Living Radical Polymerization of Non-Radically Polymerizable Monomers

乙烯基醚本身不能通过自由基机理聚合。相反，乙烯基醚只有通过阳离子聚合才能聚合成高分子量的产品。阳离子聚合是已知的受亲核性的存在的影响，如水和带有羟基的单体。然而，带有羟基的乙烯基醚是一种有趣的单体，具有通过自由基聚合的潜力。这是因为乙烯基醚中乙烯基部分的电子密度因单体的羟基和乙醚之间的氢键而改变。因此，本项目研究了含羟基乙烯基醚的直接自由基聚合，作为非自由基可聚合单体的精确自由基聚合的基础。

Vinyl ethers cannot be inherently polymerized via radical mechanism. In contrast, the vinyl ethers can be polymerized into high molecular weight products only by cationic polymerizations. The cationic polymerization is known to be influenced by the presence of nucleophiles such as water and monomer with a hydroxyl group. However, the vinyl ether with a hydroxyl group is an interesting monomer with the potential to polymerize by radical process. This is because the electron density of the vinyl moiety in vinyl ethers is changed by the hydrogen bonding between the hydroxyl group and the ether of the monomer. Thus, direct radical polymerization using the vinyl ether having a hydroxyl group was investigated in this project as the basis of precision radical polymerization of non-radically polymerizable monomers.