CN1367183A - Preparation method for hyaluronic acid-like chitosan - Google Patents
Preparation method for hyaluronic acid-like chitosan Download PDFInfo
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- CN1367183A CN1367183A CN 02103023 CN02103023A CN1367183A CN 1367183 A CN1367183 A CN 1367183A CN 02103023 CN02103023 CN 02103023 CN 02103023 A CN02103023 A CN 02103023A CN 1367183 A CN1367183 A CN 1367183A
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- hyaluronic acid
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Abstract
The present invention utilizes the chitosan, makes it undergo the process of acylation reaction, then makes it implement selective oxidation reaction to obtain the chitosan derivative whose structure is similar to that of hyaluronic acid. The said method adopts flaky chitin or chitosan to make direct reaction so that its process is simple and its production cost is low, and the said invented product possesses water solubility, adjustable viscosity, and its moisture-absorbing and moisture-retaining effects are superior to the hyaluronic acid with identical molecular weight, therfore it can be substituted for hyaluronic acid in moisture-retaining cosmetics, and the product also possesses the bacteriostatic and thickening functions, and can be used in the fields of medicine and food.
Description
Technical field
The present invention relates to a kind of preparation method of hyaluronic acid-like chitosan, it is the agent of a kind of ideal natural moisture preserving, belongs to the preparation method of the derivative of natural polymer chitin.
Background technology
Chitin is a kind of natural polymer that extracts from shrimp, crab shell, has linear structure, but owing to effect intermolecular and intramolecular hydrogen bond, makes it be insoluble to diluted acid, alkali and common organic solvent, thereby limited its application.Chitosan is the product of chitin deacetylase base, is a kind of glycosaminoglycan, dissolves in the dilute acid soln.Because good film-forming properties is arranged, functions such as Bc and absorption transition metal ion have obtained widespread use in papermaking, wastewater treatment, printing and dyeing, agricultural and daily use chemicals and medicine and other fields.But chitosan can only be dissolved in acidic solution, and aqueous solution degradation speed is fast, thereby also limits its range of application.
Chitin and chitosan have certain moisture, moisture-retaining capacity, but it is water insoluble because of it, can only be dissolved in the dilute acid soln, make its product be subacidity, not only skin is had hormesis slightly, and along with the prolongation of time, the viscosity degradation of product is very fast, this has limited its application to a certain extent, thereby it is carried out modification will fully develop talents with the preparation water-solubility chitosan derivative.At present, to preserve moisture is that the purpose water-soluble chitosan derivative is in the majority with carboxymethylation, also relate to hydroxyethyl, the report of hydroxypropyl and Quaterisation chitosan derivative, but the moisture retention of these chitosan derivatives just approaches widely used hyaluronic acid in the present moisture-keeping cosmetics.Have in the chitosan molecule-OH ,-NH
2, can prepare derivative with hyaluronic acid-like structure by design.Therefore, being better than hyaluronic chitosan derivatives by design preparation performance of keeping humidity still has living space.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of hyaluronic acid-like chitosan.
It is raw material that the present invention adopts the sheet chitin, prepares a kind of hyaluronic acid-like chitosan.
A kind of preparation method of hyaluronic acid-like chitosan is characterized in that this method may further comprise the steps: (1), take off acetyl by chitin through alkaline purification and be prepared into chitosan; (2), in the organic solvent system of above-mentioned chitosan, add the mixing solutions of acid/acid anhydrides, controlled temperature is 40～60 ℃; (3), change in the organic solvent after filtering, carry out the selective oxidation reaction; From reaction mixture, collect resultant.
A kind of hyaluronic acid-like chitosan is the preparation method more specifically, it is characterized in that this method may further comprise the steps: (1), alkaline purification: with clean sheet chitin raw material, in the alkaline solution of input 35～50%, heating mixed solution to 100～110 ℃, reacted 3 hours, filter, be washed to neutrality afterwards, dry the white plates chitosan, its deacetylation is 80～95%; (2), carboxylation reaction: above-mentioned sheet chitosan is placed organic solvent, adds the mixture of acetate and acid anhydrides, stir, be heated to 40～60 ℃, 2～6 hours reaction times, filter, wash the sheet acylation chitosan.(3), selective oxidation: above-mentioned acylation chitosan is placed organic solvent, add chromium trioxide or hydrogen peroxide under stirring as oxygenant, 30～60 ℃ of temperature of reaction, 1～10 hour reaction times; From reaction mixture, collect resultant.
Among the preparation method of hyaluronic acid-like chitosan, chitin and the weight ratio of alkali lye be 1: 20～40.
The said acid anhydrides of the present invention can be diacetyl oxide, propionic anhydride, butyryl oxide, the mixture of one of them or they of acid anhydrides.
The weight ratio of chitosan of the present invention and chromium trioxide is 1: 0.01～2.
The weight ratio of chitosan of the present invention and hydrogen peroxide is 1: 0.1～5, and wherein the concentration of hydrogen peroxide is 2～10%.
Among the preparation method of hyaluronic acid-like chitosan, used organic solvent is wherein one or more of methyl alcohol, ethanol, Virahol, tetrahydrofuran (THF).
The present invention is a raw material with the sheet chitin, a kind of hyaluronic acid-like chitosan is prepared in design, this preparation technology is simple, workable, the moisture retention of its product surpasses the hyaluronic acid with molecular weight, have antibacterially and water-soluble simultaneously, can be applicable to moisture-keeping cosmetics and medicine and fields such as food.
The preparation method's of hyaluronic acid-like chitosan of the present invention advantage is: owing to be that the chitin that extracts from marine organisms shrimp, crab shell is the preparation raw material, thereby belong to natural polymer; Adopt sheet chitin direct reaction, saved pulverizing in the chitosan derivative traditional technology, sour molten-steps such as precipitation, technological process is simple, and production cost reduces; Product has the structure close with hyaluronic acid, complete water soluble, viscosity in aqueous solution can height can be low; Experimental results show that through preserving moisture under same condition, the moisture retention of this product is better than hyaluronic acid during with molecular weight, this product also has antibacterial and thickening function simultaneously, thereby has widened the range of application of such material in fields such as daily moisture-keeping cosmetics, medicine and food greatly.
Embodiment
In conjunction with embodiments of the invention, the experiment of preserving moisture is further specified, embodiments of the invention not only are confined in the following example.
Embodiment 1:
Take by weighing the clean sheet chitin of 10g, add in 40% the sodium hydroxide solution of 200ml, be warming up to 110 ℃ of reactions 3 hours, filter, be washed to after the neutrality chitosan.Chitosan is added in the solvent system of acetate/10g diacetyl oxide of 150ml methyl alcohol and 10ml1%, behind reaction 4h under 60 ℃, filter, wash, transfer in the isopropanol reaction system of 150ml, the chromium trioxide that adds 0.2g, in the time of 30 ℃ the reaction 2 hours after-filtration, the washing, dry the white plates product.
Embodiment 2:
Take by weighing the clean flaky chitin of 10g, add in 50% the sodium hydroxide solution of 200ml, be warming up to 100 ℃ of reactions 3 hours, filter, be washed to neutrality, obtain chitosan.Chitosan is joined in the reaction system of the ethanol of 150ml and the acetate of 10ml1%/8g diacetyl oxide+5g butyryl oxide, be warming up to 50 ℃, react after 6 hours, filter, washing is transferred in the 150ml methylalcohol reaction system, the hydrogen peroxide 3ml of adding 5%, in 30 ℃ of down reactions 2 hours, washing, dry the white plates product.
Table 1 hyaluronic acid-like chitosan and hyaluronic acid performance of keeping humidity comparative result (24h) sample relative humidity 81% relative humidity 32% silica gel
(%) (%) (%) chitosan 134.3 18.3 23.1 embodiment 1 315.7 55.7 51.5 embodiment 2 369.4 94.7 45.3 hyaluronic acids 182.3 42.3 30.3
Claims (6)
1, a kind of preparation method of hyaluronic acid-like chitosan is characterized in that this method may further comprise the steps:
(1), alkaline purification: with clean sheet chitin raw material, drop in the alkaline solution of 35-50%, the heating mixed solution reacted 3 hours to 100-110 ℃, filtered, is washed to neutrality afterwards, dry the white plates chitosan, its deacetylation is 80-95%;
(2), carboxylation reaction: above-mentioned sheet chitosan is placed organic solvent, adds the mixture of acetate and acid anhydrides, stir, be heated to 40-60 ℃, reaction times 2-6 hour, filter, wash the sheet acylation chitosan;
(3), selective oxidation: above-mentioned acylation chitosan is placed organic solvent, stirs and to add chromium trioxide or hydrogen peroxide down as oxygenant, temperature of reaction 30-60 ℃, reaction times 1-10 hour; From reaction mixture, collect resultant.
2, the method for claim 1, it is characterized in that chitin and the weight ratio of alkali lye be 1: 20-40.
3, the method for claim 1 is characterized in that acid anhydrides is diacetyl oxide, propionic anhydride, butyryl oxide, the mixture of one of them or they of acid anhydrides.
4, the method for claim 1 is characterized in that the weight ratio 1 of chitosan and chromium trioxide: 0.01-2.
5, the method for claim 1, the weight ratio that it is characterized in that chitosan and hydrogen peroxide is 1: 0.1-5, wherein the concentration of hydrogen peroxide is 2-10%.
6, the method for claim 1 is characterized in that organic solvent is wherein one or more of methyl alcohol, ethanol, Virahol, tetrahydrofuran (THF).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021030235A CN1149226C (en) | 2002-02-04 | 2002-02-04 | Preparation method for hyaluronic acid-like chitosan |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021030235A CN1149226C (en) | 2002-02-04 | 2002-02-04 | Preparation method for hyaluronic acid-like chitosan |
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| CN1367183A true CN1367183A (en) | 2002-09-04 |
| CN1149226C CN1149226C (en) | 2004-05-12 |
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| CNB021030235A Expired - Fee Related CN1149226C (en) | 2002-02-04 | 2002-02-04 | Preparation method for hyaluronic acid-like chitosan |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215383B (en) * | 2008-01-14 | 2010-06-09 | 浙江大学 | Method for preparing acid and base amphiprotic dissoluble chitosan |
| CN101491353B (en) * | 2009-03-04 | 2012-05-30 | 广东药学院 | Environmental protection synthesis preparation method of bioactive substance in shrimp shell |
| CN101018811B (en) * | 2004-07-29 | 2014-06-18 | 国家科研中心 | Method for the controlled oxidation of polysaccharides |
| CN105237243A (en) * | 2015-11-19 | 2016-01-13 | 金正大生态工程集团股份有限公司 | Water-soluble plant growth nutrient solution and preparation method |
| CN109734824A (en) * | 2019-01-03 | 2019-05-10 | 昆山京昆油田化学科技有限公司 | A kind of N- succinyl group chitosan C-6 selective oxidation derivative and its preparation method and application |
-
2002
- 2002-02-04 CN CNB021030235A patent/CN1149226C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101018811B (en) * | 2004-07-29 | 2014-06-18 | 国家科研中心 | Method for the controlled oxidation of polysaccharides |
| CN101215383B (en) * | 2008-01-14 | 2010-06-09 | 浙江大学 | Method for preparing acid and base amphiprotic dissoluble chitosan |
| CN101491353B (en) * | 2009-03-04 | 2012-05-30 | 广东药学院 | Environmental protection synthesis preparation method of bioactive substance in shrimp shell |
| CN105237243A (en) * | 2015-11-19 | 2016-01-13 | 金正大生态工程集团股份有限公司 | Water-soluble plant growth nutrient solution and preparation method |
| CN105237243B (en) * | 2015-11-19 | 2019-03-22 | 金正大生态工程集团股份有限公司 | A kind of water-soluble plant growth nutrient solution and preparation method |
| CN109734824A (en) * | 2019-01-03 | 2019-05-10 | 昆山京昆油田化学科技有限公司 | A kind of N- succinyl group chitosan C-6 selective oxidation derivative and its preparation method and application |
| CN109734824B (en) * | 2019-01-03 | 2021-03-19 | 昆山京昆油田化学科技有限公司 | N-succinyl chitosan C-6 selective oxidation derivative and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1149226C (en) | 2004-05-12 |
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