CN1931883A - Prepn process of water soluble ethoxyl chitin - Google Patents
Prepn process of water soluble ethoxyl chitin Download PDFInfo
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- CN1931883A CN1931883A CN 200610116655 CN200610116655A CN1931883A CN 1931883 A CN1931883 A CN 1931883A CN 200610116655 CN200610116655 CN 200610116655 CN 200610116655 A CN200610116655 A CN 200610116655A CN 1931883 A CN1931883 A CN 1931883A
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Abstract
The preparation process of water soluble ethoxyl chitin includes the following steps: 1. alkalifying reaction of chitin and alkali solution of 35-50 wt% at the temperature of -10 deg.c to 0 deg.c for 6-24 hr to produce alkalified chitin, and defreezing, squeezing and crushing the alkalified chitin into 10-100 mesh alkalified chitin powder; and 2. gas-solid reaction of alkalified chitin powder and gaseous ethylene oxide in some container at 20-50 deg.c through stirring for 1-6 hr, and purifying the reaction product to obtain the water soluble ethoxyl chitin. The process has high yield, complete reaction, less side reaction and no corrosion to the apparatus, and the prepared ethoxyl chitin has high water solubility.
Description
Technical field
The present invention relates to a kind of preparation method of chitin, particularly relate to a kind of preparation method of water soluble ethoxyl chitin.
Background technology
Chitin, chemical name are (1-4)-2-acetamido-2-deoxidation-β-D-glucose, are to be only second to cellulosic second largest renewable organic resource on the earth, have great research and using value.Chitin degree of crystallinity height, water insoluble, also be dissolved in organic solvent commonly used hardly, thereby limited the application of chitin.The double solvents dissolving chitin that US4029727 forms with amide solvent and lithium chloride, but this solvent price height, consumption are big, the production cost height.EP051421 is solvent with the trichoroacetic acid(TCA), but trichoroacetic acid(TCA) is big to the corrodibility of equipment, has increased production cost equally.
Ethoxyl chitin is a kind of important derivatives of chitin, and molecular formula is (C
10H
17NO
6)
n, have moisture retention, film-forming properties and characteristics such as soluble in water.Existing chitin ethoxyl etherification gets method and mainly is divided into hydrophily method and solvent method.Hydrophily method equipment is simple, cost is low, but side reaction is many, and the product substitution value is low, and is water-soluble relatively poor relatively.The side reaction of solvent method is few, and reaction is even, product good water solubility, but complex process, cost height.Hydroxyethylation reagent mainly is divided into chloroethanol and oxyethane.Chloroethanol boiling point height, normal temperature are liquid, and not volatile, simple to operate, side reaction is few, but chloroethanol belongs to hypertoxic chemical, and consumption is big in the reaction, is generally 5～6 times of chitin quality; The oxyethane consumption is few, react completely, but easily and unnecessary alkali and water generation side reaction in the reaction system, the product structure more complicated.CN1199115A has introduced chitin and prepared the method for ethoxyl chitin fiber with reacting ethylene oxide under the alkali condition, and substitution value is low, the problem of poorly water-soluble but exist, and what make is fiber, has certain limitation in application facet.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of water soluble ethoxyl chitin, to remedy the deficiencies in the prior art or defective, meets the demands of production and living.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of preparation method of water soluble ethoxyl chitin comprises the steps:
(1) be that 35～50% alkaline solution carries out quaternization 6～24 hours with chitin and mass percent concentration under-10～0 ℃, the alkali chitin that generates is ground into diameter after thawing, squeezing be 10～100 purpose alkali chitin powder, and wherein the mass ratio of chitin and alkaline solution is 1: 5～1: 20;
(2) in container vacuum tightness be-0.03MPa～-condition of 0.1MPa under, alkali chitin powder and gaseous ethylene oxide are added container, under 20～50 ℃ temperature, stir and made it carry out gas-solid phase reaction in 1～6 hour, product obtains water soluble ethoxyl chitin after purifying, wherein, the consumption of oxyethane is 40～100wt% of chitin consumption.
As optimized technical scheme: described alkaline solution is the aqueous solution of sodium hydroxide or potassium hydroxide.
The alkali chitin need squeeze to about 3 times of former crust quality amount.
The method of purification of ethoxyl chitin is, the crude product that reaction is obtained is dissolved in the deionized water of 10～20 times of quality, be neutralized to solution with 10% (v/v) hydrochloric acid and be neutral, the elimination insolubles, 1: 9 (v/v) mixed solvent of acetone-ethanol that adds 5～8 times of volumes precipitates and filtration, with 80% (v/v) aqueous ethanolic solution repeatedly behind the washing leaching cake 60 ℃ of following vacuum dry to constant weight, obtain purified water soluble ethoxyl chitin.
The invention has the beneficial effects as follows: the raw material chitin wide material sources of present method are to be only second to cellulosic second largest renewable organic resource on the earth; Ethoxyl chitin yield height, the good water solubility of preparation; Oxyethane is low-consuming, react completely, side reaction is few, and conversion unit is not had corrosion.Therefore, present method preparation technology is simple, safety, and is with low cost.
Embodiment
Below in conjunction with specific embodiment the present invention is further elaborated.
Embodiment 1:
The 5g chitin was soaked 8 hours under-10 ℃ in 100ml, the 40%NaOH aqueous solution, squeeze after thawing to 15g, pulverizing is 80 purpose particles, places reaction vessel, is evacuated to vacuum tightness to be-0.1MPa; Add gaseous ethylene oxide 4g in reaction vessel, temperature is 40 ℃ in the control reaction vessel, and afterreaction finished in 2 hours; Crude product is dissolved in the 100ml deionized water, be neutralized to solution with 10% (v/v) hydrochloric acid and be neutral, behind the elimination insolubles, 1: 9 (v/v) mixed solvent precipitates and filtration to wherein adding 600ml acetone-ethanol, being placed on 60 ℃ of following vacuum for three times with 80% (v/v) aqueous ethanolic solution washing filter cake dries to constant weight, obtain water soluble ethoxyl chitin, the about 3.4g of weight, hydroxyethyl substitution value 0.8.
Embodiment 2:
The 5g chitin was soaked 6 hours under-5 ℃ in 100ml, the 35%NaOH aqueous solution, squeeze after thawing to 15g, pulverizing is 100 purpose particles, places reaction vessel, is evacuated to vacuum tightness to be-0.05MPa; Add gaseous ethylene oxide 5g in reaction vessel, temperature is 20 ℃ in the control reaction vessel, and afterreaction finished in 6 hours; Crude product is dissolved in the 100ml deionized water, be neutralized to solution with 10% (v/v) hydrochloric acid and be neutral, behind the elimination insolubles, precipitate and filtration to 1: 9 (v/v) mixed solvent of the acetone-ethanol that wherein adds 600ml, being placed on 60 ℃ of following vacuum for three times with 80% (v/v) aqueous ethanolic solution washing filter cake dries to constant weight, obtain water soluble ethoxyl chitin, the about 3.8g of weight, hydroxyethyl substitution value 0.9.
Embodiment 3:
The 10g chitin was soaked 24 hours under 0 ℃ in 200ml, the 50%NaOH aqueous solution, squeeze after thawing to 30g, pulverizing is 10 purpose particles, places reaction vessel, is evacuated to vacuum tightness to be-0.03MPa; Add gaseous ethylene oxide 6g in reaction vessel, temperature is 50 ℃ in the control reaction vessel, and afterreaction finished in 1 hour; Crude product is dissolved in the 200ml deionized water, be neutralized to solution with 10% (v/v) hydrochloric acid and be neutral, behind the elimination insolubles, 1: 9 (v/v) mixed solvent precipitates and filtration to wherein adding 1000ml acetone-ethanol, being placed on 60 ℃ of following vacuum for three times with 80% (v/v) aqueous ethanolic solution washing filter cake dries to constant weight, obtain water soluble ethoxyl chitin, the about 6.3g of weight, hydroxyethyl substitution value 0.5.
Claims (4)
1. the preparation method of a water soluble ethoxyl chitin is characterized in that, comprises the steps:
(1) be that 35～50% alkaline solution carries out quaternization 6～24 hours with chitin and mass percent concentration under-10～0 ℃, the alkali chitin that generates is ground into diameter after thawing, squeezing be 10～100 purpose alkali chitin powder, wherein, the mass ratio of chitin and alkaline solution is 1: 5～1: 20;
(2) in container vacuum tightness be-0.03MPa～-condition of 0.1MPa under, alkali chitin powder and gaseous ethylene oxide are added container, under 20～50 ℃ temperature, stir and made it carry out gas-solid phase reaction in 1～6 hour, product obtains water soluble ethoxyl chitin after purifying, wherein, the consumption of oxyethane is 40～100wt% of chitin consumption.
2. preparation method according to claim 1 is characterized in that: described alkaline solution is the aqueous solution of sodium hydroxide or potassium hydroxide.
3. preparation method according to claim 1 is characterized in that: the alkali chitin need squeeze to 3 times of former crust quality amount.
4. preparation method according to claim 1, it is characterized in that: the method for purification of ethoxyl chitin is, the crude product that reaction is obtained is dissolved in the deionized water of 10～20 times of quality, be neutralized to solution with 10% (v/v) hydrochloric acid and be neutral, the elimination insolubles, 1: 9 (v/v) mixed solvent precipitation of acetone-ethanol that adds 5～8 times of volumes is also filtered, with 80% (v/v) aqueous ethanolic solution repeatedly behind the washing leaching cake 60 ℃ of following vacuum dry to constant weight, obtain purified water soluble ethoxyl chitin.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006101166550A CN100484967C (en) | 2006-09-28 | 2006-09-28 | Preparation process of water soluble ethoxyl chitin |
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| CNB2006101166550A CN100484967C (en) | 2006-09-28 | 2006-09-28 | Preparation process of water soluble ethoxyl chitin |
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| CN1931883A true CN1931883A (en) | 2007-03-21 |
| CN100484967C CN100484967C (en) | 2009-05-06 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101036799B (en) * | 2007-04-27 | 2010-05-19 | 东华大学 | Method for preparing absorbable antimicrobial dressing for controlling bleeding wounds |
| CN101368328B (en) * | 2008-08-04 | 2011-11-09 | 东华大学 | Preparation method for hydroxyethyl group chitosan fiber |
| CN103951764A (en) * | 2014-04-25 | 2014-07-30 | 武汉大学 | Method for homogeneously preparing hydroxypropyl modified chitin with low degree of deacetylation |
| CN105000984A (en) * | 2015-07-21 | 2015-10-28 | 湖南农业大学 | Ultrafine powder type corn seed coating agent |
-
2006
- 2006-09-28 CN CNB2006101166550A patent/CN100484967C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101036799B (en) * | 2007-04-27 | 2010-05-19 | 东华大学 | Method for preparing absorbable antimicrobial dressing for controlling bleeding wounds |
| CN101368328B (en) * | 2008-08-04 | 2011-11-09 | 东华大学 | Preparation method for hydroxyethyl group chitosan fiber |
| CN103951764A (en) * | 2014-04-25 | 2014-07-30 | 武汉大学 | Method for homogeneously preparing hydroxypropyl modified chitin with low degree of deacetylation |
| CN103951764B (en) * | 2014-04-25 | 2016-01-20 | 武汉大学 | A kind of homogeneous phase prepares the method for the hydroxypropyl modified chitin of low deacetylation |
| CN105000984A (en) * | 2015-07-21 | 2015-10-28 | 湖南农业大学 | Ultrafine powder type corn seed coating agent |
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| Publication number | Publication date |
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| CN100484967C (en) | 2009-05-06 |
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Granted publication date: 20090506 Termination date: 20160928 |