CN103539868A - Method for preparing carboxymethyl chitosan - Google Patents
Method for preparing carboxymethyl chitosan Download PDFInfo
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- CN103539868A CN103539868A CN201310536202.3A CN201310536202A CN103539868A CN 103539868 A CN103539868 A CN 103539868A CN 201310536202 A CN201310536202 A CN 201310536202A CN 103539868 A CN103539868 A CN 103539868A
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 151
- 238000000034 method Methods 0.000 title claims abstract description 37
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 title claims abstract description 18
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 51
- 238000003381 deacetylation reaction Methods 0.000 claims abstract description 24
- 229920002101 Chitin Polymers 0.000 claims abstract description 23
- 238000006467 substitution reaction Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006473 carboxylation reaction Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 230000006196 deacetylation Effects 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 12
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 11
- 230000018044 dehydration Effects 0.000 claims description 11
- 238000006297 dehydration reaction Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 9
- 238000004090 dissolution Methods 0.000 claims description 9
- 229960004756 ethanol Drugs 0.000 claims description 9
- 230000003252 repetitive effect Effects 0.000 claims description 9
- 238000005201 scrubbing Methods 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 5
- 230000021523 carboxylation Effects 0.000 abstract 1
- 238000012668 chain scission Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000007774 longterm Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 238000005516 engineering process Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 12
- 239000003814 drug Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229940089960 chloroacetate Drugs 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-M chloroacetate Chemical compound [O-]C(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-M 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 229920002674 hyaluronan Polymers 0.000 description 1
- 229960003160 hyaluronic acid Drugs 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- Polysaccharides And Polysaccharide Derivatives (AREA)
- Cosmetics (AREA)
Abstract
The invention discloses a method for preparing carboxymethyl chitosan. The method comprises the following steps of by using chitin as a material, alkalifying the chitin, carrying out deacetylation reaction by using a cooling-heating alternative method to produce chitosan sodium salt; and then, carrying out carboxylation under an alkaline condition to obtain a carboxymethyl chitosan product. The method disclosed by the invention is simple in process and easy to control, so that a chain scission phenomenon appearing due to long-term high temperature reaction during deacetylation reaction of a chitosan molecular chain is avoided, thereby obtaining carboxymethyl chitosan which is high in viscosity, high in degree of substitution and better in water solubility; moreover, the method is suitable for large-scale industrial production.
Description
Technical field
What the present invention relates to is a kind of method of preparing cm-chitosan, specifically a kind of method of preparing the cm-chitosan of high viscosity and high substitution value.
Background technology
Chitin is a kind of nonpoisonous and tasteless white or the translucent solid of canescence; in water, diluted acid, diluted alkaline and general organic solvent, be difficult to dissolve; but chitin is processed N-ethanoyl through concentrated base and is sloughed that more than 55% just to become soluble chitin be chitosan; the chemical name of chitosan is β-(Isosorbide-5-Nitrae)-2-amino-2-deoxidation-β-D-Glucose.Cm-chitosan is a kind of water-solubility chitosan derivative to chitin modified rear acquisition, and it has germ resistance, is a kind of polyamphoteric electrolyte, at makeup, the aspect such as fresh-keeping, medical, has multiple application.
The method of producing cm-chitosan in prior art has a lot; for example patent CN1431229A discloses a kind of preparation method with the cm-chitosan of good moisture absorption, performance of keeping humidity; and the cm-chitosan making in this way substitutes hyaluronic acid for makeup and clinical medicine aspect; its preparation method is to take chitosan N-Acetylated Chitosans after raw material passes through the abundant acetylize of acid anhydrides; again N-Acetylated Chitosans is made to required cm-chitosan with chloroacetate reaction in sodium hydroxide solution, degree of substitution by carboxymethyl is 0.6-1.0.Can also take chitin as raw material, under certain temperature, in 40%～60%NaOH solution, soak 0.5～5h, then add while stirring Mono Chloro Acetic Acid, at 0～70 ℃ of reaction 0.5～5h, alkali acid mass ratio is controlled at (1.2～1.6) again: 1, at 0-80 ℃ of insulation 5～36h, then with dilute hydrochloric acid, neutralize, separated product, with 75% ethanolic soln washing, is drying to obtain cm-chitosan in 60 ℃.
Yet have the following disadvantages in above-mentioned traditional technology: 1. the pH scope that the cm-chitosan that traditional method obtains is dissolved is all more than or equal to 7, and at food, medicine, in the industries such as makeup, the pH area requirement dissolving for cm-chitosan is all being more than or equal to 5, in acidic solution, also can dissolve, therefore the cm-chitosan that traditional technology is produced cannot be applied in above-mentioned field completely; 2. traditional technology temperature of reaction is high, causes chain rupture, causes molecular weight to decline to a great extent, and product viscosity is low.
Summary of the invention
The object of the invention is to overcome the problem of deficiency of the prior art and existence, the preparation method of a kind of high viscosity, high substitution value and water-soluble better cm-chitosan is provided, so that it is adapted at food, medicine, the application in the industries such as makeup more.
For achieving the above object and other objects, the present invention is achieved by the following technical solutions:
A method of preparing cm-chitosan, comprises the following steps:
(1) deacetylation: chitin is added in alkaline aqueous solution and react 3～6h under agitation condition, and temperature of reaction is 50～80 ℃, then standing at 0～15 ℃, then stirs 1～4h at 50～80 ℃, last centrifuge dehydration obtains chitosan sodium salt;
(2) carboxylation reaction: under alkaline condition, dehydrated alcohol and Mono Chloro Acetic Acid are added in chitosan sodium salt, stir 12～36h at 40～70 ℃, obtain cm-chitosan sodium salt after centrifuge dehydration; Cm-chitosan sodium salt, with after water dissolution, pH being adjusted to neutrality, then is separated out with ethanol repetitive scrubbing, after centrifugal drying, obtain cm-chitosan.
Preferably, reaction standing time at 0～15 ℃ of temperature is 20h at least in above-mentioned steps (1).
Preferably, the concentration of above-mentioned steps (1) the neutral and alkali aqueous solution is 10%～65%.More preferably, the concentration of above-mentioned steps (1) the neutral and alkali aqueous solution is 40%～65%.
The pH of described alkaline aqueous solution is greater than 7.0 the aqueous solution, can be selected from alkaline aqueous solution conventional in prior art, as aqueous sodium hydroxide solution, and potassium hydroxide aqueous solution.
Preferably, the quality of above-mentioned steps (1) the neutral and alkali aqueous solution is 5～20 times of chitin quality.
Preferably, in above-mentioned steps (1), chitin carries out deacetylation by the treatment process that colds and heat succeed each other, and has reduced de-acetyl chitin degree, and the deacetylation of described chitosan sodium salt is 0.5～0.65.
Preferably, the quality of dehydrated alcohol is 2～5 times of chitosan sodium salt quality in above-mentioned steps (2);
Preferably, in above-mentioned steps (2), chloroacetic quality is 0.5～1 times of chitosan sodium salt quality.
The molecular weight of the cm-chitosan obtaining by middle aforesaid method of the present invention is 30～700,000.The molecular weight of the cm-chitosan that preferably, aforesaid method obtains is 50～600,000.
The degree of substitution by carboxymethyl of the cm-chitosan of the acquisition in above-mentioned steps (2) is 1.1～1.5.Preferably, the degree of substitution by carboxymethyl of the cm-chitosan of the acquisition in step (2) is 1.15～1.3.The degree of substitution by carboxymethyl of the cm-chitosan that traditional technology obtains is generally less than 1.0.Due to the high degree of substitution by carboxymethyl of cm-chitosan in the present invention, make its wetting ability, moisture retention and water absorbability significantly increase, the cm-chitosan that it is also produced far above traditional technology as the effect of cosmetic humectant.
The pH scope of the dissolving of the cm-chitosan being obtained by aforesaid method of the present invention is 4.5～14.0.Preferably, can be dissolved in pH be in 4.5～6.5 acidic solution to the cm-chitosan described in the present invention.The pH scope that the cm-chitosan obtaining with traditional technology is dissolved is 7.0～14.0 to compare, and the pH scope that the cm-chitosan that the inventive method obtains is dissolved is wider, has widened its Application Areas.
In traditional technology, deacetylation temperature is higher, and the technique of employing stand at low temperature in step of the present invention (1) condenses sodium hydroxide, successfully by the molecular structure expansionization of chitin, reduce the degree that is difficult to of the upper substitution reaction of 6C, thereby reduced the deacetylation of product; In addition, owing to reducing temperature of reaction, avoided the high chain rupture causing of temperature of reaction, thereby the cm-chitosan that technique of the present invention is made has high molecular weight and viscosity, its viscosity that the cm-chitosan obtaining according to the inventive method is made 1% the aqueous solution can reach 400cps, considerably beyond 50cps of the prior art.
The invention discloses a kind of method of cm-chitosan; the method be take chitin as raw material; first chitin is alkalized; the use method of colding and heat succeed each other is carried out deacetylation; produce chitosan sodium salt; under alkaline condition, carry out again carboxylation reaction, obtained the cm-chitosan of water-soluble, high viscosity and high substitution value.Overcome the deficiency of production cm-chitosan in traditional technology, and technique is simple, is easy to control, be applicable to large-scale industrialization and produce.
Embodiment
Below embodiments of the invention are elaborated: the present embodiment is implemented take technical solution of the present invention under prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
The concrete technology step of preparing cm-chitosan in the present embodiment is as follows:
(1) deacetylation: it is in 50% aqueous sodium hydroxide solution that 40Kg chitin is added to 600Kg concentration, under agitation condition, react 4h, temperature of reaction is 75 ℃, then standing 24h at 10 ℃, at 75 ℃, stir 2h again, last centrifuge dehydration obtains 150Kg chitosan sodium salt;
(2) carboxylation reaction: under alkaline condition, 400Kg dehydrated alcohol and 80Kg Mono Chloro Acetic Acid are added in the 150Kg chitosan sodium salt obtaining in step (1), stir 24h at 50 ℃, centrifugal rear acquisition cm-chitosan sodium salt; Cm-chitosan sodium salt, with after water dissolution, pH being adjusted to neutrality, then is separated out with ethanol repetitive scrubbing, after centrifugal drying, obtain cm-chitosan.
In the present embodiment step (1), the deacetylation of chitosan sodium salt is 0.6; The degree of substitution by carboxymethyl of cm-chitosan is 1.3; The viscosity of the cm-chitosan obtaining in the present embodiment being made to 1% the aqueous solution is 400cps, the dissolving pH scope of cm-chitosan is 4.5～14.0, within the scope of this pH, without insolubles (insolubles amount≤0.01%), when pH=6.5,1% aqueous solution transmittance reaches 98%.The cm-chitosan that the present embodiment obtains is adapted at food, and medicine, applies in the industries such as makeup.
Embodiment 2
The concrete technology step of preparing cm-chitosan in the present embodiment is as follows:
(1) deacetylation: it is in 65% aqueous sodium hydroxide solution that 40Kg chitin is added to 500Kg concentration, under agitation condition, react 3h, temperature of reaction is 80 ℃, then standing 30h at 15 ℃, at 80 ℃, stir 1h again, last centrifuge dehydration obtains chitosan sodium salt;
(2) carboxylation reaction: under alkaline condition, 300Kg dehydrated alcohol and 150Kg Mono Chloro Acetic Acid are added in the chitosan sodium salt obtaining in step (1), stir 24h at 40 ℃, centrifugal rear acquisition cm-chitosan sodium salt; Cm-chitosan sodium salt, with after water dissolution, pH being adjusted to neutrality, then is separated out with ethanol repetitive scrubbing, after centrifugal drying, obtain cm-chitosan.
In the present embodiment step (1), the deacetylation of chitosan sodium salt is 0.65; The degree of substitution by carboxymethyl of cm-chitosan is 1.5; The molecular weight of the cm-chitosan obtaining is 550,000, the viscosity of the cm-chitosan obtaining in the present embodiment being made to 1% the aqueous solution is 300cps, it is 4.5～14.0 that this cm-chitosan is dissolved pH scope, the cm-chitosan obtaining without insolubles (insolubles amount≤0.01%) the present embodiment within the scope of this pH is adapted at food, medicine, applies in the industries such as makeup.
Embodiment 3
The concrete technology step of preparing cm-chitosan in the present embodiment is as follows:
(1) deacetylation: it is in 40% aqueous sodium hydroxide solution that 40Kg chitin is added to 600Kg concentration, under agitation condition, react 6h, temperature of reaction is 50 ℃, then standing 20h at 0 ℃, at 50 ℃, stir 4h again, last centrifuge dehydration obtains chitosan sodium salt;
(2) carboxylation reaction: under alkaline condition, 500Kg dehydrated alcohol and 100Kg Mono Chloro Acetic Acid are added in the chitosan sodium salt obtaining in step (1), stir 20h at 70 ℃, centrifugal rear acquisition cm-chitosan sodium salt; Cm-chitosan sodium salt, with after water dissolution, pH being adjusted to neutrality, then is separated out with ethanol repetitive scrubbing, after centrifugal drying, obtain finished product cm-chitosan.
In the present embodiment step (1), the deacetylation of chitosan sodium salt is 0.5; The degree of substitution by carboxymethyl of cm-chitosan is 1.3; The molecular weight of the cm-chitosan obtaining is 500,000, and the viscosity of the cm-chitosan obtaining in the present embodiment being made to 1% the aqueous solution is 200cps; It is 4.5～14.0 that this cm-chitosan is dissolved pH scope, and the cm-chitosan obtaining without insolubles (insolubles amount≤0.01%) the present embodiment within the scope of this pH is adapted at food, and medicine, applies in the industries such as makeup.
Embodiment 4
The concrete technology step of preparing cm-chitosan in the present embodiment is as follows:
(1) deacetylation: it is in 30% aqueous sodium hydroxide solution that 40Kg chitin is added to 700Kg concentration, under agitation condition, react 6h, temperature of reaction is 65 ℃, then standing 36h at 10 ℃, at 60 ℃, stir 3h again, last centrifuge dehydration obtains chitosan sodium salt;
(2) carboxylation reaction: under alkaline condition, 450Kg dehydrated alcohol and 150Kg Mono Chloro Acetic Acid are added in the chitosan sodium salt obtaining in step (1), stir 36h at 70 ℃, centrifugal rear acquisition cm-chitosan sodium salt; Cm-chitosan sodium salt, with after water dissolution, pH being adjusted to neutrality, then is separated out with ethanol repetitive scrubbing, after centrifugal drying, obtain finished product cm-chitosan.
In the present embodiment step (1), the deacetylation of chitosan sodium salt is 0.6; The degree of substitution by carboxymethyl of cm-chitosan is 1.5; The viscosity of the cm-chitosan obtaining in the present embodiment being made to 1% the aqueous solution is 350cps; It is 4.5～14.0 that this cm-chitosan is dissolved pH scope, within the scope of this pH without insolubles (insolubles amount≤0.01%); The cm-chitosan that the present embodiment obtains is adapted at food, and medicine, applies in the industries such as makeup.
Embodiment 5
The concrete technology step of preparing cm-chitosan in the present embodiment is as follows:
(1) deacetylation: it is in 20% aqueous sodium hydroxide solution that 40Kg chitin is added to 800Kg concentration, under agitation condition, react 4h, temperature of reaction is 65 ℃, then standing 36h at 10 ℃, at 60 ℃, stir 3h again, last centrifuge dehydration obtains chitosan sodium salt;
(2) carboxylation reaction: under alkaline condition, 450Kg dehydrated alcohol and 120Kg Mono Chloro Acetic Acid are added in the chitosan sodium salt obtaining in step (1), stir 36h at 60 ℃, centrifugal rear acquisition cm-chitosan sodium salt; Cm-chitosan sodium salt, with after water dissolution, pH being adjusted to neutrality, then is separated out with ethanol repetitive scrubbing, after centrifugal drying, obtain finished product cm-chitosan.
In the present embodiment step (1), the deacetylation of chitosan sodium salt is 0.5; The degree of substitution by carboxymethyl of cm-chitosan is 1.5; The viscosity of the cm-chitosan obtaining in the present embodiment being made to 1% the aqueous solution is 410cps; It is 4.5～14.0 that this cm-chitosan is dissolved pH scope, within the scope of this pH without insolubles (insolubles amount≤0.01%); The cm-chitosan that the present embodiment obtains is adapted at food, and medicine, applies in the industries such as makeup.
Embodiment 6
The concrete technology step of preparing cm-chitosan in the present embodiment is as follows:
(1) deacetylation: it is in 65% aqueous sodium hydroxide solution that 40Kg chitin is added to 200Kg concentration, under agitation condition, react 6h, temperature of reaction is 60 ℃, then standing 36h at 5 ℃, at 60 ℃, stir 3h again, last centrifuge dehydration obtains chitosan sodium salt;
(2) carboxylation reaction: under alkaline condition, 500Kg dehydrated alcohol and 150Kg Mono Chloro Acetic Acid are added in the chitosan sodium salt obtaining in step (1), stir 36h at 50 ℃, centrifugal rear acquisition cm-chitosan sodium salt; Cm-chitosan sodium salt, with after water dissolution, pH being adjusted to neutrality, then is separated out with ethanol repetitive scrubbing, after centrifugal drying, obtain finished product cm-chitosan.
In the present embodiment step (1), the deacetylation of chitosan sodium salt is 0.52; The degree of substitution by carboxymethyl of cm-chitosan is 1.15; The viscosity of the cm-chitosan obtaining in the present embodiment being made to 1% the aqueous solution is 300cps; It is 4.5～14.0 that this cm-chitosan is dissolved pH scope, within the scope of this pH without insolubles (insolubles amount≤0.01%); The cm-chitosan that the present embodiment obtains is adapted at food, and medicine, applies in the industries such as makeup.
Embodiment 7
The concrete technology step of preparing cm-chitosan in the present embodiment is as follows:
(1) deacetylation: it is in 50% aqueous sodium hydroxide solution that 40Kg chitin is added to 200Kg concentration, under agitation condition, react 6h, temperature of reaction is 50 ℃, then standing 24h at 5 ℃, at 60 ℃, stir 3h again, last centrifuge dehydration obtains chitosan sodium salt;
(2) carboxylation reaction: under alkaline condition, 300Kg dehydrated alcohol and 100Kg Mono Chloro Acetic Acid are added in the chitosan sodium salt obtaining in step (1), stir 30h at 50 ℃, centrifugal rear acquisition cm-chitosan sodium salt; Cm-chitosan sodium salt, with after water dissolution, pH being adjusted to neutrality, then is separated out with ethanol repetitive scrubbing, after centrifugal drying, obtain finished product cm-chitosan.
In the present embodiment step (1), the deacetylation of chitosan sodium salt is 0.52; The degree of substitution by carboxymethyl of cm-chitosan is 1.1; The viscosity of the cm-chitosan obtaining in the present embodiment being made to 1% the aqueous solution is 300cps; It is 4.5～14.0 that this cm-chitosan is dissolved pH scope, within the scope of this pH without insolubles (insolubles amount≤0.01%); The cm-chitosan that the present embodiment obtains is adapted at food, and medicine, applies in the industries such as makeup.
Claims (10)
1. a method of preparing cm-chitosan, is characterized in that, described method comprises the following steps:
1) deacetylation: chitin is added in alkaline aqueous solution and react 3～6h under agitation condition, and temperature of reaction is 50～80 ℃, then standing at 0～15 ℃, then stirs 1～4h at 50～80 ℃, last centrifuge dehydration obtains chitosan sodium salt;
2) carboxylation reaction: under alkaline condition, dehydrated alcohol and Mono Chloro Acetic Acid are added in chitosan sodium salt, stir 12～36h at 40～70 ℃, centrifuge dehydration obtains cm-chitosan sodium salt; Cm-chitosan sodium salt, with after water dissolution, pH being adjusted to neutrality, then is separated out with ethanol repetitive scrubbing, after centrifugal drying, obtain cm-chitosan.
2. the method for preparing cm-chitosan as claimed in claim 1, is characterized in that, in step 1), reaction standing time at 0～15 ℃ is 20h at least.
3. the method for preparing cm-chitosan as claimed in claim 1, is characterized in that, the concentration of the step 1) neutral and alkali aqueous solution is 10%～65%.
4. the method for preparing cm-chitosan as claimed in claim 1, is characterized in that, the quality of the step 1) neutral and alkali aqueous solution is 5～20 times of chitin quality.
5. the method for preparing cm-chitosan as claimed in claim 1, is characterized in that, the deacetylation of the chitosan sodium salt described in step 1) is 0.5～0.65.
6. the method for preparing cm-chitosan as claimed in claim 1, is characterized in that step 2) described in the quality of dehydrated alcohol be 2～5 times of quality of described chitosan sodium salt.
7. the method for preparing cm-chitosan as claimed in claim 1, is characterized in that step 2) described in chloroacetic quality be 0.5～1 times of quality of described chitosan sodium salt.
8. the method for preparing cm-chitosan as claimed in claim 1, is characterized in that step 2) in the degree of substitution by carboxymethyl of cm-chitosan of acquisition be 1.1～1.5.
9. the method for preparing cm-chitosan as claimed in claim 1, is characterized in that step 2) in the degree of substitution by carboxymethyl of cm-chitosan of acquisition be 1.15～1.3.
10. the cm-chitosan that the method as described in as arbitrary in claim 1～9 obtains, is characterized in that, the pH scope that described cm-chitosan is dissolved is 4.5～14.0.
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| CN111363064A (en) * | 2020-04-28 | 2020-07-03 | 东华大学 | Preparation method of carboxymethyl chitosan with high substitution degree and high molecular weight |
| CN112125984A (en) * | 2020-11-03 | 2020-12-25 | 江苏金壳生物医药科技有限公司 | Preparation method of carboxymethyl chitosan |
| CN112813527A (en) * | 2020-12-28 | 2021-05-18 | 江苏品创纺织科技有限公司 | Chitin fiber blended mildew-proof fabric |
| US11123438B2 (en) | 2016-08-19 | 2021-09-21 | Ampsource Biopharma Shanghai Inc. | Linker peptide for constructing fusion protein |
| CN113599391A (en) * | 2021-08-24 | 2021-11-05 | 上海陶盛生物技术有限公司 | Application of carboxymethyl chitosan in promoting skin wound healing and repairing skin barrier |
| EP3981798A1 (en) | 2020-10-10 | 2022-04-13 | Shandong Eton New Material Co., Ltd. | Modified chitosan, preparation method thereof, and additive for tile adhesive and use thereof |
| US11472863B2 (en) | 2016-08-19 | 2022-10-18 | Ampsource Biopharma Shanghai Inc. | Human coagulation factor IX (FIX) fusion protein, preparation method therefor, and use thereof |
| US11471513B2 (en) | 2016-08-19 | 2022-10-18 | Ampsource Biopharma Shanghai Inc. | Highly glycosylated human blood-clotting factor VIII fusion protein, and manufacturing method and application of same |
| US11981718B2 (en) | 2020-05-27 | 2024-05-14 | Ampsource Biopharma Shanghai Inc. | Dual-function protein for lipid and blood glucose regulation |
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