Synthesis of Functional Polymers Having Multidimentional Orientation

在本研究的第一步，研究了引起聚酰胺热致液晶性的介生结构和主链结构。-， - -双（苯氧基）烷烃- 4,4 '-二羧酸，4,4 '-二乙酰氧基联苯和- n -乙酰氨基苯甲酸的三组分缩聚制得具有高熔点和各向同性温度的热致性共聚酯酰胺。由氨基苯甲酸部分形成的酰胺链少于20 mol%可形成热致性液体结晶度。结果表明，在液晶（1c）状态下对具有长亚烯间隔段的热致性聚酯进行挤压，可以得到高强度的模制试样。采用电子束固态聚合法制备了侧链型热致性聚甲基丙烯酸酯。在丙烯酸酯单体与手性环氧基和苯甲酸苯基的固态聚合中，获得了高转化率的热致性交联聚合物。4-己基氧基-4'-（ω -丙烯氧基己基）苯甲酸酯等lc丙烯酸酯在高转化率下的固态聚合得到了相当高的分子量聚合物。此外，在非lc丙烯酸酯中加入液晶低分子量化合物可显著提高聚合性。在缩合剂DCC的作用下，含肼基的聚甲基丙烯酸酯与视网膜反应，合成了含3 ~ 9mol %视黄醛基团的聚甲基丙烯酸酯。采用核磁共振波谱法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.