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CN-122011335-A - Self-healing polymer and preparation method and application thereof

CN122011335ACN 122011335 ACN122011335 ACN 122011335ACN-122011335-A

Abstract

The present invention relates to a self-healing polymer, its preparation method, and application. The present invention belongs to the field of environmentally friendly flexible polymer material preparation technology. The prepared self-healing polyoxymethylene elastomer balances the rapid self-healing properties, high mechanical strength, and recyclability of the material.

Inventors

  • GUAN QINGBAO
  • CAO DEFENG

Assignees

  • 苏州光谨高新材料科技有限公司

Dates

Publication Date
20260512
Application Date
20260303

Claims (10)

  1. 1. The self-healing polymer is characterized by having a structural general formula: ; wherein y= (1-3), z is more than 20; wherein R is an isocyanate residue; The M is ; Where n= (1, 2, 3), x= (6-8).
  2. 2. The self-healing polymer according to claim 1, wherein the isocyanate is one or more of isophorone diisocyanate IPDI, dicyclohexylmethane diisocyanate HMDI, and diphenylmethane diisocyanate MDI.
  3. 3. A process for preparing self-healing polymer includes such steps as mixing polyester polyol, solvent and catalyst, dropping isocyanate for reaction, adding dimethyl glyoxal oxime solution for reaction, and post-treating.
  4. 4. The process according to claim 3, wherein the polyester polyol has the structure: ; wherein n= (1, 2, 3) and x= (6-8), and the isocyanate is one or more of isophorone diisocyanate IPDI, dicyclohexylmethane diisocyanate HMDI and diphenylmethane diisocyanate MDI.
  5. 5. The method according to claim 3, wherein the solvent comprises N, N-dimethylformamide, the catalyst comprises dibutyltin dilaurate, and the solvent of the dimethylglyoxal oxime solution comprises N, N-dimethylformamide.
  6. 6. The preparation method according to claim 3, wherein the molar ratio of the polyester polyol to the isocyanate is 1:4-6.
  7. 7. The preparation method according to claim 3, wherein the catalyst is added in an amount of 0.4-0.5% by mass of the polyester polyol, the isocyanate and the dimethylglyoxal oxime, and the dimethylglyoxal oxime is 2-4 times by mass of the polyester polyol.
  8. 8. The preparation method according to claim 3, wherein the preparation comprises heating the polyester polyol to 110-120 ℃, vacuumizing, cooling to 80-90 ℃, adding the solvent and the catalyst, stirring, dropwise adding isocyanate for reaction for 2-4h, cooling to 55-65 ℃ and adding dimethyl glyoxal oxime solution for reaction for 14-18h, wherein the reaction process is carried out under the condition of protective gas.
  9. 9. A method according to claim 3, wherein the post-treatment is carried out by reacting at 55-65 ℃ with a temperature of 12-24 h ℃, and then heating to 80-85 ℃ to carry out the vacuuming treatment at 20-30 h.
  10. 10. Use of a self-healing polymer according to any one of claims 1-2 in the field of self-healing elastomers.

Description

Self-healing polymer and preparation method and application thereof Technical Field The invention belongs to the field of high polymer materials, and particularly relates to a self-healing high polymer, and a preparation method and application thereof. Background The traditional polyurethane is polymerized by petroleum-based polyol and isocyanate, and is widely applied to the fields of aerospace, medical appliances and the like. However, on one hand, the contradiction between the application requirement of polyurethane and the shortage of fossil energy in the raw materials thereof is increasingly severe, and on the other hand, with the rapid development of flexible electronics, wearable equipment and intelligent sensing technology, higher requirements are put on environmental adaptability, durability and functional repairability of polyurethane. In this context, the preparation of self-healing polyurethanes with biobased or recycled raw materials is a focus of research in the green chemistry field. The polyester polyol obtained by the alcoholysis of the waste PET is used as an environment-friendly raw material, can replace the traditional petroleum-based polyol, and can also be used for constructing green self-healing polyurethane by introducing reversible pi-pi interaction through benzene ring accumulation in a molecular chain, but the dynamics of pi-pi interaction in the self-healing polyurethane needs to be activated through external stimulus, so that the self-healing at room temperature cannot be realized. Among many self-healing polyurethane design strategies, oxime-urethane linkage based polyurethanes are of great interest because they can achieve dynamic bond dissociation and recombination under mild conditions. However, researches on preparing green room-temperature self-healing polyurethane by combining alcoholysis polyester polyol with oxime-carbamate bond have been freshly reported, and how to realize dynamic synergy of soft segments of alcoholysis polyester polyol and oxime-carbamate bond through molecular design, and meanwhile, the rapid self-healing property, high mechanical strength and recycling processability of the material are key problems to be solved urgently. Disclosure of Invention The invention aims to provide self-healing poly (oxime) urethane and a preparation method and application thereof. The invention provides a self-healing polymer, which has a structural general formula: wherein y= (1-3), z is more than 20; further, z is (20 or more). Wherein R is an isocyanate residue; wherein the isocyanate residue is the residue after removal of the isocyanate group. The M is Where n= (1, 2, 3), x= (6-8). Further, n=1, x=2, y=1, and z is 20 or more. The isocyanate is one or more of isophorone diisocyanate IPDI, dicyclohexylmethane diisocyanate HMDI and diphenylmethane diisocyanate MDI. Isocyanate corresponds to the structure: 、、。 The preparation of the polyurethane comprises that the polyester polyol and the dimethylglyoxal oxime are respectively used as a soft segment and a chain extender, and react with different isocyanates under the action of a catalyst to obtain the polyurethane. The invention provides a preparation method of polyoxime alamate, which comprises the steps of mixing polyester polyol, a solvent and a catalyst, dropwise adding isocyanate for reaction, then adding a dimethylglyoxal oxime solution for reaction, and carrying out post-treatment to obtain the polyoxime alamate. The preferred mode of the preparation method is as follows: The structure of the polyester polyol: Wherein n= (1, 2, 3), x= (6-8); further, the polyester polyol is an alcoholysis polyester polyol. The isocyanate is one or more of isophorone diisocyanate IPDI, dicyclohexylmethane diisocyanate HMDI and diphenylmethane diisocyanate MDI. The solvent comprises N, N-dimethylformamide, the catalyst comprises dibutyl tin dilaurate, and the solvent of the dimethylglyoxal oxime solution comprises N, N-dimethylformamide. The molar ratio of the polyester polyol to the isocyanate is 1:4-6. The feeding amount of the catalyst is 0.4% -0.5% of the total mass of the polyester polyol, the isocyanate and the dimethylglyoxime, and the dimethylglyoxime is 2-4 times of the molar amount of the polyester polyol. The preparation method comprises the steps of heating the polyester polyol to 110-120 ℃, vacuumizing, cooling to 80-90 ℃, adding a solvent and a catalyst, stirring, dropwise adding isocyanate for reaction for 2-4h, cooling to 55-65 ℃, adding dimethyl glyoxal oxime solution for reaction for 14-18h, wherein the reaction processes are all carried out under the condition of protective gas. The post-treatment is carried out at 55-65 ℃ for reaction of 12-24 h, then the temperature is raised to 80-85 ℃ for vacuumizing treatment of 20-30 h. The invention provides an application of any self-healing polymer in the field of self-healing elastomers. In the technical scheme, compared with the prior art, the invention has the followi