Synthesis and Characteriation of Novel Silicon-containing Polymers

设计合成了一类以二硅氧烷、低聚硅氧烷和聚硅氧烷为侧基的新型聚合物。为了建立分析这些聚合物分子迁移率的方法，用固体核磁共振研究了它们的自旋-晶格和自旋-自旋弛豫，发现这些聚合物的分子迁移率强烈地依赖于它们侧链上的硅原子的驰豫。我们还研究了含硅聚合物的控制合成，如聚硅氧烷、聚碳硅烷和聚硅烷，并确定了硅原子的立体化学。以光学活性的甲氧基硅烷为原料合成了光学活性的烯丙基硅烷和乙烯基二硅氧烷。这些单体的多加成反应生成了等规聚碳硅烷和旋光性和全同立构聚碳硅氧烷，其同位素反映了起始单体的光学纯度。用^1H和^&lt；13&gt；C核磁共振谱对其进行了分析。在乙烯基硅氧烷的多加成反应中也得到了副产物五元环硅氧烷。将环状聚硅氧烷开环聚合，得到了光学活性高、全同立构的高相对分子质量聚硅氧烷。以旋光性氯硅烷和旋光性硅氧烷为原料合成了旋光性二硅氧烷衍生物，有望作为合成立体正则聚硅氧烷的起始单体。其光学纯度可在光学活性固定相上用高效液相色谱法进行分析。

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.