<Abstract> The advent of the dormant species, which can be reversibly activated into the propagating species, has opened a new era in precision polymerization and changed the concept of living polymerization. The dormant species can be generated via reversible termination of the propagating species or can be transformed into the propagating species via reversible chain transfer. Reversible or degenerative chain transfer is a thermodynamically neutral and direct exchange reaction between the propagating and dormant species and its judicious use has greatly contributed to the vast developments in precision polymerization. This article presents an overview of the degenerative chain transfer method for controlling molecular weights in various chain-growth polymerizations including radical, cationic, anionic, coordination, ring-opening metathesis, and ring-opening polymerizations. In addition, it briefly focuses on novel strategies for controlling sequences in terms of stereoregularity and comonomer enchainment using reversible chain-transfer agents as chain-shuttling agents that exchange polymer chains between different active sites to produce multiblock structures.
Keywords: Living Polymerization / Degenerative Chain Transfer / Radical Polymerization / Cationic Polymerization / Anionic Polymerization / Coordination Polymerization / Ring-Opening Metathesis Polymerization / Ring-Opening Polymerization |