A Simple and Green Oxygen‐Tolerant RAFT Polymerization without Additional Catalyst and Initiator

Abstract Oxygen‐tolerant reversible addition‐fragmentation chain transfer polymerization (RAFT) can be successfully achieved through the addition of organic and inorganic photoredox catalysts or other additives. Thus, developing a simple oxygen‐tolerant RAFT without additional catalyst and initiator will augment the development of this field. In this work, two‐component systems, 2‐(dimethylamino)ethyl methacrylate (DMAEMA) and 4‐cyanopentanoic acid dithiobenzoate (CPADB), have been successfully applied to develop green and oxygen‐tolerant RAFT under aqueous conditions without any additional catalysts, where dithioester CPADB was employed as an iniferter agent (initiator‐transfer‐terminator) for polymerization control, as well as an intrinsic photoredox catalyst for deoxygenation. DMAEMA was utilized as monomer and electron donor. In the present work, dithioester‐assisted oxygen removal in aqueous RAFT photopolymerization is reported for the first time. This work provides a simple and green method for oxygen‐tolerant RAFT polymerization.