Controlled Radical Homopolymerization of Representative Cationically Polymerizable Vinyl Ethers

Facile direct radical homopolymerization of vinyl ethers without a hydroxy group was achieved up to near full conversion. This polymerization was conducted in water suspension in the presence of lithium hydroxide using a thermally triggered azo-initiator of dimethyl 2,2′-azobis­(2-methylpropionate). In the polymerization system, appropriate hydrogen bonding and cation−π interactions under basic conditions are keys to the successful direct radical homopolymerization. The hydrogen bonding between water and vinyl ether oxygen reduces the reactivity of the growing radical, thus suppressing unfavorable side reactions such as β-scission. In addition, Li+ interacts with the oxygen and the vinyl group of vinyl ethers. The vinyl ether tends to be “activated” and the polymerization can be facilitated. Based on the results of free radical polymerization of vinyl ethers, controlled polymerization was also accomplished using the appropriate dithiocarbamate RAFT agent in view of the solubilities of the radical leaving group.