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Synthesis of Organosilicon Linear Polymer with Octaorganooctasilsesquioxanes Structural Units in Main Chain

机译:主链中具有八有机八硅倍半硅氧烷结构单元的有机硅线性聚合物的合成

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摘要

A macromonomer T_8, 1,4-divinylhexamethyloctasilsesquioxane (3), was prepared by hydrolytic condensation of vinyltris(diethoxy-methylsiloxy)silane (2a). Hydrosilylation of (3) by dimethylchloro-silane, methylphenylisopropoxysilane and phenyldimethylsilane leads to functionalized derivatives 1,4-bis(2-chlorodimethylsilylethyl)-hexamethyloctasilsesquioxane (4) and 1,4-bis(2-isopropoxymethyl-phenylsilylethyl)hexamethyloctasilsesquioxane (6) and a nonfuncti-onalized derivative 1,4-bis(2-phenyldimethylsilylethyl)hexamethyl-octasilsesquioxane (5). Treating 6 with thionyl chloride yields 1,4-bis(2-chloromethylphenylsilylethyl)-hexamethyloctasilsesquioxane(7). Two approaches to the synthesis of polymers with fragments T_8 in the main chain have been proposed: (ⅰ) hydrolytic polycondensation of 7 and (ⅱ) direct hydrosilylation of the starting macromonomer 3 by 1,3-dimethyl-1,3-diphenyldisiloxane. Data obtained by GPC, DSC and ~1H NMR spectroscopy have shown the latter approach to be preferable over the former. Thermogravimetric analysis of polymers with fragments T_8 in the main chain has provided evidence for their high thermal stability.
机译:通过乙烯基三(二乙氧基-甲基甲硅烷氧基)硅烷(2a)的水解缩合制备大分子单体T_8,1,4-二乙烯基六甲基辛基倍半硅氧烷。 (3)由二甲基氯硅烷,甲基苯基异丙氧基硅烷和苯基二甲基硅烷进行硅氢加成反应会生成功能化的衍生物1,4-双(2-氯二甲基甲硅烷基乙基)-六甲基辛基倍半硅氧烷(4)和1,4-双(2-异丙氧基甲基-苯基甲硅烷基乙基)六甲基辛基倍半硅氧烷(6)和非官能化的衍生物1,4-双(2-苯基二甲基甲硅烷基乙基)六甲基-八聚倍半硅氧烷(5)。用亚硫酰氯处理6,得到1,4-双(2-氯甲基苯基甲硅烷基乙基)-六甲基辛基倍半硅氧烷(7)。已经提出了两种在主链中具有片段T_8的聚合物的合成方法:(ⅰ)7的水解缩聚和(ⅱ)1,3-二甲基-1,3-二苯基二硅氧烷对起始大分子单体3的直接氢化硅烷化。通过GPC,DSC和〜1H NMR光谱获得的数据表明,后一种方法比前一种方法更好。主链上有片段T_8的聚合物的热重分析提供了其高热稳定性的证据。

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