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

α-取代的丙烯酸酯是在烯烃上具有两个极性取代基的单体。我们报道了使用有机锂试剂的阴离子聚合是通过设计单体α-位上的取代基以全同立构特异性的方式进行的。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，主要研究结果如下：1.由于单体结构和聚合体系的成功设计，α-位上带有芳杂环、硫醚和仲氨基等极性基团的α-取代丙烯酸酯的阴离子聚合得到了高度立构规整的聚合物.虽然在自由基聚合过程中很难控制立体化学，但使用催化量的刘易斯酸作为添加剂，通过自由基方法合成了富含全同立构规整度、间同立构规整度和杂同立构规整度的聚[α-（烷氧基甲基）丙烯酸酯]。该方法成功地应用于丙烯酰胺的等规定向自由基聚合.设计的苯乙烯在邻位带有光学活性二胺的阴离子聚合得到了具有高立构规整性和基于立构规整骨架结构的手性构象的聚合物.采用阴离子聚合法合成了具有冠醚结构的大环α-（烷氧基甲基）丙烯酸酯，合成了具有孔或纳米管结构的新型聚冠醚。

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.