金属杂化倍半硅氧烷的分子设计及其催化固化树脂体系的研究

Novel metallasilsesquioxanes with well-defined structure, which is a kind of organic-inorganic hybrid materials, can be prepared via a new approach that is unsaturated double-decker-shape silsesquioxanes (DDSQ) reacting with metal halide or organometallic compounds. Above mentioned method is effective method in this field for the snythesis of novel metallized silsesquioxanes, which are useful for the development of catalyst materials. With good performance, benzoxazine is a kind of novel thermosetting resins, while benzoxazine has the disadvatage for the high temperature of curing process. In this proposal, DDSQ structure has been introduced in the metallasilsesquioxanes, then metallized silsesquioxanes containing DDSQ structure(DDOM) are used as catalysts for benzoxazine resins. The curing temperature of benzoxazine resins can be decreased by DDOM, which has good catalytic properties and good miscibility for benzoxazine resins for its unique characteristics of the organic part and hybrid structure combined precisely in nanoscale in the nature of hybrid molecules. The hybrid materials ,which is prepared by curing the blending of DDOM and benzoxazine resins，have both the advantages of the organic and inorganic materials, and the Tg or other properties of the hybrid material can be improved than that of the pure resins.The DDOM may be regarded as a novel kind of molecular level hybrid materials, and the DDOM/benzoxazine resins are considered as novel kinds of hybrid materials. The structure design and the synthetic method of present proposal are valuable for the development of high performance hybrid materials and resins for various application.

通过金属有机化合物与不饱和双塔形倍半硅氧烷（DDOH）反应，可制备具有精确结构的有机无机杂化材料-金属杂化倍半硅氧烷（metallasilsesquioxanes），这是设计合成金属杂化倍半硅氧烷的新路线，对于发展新型催化材料具有重要意义。苯并噁嗪（BZ）是一类受到广泛关注的新型热固性树脂，但是存在固化温度偏高的问题。本项目提出利用硅羟基的反应活性，将双塔形结构引入金属杂化倍半硅氧烷，制备出含双塔结构的金属杂化倍半硅氧烷，并与苯并噁嗪树脂混合制备具有较低固化温度的树脂体系。该树脂的特点是利用金属杂化倍半硅氧烷的催化特性，降低树脂固化温度，并借助双塔形倍半硅氧烷与树脂的相容性实现催化剂的良好分散，保持其固化产物原有特性，甚至提升材料的综合性能。该项目预期可研发一系列基于新型金属杂化倍半硅氧烷催化的，具有固化温度较低、综合性能优异的新型杂化热固性树脂。

金属杂化倍半硅氧烷（metallasilsesquioxanes）是通过金属有机化合物与不饱和多面体倍半硅氧烷反应制得的具有精确结构的有机无机杂化材料。其分子结构精确，宽泛的设计空间，分子尺寸属于纳米尺度，是潜在的催化剂或新型材料前驱体。项目提出了两种合成路线，其一是利用硅羟基的反应活性，将双塔形结构引入金属杂化倍半硅氧烷，制备出含双塔结构的金属杂化倍半硅氧烷；另外一个合成路线是利用羧基或氨基官能化的笼形倍半硅氧烷与金属醇盐、金属氯化物或乙酰丙酮金属化合物反应，制备系列倍半硅氧烷金属络合物。制备了系列钛、锆、铪、铝、锡等金属有机倍半硅氧烷杂化分子，其中7种杂化分子已经培养单晶进行了表征；探究了其催化苯并噁嗪和氰酸酯树脂的性质；此类化合物可催化固化苯并噁嗪和氰酸酯树脂，是氰酸酯树脂高效催化剂；制备了数十种官能化倍半硅氧烷与金属离子（主族金属、过渡金属、稀土金属）的络合物，发现此类络合物可催化固化苯并噁嗪和氰酸酯树脂，特别是氰酸酯树脂的高效催化剂；在上述工作基础上，发展了系列热固性树脂体系，其中代表性的如下：分别发展了适于165。C、140。C固化的氰酸酯树脂体系，满足实际需求；发展了120-140。C固化的苯并噁嗪树脂固化体系；发展了芘胺型苯并噁嗪树脂，将其用于石墨烯表面处理，再与氰酸酯树脂复合到高导热氰酸酯树脂复合材料；发展了具有缩醛结构的邻苯二甲腈树脂，具有较低熔点，固化产物具有较高玻璃化转变温度（Tg大于400。C）。上述工作为进一步发展具有精确结构的金属杂化分子提供了思路；所得化合物可用作苯并噁嗪树脂和氰酸酯树脂的催化剂；这些新发展的树脂在航空航天、绝缘材料和PCB板等领域具有潜在应用前景。