Polymerization of Ethylene through Reversible Addition–Fragmentation Chain Transfer (RAFT)

The present paper reports the first example of a controlled radical polymerization of ethylene using reversible addition–fragmentation chain transfer (RAFT) in the presence of xanthates (Alkyl‐OC(?S)S‐R) as controlling agents under relative mild conditions (70 °C, <200 bars). The specific reactivity of the produced alkyl‐type propagating radicals induces a side fragmentation reaction of the stabilizing O‐alkyl Z group of the controlling agents. This fragmentation, rarely observed in RAFT, was proven by NMR analyses. In addition, semicrystalline copolymers of ethylene and vinyl acetate were also prepared with a similar level of control.