In the present work, the PLLA mesophase formation and its kinetics at the advent of a chain mobility accelerator （polyethylene glycol （PEG）） are investigated by wide angle X-ray diffraction （WAXD） and time-resolved Fourier transform infrared spectroscopy （FTIR）. It is interestingly found that the presence of PEG could accelerate the formation of PLLA mesophase notably due to the enhanced chain mobility, giving rise to a substantially reduced half time （t0.5） of PLLA mesophase formation from 129 min to 8 min. The Avrami exponents （n） for the kinetics of mesophase formation are -0.5 for neat PLLA and 1 for PLLA/PEG, respectively, indicating that 1D-rod growth through heterogeneous nucleation occurs during formation of PLLA mesophase. Tensile testing demonstrates that PLLA mesophase could increase the tensile strength and modulus but decrease the elongation at break.
