CN1193044C - Carboxymethyl chitosan, its preparing method and usage - Google Patents
Carboxymethyl chitosan, its preparing method and usage Download PDFInfo
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- CN1193044C CN1193044C CNB031184340A CN03118434A CN1193044C CN 1193044 C CN1193044 C CN 1193044C CN B031184340 A CNB031184340 A CN B031184340A CN 03118434 A CN03118434 A CN 03118434A CN 1193044 C CN1193044 C CN 1193044C
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- chitosan
- ethanolic soln
- carboxymethyl chitosan
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- carboxymethyl
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Abstract
The present invention discloses carboxymethyl chitosan with good moisture absorption and moisture retention performance, a preparing method thereof and uses thereof. Raw materials of chitosan are fully acetylized by acid anhydride so as to obtain N-acetylized chitosan. Then, the N-acetylized chitosan reacts with the chloroacetic acid in sodium hydroxide solution so as to prepare the required carboxymethyl chitosan. The substitution value of carboxymethyl is from 0.6 to 1.0, and the degree of deacetylation is from 30% to 70%. Compared with hyaluronic acid, the carboxymethyl chitosan has better moisture absorption and moisture retention performance in the environment with relative moisture larger than 30%. Because of the advantages of rich source and low price, the carboxymethyl chitosan can substitute for hyaluronic acid in cosmetics and clinical medicine, resulting in wide application prospect.
Description
Technical field
The present invention relates to a kind of alternative hyaluronic acid Preparation of Carboxymethylchitosan method.
Background technology
Hyaluronic acid is described as " gold of preserving moisture ", because its good performance of keeping humidity is widely used in makeup and clinical medicine.Though hyaluronic acid is very wide in distributed in nature, total amount seldom costs an arm and a leg.
Summary of the invention
The objective of the invention is to overcome the problem of the deficiencies in the prior art and existence, and then a kind of alternative hyaluronic Preparation of Carboxymethylchitosan method is provided, this cm-chitosan preparation cost is lower and method for making is simple.
Cm-chitosan in the technical scheme provided by the invention, degree of substitution by carboxymethyl are 0.6-1.0, and deacetylation is 30-70%.
The invention provides above-mentioned Preparation of Carboxymethylchitosan method, the raw materials of chitosan of getting the 50-80g deacetylation and be 70-97% is dissolved in the acetum of 10-30wt%, in the mol ratio of acetic anhydride and chitosan is fully to stir after the ratio of 0.1-0.7 adds acetic anhydride, leaves standstill the back and forms gel or settled solution; Gel dewaters solution NH with the ethanolic soln of alkali
4The OH precipitation, products therefrom cleans repeatedly with the ethanolic soln of 60-85wt%, and vacuum-drying obtains N-acetylated chitosan sugar; Is in the sodium hydroxide solution of 40-70wt% fully after the alkalization with the N-acetylated chitosan sugar that obtains in concentration, adds 300-500ml Virahol and 50-100g Mono Chloro Acetic Acid, 40-70 ℃ of reaction 5-8 hour; Finish after product and transfer to neutrality, obtain required cm-chitosan with dilute hydrochloric acid.
The ethanolic soln of above-mentioned alkali is the ethanolic soln of sodium hydroxide or potassium hydroxide, and concentration is 0.3-0.8M.
Above-mentioned cm-chitosan can be used for substituting hyaluronic acid as wetting Agent for Printing Inks.
The chitin wide material sources are present in shrimp, crab shell constant pitch main drive thing and the fungi, and natural annual production reaches 10,000,000,000 tons, are the outer second largest natural polysaccharides of Mierocrystalline cellulose.By chitin carry out that the cm-chitosan cost of carboxymethylation reaction preparation is lower, chemical structure and hyaluronic acid be quite similar, has the good moisture preserving performance, the rate of preserving moisture reaches 40-60% in ambient relative humidity is the scope of 35%-90%, and is better than hyaluronic acid; And method for making is simple, safety, convenience; Alternative hyaluronic acid is used for makeup and clinical medicine.
Embodiment
Embodiment 1: get the 50g deacetylation in O.9 raw materials of chitosan be dissolved in 10% acetum of (weight percent, down with), fully stir after adding acetic anhydride, at room temperature place one evening the back form gel or settled solution.Gel dewaters with the ethanolic soln that contains 0.5M KOH, solution NH
4OH precipitation is cleaned product with 75% ethanolic soln then repeatedly, and vacuum-drying obtains N-acetylated chitosan sugar.After N-acetylated chitosan sugar fully being alkalized, add the 300ml Virahol again in 50% sodium hydroxide solution, add the 80g Mono Chloro Acetic Acid again, 70 ℃ were reacted 5 hours.Finish after product and transfer to neutrality with dilute hydrochloric acid, obtaining substitution value is 0.78, and deacetylation is 0.56 cm-chitosan.Its performance of keeping humidity is listed in the table 1.
Embodiment 2: get the 50g deacetylation and be 0.85 raw materials of chitosan and be dissolved in 10% the acetum, fully stir after adding acetic anhydride, at room temperature place one evening the back form gel or settled solution.Gel is with containing the O.8M ethanolic soln dehydration of NaOH, solution NH
4OH precipitation is cleaned product with 70% ethanolic soln then repeatedly, and vacuum-drying obtains N-acetylated chitosan sugar.After N-acetylated chitosan sugar fully being alkalized, add the 300ml Virahol again in 60% sodium hydroxide solution, add the 50g Mono Chloro Acetic Acid again, 70 ℃ were reacted 5 hours.Finish after product and transfer to neutrality with dilute hydrochloric acid, obtaining substitution value is 0.63, and deacetylation is 0.40 cm-chitosan.Its performance of keeping humidity is listed in the table 1.
Embodiment 3: get the 80g deacetylation and be 0.95 raw materials of chitosan and be dissolved in 30% the acetum, fully stir after adding acetic anhydride, leave standstill the back and form gel or settled solution; Gel dewaters solution NH with the ethanolic soln of 0.5M NaOH
4OH precipitation is cleaned product with 60% ethanolic soln then repeatedly, and vacuum-drying obtains N-acetylated chitosan sugar; After N-acetylated chitosan sugar fully being alkalized, add the 500ml Virahol again in 40% sodium hydroxide solution, add the 100g Mono Chloro Acetic Acid again, 40-70 ℃ was reacted 5-8 hour; Finish after product and transfer to neutrality with dilute hydrochloric acid, obtaining substitution value is 0.60, and deacetylation is 0.65 cm-chitosan.Its performance of keeping humidity is listed in the table 1.
Comparative Examples 1: get hyaluronic acid and compare, moisture absorption, moisture retention are listed in the table 1.
Table 1:
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 | |
| RH81% rate of moisture absorption (%) | 60 | 50 | 40 | 54 |
| The RH43% rate (%) of preserving moisture | 400 | 340 | 270 | 240 |
Claims (2)
1. Preparation of Carboxymethylchitosan method, it is characterized in that: the raw materials of chitosan of getting the 50-80g deacetylation and be 70-97% is dissolved in the acetum of 10-30wt%, in the mol ratio of acetic anhydride and chitosan is fully to stir after the ratio of 0.1-0.7 adds acetic anhydride, leaves standstill the back and forms gel or settled solution; Gel dewaters solution NH with the ethanolic soln of alkali
4The OH precipitation, products therefrom cleans repeatedly with the ethanolic soln of 60-85wt%, and vacuum-drying obtains N-acetylated chitosan sugar; Is in the sodium hydroxide solution of 40-70wt% fully after the alkalization with the N-acetylated chitosan sugar that obtains in concentration, adds 300-500ml Virahol and 50-100g Mono Chloro Acetic Acid, 40-70 ℃ of reaction 5-8 hour; Finish after product and transfer to neutrality, obtain required cm-chitosan with dilute hydrochloric acid.
2. method according to claim 1 is characterized in that: the ethanolic soln of alkali is the ethanolic soln of sodium hydroxide or potassium hydroxide, and concentration is 0.3-0.8M.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031184340A CN1193044C (en) | 2003-01-09 | 2003-01-09 | Carboxymethyl chitosan, its preparing method and usage |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031184340A CN1193044C (en) | 2003-01-09 | 2003-01-09 | Carboxymethyl chitosan, its preparing method and usage |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1431229A CN1431229A (en) | 2003-07-23 |
| CN1193044C true CN1193044C (en) | 2005-03-16 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB031184340A Expired - Fee Related CN1193044C (en) | 2003-01-09 | 2003-01-09 | Carboxymethyl chitosan, its preparing method and usage |
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Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308510C (en) * | 2004-07-02 | 2007-04-04 | 秦益民 | Carboxymethyl chitin amine fiber and preparing method and use |
| CN1833732A (en) * | 2005-03-17 | 2006-09-20 | 李毅彬 | Making method of and use of antibiotic surgical dressing |
| CN100484965C (en) * | 2005-10-17 | 2009-05-06 | 扬州大学 | Preparation of carboxymethyl chitosan and its application in tissue surface engineering |
| CN100439401C (en) * | 2005-11-30 | 2008-12-03 | 华南理工大学 | Carboxy methyl schizophllan polysacharide preparing method and its use for use in cosmetics and anticancer drugs |
| CN100450549C (en) * | 2006-01-16 | 2009-01-14 | 中国药科大学 | Solubilization carrier for drug, its preparation method and application |
| CN1975419B (en) * | 2006-12-11 | 2012-05-09 | 武汉大学 | Water soluble chitin pH probe and producing method thereof |
| CN102875611B (en) * | 2012-09-07 | 2014-12-10 | 河南中烟工业有限责任公司 | Humectants 1-O-carboxymethyl-D-furan mannose for cigarettes and preparation method of humectants 1-O-carboxymethyl-D-furan mannose |
| CN103007334B (en) * | 2012-12-24 | 2014-11-19 | 南通大学 | Liquid wound repairing film and preparation method thereof |
| CN105129896A (en) * | 2015-08-11 | 2015-12-09 | 厦门建霖工业有限公司 | Antibacterial activated carbon-activated carbon fiber composite filter core and preparation method |
| CN105052988A (en) * | 2015-08-11 | 2015-11-18 | 厦门建霖工业有限公司 | Antibacterial agent and preparation method |
| CN106581039B (en) * | 2016-11-02 | 2020-01-14 | 上海陶盛生物技术有限公司 | Application of carboxymethyl chitosan in preparing antiallergic product |
| CN106727664B (en) * | 2016-11-02 | 2020-01-14 | 上海陶盛生物技术有限公司 | Application of carboxymethyl chitosan in preparation of product for treating skin itch |
| FR3074044B1 (en) | 2017-11-28 | 2019-11-01 | Kiomed Pharma | CARBOXYALKYL CHITOSANE |
| FR3074043B1 (en) | 2017-11-28 | 2020-11-13 | Kiomed Pharma | ANIONIC CHARGED CHITOSAN |
| CN115637132A (en) * | 2022-10-28 | 2023-01-24 | 鞍钢集团矿业有限公司 | Ecological dust suppressant and preparation and use methods thereof |
-
2003
- 2003-01-09 CN CNB031184340A patent/CN1193044C/en not_active Expired - Fee Related
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