Multifunctionalization of polybutadiene by RAFT/MADIX technology†

Abstract

Polybutadiene, a widely used synthetic rubber containing unsaturated bonds, has traditionally undergone functionalization processes such as thiol–ene radical addition, hydrogenation, and epoxidation. In this study, we present a new approach for multi-functionalizing polybutadiene through the reversible addition–fragmentation chain transfer polymerization/macromolecular design by interchange of xanthates (RAFT/MADIX) technology. The addition of xanthates onto polybutadiene was accomplished by thermal initiation, photoinitiation, or oxygen-mediated processes. Leveraging the sustained reactivity of dithiocarbonate on functionalized polymer, we further realized dexanthylation and transformation of dithiocarbonate. Finally, xanthate crosslinkers were synthesized for the simultaneous functionalization and cross-linking of polybutadiene.