Enhancing Ultrasound-Assisted Iodine-Mediated Reversible-Deactivation Radical Polymerization by Piezoelectric Nanoparticles

The development of mechanochemical tools for regulating the polymerization process has received an increasing amount of attention in recent years. Herein, we report the example of the mechanically controlled iodine-mediated reversible-deactivation radical polymerization (mechano-RDRP) using piezoelectric tetragonal BaTiO3 nanoparticles (T-BTO) as mechanoredox catalyst and alkyl iodide as the initiator. We demonstrated a more efficient mechanochemical initiation and reversible deactivation process than sonochemical activation via a mechanoredox-mediated alkyl iodide cleavage reaction. The mechanochemical activation of the C–I bond was verified by density functional theory (DFT) calculations. Theoretical calculations together with experimental results confirmed the more efficient initiation and polymerization than the traditional sonochemical approach. The influence of BaTiO3, initiator, and solvent was further examined to reveal the mechanism of the mechano-RDRP. The results showed good controllability over molecular weight and capacity for a one-pot chain extension. This work expands the scope of mechanically controlled polymerization and shows good potential in the construction of adaptive materials.