CN1325520C - Preparation of double type amphoteric chitosan derivative - Google Patents
Preparation of double type amphoteric chitosan derivative Download PDFInfo
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- CN1325520C CN1325520C CNB2003101241558A CN200310124155A CN1325520C CN 1325520 C CN1325520 C CN 1325520C CN B2003101241558 A CNB2003101241558 A CN B2003101241558A CN 200310124155 A CN200310124155 A CN 200310124155A CN 1325520 C CN1325520 C CN 1325520C
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Abstract
The present invention relates to a gemini amphoteric chitosan derivative which is a new chitosan derivative on the aspect of polysaccharide biochemistry in the field of biochemistry. The preparation of the gemini amphoteric chitosan derivative comprises: a chitosan product with the deacetylation degree of 20 to 90% is used as a raw material, and isopropyl alcohol is used as a reaction medium; mixed materials of the gemini amphoteric chitosan derivative are prepared by the alkalization of the chitosan, the carboxy methylation by chloroacetic acid as a carboxy methylation reagent, the quaternarization by epoxypropyl trimethylammonium chloride and/or 3-chlorine-2-hydroxypropyltrimethyl ammonium chloride as a quaternarization reagent; then, mixed materials are washed by methanol and/or ethanol water solution and are washed and dewatered by anhydrous alcohol and/or propanone; finally, solid materials are dried in a vacuum drier at the temperature of 60 to 150DEG C till the water content of the materials is smaller than 0.5% to 10% so as to obtain the gemini amphoteric chitosan derivative. Because of the introduction of carboxymethyl and quaternary ammonium groups, the water solubility, the electric charge property, the antibacterial property, the wettability and moisture keeping performance, the flocculability and the emulsifying stability of the gemini amphoteric chitosan derivative are obviously improved.
Description
Technical field
Amphoteric chitosan derivative involved in the present invention is a kind of chitosan new derivatives of biochemical field polysaccharide biological chemistry aspect.
Background technology
Chitosan as by chitin through the deacetylated natural polysaecharides biological polymeric compound that obtains, its application performance compares to chitin and is significantly improved and improves.It has not only kept chitin favorable biological degradability and consistency, and the solvability in acidic medium also is significantly improved than chitin.But, make that the solubility property in simple water and in alkaline medium still is not fine, thereby influence and limited its further application because hydrogen bond action is still more intense between chitosan molecule.At this problem; people have proposed multiple different method and the approach that chitosan is carried out chemical modification and modification; wherein main modification comprises the following aspects with the method for modification: (1) alkane acidylate: promptly introduce the aliphatics or the aromatic acyl of different relative molecular masses on the amino of the hydroxyl of the C-6 position by in the chitosan molecule structure and/or C-2 position, to improve the solubility property of chitosan product in organic solvent.(2) carboxylation alkylation:, thereby obtain water-soluble weak amphoteric chitosan derivative promptly by on the amino of the hydroxyl of the C-6 position of chitosan molecule structure and/or C-2 position, introducing different carboxyalkyls.(3) hydroxyalkylation: promptly under alkaline condition, chitosan is carried out modification, thereby obtain the water-soluble chitosan derivative product that greatly improves with hydroxyalkylation reagent such as oxyethane, propylene oxide, epoxy chloropropane, halohydrins.(4) sulphating: utilize H
2SO
4, SO
3, sulfur acidizing reagent such as chlorsulfonic acid carries out sulfuric acid esterification to the hydroxyl of C-6 position, thereby obtains having the chitosan derivatives of anticoagulation function.(5) Phosphation: utilize H
3PO
4, P
2O
5Deng as Phosphation reagent, chitosan is carried out chemical modification, thereby obtain the water-soluble chitosan Phosphation derivative that is significantly improved.(6) quaternized: utilize halohydrocarbon under alkaline condition in the chitosan molecule structure-NH
2Directly carry out quaternized or with the active quaternizing agent that contains quaternary ammonium group, under certain conditions (OH) or the amino (NH of C-2 position to the C-6 position hydroxyl in the chitosan molecule structure
2) to carry out grafting quaternized for the isoreactivity group.These method of modifying to chitosan can make chitosan in a certain respect or several aspects performance obtained bigger improvement.
For at present the method for modifying of chitosan often concentrated on and adopt a kind of method that chitosan is carried out chemical modification, this makes that the performance of resulting chitosan derivatives is still more single, especially aspect the chitosan product after modification electrical.Improving or to change in the method for its charge character, is that the method for purpose have carboxylation alkylation, sulphating and Phosphation to increase its electronegativity in the existing modification that is used in chitosan; To increase its positive polarity is that the method for purpose has quaternized.But be not the modification that is used for chitosan of the method for purpose obtaining the method for strong amphoteric chitosan derivatives product not only to increase its positive polarity but also to increase its electronegativity not also, this makes also that to improve the chitosan charging performance at present be purpose chitosan is carried out the chitosan derivatives product that chemical modification obtains that more restriction is arranged on application performance.At this situation, two step grafted methods have been proposed to adopt in the present invention, not only having introduced the electrical group of bear that increases chitosan and be carboxymethyl group in molecular chain of chitosan but also having introduced the lotus positive electricity group that increases chitosan is quaternary ammonium group, contains two the substituent amphoteric chitosan derivative of the charged type of difference products thereby obtain one on the chitosan molecule structure.
In the triturating of amphoteric chitosan derivative, a lot of technical information have been contacted about chitosan chemical modification and modification aspect, wherein have mainly comprising of certain reference value: " the synthetic and structural characterization of chitosan trimethyl quaternary ammonium salt " (Ningbo College On Line's journal, 1998, Vol.10, No.4), " research of trace chromium (VI) in chitosan (CHT) adsorbent solution " (Sichuan Union University journal (engineering science version), 1997, Vol.1, No.3), " the synthetic and structural characterization of chitosan quaternary ammonium salt " (functional polymer journal, 1997, Vol.10, No.1), " O-2 '-HACC synthetic with characterize " (synthetic chemistry, 2000, Vol.8, No.2), " chitosan quaternary ammonium salt synthetic and to the flocculation and the sterilizing function of refinery water " (University of Fuzhou's journal (natural science edition), 2000, Vol.28, No.4), " the synthetic and structural characterization of alcohol-soluble chitosan derivative " (water technology, 1997, Vol.23, No.5), " preparation of HACC and moisture-absorbing moisture-keeping performance thereof " (applied chemistry, 2002, Vol.19, No.4), " the synthetic and purifying of 3-chloro-2-hydroxypropyl TMA (TriMethylAmine) ammonium chloride " (fine chemistry industry, 2002, Vol.19, No.8), " modification of chitosan and applied research " (Chinese biochemical drug magazine, 1997 Vol.18, No.1), " preparation of glycerol chitosan and analysis " (Chinese biochemical drug magazine, 1997Vol.18, No.2), " Preparation of Carboxymethylchitosan and mass analysis " (Chinese biochemical drug magazine, 1996 Vol.17, No.4), " chitin, the modification of chitosan " (Guangzhou chemistry, 2002, Vol.27, No.3), " application in water treatment of chitosan and derivative thereof " (Guangzhou chemistry, 2002, Vol.27, No.3), " cm-chitosan is to the decolouring research of water-soluble dye wastewater " (environmental science and technology, 1992,2), " test of cm-chitosan treatment of dyeing and printing " (Environmental Pollution and Control, 1995, Vol.17, No.5), " Chitosan and its derivatives in mucosal drug and vaccine delivery " (European journal of pharmaceutical science, 2001,1), " A novel N, O-carboxymethylamphoteric chitosan/poly (ethersulfone) composite MF membrane and its chargedcharacteristics " (Disalination, 2002,144), " Synthesis and antibacterial activitiesof quaternary ammonium salt of chitosan " (Carbohydrate research, 2001,333), " Conceptsfor improved regioselective placement of o-sulfo, N-sulfo, N-acetyl andN-caboxymethyl groups in chitosan derivatives " (Carbohydrate research, 2001,331), " Chitosan N-sulfate.A water-soluble polyelectrolyte " (Carbohydrate research, 1997,302).
Summary of the invention
The invention of amphoteric chitosan derivative mainly is for water-soluble, the charge characteristic that improves chitosan derivatives, anti-microbial property, wetting performance of keeping humidity, flocculating property, stable emulsifying performance.By the introducing of carboxymethyl and quaternary ammonium group, the water-soluble of amphoteric chitosan derivative is significantly improved; Charge characteristic shows as the carboxymethyl that had both comprised the bear electricity in the molecular structure of chitosan derivatives, includes the quaternary ammonium group of lotus positive electricity again, and whole molecule presents tangible strong two electrical features; Along with the introducing of quaternary ammonium group, the anti-microbial property of amphoteric chitosan derivative has had further increase on the original basis of chitosan; Amphoteric chitosan and makes wetting, performance of keeping humidity significantly improve because carboxymethyl and quaternary ammonium group in the molecular structure all have very strong hydrophilicity; The amphoteric chitosan derivative since exist in the molecular structure have different electrical groups, make it to metal ion, and other charging property micelle or ionic flocculating property are more superior, the scope of application is also more extensive; The amphoteric chitosan derivative is owing to had the structure that is similar to amphoterics, and stronger electrical property feature, has kept the constitutional features of natural polysaecharides macromolecular compound simultaneously again, makes it have special stable emulsifying characteristic.
Specific implementation method
The preparation process of amphoteric chitosan derivative mainly comprises following components: (1) chitosan alkalizes in Virahol in the presence of the finite concentration aqueous sodium hydroxide solution; (2) chitosan compound after the alkalization carries out carboxymethylation with Mono Chloro Acetic Acid as carboxymethylation reagent and obtains the carboxymethylation chitosan derivatives under alkaline condition; Or carry out the quaternized n-trimethyl chitosan chloride derivative that obtains of grafting as quaternary ammonium reagent with epoxypropyl trimethylammonium chloride ammonium and/or 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride; (3) carboxymethylation chitosan derivatives product as quaternizing agent, carries out the quaternized mixture that obtains containing the amphoteric chitosan derivative of grafting with epoxypropyl trimethylammonium chloride ammonium and/or 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride under alkaline condition; Or n-trimethyl chitosan chloride derivative product carries out the mixture that carboxymethylation obtains containing the amphoteric chitosan derivative with Mono Chloro Acetic Acid as carboxymethylation reagent under alkaline condition; Resulting mixture aqueous methanol and/or the ethanolic soln washing and desalting that contains the amphoteric chitosan derivative of (4) the 3rd steps; (5) material behind the desalination dewaters with dehydrated alcohol and/or washing with acetone; (6) material after the dehydration is dry in vacuum drying oven, can obtain amphoteric chitosan derivative product.
The preparation technology of amphoteric chitosan derivative and related process parameter thereof are that 20%～90% chitosan product is that the raw material typical case is exemplified below with 100 gram deacetylations: (1) 100 gram deacetylation is 20%～90% chitosan product, with 100～1000cm
3Mass percent be 10%～50% sodium hydroxide and/or potassium hydroxide aqueous solution, at 200～2000cm
3Virahol under 20～80 ℃, alkalize, alkalization time is 0.5～24 hour; (2) material after the alkalization as carboxymethylation reagent, under whipped state, carries out carboxymethylation, 2～10 hours carboxymethylation time with 20～300 gram Mono Chloro Acetic Acids under 20～90 ℃ condition; Perhaps the material after the alkalization is with 50～1000cm
3Mass percent be that 50% epoxypropyl trimethylammonium chloride ammonium and/or mass percent are that 50% the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride aqueous solution is as quaternizing agent, carry out quaternizedly under 20-95 ℃ at whipped state, the quaternized time is 2～15 hours; The carboxymethylation chitosan material that (3) second step process obtain is with 50～1000cm
3Mass percent is that 50% epoxypropyl trimethylammonium chloride ammonium and/or mass percent are that 50% the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride aqueous solution is quaternizing agent, carry out quaternizedly under whipped state under 20～95 ℃, the quaternized time is 2～15 hours; Perhaps the n-trimethyl chitosan chloride material that obtains of second step process as carboxymethylation reagent, under whipped state, carries out carboxymethylation in 20～90 ℃ with 20～300 gram Mono Chloro Acetic Acids, and the carboxymethylation time is 2～10 hours; The material mass percent of (4) three step process gained is 30～90% methyl alcohol and/or aqueous ethanolic solution 200～3000cm
3Wash 1～3 time, and carry out suction filtration at every turn and separate; (5) material after alcohol solution is washed dehydrated alcohol and/or acetone 200～4000cm
3Washing dehydration 1～3 time, and carry out suction filtration at every turn and separate; (6) dehydration back solid materials carries out drying under 60～150 ℃ of temperature in vacuum drier, to the mass percentage content of material water less than 0.5%～10%, promptly obtain amphoteric chitosan derivative product, and realize corresponding invention.
Claims (4)
1, a kind of preparation of amphoteric chitosan derivative, it is characterized in that: with deacetylation is that 20～90% chitosan is a raw material, with epoxypropyl trimethylammonium chloride ammonium or 3-chloro-2-hydroxyl trimethyl ammonium chloride as quaternizing agent, Mono Chloro Acetic Acid as carboxymethylation reagent, chitosan is carried out dual modified, the chitosan quaternary ammonium substitution value after the modification is 20～300%, the carboxymethylation substitution value is 20～300%.
2, the preparation method of amphoteric chitosan derivative according to claim 1 is that 20～90% chitosan raw material is a benchmark with the 100g deacetylation, it is characterized in that preparing with the following method:
1. add 100～1000cm in the chitosan
3Mass percent is 10～50% sodium hydroxide or potassium hydroxide aqueous solution and 200～2000cm
3Virahol after 0.5～24 hour, adds 20～300g Mono Chloro Acetic Acid 20～80 ℃ of alkalization, and 20～90 ℃ are continued down to stir 2～10 hours, cm-chitosan;
2. add 50～1000cm in the cm-chitosan
3Mass percent is 50% epoxypropyl trimethylammonium chloride ammonium or the 3-chloro-2-hydroxyl trimethyl ammonium chloride aqueous solution and 100～1000cm
3Mass percent is 10～50% sodium hydroxide or potassium hydroxide aqueous solution, under whipped state in 20～95 ℃ the reaction 2～15 hours after, the gained material is 30～90% methyl alcohol or aqueous ethanolic solution 200～3000cm through mass percent
3Wash 1～3 time and each suction filtration separation and acetone 200～4000cm
3Washing dehydration 1～3 time and each suction filtration separate, and are drying to obtain the amphoteric chitosan derivative in 60～150 ℃ at last in vacuum drier.
3, the preparation method of amphoteric chitosan derivative according to claim 1 is that 20～90% chitosan raw material is a benchmark with the 100g deacetylation, it is characterized in that preparing with the following method:
1. add 100～1000cm in the chitosan
3Mass percent is 10～50% sodium hydroxide or potassium hydroxide aqueous solution and 200～2000cm
3Virahol after 0.5～24 hour, adds 50～1000cm 20～80 ℃ of alkalization
3Mass percent is 50% the epoxypropyl trimethylammonium chloride ammonium or the 3-chloro-2-hydroxyl trimethyl ammonium chloride aqueous solution, and 20～95 ℃ of reactions got n-trimethyl chitosan chloride after 2～15 hours;
2. add 20～300g Mono Chloro Acetic Acid and 100～1000cm in the n-trimethyl chitosan chloride
3Mass percent is 10～50% sodium hydroxide or potassium hydroxide aqueous solution, and 20～90 ℃ are continued down to stir 2～10 hours, and the gained material is 30～90% methyl alcohol or aqueous ethanolic solution 200～3000cm through mass percent
3Wash 1～3 time and each suction filtration separation and acetone 200～4000cm
3Washing dehydration 1～3 time and each suction filtration separate, and are drying to obtain the amphoteric chitosan derivative in 60～150 ℃ at last in vacuum drier.
4, according to the preparation method of claim 2 or 3 described amphoteric chitosan derivatives, the product water content is 0.5～10%.
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| CNB2003101241558A CN1325520C (en) | 2003-12-22 | 2003-12-22 | Preparation of double type amphoteric chitosan derivative |
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| CNB2003101241558A CN1325520C (en) | 2003-12-22 | 2003-12-22 | Preparation of double type amphoteric chitosan derivative |
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| CN1325520C true CN1325520C (en) | 2007-07-11 |
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| CN101408016B (en) * | 2008-06-20 | 2011-05-18 | 南京林业大学 | Paper making wet part polyvalent metal cation refuse removal agent and preparing method and application thereof |
| CN101972489A (en) * | 2010-09-30 | 2011-02-16 | 吴奕光 | Novel wound self-healing biological material, preparation method and application thereof |
| CN102060939B (en) * | 2010-12-10 | 2012-10-03 | 北京联合大学生物化学工程学院 | Preparation method of water-soluble 2'-hydroxylpropylchitosan |
| 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 |
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| CN105254811A (en) * | 2015-11-10 | 2016-01-20 | 陕西科技大学 | Carboxymethyl chitosan quaternary ammonium salt and preparation method thereof |
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| CN110723791A (en) * | 2018-07-16 | 2020-01-24 | 陕西省石油化工研究设计院 | Preparation method of flocculant |
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| CN109762078B (en) * | 2019-04-09 | 2019-07-23 | 中国科学院烟台海岸带研究所 | A kind of hydroxypropyltrimethylammonium chloride chitosan-carboxylated polysaccharide complex salt and preparation method and application |
| CN110105462A (en) * | 2019-06-02 | 2019-08-09 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of modification of chitosan flocculant and products thereof and application |
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| CN114318669B (en) * | 2021-12-31 | 2023-01-10 | 福建恒安集团有限公司 | Preparation method of chitosan fiber non-woven fabric applied to surface layer of paper diaper |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1266922A (en) * | 2000-01-25 | 2000-09-20 | 天津大学 | Antibacterial viscose fibre and its making method |
Non-Patent Citations (3)
| Title |
|---|
| A novel N,O-carboxymethyl amphotericchitosan/poly(ethersulfone) composite MF membrane and itscharged characteristics Zhiping Zhao et al,Desalination,Vol.144 2002 * |
| A novel N,O-carboxymethyl amphotericchitosan/poly(ethersulfone) composite MF membrane and itscharged characteristics Zhiping Zhao et al,Desalination,Vol.144 2002;Synthesisi and antibacterial activities of quaternary ammoniumsalt of chitosan Zhishen Jia et al,Carbohydrate Research,Vol.333 2001 * |
| Synthesisi and antibacterial activities of quaternary ammoniumsalt of chitosan Zhishen Jia et al,Carbohydrate Research,Vol.333 2001 * |
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