Influence of the chain extension on the crystallization behavior of polylactide

A semicrystalline poly(lactic acid) (PLA) was modified with the help of an epoxy‐based chain extender (CE) during reactive extrusion. Different amounts of CE were used resulting in samples with increased and broadened molar mass distributions as revealed by size exclusion chromatography. Thermal properties were then investigated using differential scanning calorimetry (DSC) and polarized optical microscopy (POM). On one hand, the thermal ramps performed with DSC revealed that the glass transition was not modified by the chain extension process. On the other hand, thecrystallization behavior was found to be highly impacted by this molecular modification. Decreases in the cold crystallization temperatures Tcc and in the melting temperatures Tm occurred when the CE content was raised. Isothermal crystallizations from the melt were performed using both DSC and POM. It revealed that the overall crystallization process was significantly faster for the chain‐extended PLAs while crystalline ratios were lowered. An improvement of the nucleation process coupled with a reduced crystal growth was assumed to be responsible for this change. POLYM. ENG. SCI., 54:616–625, 2014. © 2013 Society of Plastics Engineers