Iodine‐Transfer Polymerization (ITP) of Ethylene and Copolymerization with Vinyl Acetate

Controlled radical polymerization of ethylene using different commercially available, cheap, and non‐toxic iodo alkyls is performed by iodine transfer polymerization (ITP) under mild conditions (≤100 °C and ≤200 bar). The formed well‐defined iodo end‐capped polyethylene (PE−I) species is very stable upon storage. Narrow molar‐mass distributions (dispersities around 1.6) were obtained up to number average molar masses of 7300 g mol −1 . The ethylene copolymerization by ITP (ITcoP) with vinyl acetate allowed to form a broad range of poly(ethylene‐ co ‐vinyl acetate) (EVA) containing from 0 to 85 mol % of VAc unit. In addition, EVA‐ b ‐PE block copolymers or EVA‐ b ‐EVA gradient block copolymers with different content of VAc in the blocks were obtained for the first time using ITP. Finally, reactivity trends were explored by a theoretical mechanistic study. This highly versatile synthetic platform provides a straightforward access to a diverse range of well‐defined PE based polymer materials.