Design and Synthesis of Novel Stereoregular and Optically Active Silicon-containing Polymers

本研究的目的是发展具有立体规则和光学活性的含硅聚合物的精确合成方法及其性能控制。我们利用我们以前开发的立体选择性溴化反应和硅氢烷与硅醇的脱氢缩聚反应，合成了光学活性和间同规富间规聚硅氧烷。我们发现，用市售的光学活性固定相可以分离一些含硅单体，使其变得光学纯净。光学纯的丙烯基硅烷和硅环丁烯的多加成和开环聚合得到光学活性聚碳硅烷。我们还通过光学活性硅基锂和光学活性氯硅烷的立体选择性亲核反应合成了光学活性低聚硅烷，并用X-射线衍射和圆二色谱表征了它们的立体结构。

The purpose of this research work is the development of precision synthetic method of stereoregular and optically active silicon-containing polymers and the control of their properties.We have synthesized optically active and syndiotactic-rich polysiloxanes by application of the reactions, such as stereoselective bromination reaction and dehydrogenative polycondensation reaction between hydrosilanes and silanols, which we have developed before. We found that some silicon-containing monomers can be separated by HPLC with commercially available optically active stationary phase to become optically pure. Polyaddition and ring-opening polymerization of resulting optically pure propargylsilane and silacyclobutene gave optically active polycarbosilanes. We also synthesized optically active oligosilanes by stereoselective nucleophilic reaction of optically active silyllithium and optically active chlorosilane, and characterized their stereostrucutures by X-ray diffraction and CD spectroscopy.