrix material can biological degradation in physical environment, and discarded back is free from environmental pollution, is a kind of green product.Fiber of the present invention is compared with now market-oriented antibiotic odourproof fiber, has advantages such as antibacterial effect is obvious and lasting, moisture retention is good.Fiber of the present invention can be used as underskirt and coat, long and short underwear especially for baby; Can also be used for medical treatment and sanitation system fabric, or soldier, field man's clothing etc.
The radiation degradation of embodiment embodiment one, O-2 '-HACC/Mierocrystalline cellulose antibacterial fiber 1. chitosans: the chitosan of molecular weight 1,080,000, degree of deacetylation 85% is by Co
60Source of radiation through the irradiation of 60kGy radiation dose, obtains the chitosan oligopolymer A of molecular weight 10～200,000, degree of deacetylation 86%.2.O-2 the preparation of '-HACC:
1. N-Ben Yajiaji chitosan is synthetic: take by weighing the A300 gram, be dissolved in 12 liter 10% the acetum, drip phenyl aldehyde 1580 grams, 50 ℃ of reactions 20 hours down.With alkali lye the pH value is adjusted to neutrality, filters.Filter cake methanol wash 2～3 times 60 ℃ of oven dry down, get light yellow solid B.
2. the preparation of O-quaternary ammonium salt-N-Ben Yajiaji chitosan: B280 gram reacted 10 hours down at 60 ℃ with 5 liters of Virahols and 900 gram 3-chloro-hydroxypropyl ammonium chlorides.Filter, filter cake methanol wash 2～3 times 60 ℃ of oven dry down, get Off-white solid C.
3. the preparation of O-2 '-HACC: add 300 gram C in the hydrochloric acid-ethanolic soln of 5 liters of 2.5mol/ liters, after fully stirring, remove ethanol, add 2.5 premium on currency again, fully dissolving is separated out product with acetone at last, throw out washing with acetone, filtration, 80 ℃ of following vacuum-dryings, obtain white O-chitosan quaternary ammonium derivative.3.O-2 '-HACC solution preparation Mierocrystalline cellulose NMMO/H
2The O spinning solution, preparation chitosan/Mierocrystalline cellulose antibacterial fiber.
10% aqueous solution of 3 kilograms of chitosan quaternary ammonium derivatives that make by embodiment 1 described method is under agitation joined 100 kilograms of Mierocrystalline cellulose NMMO/H
2In the O solution, be mixed with spinning solution, spinning obtains containing the antibiotic fiber cellulose fiber of O-chitosan derivatives 1.2～1.8% in the water precipitation bath.4.O-2 '-HACC LiCl/DMAc suspension preparation Mierocrystalline cellulose LiCl/DMAc spinning solution, preparation chitosan/Mierocrystalline cellulose antibacterial fiber.
With 10%NaOH solution 10% aqueous solution of chitosan quaternary ammonium derivative is transferred to alkalescence, the chitosan quaternary ammonium derivative is separated out obtain 6% suspension, in 1 kilogram of suspension, add 1 kilogram DMAc solution, stir, staticly settle, remove supernatant liquid, add 1 kilogram DMAc solution again, stir, staticly settle, remove supernatant liquid, with 2 kilograms of LiCl/DMAc the water in the suspension is replaced at last, make 6%O-chitosan derivatives LiCl/DMAc suspension.3 kilograms of these suspension are carried out pulverization process with ultrasonic wave, the median size of suspended particle is dropped to about 2 microns, under agitation join in 100 kilograms of cellulosic LiCl/DMAc solution, be mixed with spinning solution, spinning obtains the antibiotic fiber cellulose fiber of chitosan-containing or chitosan derivatives 1.5～3.0% in the water precipitation bath.The radiation degradation of embodiment two, O-methacryloxy trimethyl ammonium chloride chitosan/Mierocrystalline cellulose antibacterial fiber 1. chitosans: do the preparation of 2.O-methacryloxy trimethyl ammonium chloride chitosan by embodiment one, 1:
1. N-Ben Yajiaji chitosan is synthetic: by embodiment one, 2. 1. do
2. the preparation of O-quaternary ammonium salt-N-Ben Yajiaji chitosan: B280 gram reacted 10 hours down at 60 ℃ with 5 liters of Virahols and 1300 gram methyl chloride acryloxy trimethyl ammonium chlorides.Filter, filter cake methanol wash 2～3 times 60 ℃ of oven dry down, get white solid C.
3. the preparation of O-methacryloxy trimethyl ammonium chloride chitosan: add 300 gram C in the hydrochloric acid-ethanolic soln of 5 liters of 2.5mol/ liters, after fully stirring, remove ethanol, add 2.5 premium on currency again, fully dissolving is separated out product with acetone at last, throw out washing with acetone, filtration, 80 ℃ of following vacuum-dryings, obtain white O-chitosan quaternary ammonium derivative.3.O-methacryloxy trimethyl ammonium chloride chitosan solution preparation Mierocrystalline cellulose NMMO/H
2The O spinning solution, preparation chitosan/Mierocrystalline cellulose antibacterial fiber.
10% aqueous solution of 3 kilograms of chitosan quaternary ammonium derivatives that make by embodiment 1 described method is under agitation joined 100 kilograms of Mierocrystalline cellulose NMMO/H
2In the O solution, be mixed with spinning solution, spinning obtains containing the antibiotic fiber cellulose fiber of O-chitosan derivatives 1.2～1.8% in the water precipitation bath.4.O-methacryloxy trimethyl ammonium chloride chitosan LiCl/DMAc suspension preparation Mierocrystalline cellulose LiCl/DMAc spinning solution, preparation chitosan/Mierocrystalline cellulose antibacterial fiber.
With 10%NaOH solution 10% aqueous solution of chitosan quaternary ammonium derivative is transferred to alkalescence, the chitosan quaternary ammonium derivative is separated out obtain 6% suspension, in 1 kilogram of suspension, add 1 kilogram DMAc solution, stir, staticly settle, remove supernatant liquid, add 1 kilogram DMAc solution again, stir, staticly settle, remove supernatant liquid, with 2 kilograms of LiCl/DMAc the water in the suspension is replaced at last, make 6%O-chitosan derivatives LiCl/DMAc suspension.3 kilograms of these suspension are carried out pulverization process with ultrasonic wave, the median size of suspended particle is dropped to about 2 microns, under agitation join in 100 kilograms of cellulosic LiCl/DMAc solution, be mixed with spinning solution, spinning obtains the antibiotic fiber cellulose fiber of chitosan-containing or chitosan derivatives 1.5～3.0% in the water precipitation bath.
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Cited By (12)
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| CN1300178C (en) * | 2004-12-10 | 2007-02-14 | 中国海洋大学 | Chloro-N-trimethyl chitin hyamine |
| WO2007025444A1 (en) * | 2005-09-02 | 2007-03-08 | Institute Of Oceanology Chinese Academy Of Sciences | Carboxymethyl chitosan quaternary ammonium salt derivative and preparation method thereof |
| CN1308509C (en) * | 2004-06-02 | 2007-04-04 | 嘉兴学院 | A silver containing chitosan fiber having antimicrobial function and preparation method |
| CN100341900C (en) * | 2005-11-16 | 2007-10-10 | 中国药科大学 | Quaterisation chitosan derivatives, preparation method and medicinal preparation containing the derivatives |
| CN102382313A (en) * | 2011-11-24 | 2012-03-21 | 黑龙江大学 | Preparation method of N-2-hydroxypropyl trimethyl ammonium chloride chitosan/ N,O-carboxymethyl chitosan naonparticle |
| CN102464729A (en) * | 2010-11-09 | 2012-05-23 | 北京联合大学生物化学工程学院 | O-quaternary ammonium salt oligochitosan vanillina Schiff base bacteriostatic agent and preparation method thereof |
| CN105887242A (en) * | 2016-06-22 | 2016-08-24 | 天津中盛生物工程有限公司 | Preparation method of chitosan copper fibers |
| CN106435797A (en) * | 2016-09-21 | 2017-02-22 | 东华大学 | Preparation method of cellulose/carbon nanotube composite fiber |
| CN106435817A (en) * | 2016-09-21 | 2017-02-22 | 东华大学 | Preparation method of functional regenerated cellulose fiber |
| CN106987922A (en) * | 2017-05-26 | 2017-07-28 | 四川大学 | The cellulose nano-fibrous electrostatic spinning preparation method of hollow loose structure |
| CN110964205A (en) * | 2018-09-30 | 2020-04-07 | 天津大学 | Application of Chitosan Guanidine Cationic Waterborne Polyurethane in Preparation of Antibacterial Coatings |
| CN118755324A (en) * | 2024-07-25 | 2024-10-11 | 珠海市澜诺新材料科技有限公司 | Negative oxygen ion odor-free multifunctional decorative coating and preparation method thereof |
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2003
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308509C (en) * | 2004-06-02 | 2007-04-04 | 嘉兴学院 | A silver containing chitosan fiber having antimicrobial function and preparation method |
| CN1300178C (en) * | 2004-12-10 | 2007-02-14 | 中国海洋大学 | Chloro-N-trimethyl chitin hyamine |
| WO2007025444A1 (en) * | 2005-09-02 | 2007-03-08 | Institute Of Oceanology Chinese Academy Of Sciences | Carboxymethyl chitosan quaternary ammonium salt derivative and preparation method thereof |
| CN100487000C (en) * | 2005-09-02 | 2009-05-13 | 中国科学院海洋研究所 | Carboxymethyl chitosan quaternary ammonium salt and its preparation method |
| CN100341900C (en) * | 2005-11-16 | 2007-10-10 | 中国药科大学 | Quaterisation chitosan derivatives, preparation method and medicinal preparation containing the derivatives |
| CN102464729A (en) * | 2010-11-09 | 2012-05-23 | 北京联合大学生物化学工程学院 | O-quaternary ammonium salt oligochitosan vanillina Schiff base bacteriostatic agent and preparation method thereof |
| CN102464729B (en) * | 2010-11-09 | 2014-01-01 | 北京联合大学生物化学工程学院 | A kind of O-quaternary ammonium salt oligomeric chitosan vanillin Schiff base antibacterial agent and preparation method thereof |
| CN102382313A (en) * | 2011-11-24 | 2012-03-21 | 黑龙江大学 | Preparation method of N-2-hydroxypropyl trimethyl ammonium chloride chitosan/ N,O-carboxymethyl chitosan naonparticle |
| CN105887242A (en) * | 2016-06-22 | 2016-08-24 | 天津中盛生物工程有限公司 | Preparation method of chitosan copper fibers |
| CN106435797A (en) * | 2016-09-21 | 2017-02-22 | 东华大学 | Preparation method of cellulose/carbon nanotube composite fiber |
| CN106435817A (en) * | 2016-09-21 | 2017-02-22 | 东华大学 | Preparation method of functional regenerated cellulose fiber |
| CN106435797B (en) * | 2016-09-21 | 2018-11-23 | 东华大学 | A kind of preparation method of cellulose/carbon nano composite fibre |
| CN106435817B (en) * | 2016-09-21 | 2019-01-15 | 东华大学 | A kind of preparation method of functional regeneration cellulose fibre |
| CN106987922A (en) * | 2017-05-26 | 2017-07-28 | 四川大学 | The cellulose nano-fibrous electrostatic spinning preparation method of hollow loose structure |
| CN110964205A (en) * | 2018-09-30 | 2020-04-07 | 天津大学 | Application of Chitosan Guanidine Cationic Waterborne Polyurethane in Preparation of Antibacterial Coatings |
| CN118755324A (en) * | 2024-07-25 | 2024-10-11 | 珠海市澜诺新材料科技有限公司 | Negative oxygen ion odor-free multifunctional decorative coating and preparation method thereof |
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