Stereocomplex Crystallite Network in Asymmetric PLLA/PDLA Blends: Formation, Structure, and Confining Effect on the Crystallization Rate of Homocrystallites

Stereocomplex (SC) crystallites, formed between enantiomeric poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA), show a melting point 50 degrees C higher than that of PLLA or PDLA homocrystallites, which makes it possible for SC crystallites to be reserved in the melt of PLLA in asymmetric PLLA/PDLA blends and to act as a rheological modifier and a nucleation agent for PLLA. Herein, by a rheological approach, a transition from the liquid-like to solid-like viscoelastic behavior was observed for the SC crystallites reserved melt, and a frequency-independent loss tangent at low frequencies appeared at a PDLA concentration of 2.0 wt %, revealing the formation of SC crystallite network. By a delicately designed dissolution experiment, the structure of the formed network was explored. The results indicate that the network are not formed by SC crystallites connected directly with each other or by bridging molecules, but by the interparticle polymer chains which are significantly restrained by the cross-linking effect of SC crystallites. Nonisothermal and isothermal crystallization show that the reserved SC crystallites can accelerate remarkably the crystallization rate of PLLA due to heterogeneous nucleation effect. Besides, a special PDLA concentration dependence, e.g., the overall crystallization rate is almost independent of PDLA content for the blends with PDLA content higher than PDLA percolation concentration (2.0 wt %), was also observed. The increase of nuclei density for the blends containing PDLA from 2 to 5 wt % was estimated from POM observations. The result of an enhanced nucleation but an unchanged overall crystallization rate reveals the confining effect of the SC crystallite network on PLLA crystallization. This confining effect can be ascribed to the restrained diffusion ability of PLLA chains owing to the SC crystallite network.