Gao Li

The poly(D-lactide)/poly(L-lactide) (PDLA/PLLA) blends with low molecular weights were cast from solution. After heating to above the melting temperature, followed by cooling at various rates, DSC, WAXD and FTIR studies revealed that a mesomorphic phase developed in the PDLA/PLLA 90/10 and 80/20 (or 10/90 and 20/80) specimens when the temperature window spanned from 80 °C to 110 °C. The mesophase melted and reorganized into crystallites after the temperature increased to ∼130 °C. Although the formation and transition of the mesophase was observed at lower temperatures in partially crystallized specimens, the mesophase could exist steadily when the temperature did not exceed 100 °C. The content of the mesophase was proven to be strongly dependent on the cooling rate, the D/L weight ratio and the molecular weights in the blends. The formation of the mesophase could be explained by the fact that the crystallization of the PLA matrix was disturbed by the addition of small amount of enantiomeric PLA.

Poly(L‐lactide) (PLLA) is melt blended with poly(ether urethane) (PEU) based on poly(ethylene glycol) blocks via a chain‐extension reaction by diisocyanate as a chain extender to improve its flexibility without sacrificing comprehensive performance. The elongation at break of the blends with triphenyl phosphate (TPP) as a reactive blending additive is much higher than that without TPP by physical blending. When 10 wt% PEU is blended, the former elongation reaches to 298%, while the latter one is only approximately 20%. The reactive blending forms a PLLA–PEU block copolymer, thus improving their compatibility. When the weight‐average molecular weight (M_w) of PEUs is 18–90 kg mol⁻¹, the effect of M_w is very little on tensile properties of blends. The rheological properties of the blends are modified through the content and molecular weight of PEU. The complex viscosity (η*) of PLLA/PEU blends increases with increasing M_w of PEU. The η* of the PLLA blend containing 5 wt% PEU in M_w 73 kg mol⁻¹ is higher than that of neat PLLA. The water absorption of the PLLA/PEU blends enhances because of the hydrophilicity of PEUs versus neat PLLA. magnified image

Stereocomplex poly(lactide)s (sc-PLAs) were obtained from solution blending of 3-armed poly(l-lactide) (3PLLA) and linear poly(d-lactide) (PDLA) and between enantiomeric 3PLAs. Differential scanning calorimetry and wide-angle X-ray diffraction results indicated that racemic crystallites were preferentially produced in all the binary blends. The melting temperature and fusion enthalpy of racemic crystallites were remarkably different through varying the structure, constituent, and molecular weight of PLA. Through this investigation, higher melting temperatures were obtained in the middle molecular weight binary blends, and the highest melt temperature of racemic crystallites reached to 246 °C, it was the highest reported value until now. In similar molecular weight blends (or the linear PLA was similar to each branch of 3PLA enantiomers), with the composition of 3PLA increasing, the phase separation molecular weight decreased gradually (M_{linear/linear blends} > M_{linear/3-armed blends} > M_{3-armed/3-armed blends}). The structure distinction between 3PLA and linear PLA induced different thermal properties and phase behaviors of the 3PLLA/PDLA and 3PLLA/3PDLA blends. The thermal properties of these mixtures and its variations provided basic data for their industrial applications.

The confined crystallization behavior, melting behavior, and nonisothermal crystallization kinetics of the poly(ethylene glycol) block (PEG) in poly(L‐lactide)–poly(ethylene glycol) (PLLA–PEG) diblock copolymers were investigated with wide‐angle X‐ray diffraction and differential scanning calorimetry. The analysis showed that the nonisothermal crystallization behavior changed from fitting the Ozawa equation and the Avrami equation modified by Jeziorny to deviating from them with the molecular weight of the poly(L‐lactide) (PLLA) block increasing. This resulted from the gradual strengthening of the confined effect, which was imposed by the crystallization of the PLLA block. The nucleation mechanism of the PEG block of PLLA15000–PEG5000 at a larger degree of supercooling was different from that of PLLA2500–PEG5000, PLLA5000–PEG5000, and PEG5000 (the numbers after PEG and PLLA denote the molecular weights of the PEG and PLLA blocks, respectively). They were homogeneous nucleation and heterogeneous nucleation, respectively. The PLLA block bonded chemically with the PEG block and increased the crystallization activation energy, but it provided nucleating sites for the crystallization of the PEG block, and the crystallization rate rose when it was heterogeneous nucleation. The number of melting peaks was three and one for the PEG homopolymer and the PEG block of the diblock copolymers, respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3215–3226, 2006