ABSTRACT

Living ionic polymerizations include living anionic polymerization, which was first reported by Swartz in 1956, and living cationic polymerization, which was first reported by several research teams in the early 1980s. This chapter provides ten papers on the synthesis of functional polymers by living ionic polymerizations and describes four key strategies to access functional polymers. The first strategy is selective living anionic polymerization of asymmetrical divinyl monomers. The second strategy employs living anionic polymerization of acetal-protected vinyl monomers. The third strategy is based on living anionic polymerization of glycidyl-functionalized monomers, in which glycidyl functionalities are intact under the polymerization conditions. The fourth strategy utilizes living anionic polymerization of inimers, each consisting of a monomer functionality for anionic polymerization and an initiator group for cationic polymerization. Anionic polymerization of such inimers yielded well-defined polyinitiators that can initiate living cationic polymerization for further synthesis of graft copolymers.