Influence of Chain Architectures on Crystallization Behaviors of PLLA Block in PEG/PLLA Block Copolymers

摘要

The effect of the architecture of poly(ethylene glycol)/poly(L-lactide)(PEG/PLLA) block copolymers on the non-isothermal crystallization behaviors of PLLA blocks was investigated by differential scanning calorimetry(DSC) and wide angle X-ray diffraction(WAXD). 1-Arm MPEG-b-PLLA and 4-arm PEG-b-PLLA(4PEG-b-PLLA) were synthesized by the ring-opening polymerization of Llactide in the presence of poly(ethylene glycol) methyl ether(MPEG) and 4-arm poly(ethylene glycol)(4PEG). 4-Arm PLLA-b-MPEG(4PLLA-b-PEG) was synthesized by coupling 4-arm PLLA and MPEG. The WAXD results indicated that the crystalline structure of PLLA blocks did not alter due to the different chain architectures. The average values of Avrami index(ˉn) were all above 4, which indicated that the nucleation mechanism of PLLA blocks was heterogeneous nucleation, regardless of the architectures. The overall crystallization rates were decreased markedly as following: MPEG-b-PLLA > 4PEG-b-PLLA > 4PLLA-b-PEG, ascribed to the different confinement by PEG blocks and to the steric hindrance of chain architectures. Therefore, the crystallization of PLLA blocks became more difficult and the crystallization activation energy of the PLLA blocks increased due to the confinement of chain architectures.