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CN-122011433-A - Temperature-controlled hydrogel and preparation method thereof

CN122011433ACN 122011433 ACN122011433 ACN 122011433ACN-122011433-A

Abstract

The invention provides a temperature-controlled hydrogel and a preparation method thereof, which belong to the technical field of compositions of high molecular compounds, and the preparation method of the temperature-controlled hydrogel comprises the following steps of preparing polyglutamic acid-methacrylate copolymer, preparing composite chitosan and modifying fullerene with chitosan, mixing, wherein the swelling rate of the temperature-controlled hydrogel is 19.97-21.72g/g, the swelling rate of the hydrogel is high, the hydrophilicity of a hydrogel network is strong, the fullerene dispersibility is good, the biocompatibility is enhanced, the compression strength of the temperature-controlled hydrogel is 149.7-152.3kPa, the compression modulus is 25.9-28.6kPa, the fracture deformation is 70.5-73.1%, the mechanical property of the temperature-controlled hydrogel is excellent, and the critical dissolution temperature of the prepared hydrogel is 31.12-31.35 ℃.

Inventors

  • WANG MEIXIA
  • SUN JIANBO
  • TAN ZIJIE
  • TANG XUEMEI
  • SU YANCHUN

Assignees

  • 山东盈莱旺农业科技有限公司
  • 杜邦(天津)生物科技有限公司

Dates

Publication Date
20260512
Application Date
20260127

Claims (9)

  1. 1. The preparation method of the temperature-controlled hydrogel is characterized by comprising the following steps of preparing polyglutamic acid-methacrylate copolymer, preparing composite chitosan, modifying fullerene by chitosan and mixing; Adding fullerene into a container, sequentially adding concentrated nitric acid solution and concentrated sulfuric acid solution, refluxing and stirring for 10-12 hours at 65-75 ℃, washing, dialyzing and freeze-drying after stirring is finished to obtain purified fullerene, respectively adding the compound chitosan and the purified fullerene into a container containing deionized water to obtain purified fullerene solution and compound chitosan solution, respectively dripping the purified fullerene solution into the compound chitosan solution after ultrasonic oscillation of the two solutions, stirring and reacting for 8-10 hours, and filtering, washing and freeze-drying after the reaction is finished to obtain chitosan modified fullerene.
  2. 2. The method for preparing a temperature-controlled hydrogel according to claim 1, The mass ratio of the fullerene to the concentrated nitric acid solution to the concentrated sulfuric acid solution is 1:7-9:23-27; The mass ratio of the composite chitosan to the deionized water is 3-5:90-95; The mass ratio of the purified fullerene to the deionized water is 1-3:95-97; The dropping speed of the purified fullerene solution is 1mL/min; the mass ratio of the composite chitosan solution to the purified fullerene solution is 4-6:1; The mass concentration of the concentrated nitric acid solution is 96-98%, and the mass concentration of the concentrated sulfuric acid solution is 96-98%.
  3. 3. The method for preparing a temperature-controlled hydrogel according to claim 1, The method for preparing the polyglutamic acid-methacrylate copolymer comprises the steps of adding polyglutamic acid into a reaction container containing anhydrous dimethyl sulfoxide, stirring for 3-4h, adding a catalyst 4-dimethylaminopyridine and a condensing agent N, N-dicyclohexylcarbodiimide after stirring, stirring for 1-2h under the protection of nitrogen at the rotating speed of 30-50r/min, obtaining activated polyglutamic acid after stirring, raising the temperature of the container to 35-45 ℃, dropwise adding glycidyl methacrylate into the container, controlling the reaction temperature to 35-45 ℃ after dropwise adding, controlling the reaction time to 8-10h, and obtaining the polyglutamic acid-methacrylate copolymer after filtering, dialyzing, washing and drying.
  4. 4. A method for preparing a temperature-controlled hydrogel according to claim 3, The dropping speed of the glycidyl methacrylate is 1-2mL/min; the polyglutamic acid, anhydrous dimethyl sulfoxide, 4-dimethylaminopyridine and N, N-dicyclohexylcarbodiimide The mass ratio of (1.5-2.5:85-90:0.07-0.12:0.8-1.3); The mass ratio of the activated polyglutamic acid to the glycidyl methacrylate is 50-60:40-45.
  5. 5. The method for preparing a temperature-controlled hydrogel according to claim 1, The preparation method of the composite chitosan comprises the steps of adding chitosan powder into a reaction container containing acetic acid solution, uniformly stirring to form chitosan solution, sequentially adding phthalic anhydride and catalyst pyridine into the chitosan solution, controlling the reaction temperature of the container to be 55-65 ℃, reacting for 5-6 hours under the condition of avoiding light, and filtering, washing and freeze-drying after the reaction is finished to obtain the phthalic anhydride modified chitosan, namely the composite chitosan.
  6. 6. The method for preparing a temperature-controlled hydrogel according to claim 5, wherein, The mass concentration of the acetic acid solution is 2-3%, and the mass ratio of the chitosan powder to the acetic acid solution is 2-6:85.5-88; The mass ratio of the chitosan solution to the pyridine to the phthalic anhydride is 87.5-94:2-5:0.5-1.5.
  7. 7. The method for preparing a temperature-controlled hydrogel according to claim 1, The method for mixing the materials comprises the steps of adding diethyl acrylamide, polyglutamic acid-methacrylate copolymer and chitosan modified fullerene into a container containing deionized water, stirring uniformly to obtain a mixed solution, adding a cross-linking agent MBA and an initiator KPS into the mixed solution, performing ultrasonic treatment at 0-4 ℃, adding an accelerator TEMED after ultrasonic treatment is finished, controlling the polymerization time to be 6-8h, and after polymerization, pouring the polymerization solution into a mold, performing gelation molding at room temperature for 23-25h, immersing the demolded gel in pure water for 3-4 days after gelation, and obtaining the temperature-controlled hydrogel after immersion.
  8. 8. The method for preparing a temperature-controlled hydrogel according to claim 7, The mass ratio of the diethyl acrylamide to the polyglutamic acid-methacrylate copolymer to the chitosan modified fullerene to the deionized water is 8-12:3-5:0.5-2:81-88; the mass ratio of the cross-linking agent MBA to the initiator KPS to the mixed solution to the accelerator TEMED is 0.5-0.7:0.1-0.3:90-95:0.05-0.25; The mass ratio of the gel to the pure water after demolding is 6.5-9.5:90-95.
  9. 9. A temperature-controlled hydrogel prepared by the method of any one of claims 1-8.

Description

Temperature-controlled hydrogel and preparation method thereof Technical Field The invention provides a temperature-controlled hydrogel and a preparation method thereof, belonging to the technical field of compositions of high molecular compounds. Background The hydrogel is a three-dimensional network structure soft material constructed based on the functions of covalent bonds, ionic crosslinking, coordination complexing, molecular aggregation and the like, has solid appearance, flexible texture, high water absorbability and water insolubility, the water content of the hydrogel can exceed 90 percent, and the temperature control hydrogel is used as a functional branch of the hydrogel, is formed by crosslinking hydrophilic polymer chains to form a network skeleton and coating a large number of water molecules, and is characterized in that reversible sol-gel phase change can occur when the ambient temperature reaches a specific threshold value. The poly-N, N-diethyl acrylamide hydrogel (PDEA) is used as a temperature-sensitive water-soluble polymer, the critical solution temperature (LCST) of the polymer is about 31 ℃, the polymer is highly compatible with the temperature of a human body, the polymer has hydrophilic and hydrophobic groups, the volume phase transition can be triggered near the LCST to realize controllable release of a load, so that the polymer becomes an ideal carrier of a temperature-sensitive delivery system, however, the PDEA-based hydrogel still has inherent defects of insufficient mechanical strength, low load quantity and the like, the PDEA chain segment is strong in flexibility, chain segment recombination or breakage easily occurs under the action of external force, the whole anti-compression and anti-stretching capacity of the gel is poor, the strong hydrophilic groups of the hydrophilic monomers weaken the interaction of polymer chains, so that the crosslinking compactness is reduced, the mechanical strength of the hydrogel is finally reduced, the bonding site density on the PDEA molecular chain is lower, multi-point cooperative bonding is difficult to form, the molecular chain is stretched, and the limited bonding site is occupied and blocked by a large amount of water molecules, so that the effective contact probability with the load is greatly reduced, and the load quantity is reduced. In addition, the extremely light characteristic of the carbon nano tube not only can improve the bioavailability, but also can enhance the stability of the load and the mechanical strength of the hydrogel to a certain extent. However, the hydrogel containing the carbon nano tube generally has the problem of poor biocompatibility, namely the carbon nano tube is in a tubular nano structure, the edge of the tube wall has sharp characteristics, and mechanical damage is easily caused to contacted biological components; Tongyao Lin discloses a preparation method of a temperature-sensitive hydrogel, which improves the dispersibility of the carbon nanotubes by modifying the carbon nanotubes with chitosan, thereby improving the efficiency of delivering a load by the hydrogel and the biocompatibility （Lin T , Zhang J , Long H,etal.Temperature-Sensitive Hydrogels Containing CarboxylatedChitosan-Modified Carbon Nanotubes for Controlled Drug Release[J].[2025-12-15].）;, but the method of the above document has the defects that firstly carboxylated chitosan is adsorbed on the carbon nanotubes through electrostatic interaction, the binding force is weak, the separation of the chitosan from the carbon nanotubes is easy to be caused, the biocompatibility is improved to a limited extent, the carbon nanotubes are agglomerated after long-term standing, and interface defects are formed between the carbon nanotubes and a polymer matrix, so that the mechanical strength of the hydrogel is reduced. Disclosure of Invention Aiming at the defects existing in the prior art, the invention provides the temperature-control hydrogel and the preparation method thereof, and the hydrogel has good biocompatibility and high mechanical strength. In order to solve the technical problems, the invention adopts the following technical scheme: The preparation method of the temperature-controlled hydrogel comprises the following steps of preparing polyglutamic acid-methacrylate copolymer, preparing composite chitosan, modifying fullerene with chitosan, and mixing; Adding polyglutamic acid into a reaction container containing anhydrous dimethyl sulfoxide, stirring for 3-4 hours at the rotating speed of 30-50r/min, adding a catalyst 4-dimethylaminopyridine and a condensing agent N, N-dicyclohexylcarbodiimide after stirring, stirring for 1-2 hours at the rotating speed of 30-50r/min under the protection of nitrogen, obtaining activated polyglutamic acid after stirring, raising the temperature of the container to 35-45 ℃, dropwise adding glycidyl methacrylate into the container, controlling the reaction temperature to be 35-45 ℃ after dropwise addin