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CN-121991635-A - Adhesion compound with optimized adhesion performance based on metal hydroxide, preparation method and application thereof

CN121991635ACN 121991635 ACN121991635 ACN 121991635ACN-121991635-A

Abstract

The application discloses an adhesive compound with optimized adhesive performance based on metal hydroxide, a preparation method and application thereof, and belongs to the technical field of biological adhesives. The adhesive composite comprises an adhesive precursor consisting of a protein-polyphenol composite hydrogel and a hydrogen bond destructive small molecule compound, which is capable of undergoing network reconstruction comprising beta-sheet formation in aqueous phase grafting containing a metal hydroxide, the metal hydroxide being characterized by (a) -a hydration enthalpy value of from 1000kJ/mol to-4000 kJ/mol, (b) a dissociation constant of from 6pKa to 13.5pKa, and (c) a water exchange rate of from 10 5 S ‑1 to 10 10 S ‑1 . The adhesive compound can be in a network reconstruction into an advanced structure when meeting water, can generate the underwater lap joint shearing strength of more than 1MPa, can resist the long-term underwater soaking and the temperature change of-196 ℃ to 100 ℃, has good biocompatibility, can meet the requirement of the human body environment on the tissue adhesion safety, and shows the stability suitable for in-vivo tissue repair and industrial application.

Inventors

  • LUO JUN
  • LI JIANSHU
  • LU MEIJIAO
  • TANG HAIQIN

Assignees

  • 四川大学
  • 杭州汇瑞森生物科技有限公司

Dates

Publication Date
20260508
Application Date
20260213

Claims (10)

  1. 1. An adhesive composite with optimized adhesive performance based on metal hydroxide is characterized by comprising an adhesive precursor and metal hydroxide in a mass ratio of 100:1-100; The adhesion precursor consists of a protein-polyphenol composite hydrogel and a hydrogen bond destructive small molecule compound, and the adhesion precursor is capable of undergoing network reconstruction comprising beta-sheet formation in an aqueous phase containing the metal hydroxide; the metal hydroxide has the following characteristics: (a) -an enthalpy of hydration value of from 1000kJ/mol to-4000 kJ/mol; (b) A dissociation constant of 6 to 13.5pKa, and (C) Water exchange rates of 10 5 S -1 to 10 10 S -1 .
  2. 2. The adhesion composite of claim 1, wherein the metal hydroxide has the following characteristics: (a) -a hydration enthalpy value of from-1309 kJ/mol to-2099 kJ/mol; (b) Dissociation constant of 8 to 13.4pKa, and (C) Water exchange rates of 9 x 10 5 S -1 to 5.7 x 10 9 S -1 .
  3. 3. An adhesion composite according to claim 1 or 2, characterized in that the metal hydroxide is selected from hydroxides containing magnesium, calcium, strontium, barium, manganese, cobalt, copper, zinc.
  4. 4. The adhesive composite according to claim 1 or 2, wherein the protein component in the protein-polyphenol composite hydrogel is selected from at least one of silk fibroin, gelatin, collagen, keratin, soy-wire-drawing protein, gluten, and fibrin; And/or the polyphenol component in the protein-polyphenol composite hydrogel is selected from at least one of tannic acid, dopamine, caffeic acid, tea polyphenol and anthocyanin.
  5. 5. The adhesive composite of claim 4, wherein the hydrogen bond disrupting small molecule compound is selected from at least one of urea, guanidine hydrochloride, and thiourea.
  6. 6. The adhesion composite of claim 1 or 2, wherein the mass ratio of the adhesion precursor to the metal hydroxide is 100:15-100.
  7. 7. The adhesive composite of claim 1 or 2, wherein the adhesive precursor comprises a solution and a powder.
  8. 8. The adhesive composite of claim 1 or 2, wherein the adhesive composite has a lap shear strength of greater than 1MPa as determined according to astm f2255-24 after complete curing.
  9. 9. A process for the preparation of an adhesive composite according to any one of claims 1 to 8, based on optimized adhesion properties of metal hydroxides, characterized in that it comprises: Mixing the protein-polyphenol composite hydrogel with a hydrogen bond disrupting small molecule compound to produce an adhesion precursor, and mixing the adhesion precursor with a metal hydroxide to form an adhesion complex.
  10. 10. Use of the adhesion composite based on optimized adhesion properties of metal hydroxides according to any one of claims 1 to 8 for biomedical bonding, fixation and repair of bone tissue, bonding and repair of underwater structures, marine engineering, aerospace component assembly, automotive manufacturing, electronic component packaging.

Description

Adhesion compound with optimized adhesion performance based on metal hydroxide, preparation method and application thereof Technical Field The application belongs to the technical field of bio-based adhesives, and particularly relates to an adhesive compound with optimized adhesive performance based on metal hydroxide, a preparation method and application thereof. Background The adhesive is widely used in the fields of ocean engineering, biomedical use, automobile manufacturing and the like. However, the traditional adhesive is highly dependent on petroleum-based polymers such as epoxy resin, acrylic ester and polyurethane, and when the adhesive is used in the biomedical field, the traditional adhesive is easy to fail due to interference of a hydration layer because the human body is filled with complex liquid media such as blood, tissue fluid and the like, and meanwhile, the biological safety requirement of the traditional adhesive for use in the human body is high, and the traditional adhesive is limited in clinical application due to residual toxic cross-linking agents such as aldehydes and the like. Therefore, development of a bioadhesive which can maintain high-strength adhesion in a water-rich environment, has excellent biosafety, and can be tolerated by the human body and even promote tissue regeneration has become an urgent need in the fields of clinical medicine and biomaterials. At present, the related art prepares a bio-based adhesive with good adhesion performance by taking high polymer and polyphenol as raw materials. For example, patent technology with publication number CN 117323462A discloses that an adhesive composite hydrogel is formed by silk fibroin and tannic acid, and the adhesive composite hydrogel is mixed with urea or guanidine hydrochloride to prepare an adhesive hydrogel with excellent injectability, so that the requirement of biological adhesion in the biomedical field is effectively met. However, the existing bio-based adhesives such as the above generally face the problems of insufficient adhesion performance (especially underwater adhesion strength is generally less than 1 MPa), durability and long-term stability, and particularly have difficulty in considering the durable adhesion under a dynamic body fluid scouring environment and the safety to human tissues, and cannot meet the requirements of severe environments such as in-human tissue repair, underwater operation, aerospace and the like. Disclosure of Invention The application discloses an adhesive compound with optimized adhesive performance based on metal hydroxide, a preparation method and application thereof, and effectively solves the technical problems of insufficient underwater adhesive performance, durability and long-term stability of the existing bio-based adhesive. In order to achieve the above purpose, the technical scheme provided by the application is as follows: According to the 1 st aspect of the application, an adhesive compound with optimized adhesive performance based on metal hydroxide is provided, and the adhesive compound comprises an adhesive precursor and metal hydroxide in a mass ratio of 100:1-100; The adhesion precursor consists of a protein-polyphenol composite hydrogel and a hydrogen bond destructive small molecule compound, and the adhesion precursor is capable of undergoing network reconstruction comprising beta-sheet formation in an aqueous phase containing the metal hydroxide; the metal hydroxide has the following characteristics: (a) -an enthalpy of hydration value of from 1000kJ/mol to-4000 kJ/mol; (b) A dissociation constant of 6 to 13.5pKa, and (C) Water exchange rates of 10 5S-1 to 10 10S-1. According to a preferred disclosure of aspect 1, the metal hydroxide has the following features: (a) -a hydration enthalpy value of from-1309 kJ/mol to-2099 kJ/mol; (b) Dissociation constant of 8 to 13.4pKa, and (C) Water exchange rates of 9 x 10 5S-1 to 5.7 x 10 9S-1. According to a preferred disclosure of aspect 1, the metal hydroxide is selected from the group consisting of hydroxides comprising magnesium, calcium, strontium, barium, manganese, cobalt, copper, zinc. According to the preferred disclosure of the 1 st aspect, the protein component in the protein-polyphenol composite hydrogel is at least one selected from the group consisting of silk fibroin, gelatin, collagen, keratin, soy-fiber drawing protein, gluten and fibrin; The polyphenol component in the protein-polyphenol composite hydrogel is at least one selected from tannic acid, dopamine, caffeic acid, tea polyphenol and anthocyanin. According to a preferred disclosure of aspect 1, the hydrogen bond breaking small molecule compound is selected from at least one of urea, guanidine hydrochloride, and thiourea. According to the preferable disclosure of the 1 st aspect, the mass ratio of the adhesion precursor to the metal hydroxide is 100:15-100. According to a preferred disclosure of aspect 1, the adhesion precursor comprises a solution