Study on the Property of Liquid-Crystalline Polyoxetanes Containing Ion-Conducting Domains Controllable for Driving the Pendant Mesogens

合成了侧链或尾部含有三氧杂环丁烷的热致性侧链液晶聚氧杂环丁烷。所得聚合物的各向同性相转变温度（T_i）显著降低，通过差示扫描量热仪（DSC）的冷却扫描，测得了该聚合物在14.9 ℃时的T_1，并通过偏光显微镜（POM）观察到了球晶结构。当这些聚合物与LiClO_4混合时，（相对于氧杂环丁烷单元等摩尔量），它们显示DSC峰，尽管具有甲氧基尾部的聚合物在加热和冷却扫描上仅显示针状织构，表明短尾部不阻碍中间相形成，尽管较长尾部彼此排斥以阻碍中间相形成，因为Li^+-氧杂环丁烷络合物的形成使介晶之间的宽度变窄。可能是在这项研究中所需的结构被构建，因为针状织构被归因于中间相结构域的结构变化。另一方面，具有-O（CH_2CH_2O）_3-C_6H_4-p-F尾的聚合物在室温以上没有DSC峰，也没有POM织构，这些结果不受LiClO_4存在与否的影响。装入装有电压施加装置的保持器中的聚合物在1 × 3V的施加下没有显示中间相结构的任何变化。这归因于聚合物是如此粘稠以致于聚合物没有充入到保持器的满液位。向期刊提交了关于结构片段对液晶性质的影响的手稿。

Thermotropic side-chain liquid-crystalline polyoxetanes containing a tri(oxyethylene) segment in the pendant spacer or tail were synthesized. The isotropic phase transition temperature (T_i) of the resultant polymers were remarkably lowered, e.g., T_i at 14.9 ℃ on cooling scan of differential scanning calorimetry (DSC) for a polymer with a -CH_2O(CH_2)_4O(CH_2CH_2O)_3-spacer and a methoxy tail, and showed a spherulitic texture by polarized optical microscopy (POM). When these polymers were mixed with LiClO_4 (an equimolar amount with respect to the oxyethylene unit), they showed DSC peaks, although the polymer with a methoxy tail only indicated a needle-like texture on heating and cooling scans, suggesting that the short tail did not hinder the mesophase formation, although the longer tails repulsed each other to hinder the mesophase formation, since width among mesogens was narrowed by formation of Li^+-oxyethylene complexes. Possibly the structure desired in this study was constructed, since the needle-like texture was ascribed to structural change in the mesophase domain. On the other hand, a polymer with a -O(CH_2CH_2O)_3-C_6H_4-p-F tail indicated no DSC peak and no POM texture above room temperature, and these results were not influenced by the presence and absence of LiClO_4. The polymer charged in a holder equipped with a voltage impression apparatus did not indicated any change in mesophase texture under impression of 1〜3V. This is ascribed to the fact that the polymer was so viscous that the polymer did not charged up to a full level of holder. A manuscript concerning the influence of the structural segments on the liquid-crystalline property was submitted to a Journal.