Step-growth irreversible deactivation radical polymerization: synergistic developments with chain-growth reversible deactivation radical polymerization

Recent advances in chain-growth reversible deactivation radical polymerization (CG-RDRP), i.e. the so-called “living radical polymerization”, have synergistically developed step-growth radical polymerizations via controlled formation of radical species from covalent bonds followed by irreversible deactivation of the resulting radical species. The monomers for radical polyaddition are thus designed to possess carbon–halogen or thioester bonds, which can generate radical species in the presence of transition metal catalysts and radical initiators, as well as carbon‒carbon double bonds, which will irreversibly form carbon–halogen or thioester bonds. Radical polycondensations are achievable via radical coupling reactions of carbon-centered radicals generated from carbon–halogen bonds or radical quenching reactions with nitroxides. Furthermore, radical addition-condensation polymerizations are achieved by a sequence of reactions, i.e. the formation of radical species from carbon–halogen bonds, radical addition to nitroso or thiocarbonylthio compounds, and coupling or quenching reactions with the resulting stable radical. These step-growth irreversible deactivation radical polymerizations (SG-IDRP) enable the synthesis of a variety of polymers, such as polyethers, polyesters, polyamides, and polyimides, which have aliphatic, aromatic, polar, and degradable groups in their main chains. Sequence-regulated vinyl polymer structures can also be constructed by designing monomers. Combinations with CG-RDRPs further lead to unique hybrid block, multiblock, graft, hyperbranched, and network polymers.