The Crystallization Behavior of Poly(l-lactic acid)/Poly(d-lactic acid) Electrospun Fibers: Effect of Distance of Isomeric Polymers

Abstract

Blending of poly(l-lactide) (PLLA) and poly(d-lactide) (PDLA) would produce polylactide stereocomplex crystallites (PLA SC). In the PLLA/PDLA specimens prepared by solution mixing or melt blending, the isomeric polymers were mixed in the molecular level. When the distance of these isomers increased, the crystallization behaviors of PLLA/PDLA were not clear yet. In this study, PLLA/PDLA blends were prepared by different electrospinning methods, i.e., spinning by mixed solution (DL-A), side-by-side mode (DL-B), and double spinnerets (DL-C). Results revealed that the distances between isomeric molecules increased in the order of DL-A, DL-B, and DL-C, and this distance influences the phase transition and subsequently crystallization behaviors. In the DL-A, the homochiral crystallites (HC) developed at first, and then SC formed in the specimen with lower content of PDLA. The formation of SC was observed at first, and less or no content of HC was developed with higher content of PDLA. For the DL-B group, the formation of HC was observed at ∼100 °C, and the SC were produced around 140 °C irrespective of composition. More content of SC was produced during or after melting of HC. When referring to the DL-C group, the HC developed at the first stage, and the SC were produced during or after melting of PLA HC. In addition, the SC that developed in the three groups have different nucleation efficiencies for the subsequent formation of HC. The nucleation efficiency increased in the order of DL-A < DL-B < DL-C, and these results hinted that not only the content but also the distribution of SC affects the formation of HC.