Synthesis of N‐Vinyl Lactam Copolymers by Controlled Radical Polymerizations

Abstract

Free radical polymerization is one of the most versatile techniques for commercial and labscale production of high molecular weight polymers. This chapter discusses recent advances made in the synthesis of polyvinyl pyrrolidone or polyvinyl caprolactam and their copolymers with other monomers using Controlled Radical Polymerization (CRP) techniques like Nitroxide Mediated Polymerization (NMP), Atom Transfer Radical Polymerization (ATRP), Organometallic‐Mediated Radical Polymerization, and Reversible Addition Fragmentation Chain‐Transfer (RAFT) Polymerization. In NMP, nitroxides or alkoxyamines are used to direct the reactions to achieve polymerization control. ATRP is among the most effective and widely used methods of CRP. Controlled polymerization of unconjugated monomers is inherently difficult with both ATRP and NMP. RAFT utilizes a chain transfer agent to control the molecular weight and polydispersity of the resultant polymer by reversible addition and fragmentation events with the endcapped polymer containing the RAFT agent.