超支化有机硅离子液体增韧苯并噁嗪树脂的结构调控与性能研究

Benzoxazine rensins are developed class of high performance thermosetting resins in high-tech field. However, there are also several disadvantages that limit the application of common benzoxazine resins, such as high cure temperature, high viscosity and relatively brittle. Hyperbranched silicon-containing ionic liquid (HSIL) will be synthesized basing on vinyl hyperbranched polysiloxane and thio-functionalized ionic liquid. The decreased cure temperature, higher strength, improved toughness and thermal stability can be contributed to the resulted hyperbranched ionic liquid. The terminal group and molecular weight of HSIL can be controlled by cations and anions of thio-functionalized ionic liquid. Chemical structure, degree of branching and molecular weight will be characterized by FT-IR, NMR, GPC, et al. The cure mechanism of benzoxzazine resin with HSIL will be studied. The relationship between the crosslinking structure and macro-performance of PBOZ/HSIL will be established. To control phase structure of the blends, the effects of HSIL chemical micro-structures on interfacial interactions, phase morphology, mechanical performance and thermal properties of PBOZ/HSIL blends will also be studied. Through this research, a novel approach for preparing benzoxzazine resin blends with controllable phase structures will be obtained. This work may serve as an important recognition, fundamental theoretical and experimental guidance for developing benzoxzazine resins with solvent-free and high performance.

苯并噁嗪树脂是一类新型的热固性树脂，性脆、粘度高、固化温度高阻碍其广泛使用。本项目以端乙烯基超支化有机硅树脂和巯基离子液体制备对苯并噁嗪树脂具有降低固化温度、增强、增韧和耐热功能的超支化有机硅离子液体（HSIL）。巯基离子液体的阳离子、阴离子结构控制HSIL的微观化学结构（端基、分子量）。采用FT-IR、NMR、GPC等技术表征产物的结构、支化度、分子量等性质。研究HSIL苯并噁嗪树脂/HSIL共混材料的固化反应机理，建立交联结构与宏观性能之间的关系；研究微观化学结构对共混材料界面相互作用、相形态结构、机械性能、热性能的影响规律，揭示共混材料相形态结构和材料宏观性能之间的相关性，通过HSIL的微观化学结构调控苯并噁嗪树脂相形态结构。该项目为苯并噁嗪树脂的无溶剂化、高性能化开辟一种新的途径，并提供规律性认识及实验指导，推动苯并噁嗪树脂的发展和应用。

本项目以高性能超支化聚合物的制备和应用为核心，系统研究超支化聚合物改性热固性树脂的结构和性能。其工作主要包括：(1)系统研究超支化离子液体的微观化学结构对苯并噁嗪树脂固化行为、力学性能和热性能的影响规律，揭示其固化机理和增强增韧机理，获得了对苯并噁嗪树脂具有降低固化温度、增强和增韧功能的超支化离子液体。(2)利用超支化离子液体改性双酚A型环氧树脂，获得对环氧树脂具有固化促进、增强和增韧的超支化离子液体，并成功应用于耐高温无溶剂绝缘树脂。(3)深入研究低粘度超支化环氧树脂对苯并噁嗪树脂力学性能和耐热性的影响，揭示了超支化环氧树脂对苯并噁嗪树脂的增强增韧机理，为苯并噁嗪树脂的无溶剂化和高性能化提供了新的途径。(4)利用硫醇-烯烃“点击”技术，获得了端乙烯基超支化聚合物改性苯并噁嗪树脂光固化体系，拓展了苯并噁嗪树脂在紫外光树脂涂料领域的应用。本项目为构建功能性超支化离子液体和高性能苯并噁嗪树脂提供了新材料和新理论依据。本项目的实施为超支化聚合物和苯并噁嗪树脂产业的创新发展、产业升级换代提供了理论基础和实践指导。