Continuous Spectrum of Morphologies and Phase Behavior across the Contact Zone from Poly(l-lactide) to Poly(d-lactide): Stereocomplex, Homocrystal, and Between

Abstract

The enantiomeric ratio is a key factor affecting the crystallization behavior and morphology of poly-L-lactide/poly-Dlactide (PLLA/PDLA) blends. Despite a number of studies on crystallization of nonequimolar PLLA/PDLA blends, a full picture of the effect of the L/D ratio is still lacking. Here, we put the two enantiomers in contact and allow interdiffusion above the melting point of the stereocomplex crystal (SC) to prepare samples with a continuously changing L/D ratio from enantiopure PLLA (ratio 0/ 100) to enantiopure PDLA (100/0). Using polarized optical microscopy, atomic force microscopy, and microbeam X-ray diffraction, the continuous spectrum of morphologies and phase behaviors across the contact zone is investigated. The blend morphology shows clear evidence of "poisoning by purity" of SC crystallization at all blend compositions. The low birefringence of the 50/50 SC is found to be due to the meandering of broken edge-on lamellae. Its further decrease to near zero as L/D deviates further away from 50/50 is explained by transition from radial edge-on lamellae to fully random meandering lamellae, then to mixed flat-on lamellae, and finally to submicron-sized axialites. In comparison with the smooth and straight homocrystal (HC) lamellae of pure enantiomers, the lamellae in the blends often have serrated edges caused by pinning by rejected excess enantiomer acting as an impurity during lamellar growth. A feature of the binary phase diagram is pure enantiomers acting as an impurity to the SC and counter-enantiomer acting as an impurity to homocrystallization of the enantiomers. Crystallization was found to be most suppressed at 99% enantiomeric purity, where the amount of the counter-enantiomer is insufficient for creation of SC nuclei and HC growth is inhibited by the small amount of the enantio-impurity. These and other intriguing results are less likely to be noticed without the continuous composition gradient of the contact sample.

Quantitative Model of Multiple Crystal Growth Rate Minima in Polymers with Regularly Spaced Substituent Groups

“…20 Recently, the well-recognized difficulty of crystallizing the desirable "stereocomplex" from racemic melt of L and D poly(lactic acid) has been attributed to "poisoning by purity", i.e., to the rejection to the growth front of excess enantiomer resulting from concentration fluctuations. 32,33 Recent preliminary work by our team also suggests that in some cases an unstable but kinetically favored polymorph could also hinder polymer crystal growth. Further work is in progress.…”