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

合成了侧链上含有三氧乙烯链段的热致性侧链液晶聚氧乙烷。所得聚合物的各向同性相变温度(T_I)显著降低，在差示扫描量热仪(DSC)的冷却扫描下，T_I为14.9℃，并在偏光显微镜下显示球晶织构。当这些聚合物与LiClO4(相对于氧乙烯单元的等摩尔量)混合时，它们显示出DSC峰，尽管带有甲氧基尾巴的聚合物在加热和冷却扫描中只显示出针状织构，这表明短尾并不阻碍中间相的形成，尽管较长的尾巴相互排斥以阻碍中间相的形成，因为Li^+-氧乙烯络合物的形成使中间相之间的宽度变窄。可能构建了本研究中所需的结构，因为针状织构归因于中间相域的结构变化。另一方面，具有a-O(CH_2CH_2O)_3-C_6H_4-p-F尾部的聚合物在室温以上没有DSC峰和POM织构，这些结果不受LiClO_4的存在和不存在的影响。在装有电压印象仪的保持器中充电的聚合物在1~3V的压力下没有表现出任何中间相织构的变化。这归因于这样一个事实，即聚合物的粘性如此之大，以至于聚合物的电荷没有达到持有者的全部水平。一篇关于结构段对液晶性质的影响的手稿被提交给了一本期刊。

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.