Synergistic Radical Taming by Concurrent Degenerative Transfer and Atom Transfer Radical Polymerization in Emulsion

Atom transfer radical polymerization (ATRP) and reversible addition–fragmentation chain transfer polymerization (RAFT) are two independent polymer synthesis methods. Here, we show that the synergy between the ATRP and RAFT degenerative transfer mechanisms under emulsion conditions is a promising and attractive option for scalable and efficient polymerization processes, offering significant advantages over stand-alone procedures. They work synergistically, reinforcing each other and relaxing the stringent conditions required for controlled radical polymerization in emulsion. This drastically reduces the metal loading and environmental impact. Stable, well-defined latexes of poly( n -butyl methacrylate) with predetermined molecular weights and Đ < 1.5 were obtained with only 50 μM Cu (18.3 ppm) on a 1 L scale and even below this concentration on a 20 mL scale. The latex color imparted by the RAFT chain transfer agent was catalytically decolorized by a one-pot, nondisruptive method using an ATRP Cu catalyst via the oxygen reduction reaction (ORR).