Tribochemically Controlled Atom Transfer Radical Polymerization Enabled by Contact Electrification

Abstract Traditional mechanochemically controlled reversible‐deactivation radical polymerization (RDRP) utilizes ultrasound or ball milling to regenerate activators, which induce side reactions because of the high‐energy and high‐frequency stimuli. Here, we propose a facile approach for tribochemically atom transfer (tribo‐ATRP) that relies on contact‐electro‐catalysis (CEC) between titanium oxide (TiO 2 ) particles CuBr /tris(2‐pyridylmethylamine (TPMA), without any input. Under friction induced by stirring, TiO are electrified, continuously reducing /TPMA into CuBr/TPMA, thereby conversing alkyl halides active radicals start ATRP. In addition, effect reaction was elucidated theoretical simulation. The results indicated increasing frequency could reduce energy barrier electron from /TPMA. this study, design tribo‐ATRP successfully achieved, enabling CEC (ca. 10 Hz) access variety polymers with predetermined molecular weights, low dispersity, high chain‐end fidelity.