Fenton-RAFT polymerization in organic media†

Fenton-RAFT polymerization is of growing interest in the field of reversible deactivation radical polymerization (RDRP) due to its ability to efficiently initiate polymerization through homogeneous and heterogeneous catalysis. In our previous works, we described the successful synthesis of hydrophilic polymers using Fenton reaction-mediated reversible addition–fragmentation chain transfer (Fenton-RAFT) polymerization in the aqueous phase. However, the synthesis of hydrophobic polymers using this method remained challenging due to difficulties in implementing redox reactions in organic solvents. In this study, we developed the organic Fenton-RAFT method by utilizing Fe(ii)–metal–organic framework (MOF) particles to synthesize hydrophobic polymers in dimethylsulfoxide (DMSO) at ambient temperature. We achieved monomer conversion values as high as nearly quantitative and dispersity (Đ) values as low as 1.15. We also observed a good agreement between the theoretical and experimental values of number-average molecular weight (M_n). Furthermore, we demonstrated the living characteristics of the organic Fenton-RAFT through kinetic studies, chain extension experiments, and different polymer chain syntheses. MOFs possess catalytic activity in both aqueous and organic media due to their metallic and organic sections. Therefore, the concept of MOFs can facilitate the implementation of many redox-initiated RDRP techniques that were previously difficult to achieve in an organic environment.