Controlled Radical Polymerization of Cyclic Vinyl Monomer for Rigid-Rod Polymer

在这项研究中，我们研究了各种1,2-二取代环乙烯基单体的自由基（co）聚合，以可能构建定义良好的刚性和热稳定的乙烯基聚合物。将不具有均聚性的环烯烃和环苯乙烯衍生物与吸电子单体n-取代马来酰亚胺共聚，得到了高效的共聚物。特别是，当这些单体在氟醇中进行共聚时，共聚性得到了增强，得到了主要的交替共聚物。所得共聚物具有较高的Tg值和较硬的主链。此外，我们成功地进行了这些环乙烯基单体的活性/可控自由基（co）聚合。

In this study, we investigated radical (co)polymerization of various 1,2-disubstituted cyclic vinyl monomers for possible construction of well-defined rigid and thermally-stable vinyl polymers. Cyclic olefins and cyclic styrene derivatives which have little homopolymerizability were copolymerized with electron-withdrawing monomers, N-substituted maleimides, to afford copolymers efficiently. Especially, when the copolymerization of these monomers were conducted in fluoroalcohol, the copolymerizability was enhanced to give predominantly alternating copolymers. The obtained copolymers possess relatively high Tg value and stiff main-chain. Furthermore, we succeeded in living/controlled radical (co)polymerizations of these cyclic vinyl monomers.