CN105399862A - Preparation method for chitosan acetic ester - Google Patents

Preparation method for chitosan acetic ester Download PDF

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Publication number
CN105399862A
CN105399862A CN201510929915.5A CN201510929915A CN105399862A CN 105399862 A CN105399862 A CN 105399862A CN 201510929915 A CN201510929915 A CN 201510929915A CN 105399862 A CN105399862 A CN 105399862A
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Prior art keywords
chitosan
intermediate product
preparation
precipitation
acetic ester
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CN105399862B (en
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刘成圣
党奇峰
蔡金萍
高辉
范冰
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QINGDAO AORUN BIOTECHNOLOGY Co Ltd
Ocean University of China
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QINGDAO AORUN BIOTECHNOLOGY Co Ltd
Ocean University of China
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Cosmetics (AREA)

Abstract

The invention relates to a preparation method for chitosan acetic ester, and belongs to the biomaterial field. The method is as follows: firstly, chitosan, glacial acetic acid and thionyl chloride are reacted fully, acetate ions CH3COO- and acetyl CH3CO- are introduced on C2-NH2 and C6-OH of chitosan at the same time, intermediate products are prepared, then ammonium hydroxide is added drop by drop, C2-NH2 is reduced, and chitosan acetate is prepared. Tedious steps of protecting amino and removing protective groups finally are omitted, the method is simple and effective, resource waste is reduced, and the opportunity of introducing unnecessary groups is lowered. The preparation method has wide applicability to the raw material chitosan. The preparation method has good application and development prospects in many fields of medicine, foodstuff, agriculture, cosmetic and the like, and thus the technology has a strong economic development potential.

Description

A kind of preparation method of chitosan acetic ester
Technical field
The invention belongs to technical field of biological material, relate to a kind of preparation method of chitosan acetic ester.
Background technology
Chitosan is the unique polycation polysaccharide of occurring in nature, there is nontoxicity, good biocompatibility, biodegradability and broad-spectrum antibacterial, be therefore obtained at numerous areas such as pharmacopedics, biotechnology, makeup, agricultural and Food sciences and apply widely.But, the active group C that the compact crystalline structure of chitosan makes it main 2-NH 2well can not play a role, limit its application to a certain extent.To the C of chitosan 6-OH modifies, and introduces new group by esterification, simultaneously retentive activity C 2-NH 2group, and the crystalline structure destroying chitosan, can expand its range of application.
According to bibliographical information, mainly contain 2 kinds of methods at present and prepare Chitosan Ester: method one is chitosan and sour direct reaction, makees catalyzer with sulfuric acid, the shortcoming of the method is that temperature of reaction is high, and substitution value is low; Method two first protects amino, then prepares acyl chlorides and hydroxyl reaction, and reaction terminates rear amino deprotection, and the shortcoming of the method is that reaction is complicated, and can use multiple environmentally harmful reagent.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of chitosan acetic ester, to make up the deficiency of original technology.
The technical scheme that the present invention takes is:
Preparation method's concrete steps of chitosan acetic ester of the present invention are as follows:
(1) be raw material with chitosan, itself and Glacial acetic acid, thionyl chloride are fully mixed, sealing, ultrasonic (35 ~ 53kHz, 250 ~ 500W) processes 40-80 minute, and mixture is fully reacted;
(2) by reaction system cool to room temperature, add the intermediate product precipitation that dehydrated alcohol makes reaction produce, suction filtration, collection intermediate product, be dissolved in intermediate product in appropriate deionized water, obtain the aqueous solution of intermediate product;
(3) in the aqueous solution of intermediate product, drip the ammoniacal liquor of 1mol/L, until no longer include Precipitation, centrifugal collecting precipitation, and precipitate 4-6 time with deionized water wash;
(4) precipitation dehydrated alcohol soxhlet type 18-24 hour, dries at 30-60 DEG C, obtains chitosan acetic ester.
In step (1), chitosan: Glacial acetic acid: thionyl chloride=1 ~ 3:6 ~ 10:3 ~ 5 (m:v:v); The purity > 99% of Glacial acetic acid.
In step (2), the add-on of dehydrated alcohol is 5 ~ 8 times of reaction system volume, and the add-on of deionized water is 20 ~ 25 times (v:m) of intermediate product.
Positively effect of the present invention is as follows:
The present invention adopts single step reaction method at the C of chitosan 2-NH 2and C 6-OH introduces acetate ion (CH respectively 3cOO -) and ethanoyl (CH 3cO-), prepare intermediate product, then drip ammoniacal liquor reduction C 2-NH 2, prepare chitosan acetic ester, eliminate the amino tedious steps with finally sloughing protecting group of protection, method is simply effective, and decreases the wasting of resources, reduces the chance introducing unnecessary group.The present invention has suitability widely to starting material chitosan.The present invention has good application and DEVELOPMENT PROSPECT in many fields such as medicine, food, agricultural, makeup, and therefore, the technology of the present invention has stronger potentiality of economical exploit.
Embodiment:
(1) be raw material with chitosan, itself and Glacial acetic acid, thionyl chloride are fully mixed, sealing, ultrasonic (35 ~ 53kHz, 250 ~ 500W) processes 40-80 minute, and mixture is fully reacted;
(2) by reaction system cool to room temperature, add the intermediate product precipitation that dehydrated alcohol makes reaction produce, suction filtration, collection intermediate product, be dissolved in intermediate product in appropriate deionized water, obtain the aqueous solution of intermediate product;
(3) in the aqueous solution of intermediate product, drip the ammoniacal liquor of 1mol/L, until no longer include Precipitation, centrifugal collecting precipitation, and precipitate 4-6 time with deionized water wash;
(4) precipitation dehydrated alcohol soxhlet type 18-24 hour, dries at 30-60 DEG C, obtains chitosan acetic ester.
In step (1), chitosan: Glacial acetic acid: thionyl chloride=1 ~ 3:6 ~ 10:3 ~ 5 (m:v:v); The purity > 99% of Glacial acetic acid.
In step (2), the add-on of dehydrated alcohol is 5 ~ 8 times of reaction system volume, and the add-on of deionized water is 20 ~ 25 times (v:m) of intermediate product.
Following specific embodiment provides preparation method of the present invention further.
Embodiment 1.
2g chitosan, 8mL Glacial acetic acid (purity > 99%) and 3.5mL thionyl chloride are fully mixed, sealing, ultrasonic (53kHz, 250W) processes 60 minutes, and mixture is fully reacted; By reaction system cool to room temperature, add the intermediate product precipitation that 65mL dehydrated alcohol makes reaction produce, suction filtration, collection intermediate product, be dissolved in intermediate product in 45mL deionized water, obtain the aqueous solution of intermediate product; The ammoniacal liquor of 1mol/L is dripped in the aqueous solution of intermediate product, until no longer include Precipitation, centrifugal collecting precipitation, and precipitate 4 times with deionized water wash; Precipitation uses dehydrated alcohol soxhlet type 20 hours, dries, obtain pale yellow powder shape chitosan acetic ester at 40 DEG C.
Embodiment 2.
5g chitosan, 15mL Glacial acetic acid (purity > 99%) and 7.2mL thionyl chloride are fully mixed, sealing, ultrasonic (53kHz, 300W) processes 50 minutes, and mixture is fully reacted; By reaction system cool to room temperature, add the intermediate product precipitation that 140mL dehydrated alcohol makes reaction produce, suction filtration, collection intermediate product, be dissolved in intermediate product in 115mL deionized water, obtain the aqueous solution of intermediate product; The ammoniacal liquor of 1mol/L is dripped in the aqueous solution of intermediate product, until no longer include Precipitation, centrifugal collecting precipitation, and precipitate 4 times with deionized water wash; Precipitation uses dehydrated alcohol soxhlet type 18 hours, dries, obtain pale yellow powder shape chitosan acetic ester at 30 DEG C.
Embodiment 3.
3g chitosan, 12mL Glacial acetic acid (purity > 99%) and 5.1mL thionyl chloride are fully mixed, sealing, ultrasonic (35kHz, 350W) processes 70 minutes, and mixture is fully reacted; By reaction system cool to room temperature, add the intermediate product precipitation that 100mL dehydrated alcohol makes reaction produce, suction filtration, collection intermediate product, be dissolved in intermediate product in 65mL deionized water, obtain the aqueous solution of intermediate product; The ammoniacal liquor of 1mol/L is dripped in the aqueous solution of intermediate product, until no longer include Precipitation, centrifugal collecting precipitation, and precipitate 4 times with deionized water wash; Precipitation uses dehydrated alcohol soxhlet type 24 hours, dries, obtain pale yellow powder shape chitosan acetic ester at 60 DEG C.
Embodiment 4.
10g chitosan, 35mL Glacial acetic acid (purity > 99%) and 15.6mL thionyl chloride are fully mixed, sealing, ultrasonic (35kHz, 300W) processes 60 minutes, and mixture is fully reacted; By reaction system cool to room temperature, add the intermediate product precipitation that 300mL dehydrated alcohol makes reaction produce, suction filtration, collection intermediate product, be dissolved in intermediate product in 260mL deionized water, obtain the aqueous solution of intermediate product; The ammoniacal liquor of 1mol/L is dripped in the aqueous solution of intermediate product, until no longer include Precipitation, centrifugal collecting precipitation, and precipitate 6 times with deionized water wash; Precipitation uses dehydrated alcohol soxhlet type 20 hours, dries, obtain pale yellow powder shape chitosan acetic ester at 50 DEG C.

Claims (3)

1. a preparation method for chitosan acetic ester, is characterized in that the concrete steps of described method are as follows:
Step 1 take chitosan as raw material, and itself and Glacial acetic acid, thionyl chloride are fully mixed, sealing, and ultrasonic 35 ~ 53kHz, 250 ~ 500W process 40-80 minute, makes mixture fully react;
Step 2, by reaction system cool to room temperature, add the intermediate product precipitation that dehydrated alcohol makes reaction produce, suction filtration, collection intermediate product, be dissolved in intermediate product in appropriate deionized water, obtain the aqueous solution of intermediate product;
Step 3, drips the ammoniacal liquor of 1mol/L in the aqueous solution of intermediate product, until no longer include Precipitation, and centrifugal collecting precipitation, and precipitate 4-6 time with deionized water wash;
Step 4, precipitation dehydrated alcohol soxhlet type 18-24 hour, dries at 30-60 DEG C, obtains chitosan acetic ester.
2. the preparation method of chitosan acetic ester as claimed in claim 1, it is characterized in that in step 1, chitosan: Glacial acetic acid: thionyl chloride=1 ~ 3:6 ~ 10:3 ~ 5, ratio unit is m:v:v; The purity > 99% of Glacial acetic acid.
3. the preparation method of chitosan acetic ester as claimed in claim 1, it is characterized in that in step 2, the add-on of dehydrated alcohol is 5 ~ 8 times of reaction system volume, and the add-on of deionized water is 20 ~ 25 times of intermediate product.
CN201510929915.5A 2015-12-11 2015-12-11 A kind of preparation method of chitosan acetate Active CN105399862B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114982822A (en) * 2022-05-17 2022-09-02 华南理工大学 Chitosan oligosaccharide cinnamate and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101649005A (en) * 2009-09-09 2010-02-17 中国海洋大学 Para aminobenzoyl chitosan and preparing method thereof
CN102268103A (en) * 2011-09-02 2011-12-07 中国海洋大学 Method for preparing chitosan acetate
CN102399304A (en) * 2011-07-22 2012-04-04 中国科学院烟台海岸带研究所 Chitosan quaternary amine salt gallate, synthetic method thereof and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101649005A (en) * 2009-09-09 2010-02-17 中国海洋大学 Para aminobenzoyl chitosan and preparing method thereof
CN102399304A (en) * 2011-07-22 2012-04-04 中国科学院烟台海岸带研究所 Chitosan quaternary amine salt gallate, synthetic method thereof and application thereof
CN102268103A (en) * 2011-09-02 2011-12-07 中国海洋大学 Method for preparing chitosan acetate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CAI JINPING等: "Preparation, characterization and antibacterial activity of O-acetyl-chitosan-N-2-hydroxypropyl trimethyl ammonium chloride", 《INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114982822A (en) * 2022-05-17 2022-09-02 华南理工大学 Chitosan oligosaccharide cinnamate and preparation method and application thereof
CN114982822B (en) * 2022-05-17 2024-02-23 华南理工大学 Chitosan oligosaccharide cinnamic acid ester and preparation method and application thereof

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