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CN-121991489-A - Photo-thermal response type thermosetting polyurethane film and preparation method thereof

CN121991489ACN 121991489 ACN121991489 ACN 121991489ACN-121991489-A

Abstract

The invention discloses a photo-thermal response type thermosetting polyurethane film, which is characterized in that bis (2-hydroxyethyl) disulfide/selenide is fixed on a heat conducting filler by utilizing the connection effect of IPTS, and reacts with polyurethane prepolymer in situ to construct a dynamic cross-linked network structure, so that the heat conducting filler is promoted to be uniformly dispersed in a polyurethane matrix, a certain mechanical property is given to the polyurethane film, the defects of poor compatibility, easy agglomeration and the like of the heat conducting filler and the polyurethane matrix in the prior art are overcome, and meanwhile, excellent shape memory, self-repairing property, repeated processing, rapid photo-thermal response behavior, heat conduction and mechanical property are also given to the polyurethane, and the photo-thermal response type polyurethane film is applied to the fields of actuators, sensors and aerospace medical materials and has good development prospect.

Inventors

  • LI QUNYANG
  • XIE DONG
  • LI FAYONG
  • ZHAO YANG
  • ZHONG LIU

Assignees

  • 广东省科学院生物与医学工程研究所

Dates

Publication Date
20260508
Application Date
20260213

Claims (10)

  1. 1. The photo-thermal response type thermosetting polyurethane film is characterized by being prepared from the following raw materials in parts by weight: 4-6 parts of polyether polyol 4-6 Parts of polyester polyol 4-5 Parts of diisocyanate Chain extender 0.85-0.87 parts 0.1 To 0.2 part of catalyst 0.16 To 0.48 part of dynamic cross-linking agent 6-10 Parts of organic solvent 6-10 Parts of diluent; The dynamic cross-linking agent is a functional dynamic cross-linking agent of the heat conducting filler loaded bis (2-hydroxyethyl) disulfide/selenide.
  2. 2. The photo-thermal response type thermosetting polyurethane film according to claim 1, wherein the dynamic cross-linking agent is obtained by reacting isocyanatopropyl triethoxysilane with bis (2-hydroxyethyl) disulfide/selenide and a heat conducting filler sequentially, and specifically comprises the following steps of reacting the isocyanatopropyl triethoxysilane with the bis (2-hydroxyethyl) disulfide/selenide under the action of a catalyst for 1-3 hours at 60-80 ℃, wherein the catalyst is more than one of dibutyl tin dilaurate, stannous octoate and dibutyl tin diacetate, then reacting for 1-3 hours at 50-70 ℃ in an organic solvent dispersion liquid added with the heat conducting filler, and centrifuging and vacuum drying the product to obtain the dynamic cross-linking agent.
  3. 3. The photo-thermal response type thermosetting polyurethane film according to claim 2, wherein the bis (2-hydroxyethyl) disulfide/selenide is one or more of bis (2-hydroxyethyl) disulfide and bis (2-hydroxyethyl) diselenide, the heat conducting filler is one or more of MXene, graphene, hydroxylated boron nitride and carbon nano tube, and the organic solvent is one or more of N, N-dimethylformamide, N-methylpyrrolidone and butanone.
  4. 4. The photo-thermal response type thermosetting polyurethane film according to claim 2, wherein the molar ratio of the propyltriethoxysilane Isocyanate (IPTS) to the bis (2-hydroxyethyl) disulfide/selenide is 1:1, the catalyst is used in an amount of 1-3% of the mass of the propyltriethoxysilane isocyanate, and the weight ratio of the organic solvent to the heat conductive filler is (0-8): 1-3.
  5. 5. The photothermal responsive thermosetting polyurethane film according to claim 1, wherein the polyether polyol has a weight average molecular weight of 1000 to 3000 and is one or more of polytetrahydrofuran, polyethylene glycol, polypropylene glycol, and polyether alkyl ether.
  6. 6. The photothermal responsive thermosetting polyurethane film according to claim 1, wherein the polyester polyol has a weight average molecular weight of 1000 to 3000 and is one or more of poly (1, 4-butanediol), poly (1, 6-hexanediol), poly (ethylene glycol) glycol, poly (propylene glycol adipate) and poly (1, 6-hexanediol carbonate) glycol.
  7. 7. The photo-thermal response type thermosetting polyurethane film according to claim 1, wherein the diisocyanate is one or more of 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and toluene diisocyanate, the chain extender is one or more of butanediol, ethylene glycol, hexanediol, diethylene glycol and trimethylolpropane, the catalyst is one or more of dibutyltin dilaurate, stannous octoate and dibutyltin diacetate, the organic solvent is one or more of N, N-dimethylformamide, N-methylpyrrolidone and butanone, and the diluent is one or more of propione, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide.
  8. 8. The method for preparing the photo-thermal response type thermosetting polyurethane film as claimed in claim 1, which is characterized by comprising the following steps: 1) Stirring and mixing polyether polyol, polyester polyol, diisocyanate and a chain extender at 60-80 ℃ for 10-20min, adding a catalyst, and reacting for 3-5 h at 60-80 ℃ to obtain a polyurethane prepolymer; 2) Dispersing a dynamic cross-linking agent in an organic solvent to obtain a dynamic cross-linking agent dispersion liquid, mixing a polyurethane prepolymer with the dynamic cross-linking agent dispersion liquid, reacting for 1-3 hours at 50-70 ℃, and adding a diluent for dilution in the reaction process to obtain polyurethane emulsion; 3) And drying the polyurethane emulsion to form a film at 60-100 ℃ to obtain the photo-thermal response type thermosetting polyurethane film.
  9. 9. The method of claim 8, wherein the drying in step 3) is air drying at 60-100 ℃ for 8-12 hours.
  10. 10. Use of a photothermal responsive thermosetting polyurethane film as defined in claim 1, in the field of flexible actuators, flexible sensors, aerospace medical materials.

Description

Photo-thermal response type thermosetting polyurethane film and preparation method thereof Technical Field The invention relates to the technical field of functional polymer materials, in particular to a photo-thermal response type thermosetting polyurethane film and a preparation method thereof. Background Polyurethanes are a class of materials that have good wear resistance, toughness, low temperature flexibility, corrosion resistance, and processability, and exhibit various types including elastomers, sheets, adhesives, coatings, and foams. Polyurethanes have been widely used in many fields because of their excellent properties. However, polyurethane is mainly used for low-end products because of its single function, and cannot meet specific requirements. With the development of scientific technology and the improvement of living standard of people, common polyurethane products can not meet the diversified demands of people. Therefore, there is a need to develop functional polyurethanes. Functional polyurethanes can normally exhibit a stimulus response to the environment or have unique properties such as photosensitivity, thermal sensitivity, shape memory and self-healing. The heat conducting filler such as MXene, graphene, boron nitride, carbon nano tube and the like has larger specific surface area, and can rapidly conduct heat transfer under smaller load, so that the shape memory and self-repairing performance of the polymer are induced. Meanwhile, the mechanical and heat conducting properties of the polymer can be enhanced. Therefore, the use of thermally conductive fillers as light responsive additives to induce shape memory and self-healing properties of polymers is a current research hotspot. However, the direct incorporation of thermally conductive fillers into the polymer matrix may lead to polymer agglomeration, impairing the function of the polymer. Therefore, proper organic modification of the heat-conducting filler is necessary, and Chinese patent application publication No. CN110952308B discloses a flame-retardant conductive photo-thermal response shape memory paper, and a preparation method and application thereof. Although the preparation process is relatively simple, the flame retardance, the electric conduction and the shape memory of the polyurethane can be improved to a certain extent, the preparation method cannot achieve modification of the chain segment of the polyurethane in terms of reaction mechanism, so that the MXene cannot be uniformly dispersed in a polyurethane matrix, and the photo-thermal conversion efficiency of the polyurethane is affected. So the polyurethane material prepared by the method is difficult to have rapid shape memory response behavior. In addition, the polyurethane is not self-healing. The Chinese patent application with publication number CN107915826A discloses a preparation method of self-repairing type shape memory polyurethane containing a diselenide bond, and the polyurethane realizes the shape memory and self-repairing functions based on the crystallization reversibility of a polyester molecular chain and the dynamic exchange characteristic of the diselenide bond. Although the operation condition of the method is mild, the method cannot realize rapid and efficient response behavior without the assistance of the heat conducting filler, and lacks sensitivity. Disclosure of Invention The invention aims to provide a photo-thermal response type thermosetting polyurethane film and a preparation method thereof. The invention is realized by the following technical scheme: A photo-thermal response type thermosetting polyurethane film is prepared from the following raw materials in parts by weight: 4-6 parts of polyether polyol 4-6 Parts of polyester polyol 4-5 Parts of diisocyanate Chain extender 0.85-0.87 parts 0.1 To 0.2 part of catalyst 0.16 To 0.48 part of dynamic cross-linking agent 6-10 Parts of organic solvent 6-10 Parts of diluent; The dynamic cross-linking agent is a functional dynamic cross-linking agent of the heat conducting filler loaded bis (2-hydroxyethyl) disulfide/selenide. Because the dynamic cross-linking agent contains a disulfide/selenium bond with dynamic reversibility and a hydroxyl structure (-OH), the cross-linking agent can be polymerized with isocyanate groups (-NCO) in a polyurethane main chain in situ to form a dynamic cross-linking network structure with reversibility covalent bonds (disulfide/selenium bonds), so that the polyurethane is endowed with excellent shape memory, self-repairing property and repeated processability, and meanwhile, the excellent intrinsic heat conduction performance of the heat conduction filler can shorten a photo-thermal conduction path, so that the polyurethane is endowed with rapid photo-thermal response behavior and good heat conduction performance. The dynamic cross-linking agent is prepared by reacting isocyanatopropyl triethoxysilane (IPTS) with bis (2-hydroxyethyl) disulfide/selenide and a heat