Influence of melt processing conditions on poly(lactic acid) degradation: Molar mass distribution and crystallization

The degradation of poly(lactic acid) (PLA) during thermal-mechanical processing was studied and the influence of processing conditions on degradation rate was determined by size exclusion chromatography coupled with multi-angle light scattering (SEC-MALS). A two-parameter model accounting for both chain scission and recombination processes was used to describe the experimentally observed molar mass distribution. The degradation and recombination rate constants were determined for undried and dried PLA. It was highlighted that the effect of processing temperature (in the 170-210 degrees C range), processing time (until 30 min) and shear rate (rotor speed varying from 0 to 150 rpm) on molar mass reduction can be relatively well simulated insofar as self-heating related to the mechanical energy conversion into heat was taken into account. The influence of melt processing on the thermal behaviour of PLA was also investigated using temperature modulated differential scanning calorimetry (TMDSC). It was evidenced that the molar mass reduction affects the crystallizability of PLA. Cold crystallization temperature progressively decreases with decreasing molar mass and the metastable alpha' phase is formed in place of the stable alpha phase. The alpha' phase can be partially converted into alpha form during melting giving rise to a double-melting peak. The two peaks can be separated using reversing and non-reversing signals confirming that recrystallization of the alpha' form occurs. (C) 2014 Elsevier Ltd. All rights reserved.