Synthesis of Functional Polymers Having Multidimentional Orientation

在本研究的第一步中，研究了引起聚酰胺热致液晶性的介晶和主链结构。α，ω-双（苯氧基）烷烃-4，4 '-二羧酸、4，4'-二乙酰氧基联苯和对-N-乙酰氨基苯甲酸的三组分缩聚得到了具有高熔融温度和各向同性温度的热致性共聚酯酰胺。小于20摩尔%的酰胺键源于氨基苯甲酸部分被允许提供热致液晶性。结果表明，通过将具有长链烯基间隔基的热致聚酯在液晶（1c）状态下挤出，可获得高强度模塑试样。采用电子束固相聚合法合成了侧链型热致性聚（甲基）丙烯酸酯。同时具有手性环氧基和苯甲酸苯酯基的丙烯酸酯单体的固相聚合，在高转化率下得到了热致交联聚合物。这类LC丙烯酸酯如4-己氧基-4 '-（ω-丙烯酰氧基己氧基）苯甲酸酯的EB固态聚合在高转化率下得到相当高分子量的聚合物。此外，向非液晶丙烯酸酯中添加液晶低分子量化合物引起可聚合性的显著增加。通过使具有酰肼基团的聚甲基丙烯酸酯与视黄醛在缩合剂DCC的作用下反应，合成含有3至9摩尔%的亚视黄基的聚甲基丙烯酸酯。通过NMR光谱检查该DMSO可溶性聚合物的结构。

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.