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CN-122011785-A - Bone glue base high-strength membrane material, preparation method and application

CN122011785ACN 122011785 ACN122011785 ACN 122011785ACN-122011785-A

Abstract

The invention discloses a bone glue base high-strength film material which comprises the following raw materials, by mass, 5-10 parts of bone glue, 1-5 parts of hydroxyl-terminated hyperbranched polyester and 85-95 parts of dispersion medium. The invention also discloses a preparation method of the bone glue base high-strength film material, which takes glycerol and maleic anhydride as raw materials, and the hydroxyl-terminated hyperbranched polyester is synthesized through esterification reaction, and then the hydroxyl-terminated hyperbranched polyester and bone glue are compounded through a solution blending-tape casting film forming process. The hydroxyl-terminated hyperbranched polyester and bone glue form multiple hydrogen bonding action between molecules, so that the strength of the film material is improved, meanwhile, the highly branched three-dimensional spherical structure of the hydroxyl-terminated hyperbranched polyester and bone glue generates a large amount of free volume between molecular chains, and the toughness of the material is effectively improved, so that the problem that the traditional small-molecule plasticizer is easy to migrate is solved. The membrane material prepared by the invention takes biomass material as a main raw material, has certain biodegradability in natural environment, the tensile strength is more than or equal to 20 MPa, and the elongation at break is more than or equal to 5%.

Inventors

  • LV BIN
  • ZHAO CUN
  • GAO DANGGE
  • Chen Jiqi
  • YANG XU

Assignees

  • 陕西科技大学

Dates

Publication Date
20260512
Application Date
20260212

Claims (8)

  1. 1. The bone glue base high-strength film material is characterized by comprising, by mass, 5-10 parts of bone glue, 1-5 parts of hydroxyl-terminated hyperbranched polyester and 85-95 parts of dispersion medium, wherein the dispersion medium is distilled water or deionized water, and the hydroxyl-terminated hyperbranched polyester is synthesized by esterification reaction of glycerol and maleic anhydride.
  2. 2. The bone cement based high strength film material of claim 1, wherein the step of synthesizing the hydroxyl terminated hyperbranched polyester comprises: Mixing glycerol and maleic anhydride with a molar ratio of 1:0.8-1.2, stirring and reacting at 70-80 ℃ under nitrogen atmosphere for 1-2h, then sequentially reacting at 90-100 ℃ for 2h, 110-120 ℃ for 2h and 130-140 ℃ for 3-5 h, continuously introducing nitrogen after the reaction is finished, naturally cooling to 60-80 ℃ under stirring, adding a neutralizer into the system to adjust the acid value to be less than or equal to 20 mg KOH/g, washing with water and removing impurities, and distilling at vacuum degree of-0.08-MPa to 0.095 MPa and 70-100 ℃ under reduced pressure for 1.5-2 h until no fraction is distilled out and the product is sticky, thus obtaining the hydroxyl-terminated hyperbranched polyester.
  3. 3. The method for preparing the bone cement-based high-strength film material according to claim 1, which is characterized by comprising the following steps: Step 1, weighing the following raw materials, by mass, 5-10 parts of bone glue, 1-5 parts of hydroxyl-terminated hyperbranched polyester and 85-95 parts of dispersion medium; step 2, immersing the bone glue in deionized water, swelling, heating in a water bath, and continuously stirring until the bone glue is completely dissolved to obtain a bone glue solution; Step 3, adding the hydroxyl-terminated hyperbranched polyester into a dispersion medium, and stirring to form a dispersion liquid; Step 4, preparing a film forming liquid by using the bone glue solution and the hydroxyl-terminated hyperbranched polyester dispersion liquid; And 5, preparing the bone glue base high-strength film material by using the film forming liquid.
  4. 4. The method for preparing the bone glue-based high-strength film material according to claim 3, wherein in the step 2, the swelling time is 12-24 hours, and the water bath heating temperature is 40-50 ℃.
  5. 5. The method for preparing the bone cement-based high-strength film material according to claim 3, wherein in the step 4, specifically: Mixing bone glue solution with hydroxyl-terminated hyperbranched polyester dispersion, stirring for 10-15 min, regulating pH value of the mixture to 8.0-9.5, heating the mixture in 50-60deg.C water bath for 20-40 min, and performing ultrasonic emulsification under 100-150W and 40 kHz for 20-30 min to obtain uniform film forming solution.
  6. 6. The method for preparing a bone cement based high strength film material according to claim 5, wherein a NaOH solution or an HCl solution is used for adjusting the pH of the mixed solution.
  7. 7. The method for preparing the bone cement-based high-strength film material according to claim 3, wherein in the step 5, specifically: And uniformly pouring the film forming liquid on a polytetrafluoroethylene die, controlling the film thickness to be 0.1-0.3 mm, putting the film forming liquid into a 40-50 ℃ oven for drying 20-24 h, and taking out the film forming liquid after drying to obtain the bone glue base high-strength film material.
  8. 8. Use of the bone cement-based high strength film material according to any one of claims 1-7 in agricultural films and packaging materials.

Description

Bone glue base high-strength membrane material, preparation method and application Technical Field The invention belongs to the technical field of preparation of biomass polymer materials, and particularly relates to a bone cement-based high-strength membrane material, and a preparation method and application of the bone cement-based high-strength membrane material. Background The bone glue is used as a natural protein biomass material, is mainly from byproducts such as animal bones and tendons, has good biocompatibility, degradability and film forming property, and has potential application value in the fields of packaging, adhesives, biomedical and the like. However, the pure bone glue film has strong hydrogen bonding and hydrophobic interaction among molecules, so that the film material has high brittleness and poor flexibility. In order to improve the flexibility, usually glycerol, ethylene glycol and other small molecular plasticizers are added, but in the use process, the plasticizers are easy to migrate from the inside to the surface of the film, so that the film material becomes brittle secondarily and the surface is polluted, the tensile strength of the film is obviously reduced, and the practical application of the bone glue film is severely limited. As a high molecular material with unique three-dimensional topological structure, the hyperbranched polymer has the characteristics of high end group density, less entanglement of molecular chains, good solubility and the like. The hyperbranched polyester with terminal hydroxyl groups contains a large number of terminal hydroxyl groups, the hyperbranched polyester with terminal hydroxyl groups is introduced into a protein matrix, multiple hydrogen bonding effects can be formed between the hyperbranched polyester and amino groups and carboxyl groups in the matrix, the crosslinking density of the material is improved, and meanwhile, the hyperbranched structure can introduce more free volumes into the matrix, so that intermolecular aggregation is effectively relieved, and the toughness of the material is remarkably improved. Based on the background, the bone glue base high-strength film material with bone glue as a base material and hydroxyl-terminated hyperbranched polyester as a modifier is designed, so that the problems of high brittleness, easy migration of plasticizers and the like of the traditional bone glue film are solved, and the bone glue base high-strength film material has important theoretical significance and practical application value. Disclosure of Invention The first aim of the invention is to provide a bone glue base high-strength membrane material, which solves the problems of high brittleness and low strength of the existing bone glue membrane material. A second object of the present invention is to provide a method for preparing a bone cement-based high strength film material. The third object of the invention is to provide the application of the bone glue base high-strength film material in agricultural films and packaging materials. The technical scheme includes that the bone glue base high-strength film material comprises, by mass, 5-10 parts of bone glue, 1-5 parts of hydroxyl-terminated hyperbranched polyester and 85-95 parts of dispersing medium, wherein the dispersing medium is distilled water or deionized water, and the hydroxyl-terminated hyperbranched polyester is synthesized by esterification reaction of glycerol and maleic anhydride. The synthesis steps of the hydroxyl-terminated hyperbranched polyester are as follows: Mixing glycerol and maleic anhydride with a molar ratio of 1:0.8-1.2, stirring and reacting at 70-80 ℃ under nitrogen atmosphere for 1-2h, then sequentially reacting at 90-100 ℃ for 2h, 110-120 ℃ for 2h and 130-140 ℃ for 3-5 h, continuously introducing nitrogen after the reaction is finished, naturally cooling to 60-80 ℃ under stirring, adding a neutralizer into the system to adjust the acid value to be less than or equal to 20 mg KOH/g, washing with water and removing impurities, and distilling at vacuum degree of-0.08-MPa to 0.095 MPa and 70-100 ℃ under reduced pressure for 1.5-2 h until no fraction is distilled out and the product is sticky, thus obtaining the hydroxyl-terminated hyperbranched polyester. The preparation method of the bone glue base high-strength membrane material adopts another technical scheme, and is implemented according to the following steps: Step 1, weighing the following raw materials, by mass, 5-10 parts of bone glue, 1-5 parts of hydroxyl-terminated hyperbranched polyester and 85-95 parts of dispersion medium; step 2, immersing the bone glue in deionized water, swelling, heating in a water bath, and continuously stirring until the bone glue is completely dissolved to obtain a bone glue solution; Step 3, adding the hydroxyl-terminated hyperbranched polyester into a dispersion medium, and stirring to form a dispersion liquid; Step 4, preparing a film forming liquid by using the