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.
Poly(ethylene oxide) (PEO) with dithiocarbamate chain ends (PEO–SC(=S)−N(CH3)Ph and PEO–SC(=S)−NPh2, named PEO‐1 and PEO‐2, respectively) were used as macromolecular chain‐transfer agents (macro‐CTAs) to mediate the reversible addition–fragmentation chain transfer (RAFT) polymerization of ethylene in dimethyl carbonate (DMC) under relatively mild conditions (80 °C, 80 bar). While only a slow consumption of PEO‐1 was observed, the rapid consumption of PEO‐2 led to a clean chain extension and the formation of a polyethylene (PE) segment. Upon polymerization, the resulting block copolymers PEO‐b‐PE self‐assembled into nanometric objects according to a polymerization‐induced self‐assembly (PISA).
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