Synthesis of Block Copolymers Based on Polyethylene by Thermally Induced Controlled Radical Polymerization Using Mn 2 (CO) 10

Iodo functionalized polyethylene (PE‐I), prepared by the addition of iodine after catalyzed poly­ethylene chain growth on magnesium, is demonstrated to be an efficient macroinitiator for thermally induced, controlled free radical polymerization using dimanganese decacarbonyl (Mn 2 (CO) 10 ). The free radical polymerization of methyl methacrylate is initiated by thermal homolysis of (Mn 2 (CO) 10 ) at 80 °C, forming reactive manganese pentacarbonyl radical species [•Mn(CO) 5 ] capable of activating the C−I bond of PE‐I. The metal catalyzed radical generation and degenerative iodine processes yielded polyethylene‐ b ‐poly(methyl methacrylate) (PE‐ b ‐PMMA) block copolymers with relatively low dispersities. The end group functionality of the block copolymer is confirmed by the successful thermal polymerization of styrene by using PE‐ b ‐PMMA as a macro­initiator in the described process. This work conclusively provides a new approach for combining polyethylene with vinyl polymers via manganese chemistry in a simple and efficient pathway of importance in synthetic polymer chemistry and other related applications.