CN112442139B - Method for homogeneous preparation of different chitosan derivatives based on weak base system - Google Patents
Method for homogeneous preparation of different chitosan derivatives based on weak base system Download PDFInfo
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- 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 method for homogeneous preparation of different chitosan derivatives based on a weak base system. Adding a derivatization reagent into the chitosan solution, purifying and freeze-drying after specific reaction conditions to obtain the chitosan derivative. According to the preparation method, the chitosan derivative can be prepared in a weak base system by a one-pot homogeneous phase method, the operation is simple and convenient, the reaction is controllable, the method is economical and environment-friendly, and the multifunctional chitosan derivative can be obtained by changing different derivatization reagents.
Description
Technical Field
The invention designs a homogeneous preparation method of different chitosan derivatives based on a weak base system, belonging to the field of high polymer materials.
Background
Chitin is the second most biologically derived resource next to cellulose in nature, and chitosan is the deacetylated product of chitin, has good biocompatibility, is easy to degrade in natural environment, and is non-toxic, harmless and pollution-free. With the continuous development of new chitosan solvents, new materials such as chitosan fibers, chitosan films, chitosan hydrogel, chitosan aerogel, chitosan microspheres and the like are widely developed, researched and applied in the fields of separation and adsorption, biomedical materials, flexible electronic devices and the like, but the chitosan materials obtained by dissolution and regeneration can not be directly used, so that the actual requirements can not be met. In order to obtain chitosan materials with more specific functions and properties, the molecular design and directed modification of chitosan are usually required to meet various specific requirements. The homogeneous derivatization of the chitosan can avoid the problems of incomplete reaction, uncontrollable reaction sites, inhomogeneous product structure, degradation of raw materials and products caused by harsh conditions and the like under heterogeneous conditions. At present, the homogeneous derivatization system of chitosan is mainly the traditional acetic acid dissolution system, and more recently, alkali/urea system developed by researchers, including the combination of lithium hydroxide-sodium hydroxide-urea (patent 201110099176.3), the combination of lithium hydroxide-potassium hydroxide-urea (patent 201310405191.5), the combination of sodium hydroxide-urea (Zhang W, Xia W.Disolution and stability of chitosan in a sodium hydroxide/urea solution [ J ]. Journal of Applied Polymer Science,2014,131(3): 1082-. However, chitosan is easily degraded in a chitosan molecular chain in an acidic aqueous solution, a large amount of alkali is needed for dissolution in a strong alkali system, the dissolution process needs to be frozen and thawed once or for many times, the obtained solution has stable properties only under a low-temperature condition, derivatization reaction can only be performed under the low-temperature condition, the reaction efficiency is low, a large amount of energy is consumed in the process, and the large-scale application of chitosan derivatives in preparation is difficult. In a traditional alkali/urea system, solution is strong in alkalinity, is suitable for etherification reaction and esterification reaction, and limits the variety and selection of chitosan derivatives prepared by homogeneous phase. Therefore, there is a need for a method for preparing chitosan derivatives based on weak base system with low energy consumption and high efficiency.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provide a novel method for homogeneously preparing different chitosan derivatives based on a weak base system. The chitosan derivative includes acid esterification, carboxyl alkylation, hydroxylation, alkylation, acylation, quaternary ammonium salt derivative and the like.
The scheme adopted by the invention for solving the technical problems is as follows:
a method for homogeneously preparing chitosan derivatives based on a weak base system comprises the following steps:
(1) preparing a weak alkaline aqueous solution, wherein the weak alkaline aqueous solution contains bicarbonate and a stabilizer, and the concentration of the bicarbonate is 0.2-1.5 mol/kg-1More preferably 0.3 to 1.2 mol/kg-1The stabilizer is one or two of urea and thiourea, and the concentration of the urea is 0.1-5 mol kg-1More preferably 1.0 to 4.0 mol/kg-1The concentration of thiourea is 0.3 to 1.2 mol/kg-1More preferably 0.4 to 1.0 mol/kg-1The balance being water;
(2) adding chitosan into the alkalescent aqueous solution obtained in the step (1), continuously stirring for more than 30 minutes at the temperature of between freezing point and 35 ℃ to dissolve the chitosan, and defoaming to obtain a transparent chitosan solution;
(3) and (3) adding a derivatization reagent into the chitosan solution obtained in the step (2) below the gelation temperature, stirring for reaction for not less than 1h, adjusting the pH of the solution to be neutral after the reaction is finished, dialyzing, purifying and freeze-drying to obtain the chitosan derivative.
Preferably, the bicarbonate comprises alkali metal bicarbonate, alkaline earth metal bicarbonate, ammonium bicarbonate.
Preferably, the bicarbonate is one or more of sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate and magnesium bicarbonate.
Preferably, KOH is further added into the weak alkaline aqueous solution in the step (1), and the concentration of the KOH is 0-5.35 mol/kg-1。
Preferably, the concentration of the chitosan in the chitosan solution obtained in the step (2) is 0.1-15%.
Preferably, the derivatizing reagent of step (3) comprises: halogenated acids, salts of halogenated acids, epoxy compounds, acid chlorides, acid anhydrides, sulfates, haloalkanes, and α, β -unsaturated compounds.
Preferably: the derivatization reagent in the step (3) comprises: one or more of chloroacetic acid, chloropropionic acid, chlorobutyric acid, sodium chloroacetate, ethylene oxide, 2, 3-epoxypropyltrimethylammonium chloride, 2, 3-epoxypropyltripropylammonium chloride, ethyl chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride, dimethyl sulfate, p-methylbenzenesulfonyl chloride, succinic anhydride, maleic anhydride, acrylamide and acrylonitrile.
Preferably, the chitosan derivative obtained in step (3) comprises acid esterification, carboxyalkylation, hydroxylation, alkylation, acylation and quaternary ammonium salt derivatives.
Preferably, in the step (3), the mass ratio of the derivatization reagent to the chitosan monomer unit is 0.1: 1-50: 1, the reaction temperature is-15-60 ℃, and the substitution degree of the obtained derivative is 0.05-2.92.
According to the preparation method, the chitosan derivative can be efficiently and homogeneously prepared in a weak base system, the operation is simple and convenient, the reaction is controllable, the energy is saved, the environment is protected, and the multifunctional chitosan derivative can be efficiently prepared by changing different derivatization reagents.
Detailed Description
The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.
Example 1
Adding chitosan to the mixture to the concentration of 0.5 mol/kg-11 mol/kg of potassium bicarbonate-10 mol/kg of urea and potassium hydroxide-1Stirring the aqueous solution for 30min at 0 ℃, obtaining a chitosan solution with the concentration of 2.0 wt% after centrifugal deaeration, adding sodium chloroacetate into the obtained chitosan solution according to the mass ratio of the sodium chloroacetate to the chitosan monomer unit of 1:1, stirring the solution for 24h at 0 ℃, dialyzing, purifying and freeze-drying the solution to obtain the carboxymethyl chitosan with the degree of substitution of 0.28.
Example 2
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-11 mol/kg of potassium bicarbonate-10 mol/kg of urea and potassium hydroxide-1Stirring in water solution at 0 deg.C for 30min, and centrifuging to remove air bubbles to obtain a solution with a concentration of2 wt% of chitosan solution, adding sodium chloroacetate into the obtained chitosan solution according to the mass ratio of the sodium chloroacetate to the chitosan monomer unit of 1:1, stirring for 24h at 30 ℃, dialyzing, purifying and freeze-drying to obtain the carboxymethyl chitosan, wherein the substitution degree is 0.58.
Example 3
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-1Potassium bicarbonate-1 mol/kg-10 mol/kg of urea and potassium hydroxide-1Stirring the aqueous solution for 30min at 0 ℃, obtaining a chitosan solution with the concentration of 0.5 wt% after centrifugal deaeration, adding sodium chloroacetate into the obtained chitosan solution according to the mass ratio of the sodium chloroacetate to the chitosan monomer unit of 1:1, stirring the solution for 24h at 30 ℃, dialyzing, purifying and freeze-drying the solution to obtain the carboxymethyl chitosan with the degree of substitution of 0.35.
Example 4
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-11 mol/kg of potassium bicarbonate-1And (2) in the urea aqueous solution, adjusting the pH value of the solution to 12 by using potassium hydroxide, stirring the solution for 30min at 0 ℃, performing centrifugal deaeration to obtain a chitosan solution with the concentration of 2 wt%, adding sodium chloroacetate into the obtained chitosan solution according to the mass ratio of the sodium chloroacetate to the chitosan monomer unit of 1:1, stirring the solution for 24h at 30 ℃, dialyzing, purifying and freeze-drying the solution to obtain the carboxymethyl chitosan, wherein the substitution degree is 0.59.
Example 5
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-11 mol/kg of potassium bicarbonate-10.891 mol/kg of urea and potassium hydroxide-1Stirring the aqueous solution for 30min at 0 ℃, obtaining a chitosan solution with the concentration of 2 wt% after centrifugal deaeration, adding sodium chloroacetate into the obtained chitosan solution according to the mass ratio of the sodium chloroacetate to the chitosan monomer unit of 1:1, stirring the solution for 24h at 30 ℃, dialyzing, purifying and freeze-drying the solution to obtain the carboxymethyl chitosan with the degree of substitution of 0.65.
Example 6
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-11 mol/kg of potassium bicarbonate-11.78 mol/kg of urea and potassium hydroxide-1Stirring the aqueous solution for 30min at 0 ℃, obtaining a chitosan solution with the concentration of 2 wt% after centrifugal deaeration, adding sodium chloroacetate into the obtained chitosan solution according to the mass ratio of the sodium chloroacetate to the chitosan monomer unit of 1:1, stirring the solution for 24h at 30 ℃, dialyzing, purifying and freeze-drying the solution to obtain the carboxymethyl chitosan with the degree of substitution of 0.78.
Example 7
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-11 mol/kg of potassium bicarbonate-12.67 mol/kg of urea and potassium hydroxide-1Stirring the aqueous solution for 30min at 0 ℃, obtaining a chitosan solution with the concentration of 2 wt% after centrifugal deaeration, adding sodium chloroacetate into the obtained chitosan solution according to the mass ratio of the sodium chloroacetate to the chitosan monomer unit of 1:1, stirring the solution for 24h at 30 ℃, dialyzing, purifying and freeze-drying the solution to obtain the carboxymethyl chitosan with the degree of substitution of 0.81.
Example 8
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-11 mol/kg of potassium bicarbonate-15.35 mol/kg of urea and potassium hydroxide-1Stirring the aqueous solution for 30min at 0 ℃, obtaining a chitosan solution with the concentration of 2 wt% after centrifugal deaeration, adding sodium chloroacetate into the obtained chitosan solution according to the mass ratio of the sodium chloroacetate to the chitosan monomer unit of 1:1, stirring the solution for 24h at 30 ℃, dialyzing, purifying and freeze-drying the solution to obtain the carboxymethyl chitosan with the degree of substitution of 0.75.
Example 9
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-1Ammonium bicarbonate-1 mol/kg-1Stirring for 30min at 0 ℃ in urea aqueous solution, obtaining a chitosan solution with the concentration of 2 wt% after centrifugal deaeration, adding sodium chloroacetate into the obtained chitosan solution according to the mass ratio of the sodium chloroacetate to the chitosan monomer unit of 1:1, stirring for 24h at 30 ℃, dialyzing, purifying and freeze-drying to obtain the carboxymethyl chitosan with the degree of substitution of 0.64.
Example 10
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-1Magnesium bicarbonate of-1 mol·kg-1Stirring for 30min at 0 ℃ in urea aqueous solution, obtaining a chitosan solution with the concentration of 2 wt% after centrifugal deaeration, adding sodium chloroacetate into the obtained chitosan solution according to the mass ratio of the sodium chloroacetate to the chitosan monomer unit of 1:1, stirring for 24h at 30 ℃, dialyzing, purifying and freeze-drying to obtain the carboxymethyl chitosan with the degree of substitution of 0.64.
Example 11
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-11 mol/kg of lithium bicarbonate-1Stirring for 30min at 0 ℃ in urea aqueous solution, obtaining a chitosan solution with the concentration of 2 wt% after centrifugal deaeration, adding sodium chloroacetate into the obtained chitosan solution according to the mass ratio of the sodium chloroacetate to the chitosan monomer unit of 1:1, stirring for 24h at 30 ℃, dialyzing, purifying and freeze-drying to obtain the carboxymethyl chitosan with the degree of substitution of 0.64.
Example 12
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-1Sodium bicarbonate-1 mol/kg-1Stirring for 30min at 0 ℃ in urea aqueous solution, obtaining a chitosan solution with the concentration of 2 wt% after centrifugal deaeration, adding sodium chloroacetate into the obtained chitosan solution according to the mass ratio of the sodium chloroacetate to the chitosan monomer unit of 1:1, stirring for 24h at 30 ℃, dialyzing, purifying and freeze-drying to obtain the carboxymethyl chitosan with the degree of substitution of 0.64.
Example 13
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-11 mol/kg of lithium bicarbonate-1And (2) stirring the solution for 30min at 0 ℃ in thiourea aqueous solution, performing centrifugal deaeration to obtain a chitosan solution with the concentration of 2 wt%, adding sodium chloroacetate into the obtained chitosan solution according to the mass ratio of the sodium chloroacetate to the chitosan monomer unit of 1:1, stirring the solution for 24h at 30 ℃, dialyzing, purifying and freeze-drying the solution to obtain the carboxymethyl chitosan with the degree of substitution of 0.63.
Example 14
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-1Ammonium bicarbonate-1 mol/kg-1Adding thiourea into water solution, stirring at 0 deg.C for 30minAnd (3) carrying out centrifugal deaeration to obtain a chitosan solution with the concentration of 2 wt%, adding sodium chloroacetate into the obtained chitosan solution according to the mass ratio of the sodium chloroacetate to the chitosan monomer unit of 1:1, stirring for 24h at 30 ℃, dialyzing, purifying and freeze-drying to obtain the carboxymethyl chitosan with the degree of substitution of 0.63.
Example 15
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-1Potassium bicarbonate-1 mol/kg-1Stirring the mixture for 30min at 0 ℃ in a urea aqueous solution, performing centrifugal deaeration to obtain a chitosan solution with the concentration of 2 wt%, adding sodium chloroacetate into the obtained chitosan solution according to the mass ratio of the sodium chloroacetate to the chitosan monomer unit of 40:1, stirring the mixture for 24h at 30 ℃, dialyzing, purifying and freeze-drying the mixture to obtain the carboxymethyl chitosan with the degree of substitution of 2.55.
Example 16
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-1Potassium bicarbonate-1 mol/kg-1Stirring for 30min at 0 ℃ in urea aqueous solution, obtaining a chitosan solution with the concentration of 2 wt% after centrifugal deaeration, adding the chitosan solution according to the mass ratio of ethylene oxide to chitosan monomer units of 0.5:1, stirring for 24h at-15 ℃, dialyzing, purifying and freeze-drying to obtain hydroxyethyl chitosan with the degree of substitution of 0.05.
Example 17
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-1Stirring potassium bicarbonate-1 mol.kg-1 urea aqueous solution at 0 ℃ for 30min, obtaining a chitosan solution with the concentration of 2 wt% after centrifugal deaeration, adding the chitosan solution obtained in the step (a) according to the mass ratio of ethylene oxide to chitosan monomer units of 0.5:1, stirring at 30 ℃ for 24h, dialyzing, purifying and freeze-drying to obtain hydroxyethyl chitosan with the degree of substitution of 0.25.
Example 18
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-1Ammonium bicarbonate-1 mol/kg-1In thiourea aqueous solution, stirring for 30min at 0 deg.C, centrifuging to defoam to obtain 2 wt% chitosan solution, according to the substance of ethylene oxide and chitosan monomer unitAdding the chitosan solution at the ratio of 0.5:1, stirring at 30 deg.C for 24 hr, dialyzing, purifying, and freeze drying to obtain hydroxyethyl chitosan with substitution degree of 0.25.
Example 19
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-11 mol/kg of lithium bicarbonate-1And (2) stirring the thiourea aqueous solution for 30min at 0 ℃, performing centrifugal deaeration to obtain a chitosan solution with the concentration of 2 wt%, adding the chitosan solution into the chitosan solution according to the mass ratio of ethylene oxide to chitosan monomer units of 0.5:1, stirring the mixture for 24h at 30 ℃, dialyzing, purifying and freeze-drying the mixture to obtain hydroxyethyl chitosan with the degree of substitution of 0.25.
Example 20
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-1Stirring potassium bicarbonate-1 mol.kg-1 urea aqueous solution at 0 ℃ for 30min, obtaining a chitosan solution with the concentration of 2 wt% after centrifugal deaeration, adding the chitosan solution obtained in the step (a) according to the mass ratio of ethylene oxide to chitosan monomer units of 2:1, stirring at 30 ℃ for 24h, dialyzing, purifying and freeze-drying to obtain hydroxyethyl chitosan with the degree of substitution of 0.76.
Example 21
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-1Stirring potassium bicarbonate-1 mol.kg-1 urea aqueous solution at 0 ℃ for 30min, obtaining a chitosan solution with the concentration of 2 wt% after centrifugal deaeration, adding the chitosan solution obtained in the step (1) according to the mass ratio of ethylene oxide to chitosan monomer units of 8:1, stirring at 30 ℃ for 24h, dialyzing, purifying and freeze-drying to obtain hydroxyethyl chitosan with the substitution degree of 1.2.
Example 22
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-1Stirring potassium bicarbonate-1 mol.kg-1 urea aqueous solution at 0 deg.C for 30min, centrifuging, defoaming to obtain 2 wt% chitosan solution, adding the chitosan solution according to the mass ratio of ethylene oxide to chitosan monomer unit of 24:1, stirring at 30 deg.C for 24h, dialyzing, purifying, and freeze drying to obtain hydroxyethyl chitosan with substitution degree ofIs 2.78.
Example 23
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-1Stirring potassium bicarbonate-1 mol kg-1 urea aqueous solution at 0 ℃ for 30min, obtaining a chitosan solution with the concentration of 2 wt% after centrifugal deaeration, adding the chitosan solution obtained in the step (1) according to the mass ratio of acrylamide to chitosan monomer units of 20:1, stirring at 20 ℃ for 12h, dialyzing, purifying and freeze-drying to obtain the propionamide chitosan with the substitution degree of 1.24.
Example 24
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-11 mol/kg of lithium bicarbonate-1And (2) stirring the thiourea aqueous solution for 30min at 0 ℃, performing centrifugal deaeration to obtain a chitosan solution with the concentration of 2 wt%, adding the chitosan solution into the chitosan solution according to the mass ratio of acrylamide to chitosan monomer units of 20:1, stirring the mixture for 12h at 20 ℃, dialyzing, purifying and freeze-drying the mixture to obtain the propionamide chitosan with the substitution degree of 1.23.
Example 25
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-1Stirring potassium bicarbonate-1 mol kg-1 urea aqueous solution for 30min at 0 ℃, obtaining chitosan solution with the concentration of 2 wt% after centrifugal deaeration, adding the chitosan solution obtained by the step (1) according to the mass ratio of 2, 3-epoxypropyltrimethylammonium chloride to chitosan monomer unit of 16:1, stirring for 36h at 0 ℃, dialyzing, purifying and freeze-drying to obtain quaternized chitosan with the substitution degree of 0.58.
Example 26
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-1Stirring potassium bicarbonate-1 mol kg-1 urea aqueous solution for 30min at 0 ℃, obtaining chitosan solution with the concentration of 2 wt% after centrifugal deaeration, adding the chitosan solution obtained by the step (1) according to the mass ratio of 2, 3-epoxypropyltrimethylammonium chloride to chitosan monomer unit of 16:1, stirring for 36h at 25 ℃, dialyzing, purifying and freeze-drying to obtain quaternized chitosan with the substitution degree of 0.88.
Example 27
The shellAdding polysaccharide to the solution to give a polysaccharide concentration of 0.8 mol/kg-11 mol/kg of lithium bicarbonate-1And (2) stirring the thiourea aqueous solution for 30min at 0 ℃, performing centrifugal deaeration to obtain a chitosan solution with the concentration of 2 wt%, adding the chitosan solution into the chitosan solution according to the mass ratio of the 2, 3-epoxypropyltrimethylammonium chloride to the chitosan monomer unit of 16:1, stirring the mixture for 36h at 25 ℃, dialyzing, purifying and freeze-drying the mixture to obtain the quaternized chitosan with the substitution degree of 0.86.
Example 28
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-1Stirring potassium bicarbonate-1 mol kg-1 urea aqueous solution for 30min at 0 ℃, obtaining chitosan solution with the concentration of 2 wt% after centrifugal deaeration, adding the chitosan solution obtained by the step (1) according to the mass ratio of 2, 3-epoxypropyltrimethylammonium chloride to chitosan monomer units of 32:1, stirring for 36h at 25 ℃, dialyzing, purifying and freeze-drying to obtain quaternized chitosan with the substitution degree of 1.30.
Example 29
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-1Stirring potassium bicarbonate-1 mol.kg-1 urea aqueous solution for 30min at 0 ℃, obtaining chitosan solution with the concentration of 2 wt% after centrifugal deaeration, adding the chitosan solution obtained in the step (1: 5) according to the mass ratio of dimethyl sulfate to chitosan monomer units, stirring and reacting for 36h at-10 ℃, dialyzing, purifying and freeze-drying to obtain the methyl chitosan with the degree of substitution of 0.39.
Example 30
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-1Stirring potassium bicarbonate-1 mol.kg-1 urea aqueous solution for 30min at 0 ℃, obtaining chitosan solution with the concentration of 2 wt% after centrifugal deaeration, adding the chitosan solution obtained in the step (1) according to the mass ratio of dimethyl sulfate to chitosan monomer units of 10:1, stirring and reacting for 36h at-10 ℃, dialyzing, purifying and freeze-drying to obtain the methyl chitosan with the degree of substitution of 0.69.
Example 31
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-1Dissolving potassium bicarbonate-1 mol kg-1 urea in waterStirring the solution at 0 ℃ for 30min, obtaining a chitosan solution with the concentration of 2 wt% after centrifugal deaeration, adding the chitosan solution into the obtained solution according to the mass ratio of dimethyl sulfate to chitosan monomer units of 15:1, stirring the mixture at 25 ℃ for reaction for 36h, dialyzing, purifying and freeze-drying the mixture to obtain the methyl chitosan with the degree of substitution of 1.43.
Example 32
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-1Stirring potassium bicarbonate-1 mol.kg-1 urea aqueous solution for 30min at 0 ℃, obtaining chitosan solution with the concentration of 2 wt% after centrifugal deaeration, adding the chitosan solution obtained in the step (1) according to the mass ratio of dimethyl sulfate to chitosan monomer units of 40:1, stirring and reacting for 36h at-10 ℃, dialyzing, purifying and freeze-drying to obtain the methyl chitosan, wherein the degree of substitution is 2.92.
Example 33
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-1Stirring potassium bicarbonate-1 mol kg-1 urea aqueous solution at 0 ℃ for 30min, obtaining chitosan solution with the concentration of 2 wt% after centrifugal deaeration, adding the chitosan solution obtained in the step (1: 30) according to the mass ratio of succinic anhydride to chitosan monomer unit, stirring for 24h at 25 ℃, dialyzing, purifying and freeze-drying to obtain the chitosan succinate with the substitution degree of 2.51.
Example 34
Adding chitosan to the mixture to a concentration of 3.57 mol/kg-1Stirring potassium hydroxide and 1 mol/kg-1 urea aqueous solution at-30 ℃ for 30min, centrifuging and defoaming to obtain a chitosan solution with the concentration of 2 wt%, adding the chitosan solution into the chitosan solution according to the mass ratio of succinic anhydride to chitosan monomer units of 30:1, stirring at 25 ℃ for 24h, dialyzing, purifying and freeze-drying to obtain the chitosan succinate with the degree of substitution of 0.23.
Example 35
Adding chitosan to the mixture to the concentration of 0.5 mol/kg-1Dissolving potassium bicarbonate-1 mol/kg-1 urea aqueous solution at 0 deg.C for 30min under stirring, and centrifuging to remove air to obtain 2 wt% chitosan solution. According to maleic anhydride and chitosan monoAdding the chitosan solution at a ratio of 50:1, stirring at 30 deg.C for 24 hr, dialyzing, purifying, and freeze drying to obtain chitosan maleate with substitution degree of 2.33.
Example 36
Adding chitosan to the mixture to a concentration of 3.57 mol/kg-1Stirring potassium hydroxide and 1 mol/kg-1 urea aqueous solution for 30min at the temperature of minus 30 ℃, obtaining a chitosan solution with the concentration of 2 wt% after centrifugal deaeration, adding the chitosan solution into the chitosan solution according to the mass ratio of maleic anhydride to chitosan monomer units of 50:1, stirring for 24h at the temperature of 30 ℃, dialyzing, purifying and freeze-drying to obtain the chitosan succinate with the degree of substitution of 0.21.
Example 37
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-11 mol/kg of lithium bicarbonate-1And (3) dissolving the thiourea in the aqueous solution by stirring at 0 ℃ for 30min, and obtaining a chitosan solution with the concentration of 2 wt% after centrifugal deaeration. Adding the chitosan solution into the mixture according to the mass ratio of maleic anhydride to chitosan monomer unit of 50:1, stirring for 24h at 30 ℃, dialyzing, purifying and freeze-drying to obtain the maleic acid chitosan ester with the substitution degree of 2.3.
Example 38
Adding chitosan into 0.8 mol/kg-1 lithium bicarbonate-1 mol/kg-1 urea aqueous solution, stirring at 0 deg.C for 30min for dissolving, and centrifuging to remove foam to obtain 2 wt% chitosan solution. Sequentially adding the chitosan solution obtained above according to the mass ratio of sodium chloroacetate to chitosan monomer unit of 10:1 and the mass ratio of 2, 3-epoxypropyltrimethylammonium chloride to chitosan monomer unit of 10:1, stirring at 25 ℃ for 30h, adjusting the pH value of the solution to about 7, dialyzing, purifying, and freeze-drying to obtain carboxymethyl quaternized chitosan with the degree of substitution of 0.58 and 0.68 respectively.
Example 39
Adding chitosan to the mixture to the concentration of 0.8 mol/kg-11 mol/kg of lithium bicarbonate-1And (3) dissolving the thiourea in the aqueous solution by stirring at 0 ℃ for 30min, and obtaining a chitosan solution with the concentration of 2 wt% after centrifugal deaeration. In accordance withAdding the chitosan solution into sodium chloroacetate and chitosan monomer unit according to the weight ratio of 10:1 and the weight ratio of 2, 3-epoxypropyltrimethylammonium chloride to chitosan monomer unit of 10:1, stirring for 30h at 25 ℃, adjusting the pH value of the solution to about 7, dialyzing, purifying, and freeze-drying to obtain carboxymethyl quaternized chitosan with the degree of substitution of 0.56 and 0.68 respectively.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (8)
1. A method for homogeneously preparing chitosan derivatives based on a weak base system is characterized by comprising the following steps:
(1) preparing a weakly alkaline aqueous solution containing bicarbonate, a stabilizer and optionally KOH, wherein the concentration of the bicarbonate is 0.2-1.5 mol.kg-1The stabilizing agent is one or two of urea and thiourea, and the concentration of the urea is 0.1-5 mol-1The concentration of thiourea is 0.3-1.2 mol.kg-1The concentration of KOH is 0 to 5.35mol-1The balance being water;
(2) adding chitosan into the alkalescent aqueous solution obtained in the step (1), continuously stirring for more than 30 minutes at the freezing point-35 ℃ to dissolve the chitosan, and defoaming to obtain a transparent chitosan solution;
(3) and (3) adding a derivatization reagent into the chitosan solution obtained in the step (2) below the gelation temperature, stirring for reaction for not less than 1h, adjusting the pH of the solution to be neutral after the reaction is finished, dialyzing, purifying and freeze-drying to obtain the chitosan derivative.
2. The method of claim 1, wherein the bicarbonate comprises one or more of an alkali metal bicarbonate, an alkaline earth metal bicarbonate, and ammonium bicarbonate.
3. The method of claim 1, wherein the bicarbonate is one or more of sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, and magnesium bicarbonate.
4. The method according to claim 1, wherein the concentration of chitosan in the chitosan solution obtained in step (2) is 0.1-15%.
5. The method of claim 1, wherein the derivatizing agent of step (3) comprises: halogenated acids, salts of halogenated acids, epoxy compounds, acid chlorides, acid anhydrides, sulfates, haloalkanes, and α, β -unsaturated compounds.
6. The method of claim 1, wherein: the derivatization reagent in the step (3) comprises: one or more of chloroacetic acid, chloropropionic acid, chlorobutyric acid, sodium chloroacetate, ethylene oxide, 2, 3-epoxypropyltrimethylammonium chloride, 2, 3-epoxypropyltripropylammonium chloride, ethyl chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride, dimethyl sulfate, p-methylbenzenesulfonyl chloride, succinic anhydride, maleic anhydride, acrylamide and acrylonitrile.
7. The method of claim 1, wherein: the chitosan derivative obtained in the step (3) comprises acid esterification, carboxyl alkylation, hydroxylation, alkylation, acylation and quaternary ammonium salt derivatives.
8. The method of claim 1, wherein in the step (3), the mass ratio of the derivatization reagent to the chitosan monomer unit is 0.1: 1-50: 1, the reaction temperature is-15 ℃ to 60 ℃, and the degree of substitution of the derivative is in the range of 0.05 to 2.88.
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