Synthesis of Functional Polymers Having Multidimentional Orientation

在本研究的第一步，研究了导致聚酰胺热致液晶性的介晶结构和主链结构。α，欧米伽-双(苯氧基)烷烃-4，4‘-二羧酸、4，4’-二乙酰氧基联苯和Rho-N-乙酰氨基苯甲酸的三组分缩聚反应得到了具有较高熔点和各向同性温度的热致性共酯酰胺。不到20mol%的氨基苯甲酰胺键可以提供热致液晶性。结果表明，含长链烷基团的热致聚酯在液晶(1c)状态下挤出可得到高强度模压试件。采用电子束固相聚合法制备了侧链型热致聚甲基丙烯酸酯。在丙烯酸酯单体与手性环氧基和苯甲酸苯酯的固相聚合中，得到了高转化率的热致交联型聚合物。4-hexyloxy-4‘-(omega-acryloxyhexyloxy)benzoates等液晶丙烯酸酯的EB固相聚合可得到较高转化率的高相对分子质量聚合物。此外，在非LC丙烯酸酯中加入液晶低相对分子质量化合物，可显著提高聚合性。含有酰肼基团的聚甲基丙烯酸甲酯在缩合剂DCC的作用下与视网膜反应，合成了含3~9摩尔%视黄亚甲基的聚甲基丙烯酸酯。用核磁共振波谱对该聚合物的结构进行了表征。

In the first step of this study, both mesogenic and backbone structures to cause thermotropic liquid crystallinity in polyamides were investigated. Three-component polycondensation of alpha, omega-bis(phenoxy)alkane-4, 4'-dicarboxylic acid, 4, 4'diacetoxybiphenyl, and rho-N-acetylaminobenzoic acid gave thermotropic copolyesteramides having high melting and isotropic temperatures. Less than 20 mol% of the amide linkage originating from aminobenzoic moiety was allowed to afford the thermotropic liquid crystallinity. It was revealed that high strength molded test pieces were obtained from thermotropic polyesters having long alkylene spacer by extruding it in the liquid crystalline(1c)state. Side-chain type thermotropic poly(meth)acrylates were prepared by electron beam(EB)solid-state polymerization. In the solid-state polymerization of of acrylate monomers with both chiral epoxy and phenyl benzoate groups, thermotropic crosslinked polymers were obtained in high conversions. EB solid-state polymerization of such lc acrylates as 4-hexyloxy-4'-(omega-acryloxyhexyloxy)benzoates gave fairly high molecular weight polymers in high conversions. Moreover, the addition of a liquid crystalline low molecular weight compound to non-lc acrylate caused a remarkable increase in polymerizability. Polymethacrylates containing 3 to 9 mol% retinylidene groups were synthesized by reacting polymethacrylate having hydrazide groups with retinal by the action of a condensing agent DCC. The structure of this DMSO-soluble polymer was examined by NMR spectroscopy.