阅读说明：本技术 一种聚l-谷氨酸-聚丙烯酸酯可降解水凝胶及其制法 (Poly-L-glutamic acid-polyacrylate degradable hydrogel and preparation method thereof ) 是由 夏克春 于 2020-05-11 设计创作，主要内容包括：本发明涉及水凝胶技术领域,且公开了一种聚L-谷氨酸-聚丙烯酸酯可降解水凝胶,包括以下配方原料及组分：壳聚糖接枝聚L-谷氨酸、聚乙二醇丙烯酸酯、催化剂、缩合剂、光引发剂。该一种聚L-谷氨酸-聚丙烯酸酯可降解水凝胶,壳聚糖接枝聚L-谷氨酸与聚乙二醇丙烯酸酯进行缩合反应,得到聚L-谷氨酸-丙烯酸酯嵌段共聚物,通过光引发剂,引发端烯基进行自由基聚合过程,制备得到聚L-谷氨酸-聚丙烯酸酯水凝胶材料,将具有优异的生物相容性和生物降解性的聚L-谷氨酸和壳聚糖引入聚丙烯酸酯的分子链中,使聚L-谷氨酸-聚丙烯酸酯水凝胶材料很容易被生物降解,并且赋予了水凝胶材料良好的生物相容性。(The invention relates to the technical field of hydrogel, and discloses poly-L-glutamic acid-polyacrylate degradable hydrogel which comprises the following formula raw materials and components: chitosan grafted poly-L-glutamic acid, polyethylene glycol acrylate, a catalyst, a condensing agent and a photoinitiator. According to the poly-L-glutamic acid-polyacrylate degradable hydrogel, chitosan grafted poly-L-glutamic acid and polyethylene glycol acrylate are subjected to condensation reaction to obtain a poly-L-glutamic acid-acrylate block copolymer, a terminal alkenyl group is initiated to perform a free radical polymerization process through a photoinitiator to prepare a poly-L-glutamic acid-polyacrylate hydrogel material, and poly-L-glutamic acid and chitosan with excellent biocompatibility and biodegradability are introduced into a molecular chain of polyacrylate, so that the poly-L-glutamic acid-polyacrylate hydrogel material is easily biodegraded, and the hydrogel material is endowed with good biocompatibility.)

1. The poly-L-glutamic acid-polyacrylate degradable hydrogel comprises the following raw materials and components, and is characterized in that: the chitosan grafted poly-L-glutamic acid, polyethylene glycol acrylate, a catalyst, a condensing agent and a photoinitiator are mixed according to a mass ratio of 10-40:100:15-50:3-10: 0.8-1.5.

2. The degradable hydrogel of poly-L-glutamic acid-polyacrylate of claim 1, wherein: the catalyst is 4-dimethylamino pyridine, and the condensing agent is diisopropylcarbodiimide.

3. The degradable hydrogel of poly-L-glutamic acid-polyacrylate of claim 1, wherein: the photoinitiator is IRGACURE 2959.

4. The degradable hydrogel of poly-L-glutamic acid-polyacrylate of claim 1, wherein: the preparation method of the chitosan grafted poly-L-glutamic acid comprises the following steps:

(1) adding poly-L-glutamic acid, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and an activating agent N-hydroxysuccinimide into a distilled water solvent, heating to 40-60 ℃ for activation for 1-3h, adding chitosan, dropwise adding an acetic acid solution until the chitosan is dissolved, heating to 50-80 ℃, reacting for 10-20h, removing the solvent, washing and drying to prepare the chitosan grafted poly-L-glutamic acid.

5. The degradable hydrogel of poly-L-glutamic acid-polyacrylate of claim 4, wherein: the mass ratio of the poly-L-glutamic acid to the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride to the N-hydroxysuccinimide to the chitosan is 100:40-80:10-25: 80-130.

6. The degradable hydrogel of poly-L-glutamic acid-polyacrylate of claim 1, wherein: the preparation method of the poly-L-glutamic acid-polyacrylate degradable hydrogel comprises the following steps:

(1) adding chitosan grafted poly-L-glutamic acid, polyethylene glycol acrylate, a catalyst 4-dimethylaminopyridine and a condensing agent diisopropylcarbodiimide into an N, N-dimethylformamide solvent, heating to 40-80 ℃, reacting for 48-72h, precipitating, filtering, washing and drying to prepare a poly-L-glutamic acid-acrylate segmented copolymer;

(2) adding a poly-L-glutamic acid-acrylate segmented copolymer and a photoinitiator IRGACURE 2959 into an N, N-dimethylformamide solvent, performing irradiation reaction for 3-8h under an ultraviolet lamp, and performing precipitation, filtration and dialysis to remove impurities to prepare the poly-L-glutamic acid-polyacrylate degradable hydrogel.

Technical Field

The invention relates to the technical field of hydrogel, in particular to poly-L-glutamic acid-polyacrylate degradable hydrogel and a preparation method thereof.

Background

The hydrogel has strong hydrophilicity, a three-dimensional network gel structure can be quickly swelled in water, a large volume of water can be kept in a swelled state without dissolving, and the hydrogel has excellent water absorption and water retention properties.

The poly-L-glutamic acid hydrogel material has good biocompatibility and biodegradability, and the degradation product is L-glutamic acid which can be absorbed by human body, so that the poly-L-glutamic acid hydrogel material has important application in the aspects of medical drug carriers, biological materials and the like.

Polyacrylate hydrogel as a synthetic polymer hydrogel material with high water absorption and high water retention has wide application in cosmetic facial masks, analgesic patches, agricultural films, building dust depressants, food preservatives and the like, but the traditional polyacrylate hydrogel has poor biocompatibility and biodegradability, is difficult to degrade in natural environment and causes serious pollution to the environment, thereby limiting the practical application of the polyacrylate hydrogel.

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides a poly-L-glutamic acid-polyacrylate degradable hydrogel and a preparation method thereof, and solves the problem of poor biodegradability of polyacrylate hydrogel.

(II) technical scheme

In order to achieve the purpose, the invention provides the following technical scheme: a poly-L-glutamic acid-polyacrylate degradable hydrogel comprises the following raw materials and components: the chitosan grafted poly-L-glutamic acid, polyethylene glycol acrylate, a catalyst, a condensing agent and a photoinitiator are mixed according to a mass ratio of 10-40:100:15-50:3-10: 0.8-1.5.

Preferably, the catalyst is 4-dimethylaminopyridine and the condensing agent is diisopropylcarbodiimide.

Preferably, the photoinitiator is IRGACURE 2959.

Preferably, the preparation method of the chitosan grafted poly-L-glutamic acid comprises the following steps:

(1) adding a distilled water solvent, poly-L-glutamic acid, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and an activating agent N-hydroxysuccinimide into a reaction bottle, placing the reaction bottle in a constant-temperature water bath, heating the reaction bottle to 40-60 ℃, stirring and activating the reaction bottle at a constant speed for 1-3 hours, adding chitosan and slowly dropwise adding an acetic acid solution until the chitosan is dissolved, heating the reaction bottle to 50-80 ℃, stirring the reaction bottle at a constant speed for 10-20 hours, drying the solution in vacuum to remove the solvent, washing a solid product by using distilled water and a dilute acetic acid solution, and fully drying the solid product to prepare the chitosan grafted poly-L-glutamic acid.

Preferably, the mass ratio of the poly-L-glutamic acid, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, the N-hydroxysuccinimide and the chitosan is 100:40-80:10-25: 80-130.

Preferably, the preparation method of the poly-L-glutamic acid-polyacrylate degradable hydrogel comprises the following steps:

(1) adding N, N-dimethylformamide solvent, chitosan grafted poly-L-glutamic acid and polyethylene glycol acrylate into a reaction bottle, stirring and dissolving, then adding catalyst 4-dimethylaminopyridine and condensing agent diisopropylcarbodiimide, placing the mixture into a constant-temperature water bath kettle, heating to 40-80 ℃, reacting for 48-72h, placing the reaction bottle into an ice water bath for cooling, adding distilled water until a large amount of precipitate is washed out, filtering to remove the solvent, washing a solid product by using distilled water and diethyl ether, and fully drying to prepare the poly-L-glutamic acid-acrylate block copolymer.

(2) Adding an N, N-dimethylformamide solvent, a poly-L-glutamic acid-acrylate block copolymer and an IRGACURE 2959 photoinitiator into a reaction bottle, irradiating and reacting for 3-8h under an ultraviolet lamp, placing the reaction bottle in an ice-water bath, adding distilled water until a large amount of precipitates are separated out, filtering to remove the solvent, and dialyzing and removing impurities from a solid product by using the distilled water to prepare the poly-L-glutamic acid-polyacrylate degradable hydrogel.

(III) advantageous technical effects

Compared with the prior art, the invention has the following beneficial technical effects:

the poly-L-glutamic acid-polyacrylate degradable hydrogel is prepared by taking 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide as activating agents, activating carboxyl of poly-L-glutamic acid, reacting with amino of chitosan to obtain chitosan grafted poly-L-glutamic acid, then taking 4-dimethylaminopyridine as a catalyst and diisopropyl carbodiimide as a condensing agent to perform condensation reaction on hydroxyl of polyethylene glycol acrylate and the chitosan grafted poly-L-glutamic acid to obtain a poly-L-glutamic acid-acrylate block copolymer, finally taking IRGACURE 2959 as a photoinitiator to perform a free radical polymerization process on terminal alkenyl to obtain a poly-L-glutamic acid-polyacrylate hydrogel material, the poly-L-glutamic acid and the chitosan are introduced into the molecular chain of the polyacrylate, the poly-L-glutamic acid and the chitosan have excellent biocompatibility and biodegradability, so that the poly-L-glutamic acid-polyacrylate hydrogel material is easily biodegraded, the hydrogel material has good biocompatibility, and the poly-L-glutamic acid-polyacrylate degradable hydrogel has wide potential application values in the aspects of biomedical materials, drug release carriers, tissue engineering application and the like.

Detailed Description

To achieve the above object, the present invention provides the following embodiments and examples: a poly-L-glutamic acid-polyacrylate degradable hydrogel comprises the following raw materials and components: the chitosan grafted poly-L-glutamic acid, polyethylene glycol acrylate, a catalyst 4-dimethylaminopyridine, a condensing agent diisopropylcarbodiimide and a photoinitiator IRGACURE 2959 in a mass ratio of 10-40:100:15-50:3-10: 0.8-1.5.

The preparation method of the chitosan grafted poly-L-glutamic acid comprises the following steps:

(1) adding distilled water solvent, poly-L-glutamic acid, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and activating agent N-hydroxysuccinimide into a reaction bottle, placing the reaction bottle in a constant temperature water bath, heating the reaction bottle to 40-60 ℃, stirring and activating the reaction bottle at a constant speed for 1-3h, adding chitosan and slowly dropwise adding an acetic acid solution, wherein the mass ratio of the poly-L-glutamic acid to the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride to the N-hydroxysuccinimide to the chitosan is 100:40-80:10-25:80-130 until the chitosan is dissolved, heating the reaction bottle to 50-80 ℃, stirring the reaction bottle at a constant speed for 10-20h, drying the solution in vacuum to remove the solvent, washing a solid product by using distilled water and a dilute acetic acid solution, and fully drying to prepare the chitosan grafted poly-L-glutamic acid.

The preparation method of the poly-L-glutamic acid-polyacrylate degradable hydrogel comprises the following steps:

(1) adding N, N-dimethylformamide solvent, chitosan grafted poly-L-glutamic acid and polyethylene glycol acrylate into a reaction bottle, stirring and dissolving, then adding catalyst 4-dimethylaminopyridine and condensing agent diisopropylcarbodiimide, placing the mixture into a constant-temperature water bath kettle, heating to 40-80 ℃, reacting for 48-72h, placing the reaction bottle into an ice water bath for cooling, adding distilled water until a large amount of precipitate is washed out, filtering to remove the solvent, washing a solid product by using distilled water and diethyl ether, and fully drying to prepare the poly-L-glutamic acid-acrylate block copolymer.

(2) Adding an N, N-dimethylformamide solvent, a poly-L-glutamic acid-acrylate block copolymer and an IRGACURE 2959 photoinitiator into a reaction bottle, irradiating and reacting for 3-8h under an ultraviolet lamp, placing the reaction bottle in an ice-water bath, adding distilled water until a large amount of precipitates are separated out, filtering to remove the solvent, and dialyzing and removing impurities from a solid product by using the distilled water to prepare the poly-L-glutamic acid-polyacrylate degradable hydrogel.