Ethylene polymerization-induced self-assembly (PISA) of poly(ethylene oxide)-block-polyethylene copolymers via RAFT.

Poly(ethylene oxide) (PEO) with dithiocarbamate chain ends (PEO-SC(=S)-N(CH 3 )Ph and PEO-SC(=S)-NPh 2 , named PEO-1 and PEO-2 , respectively) were used as macromolecular chain transfer agents (macro-CTA) to mediate the reversible addition-fragmentation chain transfer (RAFT) polymerization of ethylene in dimethyl carbonate (DMC) under relatively mild conditions (80 degrees 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).