CN1844163A - Process for preparing non-derivative biochemical water-soluble chitosan - Google Patents
Process for preparing non-derivative biochemical water-soluble chitosan Download PDFInfo
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- CN1844163A CN1844163A CN 200610019007 CN200610019007A CN1844163A CN 1844163 A CN1844163 A CN 1844163A CN 200610019007 CN200610019007 CN 200610019007 CN 200610019007 A CN200610019007 A CN 200610019007A CN 1844163 A CN1844163 A CN 1844163A
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Abstract
This invention is the preparation method of non-derived water-soluble chitin. The procedure is as followings: drench the chitin whose deacetylation is 10-98% with 0.5-5 folded alcoholic solution, repeatcycles of freezing and thawing 2- 10 times at -18deg C--10deg C, add to ball grinding machine, disintegrating at-20deg C--1deg C vibration frequency 500-1450Hz for 2-50hours, wash to pH 6-8 with alcoholic solution, and obtain non-derived water-soluble chitin. This invention is advantageous in simple chemical modification, preserving original molecular structure but destroying its crystalline structure with our exlusive method, moderate molecular weight and high bioactivity.
Description
Technical field
The invention belongs to a kind of preparation method of non-derivative biochemical water-soluble chitosan, especially utilize chitin raw material to prepare the method for non-derivative biochemical water-soluble chitosan.
Background technology
Chitin has another name called chitin, is a kind of natural glycosaminoglycan of colorless and odorless, and resource is very abundant, and the annual chitin of producing of nature has 10,000,000,000 tons approximately, is the carbohydrate that nature is only second to Mierocrystalline cellulose output maximum in addition.Numerous scientific researches is verified, and it has, and anticancer, sterilization, anti-inflammatory, hemostasis, anticoagulation, promotion wound healing, reducing blood-fat, hypotensive, hypoglycemic, detoxication and toxicant eliminating function, adjusting organism disclose, strengthen body immunity, function such as delay senility.It is the edibility animal fibre of unique in the world cation, can be widely used in industry and fields such as biology, medicine, agricultural, food, makeup, health care, light industry, chemical industry, weaving, printing and dyeing, papermaking, heavy metal recovery, environment protection.The title that " omnipotent polysaccharide " arranged.Be described as the novel material of 21 century.
Yet chitin is water insoluble, strong acid, highly basic and most organic solvent, and its height takes off acetyl product (＞55%) chitosan and also only is dissolved in the strong acid type solution and just can be utilized, and has therefore greatly limited its application.Prepare water miscible chitin and chitosan and become competitively competition focal point of various countries.Solve water-soluble problem, just can make its widespread use in all trades and professions become a reality.
The preparation method of N,O-CMC (or chitosan) mainly contains 3 kinds:
1), introduce modification group and grafting: (1) N-acylations, (2) N-alkylation, (3) are carboxylated, (4) O-hydroxylation, (5) O-hydrocarbylation, (6) sulphating, (7) acrylonitrile grafting;
2), edman degradation Edman: (1) enzyme liberating method: chitoanase and non-specificity enzyme such as lipase, N,O-Diacetylmuramidase, proteolytic enzyme etc., (2) oxidation degradation method: 1. H
2O
2Oxidation style, 2. H
2O
2-HCl method, H
2O
2-NaClO method, NaBO
2Method, (3) acid degradation method: 1. hydrochloric acid edman degradation Edman, 2. a sour nitrite method, 3. vitriol oil method, 4. strong phosphoric acid method, HF process, peroxyacetic acid method, formic acid method, apple acid system, xitix method etc.
3) deacetylation of control chitin: make chitin under homogeneous phase condition, carry out deacetylated reaction or be that raw material carries out acetylization reaction, control 50% deacetylation by high chitosan.
In the above-mentioned the whole bag of tricks, first kind of derivative that is actually chitin (or chitosan), although can be water-soluble, structurally different with chitin (or chitosan), biological activity and security be open to suspicion.Non-derivative chitin (or chitosan) product is obviously more reasonable.The reality of second method preparation is chitin (or chitosan) oligose, although it is water-soluble that the method that does not adopt derivatization method but adopt to reduce molecular weight is given chitin (or chitosan), yet, because its molecular weight is extremely low, the category that has not belonged to polysaccharide, viscosity pole is low, can't be applied in bio-medical material etc.The third preparation method obtains is truly water-soluble chitin (or chitosan), however because its complex process, length consuming time, seriously polluted, molecular weight degradation is obviously, product colour is dark excessively, the process that has hindered its industrialization.
In above-mentioned N,O-CMC (chitosan) preparation, or changed the original structure of chitin (chitosan), or greatly reduce molecular weight, do not have the preparation method of non-derivative biochemical water-soluble chitosan truly, and seriously polluted, product color is dark excessively, inferior quality.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of non-derivative biochemical water-soluble chitosan, it can overcome the deficiency of prior art, and can not carry out the complicated chemical modification but on the basis in Chemical Pretreatment, pass through the decrystallized physical technology of original creation emphatically, destroy chitin (chitosan) crystalline texture, do not obtain the molecular weight appropriateness but do not destroy under the situation of original structure, color and luster is pure white, the non-derivative biochemical water-soluble chitosan that biological activity is high.
The technical scheme that realizes the object of the invention is: a kind of preparation method of non-derivative biochemical water-soluble chitosan, its distinctive feature is: with the chitin raw material of deacetylation 10～98% after the acid or alkaline low carbon alcohol solution swelling of 0.5～5 times of its quality, behind-18 ℃～-10 ℃ following multigelations 2～10 times, drop into the ball mill material cavity, under controlled temperature-20 ℃～-1 ℃, vibrational frequency 500～1450Hz condition, pulverized 2～50 hours, material after the pulverizing prepares non-derivative biochemical water-soluble chitosan after low carbon alcohol solution is washed till pH 6～8.
And chitin raw material is the low deacetylation chitin less than 55%, or greater than 55% chitosan with high deacetylation degree, the deacetylation scope is 10～98%.
And acid low carbon alcohol solution is a kind of in methyl alcohol, ethanol or the isopropanol water solution that contains 0.1%～3% hydrochloric acid, and the low carbon alcohol solution of alkalescence is a kind of in methyl alcohol, ethanol or the isopropanol water solution that contains 0.1%～3% sodium hydroxide.
And acid low carbon alcohol solution is suitable for the swelling of high deacetylized chitosan; The swelling of the chitin of the low carbon alcohol solution low deacetylation of alkalescence.
And each freeze thawing time is 2～24 hours.
And placing weight in the ball mill material cavity simultaneously is globe or the club that 3～20 times and hardness are higher than chitin raw material,
And the material of globe or club is stainless steel or zirconium white.
The present invention adopts the huge bulging force of the water freezing in the multigelation that the crystal region in the chitin is destroyed, reduce degree of crystallinity, further utilize simultaneously Mechanochemical Effect, the size in transforming crystalline zone and degree of crystallinity, about 90Hz can bring up to 500～1450Hz with the frequency of general milling, has improved decrystallized efficient greatly, has reduced energy consumption, adopt airtight physics ball milling method, reduced loss; Particularly adopt cryogenic pulverization to handle simultaneously, utilize the freezing fragility that strengthens chitin greatly, help the decrystallized of chitin more; Chitin under the subzero treatment also can not occur in the bad change of qualities such as, the molecular weight and molecular weight dark dark such as color and luster under high temperature, the high alkalinity.By regulating the water content of chitin, can also adjust decrystallized efficient easily.
The present invention has the following advantages:
1. present method itself is not carried out the complicated chemical modification, emphatically by the decrystallized physical technology of original creation, destroys chitin (chitosan) crystalline texture on the basis of Chemical Pretreatment, does not destroy original structure, the molecular weight appropriateness, and color and luster is pure white, the biological activity height.
2. owing to do not adopt the complicated chemical modification, avoided the residual of hazardous and noxious substances, security is good, is used for the unique advantages in field such as medicine, makeup, functional food.
3. do not have a large amount of soda acid dischargings, organic solvent pollution, meet national industrial policies.
4. if adopt the high-frequency vibration ball-milling processing of sealing, energy consumption is lower, and the treatment time is short, and product recovery rate height do not have decolouring, purification process, thereby cost is lower.
Embodiment
The invention will be further described below with reference to embodiment.Embodiment provided by the invention based on technical scheme be: a kind of preparation method of non-derivative biochemical water-soluble chitosan, its distinctive feature is: with the chitin raw material of deacetylation 10～98% after the acid or alkaline low carbon alcohol solution swelling of 0.5～5 times of its quality, behind-18 ℃～-10 ℃ following multigelations 2～10 times, drop into the ball mill material cavity, controlled temperature-20 ℃～-1 ℃, under vibrational frequency 500～1450Hz condition, pulverized 2～50 hours, material after the pulverizing prepares non-derivative biochemical water-soluble chitosan after low carbon alcohol solution is washed till pH 6～8.
Described swelling means: raw material volume after moisture absorption expands to some extent but does not dissolve.Should promptly allow moisture absorption reach equilibrium state with abundant swelling for well during concrete enforcement.
Further technical scheme can be: chitin raw material is the low deacetylation chitin less than 55%, or greater than 55% chitosan with high deacetylation degree, the deacetylation scope is 10～98%.
Further technical scheme can also be: acid low carbon alcohol solution is a kind of in methyl alcohol, ethanol or the isopropanol water solution that contains 0.1%～3% hydrochloric acid, and the low carbon alcohol solution of alkalescence is a kind of in methyl alcohol, ethanol or the isopropanol water solution that contains 0.1%～3% sodium hydroxide.
And acid low carbon alcohol solution is suitable for the swelling of high deacetylized chitosan; The swelling of the chitin of the low carbon alcohol solution low deacetylation of alkalescence.
And each freeze thawing time is 2～24 hours.
And placing weight in the ball mill material cavity simultaneously is globe or the club that 3～20 times and hardness are higher than chitin raw material,
And the material of globe or club is stainless steel or zirconium white.
Embodiment 1:
Deacetylation 11% chitin, 5 times of sodium hydroxide methanol aqueous solutions (pH 11) swelling 2 hours, in-18 ℃ of following multigelations 10 times, each 24 hours, drop into oscillatory type ball mill material cavity, placing weight in material cavity simultaneously is 20 times of steel balls, at controlled temperature-20 ℃, vibrational frequency 1450Hz, pulverized 50 hours, the material after the pulverizing is washed till pH through 60% methanol aqueous solution
6, prepare non-derivative biochemical water-soluble chitosan, the water-insoluble foreign matter content is less than 5.2%, molecular weight 720000.
Embodiment 2:
Deacetylation 32% chitin, 2 times of sodium hydroxide aqueous ethanolic solutions (pH 10) swelling 2 hours, in-18 ℃ of following multigelations 5 times, each 12 hours, drop into oscillatory type ball mill material cavity, placing weight in material cavity simultaneously is 10 times of steel balls, at controlled temperature-10 ℃, vibrational frequency 1000Hz, pulverizes 20 hours, material after the pulverizing is washed till pH6 through 50% aqueous ethanolic solution, prepare non-derivative biochemical water-soluble chitosan, the water-insoluble foreign matter content is less than 8.5%, molecular weight 580000.
Embodiment 3:
Deacetylation 62% chitosan, 2 times of hydrochloric acid isopropanol water solutions (pH 4) swelling 2 hours, in-11 ℃ of following multigelations 3 times, each 24 hours, drop into oscillatory type ball mill material cavity, placing weight in material cavity simultaneously is 20 times of steel balls, at controlled temperature-18 ℃, vibrational frequency 1450Hz, pulverizes 40 hours, material after the pulverizing is washed till pH 6 through 60% isopropanol water solution, prepare non-derivative biochemical water-soluble chitosan, the water-insoluble foreign matter content is less than 7.2%, molecular weight 680000.
Embodiment 4:
Deacetylation 90% chitosan, 1 times of acidic alcohol aqueous solution (pH 4) swelling 2 hours, in-18 ℃ of following multigelations 5 times, each 12 hours, drop into oscillatory type ball mill material cavity, placing weight in material cavity simultaneously is 10 times of steel balls, at controlled temperature-18 ℃, vibrational frequency 500Hz, pulverizes 20 hours, material after the pulverizing is washed till pH 6 through 60% aqueous ethanolic solution, prepare non-derivative biochemical water-soluble chitosan, the water-insoluble foreign matter content is less than 3.7%, molecular weight 780000.
Embodiment 5:
Deacetylation 50% chitin, 2 times of methanol aqueous solutions (pH 4) swelling 2 hours, in-18 ℃ of following multigelations 2 times, each 8 hours, drop into oscillatory type ball mill material cavity, placing weight in material cavity simultaneously is 20 times of steel balls, in controlled temperature～18 ℃, vibrational frequency 1450Hz, pulverizes 6 hours, material after the pulverizing is washed till pH 6 through 60% methanol aqueous solution, prepare non-derivative biochemical water-soluble chitosan, the water-insoluble foreign matter content is less than 2.2%, molecular weight 820000.
Embodiment 6:
Deacetylation 85% chitosan, 2 times of acidic alcohol aqueous solution (pH 3) swelling 2 hours, in-10 ℃ of following multigelations 8 times, each 8 hours, drop into oscillatory type ball mill material cavity, placing weight in material cavity simultaneously is 6 times of steel balls, at controlled temperature-10 ℃, vibrational frequency 1450Hz, pulverizes 8 hours, material after the pulverizing is washed till pH 6 through 60% aqueous ethanolic solution, prepare the non-derivative biochemical water-soluble chitosan, the water-insoluble foreign matter content is less than 6.2%, molecular weight 108000.
Claims (7)
1, a kind of preparation method of non-derivative biochemical water-soluble chitosan, it is characterized in that: with the chitin raw material of deacetylation 10～98% after the acid or alkaline low carbon alcohol solution swelling of 0.5～5 times of its quality, behind-18 ℃～-10 ℃ following multigelations 2～10 times, drop into the ball mill material cavity, under controlled temperature-20 ℃～-1 ℃, vibrational frequency 500～1450Hz condition, pulverized 2～50 hours, material after the pulverizing prepares non-derivative biochemical water-soluble chitosan after low carbon alcohol solution is washed till pH 6～8.
2, the preparation method of non-derivative biochemical water-soluble chitosan according to claim 1 is characterized in that: chitin raw material is the low deacetylation chitin less than 55%, or greater than 55% chitosan with high deacetylation degree, the deacetylation scope is 10～98%.
3, the preparation method of a kind of non-derivative biochemical water-soluble chitosan according to claim 1 and 2, it is characterized in that: acid low carbon alcohol solution is a kind of in methyl alcohol, ethanol or the isopropanol water solution that contains 0.1%～3% hydrochloric acid, and the low carbon alcohol solution of alkalescence is a kind of in methyl alcohol, ethanol or the isopropanol water solution that contains 0.1%～3% sodium hydroxide.
4, the preparation method of a kind of non-derivative biochemical water-soluble chitosan according to claim 3 is characterized in that: acid low carbon alcohol solution is suitable for the swelling of high deacetylized chitosan; The swelling of the chitin of the low carbon alcohol solution low deacetylation of alkalescence.
5, the preparation method of a kind of non-derivative biochemical water-soluble chitosan according to claim 4 is characterized in that: each freeze thawing time is 2～24 hours.
6, the preparation method of a kind of non-derivative biochemical water-soluble chitosan according to claim 5 is characterized in that: placing weight in the ball mill material cavity simultaneously is globe or the club that 3～20 times and hardness are higher than chitin raw material.
7, the preparation method of a kind of non-derivative biochemical water-soluble chitosan according to claim 6 is characterized in that: the material of globe or club is stainless steel or zirconium white.
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| CNB2006100190073A CN100469795C (en) | 2006-05-08 | 2006-05-08 | Process for preparing non-derivative biochemical water-soluble chitosan |
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| CNB2006100190073A CN100469795C (en) | 2006-05-08 | 2006-05-08 | Process for preparing non-derivative biochemical water-soluble chitosan |
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| CN1844163A true CN1844163A (en) | 2006-10-11 |
| CN100469795C CN100469795C (en) | 2009-03-18 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105837708A (en) * | 2016-05-16 | 2016-08-10 | 南京理工大学泰州科技学院 | Method for preparing chitosan with shrimp and crab shells as raw material |
| CN106422965A (en) * | 2016-09-14 | 2017-02-22 | 中国海洋大学 | Synthetic method of chitosan surface active agent for improving morphology and dispersibility of ferroferric oxide |
| CN106868629A (en) * | 2017-02-10 | 2017-06-20 | 青岛科技大学 | A kind of method for preparing the double electrically chitin nano fibers of high yield |
| CN109134701A (en) * | 2018-07-02 | 2019-01-04 | 南京林业大学 | A method of the rapidly extracting high purity and low molecular weight chitin from shrimp and crab shells |
-
2006
- 2006-05-08 CN CNB2006100190073A patent/CN100469795C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105837708A (en) * | 2016-05-16 | 2016-08-10 | 南京理工大学泰州科技学院 | Method for preparing chitosan with shrimp and crab shells as raw material |
| CN106422965A (en) * | 2016-09-14 | 2017-02-22 | 中国海洋大学 | Synthetic method of chitosan surface active agent for improving morphology and dispersibility of ferroferric oxide |
| CN106868629A (en) * | 2017-02-10 | 2017-06-20 | 青岛科技大学 | A kind of method for preparing the double electrically chitin nano fibers of high yield |
| CN109134701A (en) * | 2018-07-02 | 2019-01-04 | 南京林业大学 | A method of the rapidly extracting high purity and low molecular weight chitin from shrimp and crab shells |
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| Publication number | Publication date |
|---|---|
| CN100469795C (en) | 2009-03-18 |
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