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(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).