CN106565856A - Self-flowing chitosan material and preparation method thereof - Google Patents

Self-flowing chitosan material and preparation method thereof Download PDF

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CN106565856A
CN106565856A CN201610966675.0A CN201610966675A CN106565856A CN 106565856 A CN106565856 A CN 106565856A CN 201610966675 A CN201610966675 A CN 201610966675A CN 106565856 A CN106565856 A CN 106565856A
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chitosan
flowing
quaternary ammonium
ammonium salt
preparation
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CN106565856B (en
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殷先泽
翁普新
杨诗文
周应山
王罗新
王桦
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Wuhan Textile University
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/00272-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof

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Abstract

The invention relates to a preparation method of a self-flowing chitosan material and belongs to the technical field of high polymer materials. The preparation method is characterized by blending chitosan quaternary ammonium salt with a nonylphenol polyoxyethylene ether sodium sulfate solution, carrying out ion exchange reaction, then dialyzing and drying the mixed solution to prepare the self-flowing chitosan material. The self-flowing chitosan material obtained by the preparation method is uniform in particle size distribution and has liquid-like flowing behavior under the solvent-free condition at the temperature of 45 DEG C; polymer blend membranes can be prepared by melt processing under low temperature; the preparation method is simple in process and short in reaction period, and is non-toxic and environmentally friendly.

Description

A kind of chitosan material of flowing certainly and preparation method thereof
Technical field
The present invention relates to the preparation of high polymer material, specially a kind of from flowing chitosan material and preparation method thereof, category In technical field of polymer materials.
Background technology
Chitosan quaternary ammonium salt be shitosan it is chemically modified obtained from chitosan derivatives, chitosan quaternary ammonium salt both retained The excellent properties such as its degradability of shitosan, biocompatibility, while and be highly improved in anti-microbial property, existing document Show the antibiotic property of chitosan quaternary ammonium salt better than shitosan and other chitosan derivatives.Shitosan can only be dissolved in dilute acid soln In, it is water insoluble, the application of shitosan is which has limited, and chitosan quaternary ammonium salt is completely soluble, therefore chitosan quaternary ammonium salt exists Food, medical treatment, health care, gain great popularity in commercial Application, but all kinds of chitosan quaternary ammonium salts and shitosan of China's exploitation at present Derivative mostly is the chitosan material of normal size rank, the biologically active for failing to show shitosan completely and excellent medical science Characteristic.In material processing field, chitosan material processing temperature is higher, and processing temperature can be with the difference of viscosity average molecular weigh And it is different, unstable easy decomposition of viscosity etc. during high-temperature fusion is unfavorable for the shortcoming for shaping, and also causes chitosan quaternary ammonium The processing of salt and chitosan derivatives is limited to a certain extent.Therefore under exploitation condition of no solvent, low viscosity, the shell of high temperature resistance Chitosan material seems particularly necessary, solves the manufacturing deficiency of chitosan material and other polymer melting blendings.
The chemical modification of chitosan quaternary ammonium salt and its derivative is mainly to the hydroxyl on its strand at present Modification is learned, severe reaction conditions, the chitin modified material prepared is varied, including it is powder, microballoon, resin, film, solidifying Glue, but also it is not attempt to prepare modified chitosan nano meter level fluent material.The flowing shitosan certainly that the present invention is prepared Material solves well the processing temperature of shitosan higher than this processing difficult problem of its decomposition temperature, while Nonyl pheno Ether sodium sulfate itself also has antibiotic property so that the antibiotic property of fluent material can be lifted further, under without the need for solvent condition The mobility for representing can be applied in medical domains such as wound coatings, and the average-size of the chitosan material that flows certainly is in 10nm Within, this is that size is more rare in the current all kinds of chitosan materials developed, and nano-scale chitosan materials application prospect is non- It is often wide.
In the prior art, Chinese patent CN201410567704.7, it is publication date on January 18th, 2015, entitled " chitosan quaternary ammonium salt-galangal essential oil composite antibacterial aerosol, its preparation method and its application ", the invention utilizes shitosan season Ammonium salt and the blending of galangin oil solution prepare Chitosan Composites.Chinese patent CN201410069972.6, it is open Day is on December 17th, 2014, and entitled " a kind of chitosan quaternary ammonium salt couplant and preparation method thereof ", the invention is utilized Triethanolamine prepares chitosan quaternary ammonium salt couplant with chitosan quaternary ammonium salt, Phenoxyethanol crosslinking.Chinese patent CN201310416202.X, publication date be on December 25th, 2013, a kind of entitled " chitosan material active modification side There is oxidation reaction with oxidant by being dissolved in the chitosan solution of diluted acid in method ", the invention, then through the reagent of shitosan indissoluble Middle co-precipitation, is filtrated to get chitosan material active material.The studies above is obtained by a series of crosslinking and oxidation reaction To chitin modified material, using strong acid and strong base or oxidant, environmental pollution is larger, and reaction time is long for course of reaction.
Chinese patent CN201310232624.1, publication date September in 2013 25 days, a kind of entitled " carboxymethyl shell Glycan quaternary ammonium salt/modified zirconium phosphate nano composite material ", the invention is divided by carboxymethyl chitosan quaternary ammonium salt in the form of intercalation Dissipate and obtain Chitosan Composites in basic zirconium phosphate piece interlayer.The method course of reaction is simple, but composite is not thermally-stabilised good, work Industry processing temperature is higher.
Chinese patent CN201610144489.9, publication date on June 15th, 2016, a kind of entitled " wastewater treatment With ultrabranching polyamide modified quaternary ammonium salt of chitosan microballoon and its preparation method and application ", the invention is by by hyperbranched polyamides The reaction of amine, shitosan and alkyl halide obtains modified quaternary ammonium salt of chitosan.The method preparation process is loaded down with trivial details, and uses toxic solvent, Environmental pollution is larger, and chitosan anti-bacteria performance has also been damaged, and limits its application.
The method for preparing chitin modified material at present is more, but common method is by a series of crosslinkings and graft reaction Chitin modified material is finally prepared, feature is that reaction time is long, materials processing temperature temperature is high, and many in course of reaction Using toxic solvents, it is unfavorable for environmental protection, material modified difficult forming, chitosan quaternary ammonium salt composite blending dispersiveness is poor.
The content of the invention
For the problem that above-mentioned technology is present, it is an object of the invention to provide a kind of from flowing chitosan material and its preparation Method.To reach above-mentioned purpose, the present invention is achieved by the following technical solutions:
It is a kind of from flowing chitosan material, it is described from flowing chitosan material particle size range be 2~10nm, it is described from Flowing chitosan material more than the temperature 45 C under conditions of there is mobility.
A kind of preparation method from the chitosan material that flows, described preparation method is according to the following steps:
By 1:1~3 quality parts ratio takes chitosan quaternary ammonium salt and is dissolved in 40 mass with nonylphenol polyoxyethylene ether sulfate In number deionized water, 24h is reacted under the conditions of 65 DEG C, take out reacted mixing liquid and dialyse at room temperature 3~5 days, then By the liquid after dialysis in vacuum drying chamber in 45 DEG C of dryings 3 days, obtain shitosan from fluent material.
Described chitosan quaternary ammonium salt is synthesized by glycidyl ammonium chloride and shitosan.
Described chitosan quaternary ammonium salt glues equal viscosity average molecular weigh for 15000~200000.
As a result of above technical scheme, a kind of preparation method from flowing chitosan material of the invention has following Advantage:
The present invention carries out ion friendship using nonylphenol polyoxyethylene ether sulfate with the ammonium chloride on chitosan quaternary ammonium salt surface Change, prepare particle size range be 2~10nm, temperature be have under the conditions of 45 DEG C class I liquid I behavior from flowing shitosan material Material, the material is slightly soluble in ethanol, isopropanol, chloroform, toluene, soluble in water, and thermal degradation temperature is 200~380 DEG C.Present invention system Standby simple from flowing chitosan material process, reaction time is short, and toxic solvents are not used in course of reaction, will not pollute ring Border, it is different from the method that a series of conventionally employed crosslinkings and substitution reaction prepare chitosan material.Simultaneously prepared by the present invention From flowing chitosan material, its particle diameter distribution is homogeneous, and scope is 2~10nm, and heat decomposition temperature compares shell prepared by other methods Chitosan material is higher, then substantially reduces from the viscosity of flowing chitosan material and with other polymers processing blending processing temperature. Prepared by this method belongs to nanometer materials from flowing chitosan material, and its performance is more excellent, and it is in medical treatment, bioengineering Application prospect it is considerable, while processing of the auto-flowability of uniqueness for chitosan material at low temperature provides possibility.
Specific embodiment
The present invention is described in further detail with reference to instantiation.
A kind of chitosan material of flowing certainly and preparation method thereof:
It is a kind of from flowing chitosan material, it is described from flowing chitosan material particle size range be 2~10nm, it is described from Flowing chitosan material more than the temperature 45 C under conditions of there is mobility, be slightly soluble in ethanol, isopropanol, chloroform, toluene, easily Water is dissolved in, thermal degradation temperature is 200~380 DEG C.
A kind of preparation method from the chitosan material that flows, described preparation method is according to the following steps:
By 1:1~3 quality parts ratio takes chitosan quaternary ammonium salt and is dissolved in 40 mass with nonylphenol polyoxyethylene ether sulfate In number deionized water, 24h is reacted under the conditions of 65 DEG C, take out reacted mixing liquid and dialyse at room temperature 3~5 days, then By the liquid after dialysis in vacuum drying chamber in 45 DEG C of dryings 3 days, it is 45 DEG C to obtain particle size range for 2~10nm, in temperature Under the conditions of have class I liquid I behavior from flowing chitosan material;
Described chitosan quaternary ammonium salt is synthesized by glycidyl ammonium chloride and shitosan.
Described chitosan quaternary ammonium salt glues equal viscosity average molecular weigh for 15000~200000.
Specific embodiment
Embodiment 1
The synthesis of 1 chitosan quaternary ammonium salt:The shitosan that 1g viscosity average molecular weighs are 80000 is taken, 1% matter of 60~80ml is added dropwise The glacial acetic acid solution of amount fraction fully dissolves stirring, then the sodium hydroxide solution neutralization that 1% mass fraction of 60~80ml is added dropwise And above-mentioned chitosan solution is precipitated completely, be then washed with deionized mixed solution carries out suction filtration to PH=7~8, incited somebody to action The shitosan filter cake that filter is obtained is added to immediately in 30g isopropanols, is warming up to 80 DEG C, is configured dissolved with the glycidyl chlorine of 5g bis--three Change the 20g isopropyl alcohol mixtures of quaternized ammonium, per the above-mentioned mixed solution of three/a volume of is added every other hour, stirring is anti- After answering 20 hours, ethanol in proper amount sedimentation half an hour is added, be filtrated to get chitosan quaternary ammonium salt powder.
The preparation of 2 oneself flowing chitosan materials:Take the chitosan quaternary ammonium salt and 1g polyoxyethylene nonyl phenyls prepared in 1g Jing steps 1 Ethene ether sodium sulfate is dissolved in 40ml water, and under the conditions of 65 DEG C 24h is reacted, and reacted mixing liquid is dialysed 3 days, in vacuum The flowing shitosan certainly that particle size range is 2~10nm is obtained within 3 days in drying box in 45 DEG C of dryings.
Embodiment 2
The synthesis of 1 chitosan quaternary ammonium salt:The shitosan that 1g viscosity average molecular weighs are 80000 is taken, 1% matter of 60~80ml is added dropwise The glacial acetic acid solution of amount fraction fully dissolves stirring, then the sodium hydroxide solution neutralization of 60~80ml1% mass fractions is added dropwise simultaneously Above-mentioned chitosan solution is set to precipitate completely, be then washed with deionized mixed solution carries out suction filtration to PH=7~8, will filter The shitosan filter cake for obtaining is added to immediately in 30g isopropanols, is warming up to 80 DEG C, is configured dissolved with the glycidyl chlorinations of 5g bis--three The 20g isopropyl alcohol mixtures of quaternized ammonium, per the above-mentioned mixed solution of three/a volume of of addition every other hour, stirring reaction After 20 hours, ethanol in proper amount sedimentation half an hour is added, be filtrated to get chitosan quaternary ammonium salt powder.
The preparation of 2 oneself flowing chitosan materials:Take the chitosan quaternary ammonium salt and 2g polyoxyethylene nonyl phenyls prepared in 1g Jing steps 1 Ethene ether sodium sulfate is dissolved in 40ml water, and under the conditions of 65 DEG C 24h is reacted, and reacted mixing liquid is dialysed 4 days, in vacuum The flowing shitosan certainly that particle size range is 2~10nm is obtained within 3 days in drying box in 45 DEG C of dryings.
Embodiment 3
The synthesis of 1 chitosan quaternary ammonium salt:The shitosan that 1g viscosity average molecular weighs are 80000 is taken, 1% matter of 60~80ml is added dropwise The glacial acetic acid solution of amount fraction fully dissolves stirring, then the sodium hydroxide solution neutralization of 60~80ml1% mass fractions is added dropwise simultaneously Above-mentioned chitosan solution is set to precipitate completely, be then washed with deionized mixed solution carries out suction filtration to PH=7~8, will filter The shitosan filter cake for obtaining is added to immediately in 30g isopropanols, is warming up to 80 DEG C, is configured dissolved with the glycidyl chlorinations of 5g bis--three The 20g isopropyl alcohol mixtures of quaternized ammonium, per the above-mentioned mixed solution of three/a volume of of addition every other hour, stirring reaction After 20 hours, ethanol in proper amount sedimentation half an hour is added, be filtrated to get chitosan quaternary ammonium salt powder.
The preparation of 2 oneself flowing chitosan materials:Take the chitosan quaternary ammonium salt and 3g polyoxyethylene nonyl phenyls prepared in 1g Jing steps 1 Ethene ether sodium sulfate is dissolved in 40ml water, and under the conditions of 65 DEG C 24h is reacted, and reacted mixing liquid is dialysed 5 days, in vacuum The flowing shitosan certainly that particle size range is 2~10nm is obtained within 3 days in drying box in 45 DEG C of dryings.
Embodiment 4
The synthesis of 1 chitosan quaternary ammonium salt:The shitosan that 1g viscosity average molecular weighs are 120000 is taken, the 1% of 60~80ml is added dropwise The glacial acetic acid solution of mass fraction fully dissolves stirring, then the sodium hydroxide solution neutralization that 60~80ml1% mass fractions are added dropwise And above-mentioned chitosan solution is precipitated completely, be then washed with deionized mixed solution carries out suction filtration to PH=7~8, incited somebody to action The shitosan filter cake that filter is obtained is added to immediately in 30g isopropanols, is warming up to 80 DEG C, is configured dissolved with the glycidyl chlorine of 5g bis--three Change the 20g isopropyl alcohol mixtures of quaternized ammonium, per the above-mentioned mixed solution of three/a volume of is added every other hour, stirring is anti- After answering 20 hours, ethanol in proper amount sedimentation half an hour is added, be filtrated to get chitosan quaternary ammonium salt powder.
The preparation of 2 oneself flowing chitosan materials:Take the chitosan quaternary ammonium salt and 1g polyoxyethylene nonyl phenyls prepared in 1g Jing steps 1 Ethene ether sodium sulfate is dissolved in 40ml water, and under the conditions of 65 DEG C 24h is reacted, and reacted mixing liquid is dialysed 3 days, in vacuum The flowing shitosan certainly that particle size range is 2~10nm is obtained within 3 days in drying box in 45 DEG C of dryings.
Embodiment 5
The synthesis of 1 chitosan quaternary ammonium salt:The shitosan that 1g viscosity average molecular weighs are 120000 is taken, the 1% of 60~80ml is added dropwise The glacial acetic acid solution of mass fraction fully dissolves stirring, then the sodium hydroxide solution neutralization that 60~80ml1% mass fractions are added dropwise And above-mentioned chitosan solution is precipitated completely, be then washed with deionized mixed solution carries out suction filtration to PH=7~8, incited somebody to action The shitosan filter cake that filter is obtained is added to immediately in 30g isopropanols, is warming up to 80 DEG C, is configured dissolved with the glycidyl chlorine of 5g bis--three Change the 20g isopropyl alcohol mixtures of quaternized ammonium, per the above-mentioned mixed solution of three/a volume of is added every other hour, stirring is anti- After answering 20 hours, ethanol in proper amount sedimentation half an hour is added, be filtrated to get chitosan quaternary ammonium salt powder.
The preparation of 2 oneself flowing chitosan materials:Take the chitosan quaternary ammonium salt and 1g polyoxyethylene nonyl phenyls prepared in 1g Jing steps 1 Ethene ether sodium sulfate is dissolved in 40ml water, and under the conditions of 65 DEG C 24h is reacted, and reacted mixing liquid is dialysed 3 days, in vacuum The flowing shitosan certainly that particle size range is 2~10nm is obtained within 3 days in drying box in 45 DEG C of dryings.
Embodiment 6
The synthesis of 1 chitosan quaternary ammonium salt:The shitosan that 1g viscosity average molecular weighs are 120000 is taken, the 1% of 60~80ml is added dropwise The glacial acetic acid solution of mass fraction fully dissolves stirring, then the sodium hydroxide solution neutralization that 60~80ml1% mass fractions are added dropwise And above-mentioned chitosan solution is precipitated completely, be then washed with deionized mixed solution carries out suction filtration to PH=7~8, incited somebody to action The shitosan filter cake that filter is obtained is added to immediately in 30g isopropanols, is warming up to 80 DEG C, is configured dissolved with the glycidyl chlorine of 5g bis--three Change the 20g isopropyl alcohol mixtures of quaternized ammonium, per the above-mentioned mixed solution of three/a volume of is added every other hour, stirring is anti- After answering 20 hours, ethanol in proper amount sedimentation half an hour is added, be filtrated to get chitosan quaternary ammonium salt powder.
The preparation of 2 oneself flowing chitosan materials:Take the chitosan quaternary ammonium salt and 1g polyoxyethylene nonyl phenyls prepared in 1g Jing steps 1 Ethene ether sodium sulfate is dissolved in 40ml water, and under the conditions of 65 DEG C 24h is reacted, and reacted mixing liquid is dialysed 3 days, in vacuum The flowing shitosan certainly that particle size range is 2~10nm is obtained within 3 days in drying box in 45 DEG C of dryings.
Embodiment 7
The synthesis of 1 chitosan quaternary ammonium salt:The shitosan that 1g viscosity average molecular weighs are 160000 is taken, the 1% of 60~80ml is added dropwise The glacial acetic acid solution of mass fraction fully dissolves stirring, then the sodium hydroxide solution neutralization that 60~80ml1% mass fractions are added dropwise And above-mentioned chitosan solution is precipitated completely, be then washed with deionized mixed solution carries out suction filtration to PH=7~8, incited somebody to action The shitosan filter cake that filter is obtained is added to immediately in 30g isopropanols, is warming up to 80 DEG C, is configured dissolved with the glycidyl chlorine of 5g bis--three Change the 20g isopropyl alcohol mixtures of quaternized ammonium, per the above-mentioned mixed solution of three/a volume of is added every other hour, stirring is anti- After answering 20 hours, ethanol in proper amount sedimentation half an hour is added, be filtrated to get chitosan quaternary ammonium salt powder.
The preparation of 2 oneself flowing chitosan materials:Take the chitosan quaternary ammonium salt and 1g polyoxyethylene nonyl phenyls prepared in 1g Jing steps 1 Ethene ether sodium sulfate is dissolved in 40ml water, and under the conditions of 65 DEG C 24h is reacted, and reacted mixing liquid is dialysed 3 days, in vacuum The flowing shitosan certainly that particle size range is 2~10nm is obtained within 3 days in drying box in 45 DEG C of dryings.
Embodiment 8
The synthesis of 1 chitosan quaternary ammonium salt:The shitosan that 1g viscosity average molecular weighs are 160000 is taken, the 1% of 60~80ml is added dropwise The glacial acetic acid solution of mass fraction fully dissolves stirring, then the sodium hydroxide solution neutralization that 60~80ml1% mass fractions are added dropwise And above-mentioned chitosan solution is precipitated completely, be then washed with deionized mixed solution carries out suction filtration to PH=7~8, incited somebody to action The shitosan filter cake that filter is obtained is added to immediately in 30g isopropanols, is warming up to 80 DEG C, is configured dissolved with the glycidyl chlorine of 5g bis--three Change the 20g isopropyl alcohol mixtures of quaternized ammonium, per the above-mentioned mixed solution of three/a volume of is added every other hour, stirring is anti- After answering 20 hours, ethanol in proper amount sedimentation half an hour is added, be filtrated to get chitosan quaternary ammonium salt powder.
The preparation of 2 oneself flowing chitosan materials:Take the chitosan quaternary ammonium salt and 2g polyoxyethylene nonyl phenyls prepared in 1g Jing steps 1 Ethene ether sodium sulfate is dissolved in 40ml water, and under the conditions of 65 DEG C 24h is reacted, and reacted mixing liquid is dialysed 3 days, in vacuum The flowing shitosan certainly that particle size range is 2~10nm is obtained within 4 days in drying box in 45 DEG C of dryings.
Embodiment 9
The synthesis of 1 chitosan quaternary ammonium salt:The shitosan that 1g viscosity average molecular weighs are 160000 is taken, the 1% of 60~80ml is added dropwise The glacial acetic acid solution of mass fraction fully dissolves stirring, then the sodium hydroxide solution neutralization that 60~80ml1% mass fractions are added dropwise And above-mentioned chitosan solution is precipitated completely, be then washed with deionized mixed solution carries out suction filtration to PH=7~8, incited somebody to action The shitosan filter cake that filter is obtained is added to immediately in 30g isopropanols, is warming up to 80 DEG C, is configured dissolved with the glycidyl chlorine of 5g bis--three Change the 20g isopropyl alcohol mixtures of quaternized ammonium, per the above-mentioned mixed solution of three/a volume of is added every other hour, stirring is anti- After answering 20 hours, ethanol in proper amount sedimentation half an hour is added, be filtrated to get chitosan quaternary ammonium salt powder.
The preparation of 2 oneself flowing chitosan materials:Take the chitosan quaternary ammonium salt and 3g polyoxyethylene nonyl phenyls prepared in 1g Jing steps 1 Ethene ether sodium sulfate is dissolved in 40ml water, and under the conditions of 65 DEG C 24h is reacted, and reacted mixing liquid is dialysed 3 days, in vacuum The flowing shitosan certainly that particle size range is 2~10nm is obtained within 5 days in drying box in 45 DEG C of dryings.

Claims (2)

1. a kind of from flowing chitosan material, it is characterised in that:It is described from flowing chitosan material particle size range be 2~ 10nm, it is described from flowing chitosan material more than the temperature 45 C under conditions of there is mobility.
2. it is a kind of from flow chitosan material preparation method, it is characterised in that:Described preparation method is according to the following steps:
By 1:1~3 quality parts ratio takes chitosan quaternary ammonium salt and is dissolved in 40 mass fractions with nonylphenol polyoxyethylene ether sulfate In deionized water, 24h is reacted under the conditions of 65 DEG C, take out reacted mixing liquid and dialyse at room temperature 3~5 days, then will be saturating Liquid after analysis, in 45 DEG C of dryings 3 days, is obtained from flowing chitosan material in vacuum drying chamber;
Described chitosan quaternary ammonium salt is synthesized by glycidyl ammonium chloride and shitosan.
Described chitosan quaternary ammonium salt glues equal viscosity average molecular weigh for 15000~200000.
CN201610966675.0A 2016-11-03 2016-11-03 It is a kind of to flow chitosan material and preparation method thereof certainly Active CN106565856B (en)

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CN113754794A (en) * 2021-08-10 2021-12-07 武汉纺织大学 Carboxymethyl chitosan fluid with good antibacterial property and high-temperature resistance and capable of being processed and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN113754794A (en) * 2021-08-10 2021-12-07 武汉纺织大学 Carboxymethyl chitosan fluid with good antibacterial property and high-temperature resistance and capable of being processed and preparation method thereof
CN113754794B (en) * 2021-08-10 2022-12-23 武汉纺织大学 Carboxymethyl chitosan fluid with good antibacterial property and high-temperature resistance and capable of being processed and preparation method thereof

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