Pushing the limits of mechanoredox RAFT polymerization methods

Integral aspects of what is considered green chemistry include minimizing solvent use and utilizing energy-efficient methods to synthesize target materials. For polymer synthesis in particular, accessing copolymer sequences derived from immiscible feedstocks and masses in the ultra-high molecular weight regime (>1 MDa) often require specialized methods, extensive optimization, and may consume large amounts of energy. In this work, we report on the synthesis of diverse polyacrylates inspired by the principles of green chemistry using streamlined ball mill grinding methodology. Mechanoredox reversible addition-fragmentation chain-transfer (MR-RAFT) polymerizations are used herein to synthesize multiblock copolymers from immiscible monomers and overcome viscosity restraints to reach ultra-high molecular weights. The ability to access these traditionally challenging-to-synthesize polymers using a (nearly) solvent-free method will enable the discovery of novel materials with minimal environmental impact.