Development and Application of Precise-Stereocontrolled Polymerization of Novel Acrylic Monomers

α-取代丙烯酸酯是在烯烃上有两个极性取代基的单体。我们报道了用有机锂试剂进行阴离子聚合，通过在单体α-位置设计取代基，以等规特异性的方式进行。本研究进一步发展了基于单体设计的高度立体控制聚合方法，取得了以下成果：由于单体结构和聚合体系的设计成功，在α-位置上具有各种极性基团（如芳香杂环、硫醚和仲氨基）的己取代丙烯酸酯的阴离子聚合产生了具有高立体规整性的聚合物。虽然在自由基聚合过程中立体化学很难控制，但采用一定量的路易斯酸作为添加剂，自由基法合成了具有等规性、共规性和杂规性的聚α-（烷氧甲基）丙烯酸酯。该方法成功地应用于丙烯酰胺的等规特异性自由基聚合。设计的邻位含旋光性二胺苯乙烯通过阴离子聚合得到了具有高度立体规整性和基于立体规整主链结构的手性构象的聚合物。采用阴离子聚合法制备了具有冠醚结构的大环α（烷氧基甲基）丙烯酸酯，该化合物具有孔洞或纳米管结构，具有独特的功能。

α-Substituted acrylates are the monomers that have two polar substituents on an olefin. We reported that the anionic polymerization using the organolithium reagents proceeded in an isotactic-specific manner by designing the substituents at the α-position of the monomer. In this study, the highly stereocontrolled polymerization method based on the monomer design was further developed, and followings are the results.1. The anionic polymerization of ocsubstituted acrylates having various polar groups, such as aromatic heterocycles, thioethers, and secondary amino groups, at the α-position produced polymers with a high stereoregularlity, due to the successful design of the monomer structures and polymerization systems.2. Although it is very difficult to control the stereochemistry during the radical polymerization, poly[α-(alkoxymethyl)acrylates] rich in isotacticity, syndiotacticity, and heterotacticity are synthesized by the radical method using a catalytic amount of Lewis acids as an additive. This method was successfully applied to the isotactic-specific radical polymerization of acrylamides.3. The anionic polymerization of the designed styrenes bearing optically active diamines at the ortho-position gave polymers with a high stereoregularity and chiral conformation based on the stereoregular backbone structure.4. Macrocyclic α(alkoxymethyl)acrylates having a crown ether structure were anionically polymerized to produce novel poly(crownether)s, which showed characteristic functions due the structure with a pore or nanotube.