Recent advances in the well-controlled synthesis of poly(vinyl ether)s via cationic polymerization

This review summarizes recent progress in the controlled cationic polymerization of vinyl ethers, enabling the synthesis of isotactic poly(vinyl ether)s (PVEs) with controlled molecular weights. By addressing challenges such as highly reactive cationic species, unavoidable chain transfer, and the limitations of stereoselective initiators, several pioneering protocols have been developed to achieve well-controlled molecular weights and stereochemistry or both. Further control over the architectures of these PVEs was also discussed. Challenges remain in operational practicality, catalyst cost, and monomer scope, promoting future research towards hybrid catalysts, ligand optimization, and sustainable processes.