Mechanically mediated bulk atom transfer radical polymerization enabled by high‐performance piezoelectric Bi0.5Na0.5TiO3

Abstract This study presents the successful mechanically mediated bulk atom transfer radical polymerization (mechano‐ATRP) of methyl acrylate (MA) using the high‐performance piezoelectric material Bi 0.5 Na 0.5 TiO 3 (BNT) under ultrasonic conditions. Compared to the widely used BaTiO 3 in mechano‐ATRP, BNT demonstrates superior piezoelectric performance, enhancing carrier generation, separation, and interfacial transfer. The strong interaction between BNT and Cu catalysts facilitates the rapid capture of mechano‐induced electrons, leading to the formation of Cu I /L and efficient polymerization initiation. Factors such as piezoelectric material loading, Cu catalyst loading, targeted degrees of polymerization, and sonication power were systematically evaluated. The living nature of ATRP was confirmed by polymers with predetermined molecular weights and low dispersitis (<1.2). This work broadens the application of ATRP and offers valuable insights into the design of piezoelectric catalytic materials for mechano‐ATRP.