CN110386994A - A kind of homogeneous phase synthetic method of Quaternary Ammonium Salt of Chitosan - Google Patents
A kind of homogeneous phase synthetic method of Quaternary Ammonium Salt of Chitosan Download PDFInfo
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- CN110386994A CN110386994A CN201810351524.3A CN201810351524A CN110386994A CN 110386994 A CN110386994 A CN 110386994A CN 201810351524 A CN201810351524 A CN 201810351524A CN 110386994 A CN110386994 A CN 110386994A
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- chitosan
- ammonium salt
- quaternary ammonium
- synthetic method
- solution
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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
Abstract
The invention discloses a kind of homogeneous phase synthetic method of Quaternary Ammonium Salt of Chitosan, Chitosan powder first is scattered in potassium hydroxide/aqueous solution of urea, and chitosan solution is then obtained after low-temperature treatment；Iodomethane is added into chitosan solution, obtains Quaternary Ammonium Salt of Chitosan after mechanic whirl-nett reaction.Chitosan dissolves rapidly in alkali/aqueous solution of urea, and chitosan solvent used is environmentally protective；Entire synthesis process is homogeneous reaction, and operation is easy and does not need to be added organic solvent as dispersing agent.The degree of substitution of products obtained therefrom has controllability, good water solubility.Thus a kind of easy to operate, environmentally protective new method for preparing Quaternary Ammonium Salt of Chitosan is developed.
Description
Technical field
The invention discloses a kind of homogeneous phase synthetic methods of Quaternary Ammonium Salt of Chitosan, and in particular to dissolves chitosan in hydrogen-oxygen
Change and carries out the method that quaternization reaction prepares Quaternary Ammonium Salt of Chitosan in potassium/urea liquid.
Background technique
Quaternary Ammonium Salt of Chitosan (TMC) is a kind of water-soluble cationic chitosan derivative, and anti-microbial property is much better than
Other chitosan derivatives.Due to performances such as good filming, histocompatbility, moisture absorbability and moisture retentivity, biocidal properties, in recent years
To be widely used in the fields such as medicine, cosmetics, food.
Document (Jia Z, Xu W. 2001,333 (1): 1-6) and (Zhou Z, Yan D, Cheng X, et al.
The method that Quaternary Ammonium Salt of Chitosan is synthesized under acid and alkaline condition 2016,89:471-476) is reported respectively.(1) in alkali
Property under the conditions of hydroxyl in chitosan molecule structure and amino can be quaternized modification group substitution respectively, generate quaternary ammonium salt
Chitosan.(2) in acid condition, it is formed first with the amino in chitosan molecule structure with carbonyl-containing compound uncommon
C=N in schiff bases is then reduced to-NH-CH- by husband's alkali, is finally converted into quaternary ammonium salt with the effect of active halogenated hydrocarbons again.
However, since chitosan is difficult to dissolve under alkaline condition, so first method belongs to out-phase reaction, reaction process can only be by
It table and inner carries out.Therefore, the degree of substitution and uniformity of the Quaternary Ammonium Salt of Chitosan obtained are all extremely limited.The shell in acidic environment
Glycan only has amino that can be quaternized base group modification, and reactant degree of substitution is low.In addition, the above method is cumbersome, reacted
Journey is related to a variety of toxic chemicals, higher cost and is unfavorable for environmental protection, limits the industrialization large-scale production of the material.By
This, the hot spot that exploitation is cheap, the green new method for preparing chitosan quaternary ammonium derivative is current chitosan research.
Summary of the invention
The present invention provides a kind of new methods of Homogeneous synthesis Quaternary Ammonium Salt of Chitosan in alkali/aqueous solution of urea.
Technical solution of the present invention is specific as follows:
A kind of homogeneous phase synthetic method of Quaternary Ammonium Salt of Chitosan, comprising the following steps:
Chitosan is dispersed in potassium hydroxide (6 ~ 20%)/urea (0 ~ 30%) (w/w) aqueous solution, said components are cooled down
Chitosan solution is obtained after to 0 ~ -80 DEG C；
Iodomethane is added into chitosan solution, in 0 DEG C~60 DEG C mechanic whirl-nett reaction 1 hour to 48 hours, reaction solution is through heavy
Forming sediment, wash, obtaining degree of substitution after dehydration is 0.2~1.5 Quaternary Ammonium Salt of Chitosan.
The concentration of the chitosan solution is 0.5%~6%(w/w).
The mole that iodomethane is added is 0.5~24 times of amino of chitosan glucose unit mole.
The present invention has the following advantages that
(1) Quaternary Ammonium Salt of Chitosan has been synthesized by homogeneous reaction under potassium hydroxide/urea system for the first time, agents useful for same is nontoxic,
Pollution-free, cheap, simple synthetic method and reaction process is easy to control.
(2) compared with prior art, Quaternary Ammonium Salt of Chitosan favorable solubility prepared by the present invention and degree of substitution have controllable
Property.
Detailed description of the invention
Fig. 1 is the infared spectrum of chitosan and Quaternary Ammonium Salt of Chitosan produced by the present invention.
Specific embodiment
Further description of the technical solution of the present invention combined with specific embodiments below, but is not limited to this hair
It is bright.
Embodiment 1
0.5 part of Chitosan powder is dispersed in the aqueous solution containing 12 parts of potassium hydroxide/8 part urea (w/w) and is cooled to 0 DEG C
To bright chitosan solution (0.5wt%).Iodomethane (iodomethane and amino of chitosan grape are added into chitosan solution
The molar ratio of sugar unit is 1:2), mechanic whirl-nett reaction 24 hours at 15 DEG C, reaction solution obtains after precipitating, washing, dehydration
Quaternary Ammonium Salt of Chitosan (TMC-1), degree of substitution 0.2.
Embodiment 2
1 part of chitosan is dispersed in the aqueous solution containing 20 parts of potassium hydroxide/20 part urea (w/w) and is cooled to -80 DEG C
Obtain bright chitosan solution (1wt%).Iodomethane (iodomethane and amino of chitosan glucose are added into chitosan solution
The molar ratio of unit is 2:1), mechanic whirl-nett reaction 6 hours at 0 DEG C, reaction solution obtains quaternary ammonium after precipitating, washing, dehydration
Salt chitosan (TMC-2), degree of substitution 0.4.
Embodiment 3
2 parts of chitosans are dispersed in the aqueous solution containing 6 parts of potassium hydroxide/30 part urea (w/w) and are cooled to -60 DEG C
To bright chitosan solution (2wt%).Iodomethane (iodomethane and amino of chitosan glucose are added into chitosan solution
The molar ratio of unit is 6:1), mechanic whirl-nett reaction 12 hours at 20 DEG C, reaction solution obtains season after precipitating, washing, dehydration
Ammonium salt chitosan (TMC-3), degree of substitution 0.7.
Embodiment 4
4 parts of chitosans are dispersed in the aqueous solution containing 16 parts of potassium hydroxide/8 part urea (w/w) and are cooled to -20 DEG C
To bright chitosan solution (4wt%).Iodomethane (iodomethane and amino of chitosan glucose are added into chitosan solution
The molar ratio of unit is 8:1), mechanic whirl-nett reaction 36 hours at 30 DEG C, reaction solution obtains season after precipitating, washing, dehydration
Ammonium salt chitosan (TMC-4), degree of substitution 0.8.
Embodiment 5
6 parts of chitosans are dispersed in the aqueous solution containing 10 parts of potassium hydroxide/12 part urea (w/w) and are cooled to -40 DEG C
Obtain bright chitosan solution (6wt%).Iodomethane (iodomethane and amino of chitosan grape are added into chitosan solution
The molar ratio of sugar unit is 12:1), mechanic whirl-nett reaction 1 hour at 60 DEG C, reaction solution obtains after precipitating, washing, dehydration
To Quaternary Ammonium Salt of Chitosan (TMC-5), degree of substitution 1.2.
Embodiment 6
4 parts of chitosans are dispersed in the aqueous solution containing 8 parts of potassium hydroxide/6 part urea (w/w) and are cooled to -50 DEG C
To bright chitosan solution (4wt%).Iodomethane (iodomethane and amino of chitosan glucose are added into chitosan solution
The molar ratio of unit is 24:1), mechanic whirl-nett reaction 48 hours at 25 DEG C, reaction solution obtains season after precipitating, washing, dehydration
Ammonium salt chitosan (TMC-6), degree of substitution 1.5.
Claims (4)
1. a kind of homogeneous phase synthetic method of Quaternary Ammonium Salt of Chitosan, which comprises the following steps: disperse Chitosan powder
In potassium hydroxide/aqueous solution of urea, chitosan solution is then obtained after low-temperature treatment；Iodine is added into chitosan solution
Methane, mechanic whirl-nett reaction obtain Quaternary Ammonium Salt of Chitosan.
2. the homogeneous phase synthetic method of Quaternary Ammonium Salt of Chitosan according to claim 1, it is characterised in that: potassium hydroxide: 6 ~
20%, urea: 0 ~ 30%, chitosan 0.5%~6%, (w/w) remaining is water, and treatment temperature is 0 ~ -80 DEG C.
3. the homogeneous phase synthetic method of n-trimethyl chitosan chloride derivative according to claim 1, it is characterised in that: iodine first is added
The mole of alkane is 0.5~24 times of amino of chitosan glucose unit mole.
4. the homogeneous phase synthetic method of Quaternary Ammonium Salt of Chitosan derivative according to claim 1, it is characterised in that: in 0 DEG C~
It is 0.2~1.5 Quaternary Ammonium Salt of Chitosan that 60 DEG C, which obtain degree of substitution after mechanic whirl-nett reaction 1 hour to 48 hours,.
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2018
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| CN102140177A (en) * | 2011-04-20 | 2011-08-03 | 浙江大学 | Alkaline solvent for dissolving high-molecular-weight chitosan and using method thereof |
| CN102634040A (en) * | 2012-04-26 | 2012-08-15 | 安徽理工大学 | Basic solvent for dissolving chitosan and method for dissolving chitosan under alkaline condition |
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| CN103936887A (en) * | 2014-05-08 | 2014-07-23 | 南开大学 | New method for preparing temperature-sensitive hydroxybutyl chitosan |
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