Ethylene Polymerization‐Induced Self‐Assembly (PISA) of Poly(ethylene oxide)‐block‐polyethylene Copolymers via RAFT

Abstract

AbstractPoly(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).