Chain polymerizations are defined as chain reactions where the propagation steps occur by reaction between monomer(s) and active site(s) on the polymer chains with regeneration of the active site(s) at each step. Many forms of chain polymerization can be distinguished according to the mechanism of the propagation step (e.g., cyclopolymerization – when rings are formed, condensative chain polymerization – when propagation is a condensation reaction, group-transfer polymerization, polyinsertion, ring-opening polymerization – when rings are opened), whether they involve a termination step or not (e.g., living polymerization – when termination is absent, reversible-deactivation polymerization), whether a transfer step is involved (e.g., degenerative-transfer polymerization), and the type of chain carrier or active site (e.g., radical, ion, electrophile, nucleophile, coordination complex).
The objective of this document is to provide a language for describing chain polymerizations that is both readily understandable and self-consistent, and which covers recent developments in this rapidly evolving field.
Keywords: chain polymerization, radical, anionic, cationic, coordination, catalyst-transfer
Public review ended 31 March 2022
IUPAC Recommendations published in PAC vol. 94, no. 9, 2022, pp. 1093-1147.