Preparation of polysiloxane optical resolution membranes containing high-density chiral spaces by using sol-gel method

溶胶-凝胶法制备含高密度手性空间的聚硅氧烷光学拆分膜

• 批准号: 08651049
• 负责人: AOKI Toshiki
• 金额: $ 1.47万
• 依托单位: Niigata University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08651049/
• 关键词: pinanyl group; alkoxysilyl group; enantioselective permeation; membrane; polysiloxane; optacal resolution membrane; sol-gel method; chiral space; 末端アセチレン; キラルポリマー

Some silylacetylene polymers having bulky chiral pinanyl groups were found to show good enantioselective permeabilities. We thought that the permselectivity was caused by the difference of diffusivity between R-isomer and S-isomer through "high-density chiral spaces" surrounding by the several bulky pinanyl groups. However, since the chiral spaces were very small and the mobility of bulky pinanyl groups was low, permeation rates were pretty low. This problem was solved by introducing "polysiloxane" units into membrane polymers. Direct modification of membranes by "sol-gel method" or hydrolysis of alkylsiloxy groups made membranes very brittle, and as a result these membranes were not able to be used for separation membranes. Therefore, it is important to modify the membranes without affecting other structures.In summary, we obtained the following three conclusions.1)"High-density chiral spaces" is very important for high enantioselectivity.2) "Polysiloxane" is effective for enhancing permeability.3) "Sol-gel method" has to be controlled more precisely to maintain membrane strength.

一些具有大手性蒎基基团的甲硅烷基乙炔聚合物被发现表现出良好的对映选择性渗透性。我们认为选择性渗透是由R-异构体和S-异构体之间通过几个庞大的蒎基基团包围的“高密度手性空间”的扩散率差异引起的。然而，由于手性空间非常小并且庞大的蒎基基团的迁移率很低，因此渗透率相当低。通过将“聚硅氧烷”单元引入膜聚合物中解决了这个问题。通过“溶胶-凝胶法”直接改性膜或烷基甲硅烷氧基的水解使膜非常脆，因此这些膜不能用于分离膜。因此，在不影响其他结构的情况下对膜进行改性非常重要。综上所述，我们得到以下三个结论。1）“高密度手性空间”对于高对映选择性非常重要。2）“聚硅氧烷”对于增强渗透性是有效的.3) 必须更精确地控制“溶胶-凝胶法”以保持膜强度。

项目成果

Toshiki Aoki: "Enantioselective Permeation of Various Racemates through an Optically Active Poly{1-〔dimethyl(10-pinanyl)silyl〕-1-propyne}Membrane" Macromolecules. 29(12). 4192-4198 (1996)

Toshiki Aoki：“各种外消旋物通过光学活性聚{1-[二甲基(10-蒎基)甲硅烷基]-1-丙炔}膜的对映选择性渗透”29(12) 4192-4198。

Toshiki Aoki: "Synthesis and Properties of Polymers from Disubstituted Acetylenes with Chiral Pinanyl Groups" Macromolecules. 32 (1). 79-85 (1999)

Toshiki Aoki：“具有手性蒎基基团的二取代乙炔聚合物的合成和性能”大分子。

青木 俊樹: "光学分割固体膜素材用合成高分子の設計" 膜. 22. 126-134 (1997)

Toshiki Aoki：“光学解析固体薄膜材料的合成聚合物的设计”膜。22. 126-134 (1997)

Ken-ichi Shinohara: "Detection of the Site of an Enantioselective Interaction between Chiral Polypinanylsilane and an Hydrophobic Enantiomer by Use of Circular Dichroism" Chem.Lett.1997. 361-362 (1997)

Ken-ichi Shinohara：“利用圆二色性检测手性聚蒎基硅烷和疏水性对映异构体之间的对映选择性相互作用位点”Chem.Lett.1997。

Toshiki Aoki: "Enantioselective Permeation of Racemates through a Solid(+)-Poly{2-[dimethyl(10-pinanyl)silyl]norbornadiene} Membrane" Polym.Commun.38(1). 235-238 (1997)

Toshiki Aoki：“外消旋物通过固体( )-聚{2-[二甲基(10-蒎基)甲硅烷基]降冰片二烯}膜的对映选择性渗透”Polym.Commun.38(1)。