基于醚键极性化端羟基聚丁二烯热固树脂的构筑、结构调控及构效关系研究

Hydroxyl-terminated polybutadiene (HTPB) is widespread used as a matrix resin for low-temperature-resistant composites. However, the major drawback of HTPB is its poor compatibility with polar functional components, which is attribute to its weak polar backbone. Thus, it is a challenging topic to construct HTPB with polar without sacrificing its excellent properties. In this proposal, based on the previous works on construction of polyether-b-polybutadiene-b-polyether triblock copolymers, a series of hydroxyl-terminated polybutenediol were proposed and synthesized by polycondensation reaction using ruthenium complexes or alkali as catalysts, respectively. As the polar ether bond is introduced into the polymer repeating unit, the microstructure can be controlled precisely. Through compare studies on properties, the influence and action mechanism of ether bond introduction forms (introduced into the segments which are local at both ends of HTPB and form block copolymer or introduced into the polymer repeating unit as a polar functional group) and the isomer of unsaturated double bonds (cis-2-butenyl ether, trans-2-butenyl ether, 2-vinyl ethyl ether) on the properties of polymers and elastomers will be revealed. On the basis of this theoretical study, the structure of the polymer will be redesigned, and a novel polymeric matrix material based on polar HTPB will be constructed. The implementation of the proposal can provide new ideas and new methods for the construction of polar HTPB, moreover that can provide theoretical basis for the design of such material structure.

端羟基聚丁二烯（HTPB）是一种应用广泛的耐低温复合材料基体，其存在着分子主链极性弱，与极性功能组分相容性差的固有缺陷。在保留HTPB优异性能的同时，构筑极性化HTPB是一具有挑战性的研究课题。项目在前期构筑聚醚-聚丁二烯-聚醚三嵌段共聚物的研究基础上，提出分别利用钌配合物及碱催化的缩聚反应构筑一系列端羟基聚丁烯二醇，将极性醚键引入聚合物重复单元结构内，同时可实现聚合物微观结构的精确调控。通过一系列性能对比，揭示醚键的引入形式（以嵌段聚合物形式引入HTPB的两端或以极性功能基团形式引入聚合物单元结构内）及不饱和双键的异构体形式（顺式2-丁烯醚、反式2-丁烯醚及2-乙烯基醚）对聚合物及固化后弹性体性能的影响规律和作用机理。在此理论研究基础上，对聚合物的结构进行再设计，构筑新型极性HTPB聚合物基体材料。项目实施不仅为极性HTPB的构筑提供新思路与新方法，更为此类材料结构的设计提供理论依据。