The development of fully metal-free strategies for the synthesis and functionalization of polymers is crucial for advancing sustainable materials. This study introduces a platform that integrates metal-free reversible addition–fragmentation chain-transfer (RAFT) polymerization with sulfur(VI) fluoride exchange (SuFEx) chemistry to enable the controlled polymerization and postpolymerization side-chain modification of renewable polymers. Silyl-protected poly(vinylphenol) (PSVP)s and poly(vinyl catechol) (PSVC) derived from cinnamic acid analogs were synthesized and subsequently functionalized with a range of sulfonyl fluorides bearing electron-donating or electron-withdrawing substituents. High degrees of modification were achieved for para-substituted PSVP, while meta-substituted PSVP and their corresponding block copolymers exhibited high conversions with minimal side reactions. By contrast, ortho-substituted PSVP and PSVC systems generally exhibited moderate efficiencies, consistent with steric hindrance. This fully metal-free sequence provides a sustainable and versatile strategy for the functionalization of biobased polymers, expanding the scope of SuFEx chemistry and contributing to the development of environmentally sustainable polymer materials.
Inagaki et al. (2026) studied this question.