Understanding synthesis and degradation of backbone deconstructable (co)polymers by radical ring-opening polymerization through theoretical calculation and numerical simulation

Radical ring-opening polymerization (rROP) has gained widespread attention due to the facile incorporation of cleavable groups (e.g. ester, thioesters) into all-carbon backbone vinyl polymers. The inclusion of a cleavable comonomer makes the vinyl copolymers biodegradable. However, competition between the ring-opening of cyclic monomer and vinyl addition without ring-opening, as well as efficient insertion of cleavable comonomer into the backbone, are challenging for rROP. This minireview discusses the latest developments in theoretical and numerical simulations of rROP, offering deep insights into both polymerization and degradation processes, including mechanistic identification, kinetic features, and chain microstructure tuning. Besides, challenges and future directions are included to attract more efforts to better perform rROP and deconstruction process.