Achieving High‐Conversion Bulk ATRP with Good Livingness and Well Controlled by Design and Optimization of Polymerization Temperature Profile

Abstract Controlled radical polymerization (CRP) such as atom transfer radical polymerization (ATRP) is often conducted in solution processes and stopped at medium monomer conversions to yield well controlled polymer samples. A great challenge lies in running bulk CRP up to high conversions but still retaining system livingness and molecular weight control. In this work, we demonstrate the achievement of good living and well controlled high‐conversion bulk ATRP by means of design and optimizing polymerization thermal histories. The initiator‐for‐continues‐activator‐regeneration (ICAR) ATRP of methyl methacrylate (MMA) is used as a model system. Employing step functions in temperature, MMA conversions are pushed up to 98% and the PMMA samples possess polydispersities <1.3. Chain extension experiments confirm good livingness of synthesized polymers collected at high conversions.