Abstract The chloro-functionalized poly(ε-caprolactone) [P(CL-co-αClεCL)] was prepared by the ring-opening polymerization of chloro-functionalized ε-caprolactone (αClεCL) and unsubstituted ε-caprolactone (CL). The halide groups of P(CL-co-αClεCL) were then converted to azides. The amphipathic graft copolymers (PCL-g-PEG) bearing the PCL backbone and poly(ethylene glycol) (PEG) grafting chain were prepared by the azide-alkyne click chemistry and their micellar self-assembly in the aqueous solution was investigated. It was found that the PCL-g-PEG graft copolymers self-assembled into the micelles containing the PCL core and PEG shell in the aqueous solution. The critical micelle concentration(CMC) of graft copolymers were in the range of 30 mg/L to 66 mg/L and their Dh values were in the range of 104 nm to 136 nm. The CMC and Dh of graft copolymers increased with the grafting length. At the same grafting length, Dh increased as the grafting density was decreased.
