Control of Free‐Radical Polymerization by Chain Transfer Methods

This chapter describes the various chain transfer methods currently used in free-radical polymerization for the control of molecular weight, structure, and functionality. The basic concepts on chain transfer are introduced and some of the traditional chain transfer methodologies that are still in use today are illustrated. The development of chain transfer techniques toward more efficient methods of molecular weight, polydispersity, and structural control in polymers are presented. The authors introduce the concept of chain transfer by addition-fragmentation and show how macromonomers can act as chain transfer agents for reducing molecular weight. The chapter concludes with comparisons with other reversible (degenerative) chain transfer methods employing alkyl iodides and diphenyl ditellurides.