Stereospecific Living Polymerization of Methacrylate with Binary Initiator Systems

Abstract

Three kinds of stereospecific polymerizations of methacrylate are described; isotactic-specific, syndiotactic-specific, and heterotactic-specific ones, all of which utilize binary initiator systems comprising bulky anionic initiator and Lewis acid; the latter works as stereo specificity modifier. Particular emphasis is placed on the unique synthetic utility of bulky aluminum phenoxides in methacrylate polymerization; heterotactic polymerization of primary and secondary alkyl esters, syndiotactic polymerization of tertiary esters, monomer-selective copolymerization leading to the formation of block copolymer with high stereoregularity, regioselective polymerization of a dimethacrylate, affording a soluble, reactive polymer, and polymerization of methacrylate having sterically protected phenol group by anionic mechanism.