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

α取代的丙烯酸酯是一种在烯烃上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通过在单体的α位设计取代基，以全同立构的方式进行。在本研究中，进一步发展了基于单体设计的高度立体可控聚合方法，并取得了如下结果。由于单体结构和聚合体系的成功设计，在α位上具有不同极性基团的八取代丙烯酸酯(如芳杂环、硫醚和仲氨基)的阴离子聚合产生了具有高立体规整性的聚合物。尽管自由基聚合过程中的立体化学很难控制，但通过自由基法合成了具有等规性、间规性和异规性的聚[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聚合法。所设计的含旋光活性二胺的苯乙烯类邻位阴离子聚合产物具有较高的立体规整性和基于立体正则主链结构的手性构象。将具有冠醚结构的大环α(烷氧甲基)丙烯酸酯进行阴离子聚合，合成了具有孔道或纳米管结构的新型聚冠醚S。

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.