Development of electrical conjugated polymers with liquid crystalline and magnetic properties

具有液晶和磁性的电共轭聚合物的开发

• 批准号: 07651092
• 负责人: AKAGI Kazuo
• 金额: $ 1.47万
• 依托单位: University of Tsukuba
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07651092/
• 关键词: Conjugated polymers; Polyacetylene derivatives; Liquid crystallinity; Stable radical group; Magnetic properties; Macroscopic orientation; Spin alignment; Organic ferromagnet; 導電性高分子; 磁性; ESR; 高分子液晶; 二置換ポリアセチレン; ラジカル基; 配向制御; 電子スピン共鳴; Conjugated polymers; Polyacetylene derivatives; Liquid crystallinity; Stable radical group; Magnetic properties; Macroscopic orientation; Spin alignment; Organic ferromagnet; 導電性高分子; 磁性; ESR; 高分子液晶; 二置換ポリアセチレン; ラジカル基; 配向制御; 電子スピン共鳴

Side-chain liquid crystalline (LC) conjugated polymer with stable radical group is expected to afford a parallel spin alignment with aids of spontaneous orientation and externally forced macroscopic alignment of LC side chains. The present study is aimed to achieve a macroscopic spin alignment through LC orientation, For this aim, di-substituted polyacetylene with LC group and stable radical group in side chains is useful, where the intrachain parallel spin alignment can be easily constructed on the basis of topological stereoregularity satisfying Ovchinnikov rule.Di-substituted polyacetylene was synthesized by introducing both liquid crystalline LC group and stable radical group into side chains. Di-tert-butylphenol derivative, where the hydroxy moiety of the phenyl group was protected by trimethylsilyl group, was adopted as a stable radical precursor. Acetylene monomer substituted with the LC group and the radical precursor was polymerized using metathesis catalyst of TaCI_5-(n-Bu)_4Sn. The polymer synthesized was soluble in organic solvents and showed an enantiotropic smectic phase. ESR spin intensity of the polymer was evaluated after the radical precursor was deprotected and oxidized, Anisotropy in spin intensity, owing to spontaneous alignment of LC side chains, was confirmed.Next, the mono-substituted polyacetylene copolymer was synthesized, where either the LC group or the radical group was substituted into the unit cell of main chain. The copolymer, in which the ratio of radical group-substituted polyene segment is less than 10 %, showed a smectic phase in 150 - 160ﾟC.The ESR intensity increased in the LC temperature. This is ascribed to the spin alignment of phenoxy radical electrons within LC domains.

侧链液晶（LC）与稳定的激进基团共轭聚合物有望提供平行的自旋对齐，并具有赞助方向的辅助以及LC侧链的外部强制宏观比对。本研究的目的是通过LC取向实现宏观的自旋对齐，为此，为此目的，与LC组的Di叠定的聚乙炔和侧链中稳定的激进基团具有有用，可以轻松地基于拓扑结构的Ovchinnikov ovchinnikov prolity ovchinnikov proliate ovchinnikov proliate ovchinnikov proly.polotolacy polotiatiendii-wasennikov proy.dotolacy。将液晶LC组和稳定的自由基组引入侧链。 Di-TERT-丁基苯酚衍生物（其中该苯基的羟基部分受三甲基甲硅烷基群体保护）被用作稳定的自由基前体。用LC组取代并使用TACI_5-（N-BU）_4SN的元理解催化剂聚合的乙炔单体进行聚合。合成的聚合物在有机溶液中是固体的，并且显示出对映射晶状体相。在自由基前体被脱离并氧化后，评估了聚合物的ESR自旋强度，旋转强度的各向异性，由于LC侧链的赞助对齐。next，单叠加的单叠式聚乙二醇聚合物合成了LC组，在该组合中，LC组或放射线组都替代了INTICTICERTICE cOLTITER COLTITERITE in INTICTITERETITE cOLTITES INTICTITERETITERETITERITED。共聚物，其中自由基群体取代的多烯段的比率小于10％，显示出150-160°C的近晶相。这分配给了LC域内稳态自由基电子的自旋比对。