Controlled radical polymerization of ethylene using different commercially available,c heap,a nd non-toxici odo alkyls is performed by iodine transfer polymerization (ITP) under mild conditions (100 8 8Ca nd 200 bar). The formed well-defined iodo end-capped polyethylene (PEÀI) species is very stable upon storage.N arrow molar-mass distributions (dispersities around 1.6) were obtained up to number average molar masses of 7300 gmol À1 .T he ethylene copolymerization by ITP (ITcoP) with vinyl acetate allowed to form ab road range of poly(ethylene-co-vinyl acetate) (EVA) containing from 0to85mol %ofV Ac unit. In addition, EVA-b-PE block copolymers or EVA-b-EVAg radient blockc opolymers with different content of VA cinthe blocks were obtained for the first time using ITP.F inally,r eactivity trends were explored by at heoretical mechanistic study.T his highly versatile synthetic platform provides astraightforwardaccess to adiverse range of well-defined PE based polymer materials. À1 represent reaction rate coefficients for iodine transfer.

PhMg(CH2)5MgPh and MesMg(CH2)5MgMes – divalent bis-metalated chain transfer agents (CTA) – were designed, synthesized and implemented in the polymerization of ethylene or the copolymerization of ethylene with butadiene mediated by...