Synthesis and Characteriation of Novel Silicon-containing Polymers

设计并合成了一类含二硅氧烷、低聚硅氧烷和聚硅氧烷侧基的新型聚合物。为了发展分析这些聚合物分子运动性的方法，用固体~ 13 Si NMR研究了它们的自旋-晶格弛豫和自旋-自旋弛豫<29>，发现这些聚合物的分子运动性强烈地依赖于它们侧链上硅原子的弛豫，并对含硅聚合物如聚硅氧烷、聚碳硅烷、和聚硅烷，具有明确的硅原子立体化学。以光学活性的孟氧基硅烷衍生物为原料，合成了光学活性的烯丙基硅烷和乙烯基氢二硅氧烷。这些单体的加聚反应得到全同立构聚碳硅烷和光学活性和全同立构聚碳硅氧烷，其全同立构度反映了起始单体的光学纯度。通过^1H和11 C NMR光谱分析立构规整度<13>。在乙烯基硅氧烷的加聚反应中，还得到了五元环状碳硅氧烷作为副产物。环状碳硅氧烷的开环聚合得到高光学活性和高分子量的全同立构聚碳硅氧烷。还从光学活性的氯硅烷和光学活性的硅醇盐合成了光学活性的二硅氧烷衍生物，其预期用作起始单体以获得以前没有合成的有规立构的聚硅氧烷。其光学纯度可在光学活性固定相上用HPLC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.