Functions Realized by Controlled Configuration of Optically active Polymers

通过光学活性聚合物的受控构型实现的功能

• 批准号: 14550835
• 负责人: NOZAKI Kyoko
• 金额: $ 2.5万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14550835/
• 关键词: optically active polymer; configuration; polyketone; olefin; carbon monoxide; methylenation; azobennzene; photoisomerization; 光学活性; γ-ポリケトン; 配座制御; ペルフルオロアルキル基; ポリアセタール; 側鎖型液晶ポリマー; キラルネマチック

The project purposed to realize new functions of optically active polymers by controlling the configuration. For this purpose, the relation between the main-chain configuration and either the main-chain or the side-chain was investigated. The research was particularly focused on the optically active polymers obtained by the alternating copolymerization of α-olefin and CO. the following three achievements were obtained.(1)it was suggested that the formation of stable helical structure is less probable for the optically active polyketone which was produced by the asymmetric alternating copolymerization of propene with CO, by comparing the CD and ORD spectra of polyketone with those of a single-unit model compound. (2) Optically active hydrocarbon polymer was successfully produced by the reaction of poly (propene-alt-CO) or the mobility of the main chain was lowered when the side chain is butyl instead of methyl. (3)Optically active polyketone bearing an azobenzene side chain was produced. When the polyketone was completely in it's the other hand, the switching of the main chain structure was detedcted by CD when the main chain contained 25% of spiroacetal unit which is an isomeric from of polyketone.

本课题旨在通过控制光学活性聚合物的结构来实现其新的功能。为此，研究了主链构型与主链或侧链之间的关系。本文着重研究了α-烯烃与CO交替共聚的光学活性聚合物，取得了以下三个方面的成果。(1)it通过比较聚酮与单单元模型化合物的CD谱和ORD谱，认为由丙烯与CO不对称交替共聚制得的光学活性聚酮不太可能形成稳定的螺旋结构。(2)通过聚（丙撑-alt-CO）反应成功地制备了具有光学活性的烃类聚合物，或者当侧链为丁基而不是甲基时，主链的移动性降低。（3）合成了含偶氮苯侧链的光学活性聚酮。另一方面，当聚酮完全处于主链中时，当主链中含有25%的聚酮异构体螺缩醛单元时，用圆二色谱（CD）检测到主链结构的转换。

项目成果

N.Kosaka, K.Nozaki, T.Hiyama, M.Fujiki, N.Tamai, T, Matsumoto: "Conformational Studies on an Optically Active 1,4-Polyketone in Solution"Macromolecules. 36. 6884-6887 (2003)

N.Kosaka、K.Nozaki、T.Hiyama、M.Fujiki、N.Tamai、T、Matsumoto：“溶液中光学活性 1,4-聚酮的构象研究”大分子。

N.Kosaka, K.Nozaki, T.Hiyama, M.Fujiki, N.Tamai, T, Matsumoto: "Conformational Studies on an Optically Active 1,4-Polydetone in Solution"Macromolecules. 36. 6884-6887 (2003)

N.Kosaka、K.Nozaki、T.Hiyama、M.Fujiki、N.Tamai、T、Matsumoto：“溶液中光学活性 1,4-聚酮的构象研究”大分子。

N.Kosaka, K.Nozaki, T.Hiyama, M.Fujiki, N.Tamai, T.Matsumoto.: "Conformational studies on an Optically Active 1,4-Plyketone in Solution."Macromolecules. 36. 6884-6887 (2003)

N.Kosaka、K.Nozaki、T.Hiyama、M.Fujiki、N.Tamai、T.Matsumoto.：“溶液中光学活性 1,4-聚酮的构象研究。”大分子。

Y.Kawashima, K.Nozaki, T.Hiyama, M.Yoshio, K.Kanie, T.Kato: "Liquid-crystalline Stereoregular Polyketone Prepared from a Mesogenic Vinyl arene and Carbon Monoxide"Journal of Polymer Science Part A : Polymer Chemistry. 41. 3356-3563 (2003)

Y.Kawashima、K.Nozaki、T.Hiyama、M.Yoshio、K.Kanie、T.Kato：“由介晶乙烯基芳烃和一氧化碳制备的液晶立构聚酮”高分子科学杂志 A 部分：高分子化学。

N.kosaka, T.Oda, T.Hiyama, K.Nozaki: "synthesis and Photoisomerization of Optically Active γ-Polyketones Substituted by Azobenzene Side Chains."Macromolecules. (in press).

N.kosaka、T.Oda、T.Hiyama、K.Nozaki：“偶氮苯侧链取代的光学活性 γ-聚酮的合成和光异构化”。大分子（正在出版）。