The graft copolymers of starch with polycaprolactone (PCL) were prepared through ring opening polymerization of ε‐CL in bulk using N‐methylimidazole (NMI) as catalyst. The graft reaction was detected by FTIR, NMR, and the resultant starch‐g‐PCL copolymers were characterized by DSC, MEB, and XRD. Homopolymerization of CL monomer did not occur during the grafting polymerization and hydrophobicity of the resulting material was highlighted by solvent test and water contact angle measurement.
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