Effects of Molecular Weight on the Crystallization and Melting Behaviors of Poly(L-lactide)

In this study, a series of monodispersed poly（L-lactide）（PLLA） were synthesized by the ring-opening polymerization with Schiff base aluminum catalyst, and the effects of the number-average molecular weight（Mn） on the crystallization and melting behaviors of PLLA were investigated by differential scanning calorimetry（DSC） and wide-angle X-ray diffraction（WAXD）. The total crystallization rate of PLLA was Mn-dependent, which reached the maximum value for PLLA with Mn of 18.6 kg/mol. In addition, when Mn of PLLA was 18.6 kg/mol, the melting enthalpy（ΔHm） showed a maximum value（87.1 J/g）, which was the highest reported value till now. The critical temperature for change of crystal formation from ？-form to ？-form crystals increased in the isothermal crystallization process with Mn increasing. In the reheating procedure, high-Mn PLLA demonstrated a small exothermal peak prior to the dominant melting peak, corresponding to crystal transition from ？- to ？-form, but low-Mn PLLA didn＇t show the peak of crystal transition. These different crystallization and melting behaviors were attributed to the different chain mobility of PLLA with different Mn.

Equilibrium Crystallization Temperature of Syndiotactic Polystyrene γ Form

The crystallization behavior of syndiotactic polystyrene（s PS） γ form undergoing annealing at various temperatures was investigated using the thermodynamic phase diagram based on Strobl＇s crystallization theory. On the basis of the differential scanning calorimetric results, it was observed that γ form melt-recrystallization occurred at a higher temperature with the increasing lamellar thickness, which resulted from the pre-annealing at the elevating temperature after acetone induced crystallization. Further temperature dependent small-angle X-ray scattering（SAXS） measurement revealed the evolution of the γ form lamellae upon heating until phase transition, involving three different regimes： lamellae stable region（25-90 °C）, melt-recrystallization region（90-185 °C） and pre-phase transition region（185-195 °C）. As a result, recrystallization line, equilibrium recrystallization line and melting line were developed for the s PS γ form crystallization process. Since the melt of γ form involved a γ-to-α/β form phase transition, the melting line was also denoted as the phase transition line in this special case. Therefore, the equilibrium crystallization temperature and melting（phase transition） temperatures were determined at around 390 and 220 °C on the basis of the thermodynamic phase diagram of the s PS γ form.