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Previously, well-defined polyethylene-b-poly(ethylene glycol) diblock copolymers (PE-b-PEG) was prepared by ATRP, RAFT or click chemistry.These methods were complicated and difficult to be industrialized.[1-6] In this paper, PE-b-PEG was successfully synthesized by a coupling reaction of hydroxyl-terminated polyethylene (PE-OH) and isocyanate-terminated poly(ethylene glycol) (PEG-NCO).