Synthesis and Characteriation of Novel Silicon-containing Polymers

设计并合成了一类以二硅氧烷、低聚硅氧烷和聚硅氧烷为垂基团的新型聚合物。为了建立分析这些聚合物分子迁移率的方法，利用固态^<29>Si核磁共振光谱研究了这些聚合物的自旋晶格弛豫和自旋弛豫。结果表明，这些聚合物的分子迁移率强烈依赖于其侧链中硅原子的弛豫。对硅原子具有明确立体化学性质的聚硅氧烷、聚碳硅烷、聚硅烷等含硅聚合物的可控合成进行了研究。以旋光性甲基氧基硅烷衍生物为原料合成了旋光性烯丙基硅烷和乙烯氢二硅氧烷。这些单体的多加成反应得到等规聚碳硅烷和光学活性的等规聚碳硅烷，其等规性反映了起始单体的光学纯度。用^1 H和^<13> C核磁共振谱分析了其结构。在乙烯基硅氧烷的聚加成反应中，还得到了副产物五元环碳硅氧烷。环硅氧烷的开环聚合得到了高旋光性和高分子量等规聚硅氧烷。光活性二硅氧烷衍生物也由光活性氯硅烷和光活性硅酸酯合成而成，有望作为起始单体获得以前未合成的立体规整聚硅氧烷。在光学活性固定相上，用高效液相色谱法分析其光学纯度。

A novel class of polymers containing disiloxane, oligosiloxane, and polysiloxane as pendant groups were designed and synthesized. In order to develop the method to analyze the molecular mobility of these polymers, spin-lattice and spin-spin relaxations were investigated by solid state ^<29>Si NMR spectroscopy, It was found that the molecular mobility of these polymers were strongly dependent on the relaxation of silicon atoms in their side chain.Investigation was also made on the controlled synthesis of silicon containing polymers, such as polysiloxanes, polycarbosilanes, and polysilanes, with definite stereochemistry of silicon atoms. Optically active allylsilane and vinyIhydrodisiloxane were synthesized from optically active menthyloxysilane derivatives. Polyaddition reactions of these monomers gave isotactic polycarbosilane and optically active and isotactic polycarbosiloxane whose isotacticities reflected the optical purity of the starting monomers. The tacticity was analyzed by ^1 H and ^<13> C NMR spectroscopies. Five-membered cyclic carbosiloxane was also obtained as a by-product in the polyaddition of the vinylsiloxane. Ring-opening polymerization of the cyclic carbosiloxane gave highly optically active and isotactic polycarbosiloxane of high molecular weight. Optically active disiloxane derivative, which is expected to be used as a starting monomer to obtain stereoregular polysiloxane which had not been synthesized before, was also synthesized from an optically active chIorosilane and an optically active silanolate. Its optical purity could be analyzed by HPLC on an optically active stationary phase.