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CN-122011334-A - Polytetrahydrofuran ether glycol-based shape memory polyurethane and preparation method thereof

CN122011334ACN 122011334 ACN122011334 ACN 122011334ACN-122011334-A

Abstract

The invention discloses polytetrahydrofuran ether glycol based shape memory polyurethane and a preparation method thereof, wherein polytetrahydrofuran ether glycol based shape memory polyurethane is successfully prepared by a solution polymerization method by taking polytetrahydrofuran ether glycol as a soft segment and diisocyanate and a polyol chain extender as a hard segment. Experimental result analysis shows that the melting transition temperature and the crystallization temperature of the obtained polytetrahydrofuran ether glycol-based polyurethane can be adjusted by adjusting the proportion of soft and hard segments, and experimental results show that the polytetrahydrofuran ether glycol-based polyurethane prepared by the invention not only has good shape memory cycle performance, large strain performance and excellent stability, but also has flexible expandability, so that the polytetrahydrofuran ether glycol-based polyurethane becomes a good choice of flexible intelligent textile substrate, and can be used for thermal comfort management of clothing.

Inventors

  • LIU HAIHUI
  • LUO JIANXIANG
  • Ju Jiancheng
  • DONG QIANQIAN
  • SUN QINGYI
  • JI XUE
  • XU QIANG

Assignees

  • 天津工业大学

Dates

Publication Date
20260512
Application Date
20260302

Claims (9)

  1. 1. A method for preparing polytetrahydrofuran ether glycol-based shape memory polyurethane, which is characterized by comprising the following steps: S1, fully mixing polytetrahydrofuran ether and diisocyanate in a solvent, and then carrying out a prepolymerization reaction under the action of a tin-based catalyst to obtain a polyurethane prepolymer; S2, adding a polyol chain extender into the obtained polyurethane prepolymer, continuing to react at constant temperature, removing bubbles in vacuum, and curing to obtain polytetrahydrofuran ether glycol-based shape memory polyurethane.
  2. 2. The method for preparing polytetrahydrofuran ether glycol based shape memory polyurethane according to claim 1, wherein in step S1, the temperature of the prepolymerization reaction is 65-75 ℃ for 30-120min.
  3. 3. The method for producing polytetrahydrofuran ether glycol based shape memory polyurethane according to claim 1, wherein the continuous reaction time is 25-40min in step S2.
  4. 4. The method for preparing polytetrahydrofuran ether glycol based shape memory polyurethane according to claim 1, wherein the molar ratio of polytetrahydrofuran ether glycol, diisocyanate and polyol chain extender is 1:2-4:1-4.
  5. 5. The method for producing a polytetrahydrofuran ether glycol based shape memory polyurethane according to claim 1, wherein the polytetrahydrofuran ether glycol has an average molecular weight of 1000 to 3000.
  6. 6. The method for producing polytetrahydrofuran ether glycol based shape memory polyurethane according to claim 1, wherein the diisocyanate is at least one of hexamethylene diisocyanate, 2,4 '-diphenylmethane diisocyanate, 4' -diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate.
  7. 7. The method for producing polytetrahydrofuran ether glycol based shape memory polyurethane according to claim 1, wherein the polyol chain extender is one or a combination of two or more of 1, 4-butanediol, 1, 3-propanediol, 1, 6-hexanediol and ethylene glycol.
  8. 8. The method for preparing polytetrahydrofuran ether glycol based shape memory polyurethane according to claim 1, wherein the solvent is at least one of N, N-dimethylformamide, ethyl acetate and isopropanol, and the tin-based catalyst is dibutyl tin dilaurate.
  9. 9. A polytetrahydrofuran ether glycol-based shape memory polyurethane prepared by the method of any one of claims 1-8.

Description

Polytetrahydrofuran ether glycol-based shape memory polyurethane and preparation method thereof Technical Field The invention relates to the technical field of intelligent materials, and relates to polytetrahydrofuran ether glycol-based shape memory polyurethane and a preparation method thereof. Background Shape Memory Polyurethane (SMPU) materials are one of the most interesting intelligent polymer materials, polyurethane is usually composed of small molecule polyol as soft segments, isocyanate and chain extender as hard segments, and the main chain is a block structure formed by alternately connecting the soft segments and the hard segments, the incompatibility of the soft segments and the hard segments forms good microphase separation, and a good morphological foundation is provided for shape memory. The hard segment of the SMPU with temperature response can play a role of fixing a permanent shape, the soft segment is responsible for fixing a temporary shape, and when the external temperature is lower than the crystallization temperature of the soft segment, the crystallization-induced elongation is in the temporary shape, and when the temperature is higher than the melting temperature of the soft segment phase, the soft segment phase can be autonomously recovered to the original shape. The SMPU has excellent properties such as excellent strength and elasticity, controllable memory transition temperature, structural diversity, light weight, wide acquisition path, low cost, easy processing, good mechanical property, excellent biocompatibility, biodegradability and the like, and has wide application prospect in the fields of medical appliances, textiles, intelligent structures and the like. SMPU exhibits a pronounced shape memory effect due to microphase segregation, which is related to the chemistry of the synthesis and the processing method. SMPU is generally composed of two phases, a "stationary phase" and a "reversible phase", also known as hard and soft segments, respectively. The hard segments typically contain long sequences of hydrogen bonding sites that also act as physical crosslinks that prevent adjacent chains from sliding relative to each other when subjected to deformation and corresponding stress build-up, while physical crosslinks also act as dots during shape recovery, so the location of the crosslinks is one of the most important factors affecting the shape memory effect and mechanical properties of the SMP. Although the conventional SMPU has many advantages, it has certain limitations, such as poor heat resistance, low mechanical strength, difficult control of transition temperature, poor conductivity and heat conductivity, and the like, which limits its application range. Polytetrahydrofuran ether glycol (PTMEG) is a thermoplastic polyether with good crystallinity, has a low melting point and glass transition temperature, and has not been reported in the preparation of SMPU based on PTMEG through searching. Disclosure of Invention Aiming at the technical problems in the background technology, the invention aims to provide polytetrahydrofuran ether glycol-based shape memory polyurethane and a preparation method thereof. In order to achieve the above purpose, the present invention adopts the following technical scheme: The first aspect of the invention provides a method for preparing polytetrahydrofuran ether glycol-based shape memory polyurethane, which comprises the following steps: S1, fully mixing polytetrahydrofuran ether and diisocyanate in a solvent, and then carrying out a prepolymerization reaction under the action of a tin-based catalyst to obtain a polyurethane prepolymer; S2, adding a polyol chain extender into the obtained polyurethane prepolymer, continuing to react at constant temperature, removing bubbles in vacuum, and curing to obtain polytetrahydrofuran ether glycol-based shape memory polyurethane. Preferably, in step S1, the temperature of the prepolymerization reaction is 65-75 ℃ and the time is 30-120min. Preferably, in step S2, the continuous reaction time is 25-40min. Preferably, the molar ratio of the polytetrahydrofuran ether glycol, the diisocyanate and the polyol chain extender is 1:2-4:1-4. Preferably, the polytetrahydrofuran ether glycol has an average molecular weight of 1000 to 3000. Preferably, the diisocyanate is at least one of Hexamethylene Diisocyanate (HDI), 2,4 '-diphenylmethane diisocyanate, 4' -diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate. Preferably, the polyol chain extender is one or a combination of more than two of 1, 4-Butanediol (BDO), 1, 3-propanediol, 1, 6-hexanediol and ethylene glycol. Preferably, the solvent is at least one of N, N-Dimethylformamide (DMF), ethyl acetate and isopropanol. Preferably, the tin-based catalyst is dibutyl tin dilaurate (DBTDL). The second aspect of the invention provides polytetrahydrofuran ether glycol-based shape memory polyurethane prepared by the pr