CN101050242A - Method for synthesizing polymer of amphoteric chitosan - Google Patents
Method for synthesizing polymer of amphoteric chitosan Download PDFInfo
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- CN101050242A CN101050242A CN 200710022541 CN200710022541A CN101050242A CN 101050242 A CN101050242 A CN 101050242A CN 200710022541 CN200710022541 CN 200710022541 CN 200710022541 A CN200710022541 A CN 200710022541A CN 101050242 A CN101050242 A CN 101050242A
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Abstract
This invention relates to a method for synthesizing amphiphilic chitosan. The method comprises: dissolving chitosan, reacting, precipitating, cooling, washing, vacuum-filtering, vacuum-drying, alkalizing, carboxymethylating, desalting, dehydrating and drying to obtain amphiphilic chitosan. The method introduces electrically negative carboxymethyl group and electrically positive quaternary ammonium group onto the molecular chain of chitosan, thus the molecular chain of chitosan contains substituents with two different charge types. After modification, the quaternization degree and the carboxymethylation degree of chitosan are 80% and 70%, respectively. Amphiphilic chitosan has higher apparent viscosity, higher solubility, lower pH value, better pH stability, and wider applications than chitosan.
Description
Technical field
The present invention relates to a kind of synthetic method of polymer of amphoteric chitosan, belong to the analysis biological technical field.
Background technology
Organism in the biology is the main expression-form that life on earth exists, and also is the basis of current bio-science and technology, and they are to be grouped into by carbohydrate, protein and ribose three great achievements.What nature existed produces maximum organism with every year, be exactly carbohydrate be polysaccharide, the number maximum is Mierocrystalline cellulose in the polysaccharide, secondly is chitin, is starch once more.Chitin is present in the solid waste after the crustaceans processing of aquatic products such as shrimp shell and crab shell in a large number, and these wastes are stacked couple of days, will be rancid, cause environmental pollution.Chitosan is that chitin obtains through deacetylation, is the unique alkaline polysaccharide of occurring in nature.Chitin and chitosan are of many uses, be the Biological resources of a class preciousness in fact, be used for food and foodstuff additive mostly, also can be used for producing various medicines and medicine, and nontoxic flocculation agent, makeup, some other chemical etc., their development and use will play a significant role in high-tech area and people's daily life.
The intramolecularly of chitosan, intermolecular stronger hydrogen bond action arranged, formed orderly macromolecular structure xln, make chitosan be crystalline structure closely, be insoluble to usual vehicle, cause processing difficulties, limited it and applied.Therefore, chitosan is carried out chemical modification, improve its solvability and processing characteristics, become comparatively active subject.The method of chitosan being carried out modification mainly contains the following aspects: (1) crosslinking reaction: the aldehyde that chitosan can be by bifunctional or acid anhydrides etc. carry out crosslinked, and crosslinking reaction mainly is in intermolecular generation, also can take place at intramolecularly.In the crosslinking reaction, mainly being aldehyde radical and the western Buddhist alkali structure of amino generation, secondly is the reaction of aldehyde radical and hydroxyl.(2) graft copolymerization: the active group on the chitosan molecule chain is a lot, can carry out graft copolymerization.Grafting vinyl monomers or other monomer on the glucose unit of chitosan, synthetic half polymkeric substance polysaccharide is a focus of modification.(3) carboxymethylation: under alkaline condition, chitosan and chloroacetate reaction get cm-chitosan.Owing to be accompanied by deacetylated and DeR in this reaction process, therefore obtain water-soluble polyamphoteric electrolyte product at last.It is water-soluble that carboxymethylation can improve chitosan ground significantly.(4) cationization: chitosan can react with cation compound in some organic solvents, obtains cationic chitosan, increases its solvability.Cationization can strengthen the positive polarity effect of chitosan preferably.
By above-mentioned method of modifying can be in various degree the performance of raising chitosan, but owing to be to adopt single method to carry out chemical modification all to chitosan, the chitosan derivatives performance that obtains is often more single, can not make chitosan have two kinds or more property simultaneously.
Summary of the invention
The objective of the invention is to overcome the above-mentioned weak point of prior art, thereby provide a kind of chitosan is adopted method quaternized and that carboxymethylation is carried out modification, on molecular chain of chitosan, introduce electronegative group carboxymethyl group and positively charged group quaternary ammonium salt group, make the substituting group that contains two kinds of different charge types on the molecular chain of chitosan, finally obtain a kind of novel chitosan derivatives---polymer of amphoteric chitosan.
Main solution of the present invention is achieved in that
The synthetic method of polymer of amphoteric chitosan of the present invention adopts following work step rapid:
1, dissolving: chitosan is dissolved in the acetum of 1000ml 5%-10%, is dissolved as chitosan solution while stirring;
2, reaction: add initiator ceric ammonium nitrate and diallyldimethylammonium chloride solution (the DMDAAC aqueous solution) 20-100g of 0.5-1.0mmol/L in chitosan solution successively, to react 3-10h be ceric ammonium nitrate solution to logical nitrogen under 90～100 ℃ of temperature condition;
3, precipitation, washing, suction filtration: the above-mentioned ceric ammonium nitrate solution that obtains is cooled off down in 40 ℃-50 ℃, with ethanol sedimentation, methanol wash 3-5 time of 70%-90%, utilize vacuum pump to carry out suction filtration, vacuum-drying, extracting 6-20h in soxhlet's extractor removes homopolymer with 50ml-100ml acetone, temperature: 70-100 ℃, vacuum tightness: dry 10-15h under the 0.5-1.0MPa condition, purifying obtains n-trimethyl chitosan chloride;
4, alkalization: in the solvent Virahol of 1000ml, adding concentration is the aqueous sodium hydroxide solution of 30%-50% with the above-mentioned 100g n-trimethyl chitosan chloride that obtains, at the 40-60 ℃ of 1-3h that alkalizes down;
5, carboxymethylation: the n-trimethyl chitosan chloride after the alkalization is that carboxymethylation reagent carries out carboxymethylation 6-8h to the n-trimethyl chitosan chloride of alkalization and obtains the amphoteric chitosan material under 40-90 ℃ of condition with the Monochloro Acetic Acid of 50-100g under alkaline condition;
6, suction filtration, desalination, dehydration: the amphoteric chitosan material is carried out suction filtration with B, with the ethanol 500ml washing and desalting of 70%-90%, again with dehydrated alcohol 300-500ml and 2-5 dehydration of acetone 300-500ml washing;
7, oven dry: the amphoteric chitosan material after the dehydration is dried 10-20h and is promptly obtained amphoteric chitosan under 80 ℃ of-90 ℃ of conditions.
Compared with the prior art the present invention has the following advantages:
The present invention adopts quaternized and carboxymethyl-modification to chitosan, on molecular chain of chitosan, introduced electronegative group carboxymethyl group and positively charged group quaternary ammonium salt group, made the substituting group that contains two kinds of different charge types on the molecular chain of chitosan; With the chitosan of deacetylation about 90% is raw material, be respectively quaternizing agent and carboxymethylation reagent carries out modification to chitosan with diallyldimethylammonium chloride and Monochloro Acetic Acid, the quaternized degree of chitosan reaches 80% after the modification, and degree of substitution by carboxymethyl reaches 70%; The apparent viscosity of amphoteric chitosan (4-8mPas) increases than chitosan, solvability is (water-soluble, acid, alkali) be improved, the pH value (4-5) of amphoteric chitosan solution descends, pH value stabilization (2-11) also is greatly improved, and whole molecule presents two electrical features, makes its scope of application more extensive.
Embodiment
Embodiment one:
The preparation method of polymer of amphoteric chitosan of the present invention adopts following processing step:
The 100g deacetylation is dissolved in the acetum of 1000ml 5% at 90% chitosan, is dissolved as chitosan solution while stirring.At 90 ℃ of down logical N
2The initiator ceric ammonium nitrate solution and the DMDAAC aqueous solution 20g that add 0.5mmol/L under gas, the agitation condition successively, reaction 3h obtains ceric ammonium nitrate solution.The above-mentioned ceric ammonium nitrate solution that obtains is cooled off down at 40 ℃, ethanol sedimentation with 70%, methanol wash 3 times, utilize vacuum pump to carry out suction filtration, vacuum-drying gets thick product, after extracting 6h removes homopolymer in soxhlet's extractor with 50ml acetone thick product again, at 70 ℃, vacuum tightness is dry 10h under the condition of 0.5MPa, obtains n-trimethyl chitosan chloride.The 100g n-trimethyl chitosan chloride is joined in the solvent Virahol of 1000ml, adding concentration is 30% sodium hydroxide solution, at 40 ℃ of 1h that alkalize down.With the Monochloro Acetic Acid of 50g is that carboxymethylation reagent carries out carboxymethylation 6h at 40 ℃ of n-trimethyl chitosan chlorides to alkalization and obtains the amphoteric chitosan material.With the amphoteric chitosan material B suction filtration that obtains, the ethanol 500ml washing and desalting with 70%, with dehydrated alcohol 300ml and 2 dehydrations of acetone 300ml washing, the material after the dehydration dries by the fire 10h under 80 ℃ of conditions, obtain the polymer of amphoteric chitosan product again.Through test determination, the quaternized degree of chitosan reaches 80% after the modification, and degree of substitution by carboxymethyl reaches 70%, and its structure is as follows:
R
1, R
2=H ,-COCH
3,-CH
2COOH ,-CH
2COONa or N
+(CH
3)
2(CH
2CH=CH
2)
2Cl
Embodiment two:
The preparation method of polymer of amphoteric chitosan of the present invention adopts following processing step:
The 100g deacetylation is dissolved in the acetum of 1000ml 8% at 90% chitosan, and dissolving while stirring is at 90 ℃ of down logical N
2The initiator ceric ammonium nitrate solution and the DMDAAC aqueous solution 60g that add 0.7mmol/L under gas, the agitation condition successively, reaction 7h obtains ceric ammonium nitrate solution.The above-mentioned ceric ammonium nitrate solution that obtains is cooled off down at 45 ℃, ethanol sedimentation with 80%, methanol wash 4 times, utilize vacuum pump to carry out suction filtration, get thick product in vacuum-drying, after extracting 14h removes homopolymer in soxhlet's extractor with acetone thick product again, at 80 ℃, vacuum tightness is dry 12h under the 0.8MPa condition, obtains n-trimethyl chitosan chloride.The 100g n-trimethyl chitosan chloride is joined in the solvent Virahol of 1000ml, adding concentration is 40% sodium hydroxide, at 50 ℃ of 2h that alkalize down.With the Monochloro Acetic Acid of 70g is that carboxymethylation reagent carries out carboxymethylation 6.5h at 60 ℃ of n-trimethyl chitosan chlorides to alkalization and obtains the amphoteric chitosan material.With the amphoteric chitosan material B suction filtration that obtains, the ethanol 500ml washing and desalting with 75%, with dehydrated alcohol 300ml and 5 dehydrations of acetone 300ml washing, the material after the dehydration dries by the fire 15h under 85 ℃ of conditions, obtain the polymer of amphoteric chitosan product again.
Embodiment three:
The preparation method of polymer of amphoteric chitosan of the present invention adopts following processing step:
The 100g deacetylation is dissolved in the acetum of 1000ml 10% at 90% chitosan, and dissolving while stirring is at 90 ℃ of down logical N
2The initiator ceric ammonium nitrate solution and the DMDAAC aqueous solution 100g that add 1.0mmol/L under gas, the agitation condition successively, reaction 10h obtains ceric ammonium nitrate solution.50 ℃ of coolings down, ethanol sedimentation with 80%, methanol wash 5 times, utilize vacuum pump to carry out suction filtration, get thick product in vacuum-drying, after extracting 20h removes homopolymer in soxhlet's extractor with acetone thick product again, at 100 ℃, vacuum tightness is dry 15h under the condition of 1.0MPa, obtains n-trimethyl chitosan chloride.The 100g n-trimethyl chitosan chloride is joined in the solvent Virahol of 1000ml, adding concentration is 50% sodium hydroxide, at 60 ℃ of 3h that alkalize down; With the Monochloro Acetic Acid of 100g is that carboxymethylation reagent carries out carboxymethylation 8h at 90 ℃ of n-trimethyl chitosan chlorides to alkalization and obtains the amphoteric chitosan material.With the amphoteric chitosan material B suction filtration that obtains, the ethanol 500ml washing and desalting with 90%, with dehydrated alcohol 500ml and 5 dehydrations of acetone 500ml washing, the material after the dehydration dries by the fire 20h under 90 ℃ of conditions, obtain the polymer of amphoteric chitosan product again.
Claims (3)
1, a kind of synthetic method of polymer of amphoteric chitosan is characterized in that adopting following work step rapid:
(1), dissolving: chitosan is dissolved in the acetum, through stirring, be dissolved as chitosan solution;
(2), reaction: add initiator and diallyldimethylammonium chloride solution in chitosan solution, temperature reaction 3-10h is an initiator solution, and temperature is: 90～100 ℃;
(3), precipitation, washing, suction filtration: in 40 ℃-50 ℃ coolings down, acetone extracting 6-20h is used in precipitation, washing, suction filtration, vacuum-drying with the above-mentioned initiator solution that obtains, and vacuum-drying is purified and obtained n-trimethyl chitosan chloride again;
(4), alkalization: the above-mentioned n-trimethyl chitosan chloride that obtains in aqueous isopropanol, is added aqueous sodium hydroxide solution, at 40-60 ℃ of alkalization 1-3h;
(5), carboxymethylation: the n-trimethyl chitosan chloride after the alkalization is that carboxymethylation reagent carries out carboxymethylation 6-8h at 40-90 ℃ and obtains the amphoteric chitosan material with the Monochloro Acetic Acid;
(6), suction filtration, desalination, dehydration: with amphoteric chitosan material suction filtration, use the washing with alcohol desalination, again with dehydrated alcohol and washing with acetone dehydration;
(7), oven dry: the amphoteric chitosan drying materials 10-20h after the dehydration promptly obtains amphoteric chitosan.
2, the synthetic method of polymer of amphoteric chitosan according to claim 1, it is characterized in that the described vacuum-drying time is: 10-15h, temperature are: 70-100 ℃, vacuum tightness are: 0.5-1.0MPa.
3, the synthetic method of polymer of amphoteric chitosan according to claim 1 is characterized in that described initiator adopts ceric ammonium nitrate solution.
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| CNB2007100225414A CN100537607C (en) | 2007-05-11 | 2007-05-11 | Method for synthesizing polymer of amphoteric chitosan |
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| CNB2007100225414A CN100537607C (en) | 2007-05-11 | 2007-05-11 | Method for synthesizing polymer of amphoteric chitosan |
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| CN101050242A true CN101050242A (en) | 2007-10-10 |
| CN100537607C CN100537607C (en) | 2009-09-09 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951758A (en) * | 2014-04-11 | 2014-07-30 | 昆山京昆油田化学科技开发公司 | Preparation method for amphoteric hydroxypropyl guar gum derivative |
| CN106565856A (en) * | 2016-11-03 | 2017-04-19 | 武汉纺织大学 | Self-flowing chitosan material and preparation method thereof |
| CN109293796A (en) * | 2018-09-11 | 2019-02-01 | 北京华城新创环境科技有限公司 | A kind of preparation method and applications of n-trimethyl chitosan chloride |
| 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 |
| CN111320711A (en) * | 2020-04-28 | 2020-06-23 | 东华大学 | Chitosan with high deacetylation degree and high molecular weight and preparation method thereof |
| CN112586712A (en) * | 2020-12-07 | 2021-04-02 | 安徽省美极调味食品有限公司 | Wet diced meat seasoning capable of being stored at normal temperature and preparation method thereof |
-
2007
- 2007-05-11 CN CNB2007100225414A patent/CN100537607C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951758A (en) * | 2014-04-11 | 2014-07-30 | 昆山京昆油田化学科技开发公司 | Preparation method for amphoteric hydroxypropyl guar gum derivative |
| CN106565856A (en) * | 2016-11-03 | 2017-04-19 | 武汉纺织大学 | Self-flowing chitosan material and preparation method thereof |
| CN106565856B (en) * | 2016-11-03 | 2019-05-03 | 武汉纺织大学 | It is a kind of to flow chitosan material and preparation method thereof certainly |
| CN109293796A (en) * | 2018-09-11 | 2019-02-01 | 北京华城新创环境科技有限公司 | A kind of preparation method and applications of n-trimethyl chitosan chloride |
| 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 |
| CN111320711A (en) * | 2020-04-28 | 2020-06-23 | 东华大学 | Chitosan with high deacetylation degree and high molecular weight and preparation method thereof |
| CN112586712A (en) * | 2020-12-07 | 2021-04-02 | 安徽省美极调味食品有限公司 | Wet diced meat seasoning capable of being stored at normal temperature and preparation method thereof |
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|---|---|
| CN100537607C (en) | 2009-09-09 |
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Granted publication date: 20090909 Termination date: 20160511 |