超支化聚硅氧基硅烷的合成及其表征

基于线性聚硅氧烷在国防、能源和化工等领域的广泛应用,具有新颖拓扑结构和大量功能性端基的超支化聚硅氧烷引起了国内外科学工作者的广泛兴趣1~7].到目前为止,主要是采用水解缩聚的方法合成超支化单体,在铂系催化剂存在下进行硅氢加成反应或者在碱催化剂存在下进行质子转移聚合制备超支化聚合物8~12].然而,以上合成超支化聚硅氧烷的方法仍然存在一定的不足.例如,水解法步骤繁琐,通常在第一步反应结束后需要多次除水,并继续滴加单氯硅烷以得到完全取代的大单体;同时多官能度单体容易水解自缩聚,产生A2B4或A3B6等副产物,不仅不利于结构控…

SYNTHESIS AND CHARACTERIZATION OF HYPERBRANCHED POLY(SILOXYSILANES)

Three hyperbranched poly(siloxysilanes) were prepared from AB_3-type monomers at the presence of Karstedt catalyst.The detailed synthesis procedures of AB_3-type monomers by reaction between γ-methacryloyloxy propyltrimethoxysilane or vinyltrimethoxysilane with chlorosilane using anhydrous ferric chloride as the catalyst were described.This new approach can simplify the synthetic routes for hyperbranched polysiloxanes.FTIR,()~1H-NMR,(()~(13)C-NMR,)()~(29)Si-NMR,elemental analysis and SEC/MALLS were employed to identify the structure of the polymers. The analyses revealed that the reaction between alkoxysilane and chlorosilane could be feasibly catalyzed by anhydrous ferric chloride.The reaction of vinyltrimethoxysilane with chlorosilane could be carried out more easily than that of γ-methylacrylacyloxypropyltrimethoxylsilane with chlorosilane due to its steric hindrance effect.