Role of PEG Segment in Stereocomplex Crystallization for PLLA/PDLA-b-PEG-b-PDLA Blends

The isothermal crystallization behavior and morphology of neat poly(l-lactic acid) (PLLA) and its blends with poly(d-lactic acid) (PDLA) and PDLA-b-poly(ethylene glycol) (PEG)-b-PDLA have been investigated. The glass transition temperature of the PLLA/PDLA blend, and especially the PLLA/PDLA-b-PEG-b-PDLA blend, is much lower than that of neat PLLA, indicating the plasticization effect of both low molecular weight PDLA and flexible PEG block. Both the PLLA/PDLA and PLLA/PDLA-b-PEG-b-PDLA blends can form stereocomplex (SC) crystals. However, the PDLA in the PLLA/PDLA blend postponed the crystallization rate of the blend, whereas the PEG chains in PLLA/PDLA-b-PEG-b-PDLA not only promoted the formation of SC crystals but also facilitated the crystallization of the PLLA matrix. The evolution of the crystal structure and morphologies of PLLA and its blends during the isothermal crystallization process have revealed the significant role of flexible PEG chains in the stereocomplex crystallization.