Synthesis and application of novel optically active maleimide polymers with thermostability

合成了含有甲基苄基、L-薄荷基和氨基酸残基的新型马来酰亚胺，并与苯乙烯和甲基丙烯酸甲酯进行均聚和共聚。用圆二色谱和比旋光度研究了聚合物和共聚物的旋光性。聚合物和共聚物的主链发生了不对称诱导。光学不活跃的N-取代马来酰亚胺(N-取代基：环己基，苯基)与有机金属手性配体进行不对称阴离子聚合，得到比旋度为+117~-155°的旋光性聚合物。聚合物的旋光活性归因于主链上的三个双等规结构导致(S，S)和(R，R)绝对构型的不同。从激子手性方法和模型化合物看，(+)-聚合物的(S，S)绝对构型比(R，R)多，(-)-聚合物的(R，R)绝对构型比(S，S)多。将N-取代基团较大的马来酰亚胺与有机金属手性配体进行不对称聚合，得到具有光学活性的聚合物。由于聚合物具有相对较高的比旋光度，因此被应用于光学拆分试剂。

New types of maleimides having methylbenzyl, L-menthyl and amino-acid residual group were synthesized and homopolymerized and copolymerized with stirene and methyl methacrylate. Optical activity of the polymers and copolymers were investigated by circular dichroism and specific rotation measurements. Asymmetric induction took place to the main chain of the polymer and copolymer. Asymmetric anionic polymerizations of optically inactive N-substituted maleimide (N-substituent : cyclohexyl, phenyl) were performed with organometal - chiral ligands to obtain the optically active polymers having + 117 to -155 deg.of specific rotation, which were the highest in the values resported previously. The optical activity of the polymers was attributed to the different content between (S,S) and (R,R) absolute configuration by the threo-diisotactic structures in the main chain. It is considered that the (+) -polymer has more (S,S) absolute configuration than (R,R) and the (-) -polymer has more (R,R) absolute configuration than (S,S), judging from the exciton chirality method and the model compounds. The asymmetric polymerizations of the maleimides having bulky group in the N-substituents such as triphenylmethyl, diphenylmethyl and fluorenyl were also carried out with organometal-chiral ligand to give optically active polymers. The polymers were applied for optical resolution reagents because the polymers have relatively higher specific rotation.