CN108299572A - A method of preparing 6-O- carboxymethyl chitins using imidazole ion liquid - Google Patents

A method of preparing 6-O- carboxymethyl chitins using imidazole ion liquid Download PDF

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Publication number
CN108299572A
CN108299572A CN201810217880.6A CN201810217880A CN108299572A CN 108299572 A CN108299572 A CN 108299572A CN 201810217880 A CN201810217880 A CN 201810217880A CN 108299572 A CN108299572 A CN 108299572A
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preparation
chitins
chitin
carboxymethyl
emim
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吕兴梅
冯咪
张�杰
石春艳
周清
侯丹峰
张锁江
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Institute of Process Engineering of CAS
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Institute of Process Engineering of CAS
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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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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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)
  • Cosmetics (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

The present invention relates to a kind of methods preparing 6 O carboxymethyl chitins using imidazole ion liquid, and described method includes following steps：After chitin, sodium chloroacetate and ionic liquid are mixed in a certain ratio uniformly, certain time is dissolved at a certain temperature, obtains clarifying bright mixed solution.Diluted hydrochloric acid aqueous solution is added in this mixed solution, certain time is stirred at room temperature, obtains white flock precipitate, white solid is centrifuged to obtain, is washed with distilled water, is dried to get 6 O carboxymethyl chitins of product.The present invention realizes the homogeneous preparation of O carboxymethyl chitins using ionic liquid as solvent, improves reaction efficiency, and ionic liquid used is not volatile, environmental-friendly.

Description

A method of preparing 6-O- carboxymethyl chitins using imidazole ion liquid
Technical field
The invention belongs to marine chemical industry field of engineering technology, are related to a kind of utilization imidazole ion liquid preparation 6-O- carboxymethyls The method of chitin.
Background technology
Chitin is that one kind is widely present in Crustaceans shrimp, crab shell, insect shell, in seaweed and fungal cell wall A kind of biological polyoses, have good biocompatibility, biodegradability, biocidal property and promote wound healing the features such as. However, chitin has a large amount of intermolecular and intramolecular hydrogen bond, so that it is not dissolved in conventional organic solvent, limit its use. Therefore, chitin is chemically modified, improves its solubility property, its application range can be expanded.Wherein, 6-O- carboxymethyl crustas Element is a kind of common chitin derivativ, has the advantages that good biocompatibility, biodegradability, antibiotic property, extensively It is general for weaving, medicine, the fields such as cosmetics and food processing.
Currently, the industrial method for preparing 6-O- carboxymethyl chitins is mainly multi-phases process, chitin is through sodium hydroxide Aqueous solution is handled after obtaining alkalization chitin, and dispersion in organic solvent, with chloroacetate reaction, obtains product.The method pollutes Greatly, and to the product degree of polymerization it destroys big.Patent CN 103288980A utilize sodium hydroxide and aqueous solution of urea, utilize freeze thawing Method is reacted after obtaining chitin solution with sodium chloroacetate, and after pH is adjusted to neutrality, dialysis removal sodium ion obtains carboxymethyl Chitin.The method realizes the homogeneous reaction of carboxymethyl chitin, but still needs to use sodium hydroxide, causes certain environment dirty Dye.
Currently, the patent for homogeneously preparing carboxymethyl chitin is still few, and it there is no and prepare carboxymethyl crusta using ionic liquid The technique of element.This patent realizes the homogeneous preparation of carboxymethyl chitin using imidazole ion liquid as solvent.Imidazol ion used Liquid is non-volatile, environmental-friendly, realizes the clean manufacturing for preparing carboxymethyl chitin.Products obtained therefrom degree of substitution is high, and substitution is equal It is even.
Invention content
The present invention is intended to provide a kind of homogeneous method for preparing 6-O- carboxymethyl chitins, solve prior art pollution it is big, The problems such as degree of substitution is not high and substitution is uneven.Technical solution of the present invention includes the following steps：
Chitin, sodium chloroacetate and ionic liquid are mixed in a certain ratio uniformly, are stirred certain time in certain temperature, are obtained Clarify bright solution；Dilute hydrochloric acid solution is added in this mixed solution, certain time is stirred at room temperature, it is heavy to obtain white flock It forms sediment, centrifuges to obtain white solid, be washed with distilled water, dry, obtain carboxymethyl chitin.
Preferably, the chitin powder diameter is 60~120 mesh.
Preferably, the imidazole ion liquid is 1- ethyl-3-methylimidazoles acetate ([Emim] OAc), 1- ethyls -3- Methylimidazolium hydrogen sulphate salt ([Emim] HSO4), 1- ethyl-3-methylimidazoles trimethyl phosphate ([Emim] DMP), 1- ethyls -3- Methylimidazole triethyl phosphate ([Emim] DEP), 1- butyl -3- methylimidazoles trimethyl phosphate ([Bmim] DMP), 1,3- diformazan Base imidazoles trimethyl phosphate ([Mmim] DMP) and 1- butyl -3- methylimidazoles tributyl phosphate ([Bmim] DBP).
Preferably, ranging from the 1 of the mass ratio of chitin and imidazole ion liquid:20~1:100.
Preferably, the molar ratio of chitin monomer and sodium chloroacetate is 1:2~1:20.
Preferably, solution temperature is 80~130 DEG C, and dissolution time is 3~24 hours.
Preferably, ranging from the 5~30% of dilute hydrochloric acid concentration mass concentration.
Preferably, mixing time is 3~24 hours after dilute hydrochloric acid is added.
Preferably, the yield of 6-O- carboxymethyl chitins is 95~98%.
Compared with prior art, the present invention having the advantages that：(1) imidazole ion liquid used in can dissolve crust Element realizes homogeneous reaction；(2) imidazole ion liquid used in is non-volatile, environmental-friendly；(3) products obtained therefrom degree of substitution is high, and substitution is equal It is even.
Specific implementation mode
It will illustrate the method for the invention described by specific embodiment below, but the invention is not limited in these to implement Example.
Embodiment 1：
By 0.05g chitins, 0.057g sodium chloroacetates and the 1g 1- ethyl-3-methylimidazole acetate that grain size is 60 mesh ([Emim] OAc) after mixing, 80 DEG C are heated 3 hours, and clarification viscous solution is obtained.It is molten that the hydrochloric acid that mass concentration is 5% is added Liquid is stirred at room temperature 3 hours, obtains fluffy white precipitate, centrifuges to obtain white solid, be washed with distilled water, and drying obtains 6-O- Carboxymethyl chitin, yield 95%.
Embodiment 2：
By 0.05g chitins, 0.057g sodium chloroacetates and the 1g 1- ethyl-3-methylimidazole acetate that grain size is 120 mesh ([Emim] OAc) after mixing, 80 DEG C are heated 3 hours, and clarification viscous solution is obtained.It is molten that the hydrochloric acid that mass concentration is 5% is added Liquid is stirred at room temperature 3 hours, obtains fluffy white precipitate, centrifuges to obtain white solid, be washed with distilled water, and drying obtains 6-O- Carboxymethyl chitin, yield 95%.
Embodiment 3：
By 0.05g chitins, 0.057g sodium chloroacetates and the 5g 1- ethyl-3-methylimidazole acetate that grain size is 60 mesh ([Emim] OAc) after mixing, 80 DEG C are heated 3 hours, and clarification viscous solution is obtained.It is molten that the hydrochloric acid that mass concentration is 5% is added Liquid is stirred at room temperature 3 hours, obtains fluffy white precipitate, centrifuges to obtain white solid, be washed with distilled water, and drying obtains 6-O- Carboxymethyl chitin, yield 97%.
Embodiment 4：
By 0.05g chitins, 0.57g sodium chloroacetates and the 1g 1- ethyl-3-methylimidazole acetate that grain size is 60 mesh ([Emim] OAc) after mixing, 80 DEG C are heated 3 hours, and clarification viscous solution is obtained.It is molten that the hydrochloric acid that mass concentration is 5% is added Liquid is stirred at room temperature 3 hours, obtains fluffy white precipitate, centrifuges to obtain white solid, be washed with distilled water, and drying obtains 6-O- Carboxymethyl chitin, yield 98%.
Embodiment 5：
By 0.05g chitins, 0.057g sodium chloroacetates and the 1g 1- ethyl-3-methylimidazole acetate that grain size is 60 mesh ([Emim] OAc) after mixing, 130 DEG C are heated 3 hours, and clarification viscous solution is obtained.It is molten that the hydrochloric acid that mass concentration is 5% is added Liquid is stirred at room temperature 3 hours, obtains fluffy white precipitate, centrifuges to obtain white solid, be washed with distilled water, and drying obtains 6-O- Carboxymethyl chitin, yield 98%.
Embodiment 6：
By 0.05g chitins, 0.057g sodium chloroacetates and the 1g 1- ethyl-3-methylimidazole acetate that grain size is 60 mesh ([Emim] OAc) after mixing, 80 DEG C are heated 24 hours, and clarification viscous solution is obtained.It is molten that the hydrochloric acid that mass concentration is 5% is added Liquid is stirred at room temperature 3 hours, obtains fluffy white precipitate, centrifuges to obtain white solid, be washed with distilled water, and drying obtains 6-O- Carboxymethyl chitin, yield 97%.
Embodiment 7：
By 0.05g chitins, 0.057g sodium chloroacetates and the 1g 1- ethyl-3-methylimidazole acetate that grain size is 60 mesh ([Emim] OAc) after mixing, 80 DEG C are heated 3 hours, and clarification viscous solution is obtained.It is molten that the hydrochloric acid that mass concentration is 30% is added Liquid is stirred at room temperature 3 hours, obtains fluffy white precipitate, centrifuges to obtain white solid, be washed with distilled water, and drying obtains 6-O- Carboxymethyl chitin, yield 97%.
Embodiment 8：
By 0.05g chitins, 0.057g sodium chloroacetates and the 1g 1- ethyl-3-methylimidazole acetate that grain size is 60 mesh ([Emim] OAc) after mixing, 80 DEG C are heated 3 hours, and clarification viscous solution is obtained.It is molten that the hydrochloric acid that mass concentration is 5% is added Liquid is stirred at room temperature 24 hours, obtains fluffy white precipitate, centrifuges to obtain white solid, be washed with distilled water, and drying obtains 6- O- carboxymethyl chitins, yield 98%.
Embodiment 9：
By 0.05g chitins, 0.057g sodium chloroacetates and the 1g 1- ethyl-3-methylimidazole hydrogen sulfates that grain size is 60 mesh Salt ([Emim] HSO4) after mixing, 90 DEG C are heated 3 hours, and clarification viscous solution is obtained.The hydrochloric acid that mass concentration is 5% is added Solution is stirred at room temperature 3 hours, obtains fluffy white precipitate, centrifuges to obtain white solid, be washed with distilled water, and drying obtains 6- O- carboxymethyl chitins, yield 96%.
Embodiment 10：
By 0.05g chitins, 0.057g sodium chloroacetates and the 1g 1- ethyl-3-methylimidazole tricresyl phosphates that grain size is 60 mesh After mixing, 100 DEG C are heated 3 hours methyl esters ([Emim] DMP), obtain clarification viscous solution.The salt that mass concentration is 5% is added Acid solution is stirred at room temperature 3 hours, obtains fluffy white precipitate, centrifuges to obtain white solid, be washed with distilled water, and drying obtains 6-O- carboxymethyl chitins, yield 95%.
Embodiment 11：
By 0.05g chitins, 0.057g sodium chloroacetates and the 1g1- ethyl-3-methylimidazole tricresyl phosphate second that grain size is 60 mesh After mixing, 110 DEG C are heated 3 hours ester ([Emim] DEP), obtain clarification viscous solution.The hydrochloric acid that mass concentration is 5% is added Solution is stirred at room temperature 3 hours, obtains fluffy white precipitate, centrifuges to obtain white solid, be washed with distilled water, and drying obtains 6- O- carboxymethyl chitins, yield 95%.
Embodiment 12：
By 0.05g chitins, 0.057g sodium chloroacetates and the 1g1- butyl -3- methylimidazole tripotassium phosphates that grain size is 60 mesh After mixing, 120 DEG C are heated 3 hours ester ([Bmim] DMP), obtain clarification viscous solution.The hydrochloric acid that mass concentration is 5% is added Solution is stirred at room temperature 3 hours, obtains fluffy white precipitate, centrifuges to obtain white solid, be washed with distilled water, and drying obtains 6- O- carboxymethyl chitins, yield 95%.
Embodiment 13：
By 0.05g chitins, 0.057g sodium chloroacetates and the 1g1,3- methylimidazole trimethyl phosphates that grain size is 60 mesh ([Mmim] DMP) after mixing, 90 DEG C are heated 3 hours, and clarification viscous solution is obtained.It is molten that the hydrochloric acid that mass concentration is 5% is added Liquid is stirred at room temperature 3 hours, obtains fluffy white precipitate, centrifuges to obtain white solid, be washed with distilled water, and drying obtains 6-O- Carboxymethyl chitin, yield 95%.
Embodiment 14：
By 0.05g chitins, 0.057g sodium chloroacetates and the 1g1- butyl -3- methylimidazole tricresyl phosphate fourths that grain size is 60 mesh After mixing, 110 DEG C are heated 3 hours ester ([Bmim] DBP), obtain clarification viscous solution.The hydrochloric acid that mass concentration is 5% is added Solution is stirred at room temperature 3 hours, obtains fluffy white precipitate, centrifuges to obtain white solid, be washed with distilled water, and drying obtains 6- O- carboxymethyl chitins, yield 95%.

Claims (9)

1. a kind of method preparing 6-O- carboxymethyl chitins using imidazole ion liquid, specifically comprises the following steps：Chitin, Sodium chloroacetate is mixed in a certain ratio uniformly with ionic liquid, is stirred certain time in certain temperature, must be clarified bright solution；It will Dilute hydrochloric acid solution is added in this mixed solution, and certain time is stirred at room temperature, and obtains white flock precipitate, centrifuges white Solid is washed with distilled water, and drying obtains 6-O- carboxymethyl chitins.
2. preparation method according to claim 1, the chitin powder diameter is 60 ~ 120 mesh.
3. preparation method according to claim 1, which is characterized in that the imidazole ion liquid is 1- ethyl -3- methyl Imidazoles acetate（[Emim]OAc）, 1- ethyl-3-methylimidazole disulfates（[Emim]HSO4）, 1- ethyl-3-methylimidazoles Trimethyl phosphate（[Emim]DMP）, 1- ethyl-3-methylimidazole triethyl phosphates（[Emim]DEP）, 1- butyl -3- methyl miaows Azoles trimethyl phosphate（[Bmim]DMP）, 1,3- methylimidazole trimethyl phosphates（[Mmim]DMP）With 1- butyl -3- methyl miaows Azoles tributyl phosphate（[Bmim]DBP）.
4. preparation method according to claim 1, which is characterized in that the model of the mass ratio of chitin and imidazole ion liquid Enclose is 1:20 ~ 1:100.
5. preparation method according to claim 1, which is characterized in that the molar ratio of chitin monomer and sodium chloroacetate is 1: 2 ~1:20。
6. preparation method according to claim 1, solution temperature is 80 ~ 130 DEG C, and dissolution time is 3 ~ 24 hours.
7. preparation method according to claim 1, ranging from the 5 ~ 30% of dilute hydrochloric acid concentration mass concentration.
8. preparation method according to claim 1, mixing time is 3 ~ 24 hours after dilute hydrochloric acid is added.
9. the yield of preparation method according to claim 1,6-O- carboxymethyl chitins is 95 ~ 98%.
CN201810217880.6A 2018-03-16 2018-03-16 A method of preparing 6-O- carboxymethyl chitins using imidazole ion liquid Pending CN108299572A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116041568A (en) * 2023-01-11 2023-05-02 武汉大学中南医院 Water-soluble imidazole salt chitin with broad-spectrum antibacterial property, preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103288980A (en) * 2013-06-14 2013-09-11 湖北省潜江市华山水产食品有限公司 Preparation method of carboxymethyl chitin
CN106749763A (en) * 2016-12-30 2017-05-31 中国科学院过程工程研究所 A kind of method that utilization ionic liquid prepares high-purity crust from shrimp shell meal
CN107556498A (en) * 2017-09-30 2018-01-09 中国科学院过程工程研究所 A kind of method that chitin balls are prepared using glyoxaline ion liquid
CN107602726A (en) * 2017-10-26 2018-01-19 中国科学院过程工程研究所 Low molecule amount C6 carboxy chitins and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103288980A (en) * 2013-06-14 2013-09-11 湖北省潜江市华山水产食品有限公司 Preparation method of carboxymethyl chitin
CN106749763A (en) * 2016-12-30 2017-05-31 中国科学院过程工程研究所 A kind of method that utilization ionic liquid prepares high-purity crust from shrimp shell meal
CN107556498A (en) * 2017-09-30 2018-01-09 中国科学院过程工程研究所 A kind of method that chitin balls are prepared using glyoxaline ion liquid
CN107602726A (en) * 2017-10-26 2018-01-19 中国科学院过程工程研究所 Low molecule amount C6 carboxy chitins and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
SHOZABURO MINE等: "Acetylation of a-chitin in ionic liquids", 《CARBOHYDRATE RESEARCH》 *
蔡玲: "甲壳素在离子液体中的溶解与改性", 《科技资讯》 *
高福成主编: "《食品分离重组工程技术（第1版）》", 31 July 1998, 中国轻工业出版社 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116041568A (en) * 2023-01-11 2023-05-02 武汉大学中南医院 Water-soluble imidazole salt chitin with broad-spectrum antibacterial property, preparation method and application thereof

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