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

Atom transfer radical polymerization (ATRP) and reversible\naddition–fragmentation\nchain transfer polymerization (RAFT) are two independent polymer synthesis\nmethods. Here, we show that the synergy between the ATRP and RAFT\ndegenerative transfer mechanisms under emulsion conditions is a promising\nand attractive option for scalable and efficient polymerization processes,\noffering significant advantages over stand-alone procedures. They\nwork synergistically, reinforcing each other and relaxing the stringent\nconditions required for controlled radical polymerization in emulsion.\nThis drastically reduces the metal loading and environmental impact.\nStable, well-defined latexes of poly(<i>n</i>-butyl methacrylate)\nwith predetermined molecular weights and <i>Đ</i> <\n1.5 were obtained with only 50 μM Cu (18.3 ppm) on a 1 L scale\nand even below this concentration on a 20 mL scale. The latex color\nimparted by the RAFT chain transfer agent was catalytically decolorized\nby a one-pot, nondisruptive method using an ATRP Cu catalyst via the\noxygen reduction reaction (ORR).