CN106046200A - Preparation method of carboxymethyl chitosan - Google Patents
Preparation method of carboxymethyl chitosan Download PDFInfo
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- CN106046200A CN106046200A CN201610686655.8A CN201610686655A CN106046200A CN 106046200 A CN106046200 A CN 106046200A CN 201610686655 A CN201610686655 A CN 201610686655A CN 106046200 A CN106046200 A CN 106046200A
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- chitosan
- carboxymethyl chitosan
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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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Abstract
The invention relates to a preparation method of carboxymethyl chitosan, and particularly relates to a preparation method of the carboxymethyl chitosan with a semi-dry grinding method. The preparation method includes the steps of: 1) adding sodium hydroxide to chitosan and fully grinding the components to uniformly mix the components, adding distilled water and uniformly mixing and grinding the components for 2-3 h, and allowing the mixture to stand for 12-18 h for alkalization; 2) adding monochloroacetic acid to the alkalized chitosan, uniformly grinding and mixing the components, wherein the molar ratio of the chitosan, the sodium hydroxide to the monochloroacetic acid is 1:3.5-5.5:3; and 3) dropwisely adding distilled water and meanwhile grinding the mixture for 4-6 h to prepare a carboxymethyl chitosan initial product, washing the carboxymethyl chitosan initial product with an organic solution, and performing suction filtration and drying to prepare the carboxymethyl chitosan. The preparation method has simple operations, wherein only is a less amount of water employed as a reaction medium, so that a large use amount of organic solvent is avoided. The method is low in production cost and environment pollution and is high in synthesis efficiency and productivity.
Description
Technical field
The present invention relates to the preparation method of carboxymethyl chitosan, be specifically related to a kind of carboxymethyl shell using half-dried polishing
The preparation method of polysaccharide.
Background technology
Carboxymethyl chitosan (be called for short CMC) is chitosan important derivatives, has good water solublity, antibiotic property, moisture absorption
Moisture retention, film property, the performance such as sequestering so that it is wide in fields such as article of everyday use, chemical industry, agricultural, food processing, medicine, environmental protection
General application.
At present, the preparation method of carboxymethyl chitosan is mainly organic solvent method: be former with chitosan or chitin respectively
Material, with organic solvents such as ethanol, isopropanol, DMSO as reaction medium, concentrated base alkalizes, add chloroacetic acid make it with chitosan or
Chitin generation substitution reaction, prepares carboxymethyl chitosan.The major defect of said method is: the 1) extraction of raw material chitin
Cost is high, have employed Crusta Penaeus seu Panulirus Carapax Eriocheir sinensis diluted acid decalcification, then the alkali liquor high cooking deproteinization technique through 5%～8%, not only acid
Alkali and energy consumption are big, and cause Heavy environmental pollution.It is easily caused degradation of chitin during acid treatment, wastes the biology of preciousness
Calcium resource.2) chitosan consumes a large amount of alkali and organic solvent when preparing carboxymethyl chitosan, and production cost is high, and environmental pollution is tight
Weight, alkaline consumption, energy consumption, wastewater flow rate are big.
Summary of the invention
For solving above-mentioned technical problem, the present invention provides a kind of with chitosan as raw material, significantly improves in traditional handicraft and makes
With organic solvent, consume the shortcoming such as a large amount of sodium hydroxide and washing ethanol/water, use the carboxymethyl chitosan of half-dried polishing
The preparation method of sugar.
The technical scheme is that the preparation method that a kind of carboxymethyl chitosan is provided, comprise the steps: chitosan
Hydro-oxidation sodium is fully ground and makes it uniformly mix, and instills distilled water uniform mixed grinding 2-3h, places 12-18h alkalization, to alkali
Adding chloroacetic acid in chitosan after change, ground and mixed is uniform, the material of described chitosan, sodium hydroxide and chloroacetic acid
Amount ratio is: 1:3.5-5.5:3, and 4-6h is ground in dropping distillation waterside, limit, prepares carboxymethyl chitosan head product, washes by organic solution
Wash carboxymethyl chitosan head product, sucking filtration, dry, i.e. obtain carboxymethyl chitosan.
Preferably, in the preparation method of above-mentioned carboxymethyl chitosan, described chitosan, sodium hydroxide and chloroacetic acid
The amount ratio of material is: 1:4.5:3.
Preferably, in the preparation method of above-mentioned carboxymethyl chitosan, described " wash carboxymethyl chitosan by organic solution
Head product, sucking filtration, dry " particularly as follows: with 75% ethanol solution washing carboxymethyl chitosan head product until the supernatant without
Cl-, sucking filtration, put into 60 DEG C of drying in oven, i.e. obtain carboxymethyl chitosan.
Preferably, the preparation method of above-mentioned carboxymethyl chitosan specifically includes following steps: weigh 1.0g chitosan in
In mortar, add 0.6g sodium hydroxide, be fully ground and make it uniformly mix, instill distilled water uniform mixed grinding 3 h, place alkali
Changing 12h, add 0.8g chloroacetic acid in the chitosan after alkalization, ground and mixed is uniform, and 4-6h is ground in dropping distillation waterside, limit,
Prepare carboxymethyl chitosan head product, with the ethanol solution washing carboxymethyl chitosan head product that Solute mass percent is 75%
Until the supernatant is without Cl-, sucking filtration, put into 60 DEG C of drying in oven, i.e. obtain carboxymethyl chitosan.
The beneficial effects of the present invention is: the preparation method of the carboxymethyl chitosan of the present invention is easy and simple to handle, use a small amount of
Water is reaction medium, it is to avoid a large amount of uses of organic solvent, and production cost is low, and environmental pollution is little, and combined coefficient and productivity
Higher, significantly improve and traditional handicraft uses organic solvent, consume the shortcoming such as a large amount of sodium hydroxide and washing ethanol/water.
Detailed description of the invention
By describing the technology contents of the present invention in detail, being realized purpose and effect, it is explained in detail below in conjunction with embodiment.
The raw material used in the preparation method of carboxymethyl chitosan of the present invention is as follows: chitosan: deacetylation 85.7%, Ji
South Sea get Bei marine biotechnology company limited；Sodium hydroxide: analytical pure, Tianjin Standard Science company limited；Chloroacetic acid:
Analytical pure, Shanghai reagent two factory；95% ethanol: analytical pure.
Embodiment 1
The preparation method of a kind of carboxymethyl chitosan, comprises the steps: that chitosan hydro-oxidation sodium is fully ground and makes it uniform
Mixing, instills distilled water uniform mixed grinding 2h, places 12h alkalization, adds chloroacetic acid, grind in the chitosan after alkalization
Mix homogeneously, the amount ratio of the material of described chitosan, sodium hydroxide and chloroacetic acid is: 1:3.5:3；Dropping distillation waterside, limit is ground
Mill 4h, prepares carboxymethyl chitosan head product, and the ethanol solution washing carboxymethyl chitosan head product with 75% is until the supernatant
Without Cl-, sucking filtration, put into 70 DEG C of drying in oven, i.e. obtain carboxymethyl chitosan.The carboxylation degree of gained carboxymethyl chitosan reaches
1.65, the viscosity of 1% carboxymethyl chitosan sugar aqueous solution is 83mPa s.
Embodiment 2
The preparation method of a kind of carboxymethyl chitosan, comprises the steps: that chitosan hydro-oxidation sodium is fully ground and makes it uniform
Mixing, instills distilled water uniform mixed grinding 3h, places 18h alkalization, adds chloroacetic acid, grind in the chitosan after alkalization
Mix homogeneously, the amount ratio of the material of described chitosan, sodium hydroxide and chloroacetic acid is: 1:5.5:3；Dropping distillation waterside, limit is ground
Mill 6h, prepares carboxymethyl chitosan head product, and the ethanol solution washing carboxymethyl chitosan head product with 75% is until the supernatant
Without Cl-, sucking filtration, put into 60 DEG C of drying in oven, i.e. obtain carboxymethyl chitosan.The carboxylation degree of gained carboxymethyl chitosan reaches
1.68, the viscosity of 1% carboxymethyl chitosan sugar aqueous solution is 85mPa s.
Embodiment 3
The preparation method of a kind of carboxymethyl chitosan, comprises the steps: that chitosan hydro-oxidation sodium is fully ground and makes it uniform
Mixing, instills distilled water uniform mixed grinding 2.5h, places 16h alkalization, adds chloroacetic acid, grind in the chitosan after alkalization
Mill mix homogeneously, the amount ratio of the material of described chitosan, sodium hydroxide and chloroacetic acid is: 1:4.5:3；Dropping distillation waterside, limit
Grinding 5h, prepare carboxymethyl chitosan head product, the ethanol solution with 75% washs carboxymethyl chitosan head product until upper strata is clear
Liquid is without Cl-, sucking filtration, put into 60 DEG C of drying in oven, i.e. obtain carboxymethyl chitosan.The carboxylation degree of gained carboxymethyl chitosan reaches
To 1.73, the viscosity of 1% carboxymethyl chitosan sugar aqueous solution is 89mPa s.
The carboxymethylated analysis of Influential Factors of embodiment 4 chitosan
The preparation method of a kind of carboxymethyl chitosan, comprises the steps: to weigh 1.0g chitosan in mortar, adds 0.6g hydrogen
Sodium oxide, is fully ground and makes it uniformly mix, and instills distilled water uniform mixed grinding again, the most repeatedly grinds 3 h, and alkalize 12h.
Adding 0.8g chloroacetic acid in chitosan after alkalization, ground and mixed is uniform, and dropping distillation waterside, limit is ground, and so carries out 4-
6h, prepares carboxymethyl chitosan sugar product.Ethanol solution cleaning product with 75% is until the supernatant is without Cl-, sucking filtration, put into 60
DEG C drying in oven, i.e. obtains carboxymethyl chitosan sample.
1, said method changes the impact of alkalization time
The effect of alkali mainly destroys the crystal region of chitosan so that it is expands, and reacts with chitosan, forms carboxy methylation
The active centre of reaction so that it is easily react with chloroacetic acid.The carboxymethylated important symbol of chitosan be neutral or
Can dissolve under weak basic condition.Therefore, when set casing polysaccharide, sodium hydroxide, the amount ratio of chloroacetic acid and etherificate
Between wait other except alkalization time in addition under the conditions of, change alkalization time, have studied alkalization time to product dissolubility in water
Impact.Shown in result table 1.
The impact deliquescent on product of table 1 alkalization time
| Time (h) | 2 | 4 | 6 | 12 |
| Dissolubility | Insoluble | Insoluble | It is partly dissolved | Dissolve |
As shown in Table 1, alkalization time is short, and the dissolubility of product is poor, if chitosan alkalizes 12-18h, then product can be dissolved in
In water.Chitosan carboxymethylation reaction is base catalyzed reactions, and chitosan fully alkalizes before carboxymethylation reaction is smoothed out
Carrying, therefore, proper extension alkalization is more beneficial for the carrying out of carboxymethylation reaction.
2, said method changes merely the impact after alkali consumption
On the one hand sodium hydroxide is used for neutralizing chloroacetic acid, on the one hand alkalization chitosan hydroxyl, but the consumption of alkali also can be to product
Performance produce impact.The all conditions in addition to the consumption of alkali such as the consumption of fixed acid, alkalization time, etherification time, changes
The consumption of alkali, the consumption of research alkali is for the impact of properties of product.Result is as shown in table 2.
The impact on properties of product of table 2 sodium hydroxide concentration
Can be obtained from above, when alkali number it cannot be guaranteed that during reaction medium alkalescence (such as 1:1:2), carboxymethylation reaction can not be carried out.Understand,
When the amount of acid is fixed, along with the consumption of alkali increases, the carboxylation degree of product and viscosity present and significantly first increase the trend dropped afterwards.
This is owing to along with the increase of alkali number, forming more active center, beneficially carboxymethylation reaction in chitosan structure unit
Carrying out, therefore the carboxylation degree of product can improve accordingly；But when the consumption of alkali is too high, side reaction can be caused to increase, reduce acid
Utilization rate, brokenization glycosidic bond molecular weight and molecular weight simultaneously, product viscosity decline.Test result indicate that, when chitosan, sodium hydroxide
When being 1:3.5:2 with the ratio of the amount of the material of chloroacetic acid, say, that the consumption of sodium hydroxide is little over amount, the substitution value of product
Higher with viscosity.
3, the impact after the consumption that in said method, simple change is sour
Fixing alkalization time, etherification time, increase the consumption of chloroacetic acid, probe into the consumption of chloroacetic acid for properties of product
Impact.Result is as shown in table 3.
The impact on properties of product of the table 3 chloroacetic acid consumption
As shown in Table 3, when the consumption of chloroacetic acid is relatively low, carboxymethylation reaction carries out the most thorough, the carboxylation degree of product
It is relatively low (such as 1:3.5:1)；But when the consumption of chloroacetic acid is too high, it is the most acid that reaction system can become neutrality, this
Time carboxymethylation reaction will stop, even having side reaction to occur, thus can not get carboxymethyl chitosan (such as 1:3.5:4).Cause
This ensure base excess but excess constant on the basis of, increase chloroacetic acid consumption, although carboxylation degree is changed, but
Impact is little.
4, in above-described embodiment 4, the preparation method of carboxymethyl chitosan and conventional organic solvents method prepare carboxymethyl chitosan
Comparative result as shown in table 4.
The comparison of table 4 carboxymethyl chitosan difference preparation method
By table 4 it can be seen that in the case of product carboxymethyl chitosan important indicator carboxylation degree is essentially identical, in this method,
Greatly reduce the consumption of alkali and chloroacetic acid, and a small amount of water is medium, it is to avoid using organic solvent, cost drops significantly
Low, comply with environmental requirement.
5, conclusion
Use half-dried polishing, with water as medium, make chitosan react with chloroacetic acid in the basic conditions, synthesize N, O-
Carboxymethyl chitosan.The impact prepared carboxymethyl chitosan by the consumption of alkalization time, the consumption of alkali and acid, has obtained half
Dry grinding method prepares the most best reaction condition of carboxymethyl chitosan: n (chitosan unit): n (sodium hydroxide): a n (chlorine
Acetic acid)=1:4.5:3, alkalization grinding 2-3 h, to place 12-18h, be etherified 4-6 h, the carboxylation degree of gained carboxymethyl chitosan reaches
1.73, the viscosity of 1% carboxymethyl chitosan sugar aqueous solution is 89mPa s.Compared with conventional preparation techniques, half-dried polishing alkali charge
Little, with water as solvent, it is to avoid use organic solvent and also without heating, alkali charge greatly reduces, with low cost, pollutes little, behaviour
Making simplicity, the viscosity of product also compares high with carboxylation degree, be a kind of simply, economy, environmental protection, efficient preparation method.
The foregoing is only embodiments of the invention, not thereby limit the scope of the claims of the present invention, every utilize this
Equivalent formulas or equivalence flow process that bright description is made convert, or are directly or indirectly used in other relevant technical fields, all
In like manner it is included in the scope of patent protection of the present invention.
Claims (4)
1. the preparation method of a carboxymethyl chitosan, it is characterised in that comprise the steps: that chitosan hydro-oxidation sodium is abundant
Grinding makes it uniformly mix, and instills distilled water uniform mixed grinding 2-3h, places 12-18h alkalization, in the chitosan after alkalization
Adding chloroacetic acid, ground and mixed is uniform, and the amount ratio of the material of described chitosan, sodium hydroxide and chloroacetic acid is: 1:3.5-
5.5:3, dropping distillation waterside, limit is ground 4-6h, is prepared carboxymethyl chitosan head product, wash carboxymethyl chitosan by organic solution
Sugar head product, sucking filtration, dry, i.e. obtain carboxymethyl chitosan.
The preparation method of carboxymethyl chitosan the most according to claim 1, it is characterised in that described chitosan, hydroxide
The amount ratio of the material of sodium and chloroacetic acid is: 1:4.5:3.
The preparation method of carboxymethyl chitosan the most according to claim 1, it is characterised in that described " wash by organic solution
Wash carboxymethyl chitosan head product, sucking filtration, dry " particularly as follows: the ethanol solution washing carboxymethyl chitosan head product with 75% is straight
To the supernatant without Cl-, sucking filtration, put into 60 DEG C of drying in oven, i.e. obtain carboxymethyl chitosan.
The preparation method of carboxymethyl chitosan the most according to claim 1, it is characterised in that specifically include following steps:
Weigh 1.0g chitosan in mortar, add 0.6g sodium hydroxide, be fully ground and make it uniformly mix, instill distilled water and uniformly mix
Closing and grind 3 h, place alkalization 12h, add 0.8g chloroacetic acid in the chitosan after alkalization, ground and mixed is uniform, and limit drips
4-6h is ground in distillation waterside, prepares carboxymethyl chitosan head product, with the ethanol solution washing carboxymethyl that mass percent is 75%
Chitosan head product is until the supernatant is without Cl-, sucking filtration, put into 60 DEG C of drying in oven, i.e. obtain carboxymethyl chitosan.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107638345A (en) * | 2017-09-29 | 2018-01-30 | 乔银娣 | Moistening bath and preparation method thereof |
| CN110563860A (en) * | 2019-10-25 | 2019-12-13 | 石家庄亿生堂医用品有限公司 | preparation method of carboxymethyl chitosan |
| 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 |
| CN113045688A (en) * | 2021-04-12 | 2021-06-29 | 仲恺农业工程学院 | Preparation method of carboxymethyl chitosan by solid-phase reaction |
| 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 |
| CN115873145A (en) * | 2023-03-08 | 2023-03-31 | 山东东瑞生物技术有限公司 | Preparation method of carboxymethyl chitosan |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329095A (en) * | 2001-07-27 | 2002-01-02 | 唐梓进 | Semi-dry microwave synthesis of carboxymethyl chitosan |
| CN101701045A (en) * | 2009-12-10 | 2010-05-05 | 中华全国供销合作总社南京野生植物综合利用研究院 | Method for preparing carboxymethyl chitosan by micro-aqueous phase |
| CN103113491A (en) * | 2011-11-17 | 2013-05-22 | 中国科学院海洋研究所 | Carboxymethyl chitosan, and preparation and application thereof |
| CN104284904A (en) * | 2012-04-05 | 2015-01-14 | 斯托拉恩索公司 | Method for the preparation of cellulose ethers with high solids process, product obtained and uses of the product |
-
2016
- 2016-08-19 CN CN201610686655.8A patent/CN106046200A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329095A (en) * | 2001-07-27 | 2002-01-02 | 唐梓进 | Semi-dry microwave synthesis of carboxymethyl chitosan |
| CN101701045A (en) * | 2009-12-10 | 2010-05-05 | 中华全国供销合作总社南京野生植物综合利用研究院 | Method for preparing carboxymethyl chitosan by micro-aqueous phase |
| CN103113491A (en) * | 2011-11-17 | 2013-05-22 | 中国科学院海洋研究所 | Carboxymethyl chitosan, and preparation and application thereof |
| CN104284904A (en) * | 2012-04-05 | 2015-01-14 | 斯托拉恩索公司 | Method for the preparation of cellulose ethers with high solids process, product obtained and uses of the product |
Non-Patent Citations (4)
| Title |
|---|
| 何卫东 等: "《高分子化学实验》", 30 September 2012, 中国科学技术大学出版社 * |
| 朱婉萍 等: "《甲壳素及其衍生物的研究与应用》", 30 November 2014, 浙江大学出版社 * |
| 王涛 等: "羧甲基淀粉钠工业品的生产工艺研究", 《安徽理工大学学报 (自然科学版 )》 * |
| 邓子祥 等: "羧甲基壳聚糖的合成和性质研究", 《广东化工》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107638345A (en) * | 2017-09-29 | 2018-01-30 | 乔银娣 | Moistening bath and preparation method thereof |
| CN110563860A (en) * | 2019-10-25 | 2019-12-13 | 石家庄亿生堂医用品有限公司 | preparation method of carboxymethyl chitosan |
| 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 |
| 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 |
| CN113045688A (en) * | 2021-04-12 | 2021-06-29 | 仲恺农业工程学院 | Preparation method of carboxymethyl chitosan by solid-phase reaction |
| CN115873145A (en) * | 2023-03-08 | 2023-03-31 | 山东东瑞生物技术有限公司 | Preparation method of carboxymethyl chitosan |
| CN115873145B (en) * | 2023-03-08 | 2023-05-30 | 山东东瑞生物技术有限公司 | Preparation method of carboxymethyl chitosan |
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Inventor after: Liu Changxia Inventor after: Fan Xiaozhen Inventor after: Yan Junqin Inventor after: Wang Huanyun Inventor before: Liu Changxia Inventor before: Yan Junqin Inventor before: Wang Huanyun |
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Application publication date: 20161026 |