CN109776808B - Preparation method of water-soluble modified chitosan - Google Patents
Preparation method of water-soluble modified chitosan Download PDFInfo
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- CN109776808B CN109776808B CN201910105830.3A CN201910105830A CN109776808B CN 109776808 B CN109776808 B CN 109776808B CN 201910105830 A CN201910105830 A CN 201910105830A CN 109776808 B CN109776808 B CN 109776808B
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Abstract
The invention discloses a preparation method of water-soluble modified chitosan, which mainly comprises the following steps: firstly, preparing quaternized chitosan; simultaneously preparing carboxyl-terminated polyoxazoline by cationic ring-opening polymerization; then grafting carboxyl-terminated polyoxazoline on the quaternized chitosan through amidation reaction, thereby preparing the water-soluble modified chitosan. The water-soluble modified chitosan has the characteristics of antibiosis, anti-adhesion and excellent biocompatibility.
Description
Technical Field
The invention belongs to the field of chitosan modification, and particularly relates to a preparation method of water-soluble modified chitosan.
Background
Chitosan is the second largest biological macromolecule second to cellulose in nature, is widely applied in industrialization, and has biocompatibility, hemostatic property, antibacterial property and wound healing promoting ability. However, pure chitosan has poor water solubility and antibacterial performance, and various chitosan derivatives prepared by modifying chitosan have certain antibacterial performance, wherein the antibacterial performance of quaternized chitosan is obviously superior to that of pure chitosan and other chitosan derivatives. In addition, the quaternization of the chitosan can also obviously improve the water solubility of the chitosan and endow the chitosan with more efficient and more environment-friendly post-modification capability.
Polyoxazoline (POx) as a polymer with a polypeptide-like structure has the advantages of good biocompatibility, low cytotoxicity, extremely strong hydrophilicity, protein adhesion resistance and the like, and is widely used in the field of medical biomaterials such as targeted drug loading and the like. The carboxyl-terminated polyoxazoline can be grafted to the chitosan through amidation reaction, so that the water solubility, the anti-adhesion performance and the biocompatibility of the quaternized chitosan are improved.
The water-soluble modified chitosan has the characteristics of antibacterial and anti-adhesion functions and excellent biocompatibility, and is expected to be used in the fields of medical biomaterials such as preparation of surface interface functionalized coatings, nano-micelles, drug loading and the like.
Disclosure of Invention
The invention aims to optimize the existing material and provide a preparation method of water-soluble modified chitosan, which can improve the water solubility and the antibacterial performance of the chitosan through quaternization of the chitosan, and improve the water solubility, the anti-adhesion performance and the biocompatibility of the chitosan through polyoxazoline treatment of the chitosan, thereby obtaining the material with good water solubility, antibacterial performance, anti-adhesion performance and biocompatibility.
The technical scheme of the invention is as follows:
a preparation method of water-soluble modified chitosan comprises the following steps: firstly, preparing quaternized chitosan and carboxyl-terminated polyoxazoline, and then grafting the carboxyl-terminated polyoxazoline onto the quaternized chitosan through amidation reaction, thereby obtaining the water-soluble modified chitosan.
Further, the preparation method of the quaternized chitosan comprises the following steps: and adding glycidol trimethyl ammonium chloride into the chitosan acetic acid aqueous solution, and heating for reaction for 3-10 hours to obtain the quaternized chitosan.
Further, the preparation steps of the carboxyl-terminated polyoxazoline are as follows: firstly, under the anhydrous and anaerobic heating condition of 70 ℃, 1, 4-dibromo-2-butylene is added for catalysis, the cationic ring-opening polymerization of monomer 2-methyl-2-oxazoline is carried out in an ultra-dry acetonitrile solvent, and then acrylic acid is added for termination reaction, so as to obtain the end-carboxylated polyoxazoline.
Further, the amidation reaction steps are as follows: firstly, quaternary ammonium chitosan and carboxyl-terminated polyoxazoline are dissolved in aqueous solution, and then 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide is added for reaction for 6-12 hours.
The invention is realized by the following steps:
(1) preparing a chitosan acetic acid aqueous solution with the mass fraction of 1-5%;
(2) adding glycidol trimethyl ammonium chloride into chitosan acetic acid water solution, and heating for reaction for 3-10 hours;
(3) simultaneously adding 1, 4-dibromo-2-butylene into an ultra-dry acetonitrile solvent for catalysis, carrying out cationic ring-opening polymerization on monomer 2-methyl-2-oxazoline, and then adding acrylic acid for terminating the reaction;
(4) and (3) adding the carboxyl-terminated polyoxazoline prepared in the step (3) into the quaternized chitosan prepared in the step (2), and further performing amidation reaction.
The water-soluble modified chitosan obtained by the method has the functions of antibiosis and adhesion resistance and has excellent biocompatibility.
Compared with the prior art, the invention has the following advantages:
1) according to the invention, the chitosan is modified by quaternization, and the quaternary ammonium salt group is grafted to the chitosan by utilizing the ring-opening reaction of the active amino group on the chitosan and the epoxy group, so that the water solubility and the antibacterial property of the chitosan can be improved.
2) The invention carries out polyoxazoline reaction on chitosan, utilizes amidation reaction of active amino on the chitosan and terminal carboxyl on modified polyoxazoline to graft carboxyl-terminated polyoxazoline onto the chitosan, and can improve the water solubility, the anti-adhesion property and the biocompatibility of the chitosan.
Drawings
FIG. 1 is a schematic representation of the reaction process of quaternized chitosan of the present invention and chitosan grafted with carboxylated polyoxazoline at the end.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
The molecular weight of the adopted chitosan is 3-150 ten thousand, and the deacetylation degree is 50-95%.
Example 1:
1) the following solutions were prepared for use: 5% of chitosan acetic acid aqueous solution by mass;
2) adding 1.5mL of glycidol trimethyl ammonium chloride into 7mL of chitosan acetic acid aqueous solution, and heating for reaction for 10 hours;
3) simultaneously, under the anhydrous and anaerobic heating condition of 70 ℃, 1, 4-dibromo-2-butylene is added into an ultra-dry acetonitrile solvent for catalysis, the cationic ring-opening polymerization of the monomer 2-methyl-2-oxazoline is carried out, and then acrylic acid is added for terminating the reaction;
4) adding the end-carboxylated polyoxazoline prepared in the step 3) into the quaternized chitosan prepared in the step 2), and performing amidation reaction to obtain the water-soluble modified chitosan.
Example 2:
1) preparing the following solutions with certain concentrations for standby: 1% of chitosan acetic acid aqueous solution;
2) 5mL of glycidol trimethyl ammonium chloride is added into 6mL of chitosan acetic acid aqueous solution, and the mixture is heated and reacted for 6 hours;
3) simultaneously, under the anhydrous and anaerobic heating condition of 70 ℃, 1, 4-dibromo-2-butylene is added into an ultra-dry acetonitrile solvent for catalysis, the cationic ring-opening polymerization of the monomer 2-methyl-2-oxazoline is carried out, and then acrylic acid is added for terminating the reaction;
4) adding the end-carboxylated polyoxazoline prepared in the step 3) into the quaternized chitosan prepared in the step 2), and performing amidation reaction to obtain the water-soluble modified chitosan.
Example 3:
1) preparing the following solutions with certain concentrations for standby: 2% of chitosan acetic acid aqueous solution;
2) adding 0.5mL of glycidol trimethyl ammonium chloride into 3mL of chitosan acetic acid aqueous solution, and heating for reaction for 3 hours;
3) simultaneously, under the anhydrous and anaerobic heating condition of 70 ℃, 1, 4-dibromo-2-butylene is added into an ultra-dry acetonitrile solvent for catalysis, the cationic ring-opening polymerization of the monomer 2-methyl-2-oxazoline is carried out, and then acrylic acid is added for terminating the reaction;
4) adding the end-carboxylated polyoxazoline prepared in the step 3) into the quaternized chitosan prepared in the step 2), and performing amidation reaction to obtain the water-soluble modified chitosan.
Claims (3)
1. The preparation method of the water-soluble modified chitosan is characterized by comprising the following steps: firstly, preparing quaternized chitosan; simultaneously preparing carboxyl-terminated polyoxazoline by cationic ring-opening polymerization; then grafting carboxyl-terminated polyoxazoline on the quaternized chitosan through amidation reaction so as to prepare water-soluble modified chitosan;
the preparation steps of the carboxyl-terminated polyoxazoline are as follows: firstly, under the anhydrous and anaerobic heating condition of 70 ℃, 1, 4-dibromo-2-butylene is added into an ultra-dry acetonitrile solvent for catalysis, the cationic ring-opening polymerization of monomer 2-methyl-2-oxazoline is carried out, and then acrylic acid is added for termination reaction, so as to obtain carboxyl-terminated polyoxazoline;
the amidation reaction steps are as follows: firstly, quaternary ammonium chitosan and carboxyl-terminated polyoxazoline are dissolved in aqueous solution, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide is added, and reaction is carried out for 6-12 hours.
2. The method for preparing water-soluble modified chitosan according to claim 1, wherein the method for preparing quaternized chitosan comprises the following steps: and adding glycidol trimethyl ammonium chloride into the chitosan acetic acid aqueous solution, and heating for reaction for 3-10 hours to obtain the quaternized chitosan.
3. The preparation method of the water-soluble modified chitosan according to claim 1, wherein the specific preparation steps are as follows:
(1) preparing a chitosan acetic acid aqueous solution with the mass fraction of 1% -5% for later use;
(2) adding glycidol trimethyl ammonium chloride into chitosan acetic acid aqueous solution, and heating for reaction for 3-10 hours to obtain quaternized chitosan;
(3) simultaneously adding 1, 4-dibromo-2-butylene into an ultra-dry acetonitrile solvent for catalysis, carrying out cationic ring-opening polymerization on monomer 2-methyl-2-oxazoline, and then adding acrylic acid to terminate the end capping to prepare carboxyl-terminated polyoxazoline;
(4) and (3) adding the end-carboxylated polyoxazoline prepared in the step (3) into the quaternized chitosan prepared in the step (2), and performing amidation reaction to obtain the water-soluble modified chitosan.
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| JP2003012806A (en) * | 2001-07-02 | 2003-01-15 | Hiroshi Takimoto | Biodegradable highly water-absorbing resin |
| CN101130574A (en) * | 2006-08-23 | 2008-02-27 | 中国科学院海洋研究所 | Chitosan quaternary ammonium salt, preparing method and application of the same |
| CN101353428B (en) * | 2008-07-15 | 2011-01-19 | 中山大学 | Cellulose derivative containing poly(2-ethyl-2-oxazoline) block and preparation thereof |
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Inventor after: Bao Xiaojiong Inventor after: Dong Xiaofei Inventor after: Liu Zhang Inventor after: Qiao Fenghui Inventor after: Jiang Zhiqi Inventor after: Jin Xiaoqiang Inventor after: Fu Beijia Inventor after: Hu Qiaoling Inventor after: Wang Zhengke Inventor before: Wang Zhengke Inventor before: Bao Xiaojiong Inventor before: Dong Xiaofei Inventor before: Liu Zhang Inventor before: Qiao Fenghui Inventor before: Jiang Zhiqi Inventor before: Jin Xiaoqiang Inventor before: Fu Beijia Inventor before: Hu Qiaoling |