Dithioketal Polymers Via Radical Polymerization of γ‐Dithiobutyrolactone

ABSTRACT Polymers bearing in‐chain dithioketal groups are an emerging class of materials with specific properties like reactive oxygen species (ROS)‐responsiveness and vitrimer‐type behavior. Until now, these polymers have been exclusively produced by step‐growth polymerization or polyaddition; herein, we report the first chain polymerization leading to dithioketal polymers. γ‐dithiobutyrolactone (DTBL) is radically copolymerized with a series of conjugated monomers to yield copolymers with ring‐retained dithioketal units exclusively. DFT calculations rationalize the contrasting behaviors of DTBL and its thionolactone analogue γ‐thionobutyrolactone (TBL), highlighting how electronic effects of the ring heteroatoms govern propagation efficiency and ring‐retention versus ring‐opening pathways. The ability of DTBL to bring degradability to thermosets, latexes, and RAFT‐derived complex architectures is revealed.