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

新型立构规整光学活性含硅聚合物的设计与合成

• 批准号: 11450354
• 负责人: KAWAKAMI Yusuke
• 金额: $ 6.91万
• 依托单位: Japan Advanced Institute of Science and Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11450354/
• 关键词: polysiloxanes; polycarbosilanes; polysilanes; stereoregularity; optical activity; polycondensation; polyaddition; ring-opening polymerization; シリルリチウム; ハロシラン; 求核置換反応; オリゴシラン; 結晶構造解析; 円二色性スペクトル; ポリシルセスキオキサンゲル; 位置選択性; シンジオタクチック; ポリカルボシロキサン

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.

本研究工作的目的是开发有规立构、光学活性含硅聚合物的精确合成方法并控制其性能，利用我们以前开发的立体选择性溴化反应和氢硅烷与硅醇之间的脱氢缩聚反应等反应合成了光学活性且富含间规立构的聚硅氧烷。我们发现，一些含硅单体可以通过HPLC与市售的光学活性固定相分离，成为光学纯。所得光学纯的炔丙基硅烷和硅环丁烯的加聚和开环聚合得到光学活性聚碳硅烷。通过光学活性硅基锂与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射线衍射和圆二色性光谱表征了它们的立体结构。

项目成果

Takahiko Kawakita, Hyunshik Oh, Jeon-Yeol Moon, Yang Liu, Ichiro Imae, Yusuke Kawakami: "Synthesis, Characterization and Thermal Properties of Phenylene-disiloxane Polymers Obtained from Catalytic Cross-dehydrocoupling Polymerization of Bis(dimethylsilyl)

Takahiko Kawakita、Hyunshik Oh、Jeon-Yeol Moon、Yang Liu、Ichiro Imae、Yusuke Kawakami：“双（二甲基甲硅烷基）催化交叉脱氢偶联聚合得到的亚苯基二硅氧烷聚合物的合成、表征和热性能

K. Komuro, Y. Kawakami: "Synthesis and Characterization of Side-Chain Liquid Crystalline Polycarbosilanes with Siloxane Spacer"Polym. Bull.. 42(6). 669-674 (1999)

K. Komuro，Y. Kawakami：“具有硅氧烷间隔基的侧链液晶聚碳硅烷的合成和表征”Polym。

J.-Y. Moon, T. Miura, I. Imae, D.-W. Park, Y. Kawakami: "Synthesis and Thermal Properties of Disiloxane-Arylene Polymers by Dehydrocoupling Polymerization of Bis(dimethylsilyl)arylene with Water"Silicon Chemistry. 1(2). 139-143 (2002)

J.-Y。

H.-S. Oh, I. Imae, Y. Kawakami, S. S. S. Raj, T. Yamane: "Synthesis, Stereochemistry and Chiroptical Properties of Naphthylphenyl-Substituted Optically Active Oligosilanes with α,ω-Chiral Silicon Centers"J. Organomet. Chem.. in press. (2003)

H.-S. Oh，I. Imae，Y. Kawakami，S. S. S. Raj，T. Yamane：“具有 α,ω-手性硅中心的萘基苯基取代的光学活性低聚硅烷的合成、立体化学和手性光学性质”J. ..正在出版。（2003）

Y.Li and Y.Kawakami: "Catalytic Cross-Dehydrocoupling Polymerization of 1,4-Bis(dimethylsilyl)benzene with Water.A New Approach to Poly[(oxydimethylsilylene)(1,4-phenylene)(dimethyldimethylsilylene)]"Macromolecules. Vol.32no.10. 3540-3542 (1999)

Y.Li 和 Y.Kawakami：“1,4-双(二甲基硅基)苯与水的催化交叉脱氢偶联聚合。聚[(氧二甲基硅基)(1,4-亚苯基)(二甲基二甲基硅基)]”大分子的新方法。