CN1209378C - 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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- CN1209378C CN1209378C CN 03119103 CN03119103A CN1209378C CN 1209378 C CN1209378 C CN 1209378C CN 03119103 CN03119103 CN 03119103 CN 03119103 A CN03119103 A CN 03119103A CN 1209378 C CN1209378 C CN 1209378C
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Abstract
The present invention discloses an antibacterial agent of chitosan, a preparation thereof, and a method for preparing antibacterial chitosan / cellulose fiber solvent spinning solution, and belongs to an antibacterial agent of chitosan and a spinning technique by applying cellulose fiber. The chitosan antibacterial agent is O-2'-hydroxypropyl trimethylammonium chitosan and O-methylpropene acyloxy trimethylammonium chitosan. The chitosan antibacterial agent has the preparation method that the degraded chitosan and benzaldehyde react to generate a product; the product, 3-chlorine-hydroxypropyltrimethyl ammonium chloride and the chlorinated methylpropene acyloxy trimethylammonium chloride react in an isopropyl alcohol medium, and thus, an O-chitosan quaternary ammonium derivative is prepared. The chitosan antibacterial agent water solution or a DMAc dispersed system is added into cellulose NMMO/H2O/ water solution or LiCl/DMAc solution, and thus, antibacterial chitosan / cellulose fiber spinning liquid is prepared. The present invention has the advantage that the method and the technique for preparing the spinning liquid are simple, and are easy to operate; the self spinning devices can be used for producing the spinning liquid.
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 and cellulose composite fiber 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 and the 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 lithium chloride and N,N-dimethylacetamide (LiCl/DMAc) double solvents and N-methyl beautiful jade-N-oxide water solution (NMMO/H
2O) two kinds.The germ resistance chitosan (derivative) that patent of the present invention relates to and the solvent method spinning method for genuine of cellulosic fibre are 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 and cellulose composite fiber 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 O-methacryloxy trimethyl ammonium chloride chitosan, its constitutional features is:
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 the acetum of 10%wt, 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%wt aqueous solution of this O-chitosan quaternary ammonium derivative, the 0.5-3%wt by chitosan antimicrobial agent weight ratio in the prepared antibacterial fiber under agitation joins in Mierocrystalline cellulose N-methyl beautiful jade-N-oxide water solution, is mixed with NMMO/H
2The germ resistance chitosan of O solvent system and cellulose composite fiber spinning solution;
Also available 10%wtNaOH solution transfers to alkalescence with the 8-10%wt aqueous solution of chitosan quaternary ammonium derivative, the chitosan quaternary ammonium derivative is separated out obtain 4-10%wt suspension, the N that in 100ml suspension, adds 100ml, the N-dimethylacetamide solution, stir, staticly settle, remove supernatant liquid, the N that adds 100ml again, the N-dimethylacetamide solution stirs, and staticly settles, remove supernatant liquid, with 200ml lithium chloride and N,N-dimethylacetamide double solvents the water in the suspension is replaced at last, make the LiCl/DMAc solvent suspension liquid of the O-chitosan derivatives of 4-10%wt, this suspension is carried out pulverization process with ultrasonic wave, make the median size of suspended particle drop to 2 microns, the 0.5-3%wt by chitosan antimicrobial agent weight ratio in the prepared antibacterial fiber under agitation joins cellulosic lithium chloride and N, in the N-dimethylacetamide solution, be mixed with the germ resistance chitosan and the cellulose composite fiber spinning solution of LiCl/DMAc solvent 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%wt 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.
Embodiment
Embodiment one, O-2 '-HACC and Mierocrystalline cellulose composite antibacterial fibre
1. the radiation degradation of chitosan: 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 the acetum of 12 liters of 10%wt, drip phenyl aldehyde 1580 grams, reaction is 20 hours under 50 ℃.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 and Mierocrystalline cellulose composite antibacterial fibre.
The 10%wt 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%wt in the water precipitation bath.
4.O-2 '-HACC LiCl/DMAc suspension preparation Mierocrystalline cellulose LiCl/DMAc spinning solution, preparation chitosan and Mierocrystalline cellulose composite antibacterial fibre.
With 10%wtNaOH solution the 10%wt aqueous solution of chitosan quaternary ammonium derivative is transferred to alkalescence, make the chitosan quaternary ammonium derivative separate out the suspension that obtains 6%wt, 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%wt 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%wt in the water precipitation bath.
Embodiment two, O-methacryloxy trimethyl ammonium chloride chitosan and Mierocrystalline cellulose composite antibacterial fibre
1. the radiation degradation of chitosan: do by embodiment one, 1
2.O-the preparation of methacryloxy trimethyl ammonium chloride chitosan:
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 and Mierocrystalline cellulose composite antibacterial fibre.
The 10%wt 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%wt in the water precipitation bath.
4.O-methacryloxy trimethyl ammonium chloride chitosan LiCl/DMAc suspension preparation Mierocrystalline cellulose LiCl/DMAc spinning solution, preparation chitosan and Mierocrystalline cellulose composite antibacterial fibre.
With 10%wtNaOH solution the 10%wt aqueous solution of chitosan quaternary ammonium derivative is transferred to alkalescence, make the chitosan quaternary ammonium derivative separate out the suspension that obtains 6%wt, 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%wtO-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%wt in the water precipitation bath.
Claims (3)
1. antiseptic-germicide chitosan, it is 6 O-quaternary ammonium derivatives of chitosan ring carbon, comprising: O-2 '-HACC and O-methacryloxy trimethyl ammonium chloride chitosan, its constitutional features is:
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.
2. preparation method by the described antiseptic-germicide chitosan of claim 1, it is characterized in that: the molecular weight that adopts the gamma-rays radiation degradation to obtain is the chitosan between the 10-60 ten thousand, in the acetum of mass concentration 10%wt, with the phenyl aldehyde reaction generation N-Ben Yajiaji chitosan of 3 times of weight; Reaction product is that the 3-chloro-hydroxypropyl-trimethyl ammonium chloride and the methyl chloride acryloxy trimethyl ammonium chloride of 1.5 times of chitosan pyranoid ring equivalents reacts in isopropanol medium with molar weight again, product removes the N-Ben Yajiaji in the HCl of 0.25mol/L ethanolic soln, product obtains serial O-chitosan quaternary ammonium derivative through the acetone precipitating, after refining.
3. method by the described antiseptic-germicide chitosan preparation of claim 1 or claim 2 cellosolve spinning solution, it is characterized in that: the 10-15%wt aqueous solution of O-chitosan quaternary ammonium derivative, 0.5-3%wt by chitosan antimicrobial agent weight ratio in the prepared antibacterial fiber, under agitation join in Mierocrystalline cellulose N-methyl beautiful jade-N-oxide water solution, be mixed with NMMO/H
2The germ resistance chitosan of O solvent system and cellulose composite fiber spinning solution; Or the 8-10%wt aqueous solution of chitosan quaternary ammonium derivative is transferred to alkalescence with 10%wtNaOH solution, the chitosan quaternary ammonium derivative is separated out obtain 4-10%wt suspension, the N that in 100ml suspension, adds 100ml, the N-dimethylacetamide solution, stir, staticly settle, remove supernatant liquid, the N that adds 100ml again, the N-dimethylacetamide solution stirs, and staticly settles, remove supernatant liquid, with 200ml lithium chloride and N,N-dimethylacetamide double solvents the water in the suspension is replaced at last, make the LiCl/DMAc solvent suspension liquid of the O-chitosan derivatives of 4-10%wt, this suspension is carried out pulverization process with ultrasonic wave, make the median size of suspended particle drop to 2 microns, the 0.5-3%wt by chitosan antimicrobial agent weight ratio in the prepared antibacterial fiber under agitation joins cellulosic lithium chloride and N, in the N-dimethylacetamide solution, be mixed with the germ resistance chitosan and the cellulose composite fiber spinning solution of LiCl/DMAc solvent system.
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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 |
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 |
CN102464729B (en) * | 2010-11-09 | 2014-01-01 | 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 |
CN102382313B (en) * | 2011-11-24 | 2012-11-28 | 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 |
CN106435817B (en) * | 2016-09-21 | 2019-01-15 | 东华大学 | A kind of preparation method of functional regeneration cellulose fibre |
CN106435797B (en) * | 2016-09-21 | 2018-11-23 | 东华大学 | A kind of preparation method of cellulose/carbon nano composite fibre |
CN106987922B (en) * | 2017-05-26 | 2019-02-26 | 四川大学 | The cellulose nano-fibrous electrostatic spinning preparation method of hollow porous structure |
CN110964205A (en) * | 2018-09-30 | 2020-04-07 | 天津大学 | Application of chitosan guanidine cation waterborne polyurethane in preparation of antibacterial coating |
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