Effect of Sn Atom on Poly(Ｌ-lactic acid) Pyrolysis

Tin 2-ethylhexanoate is an indispensable component of commercially available poly(L-lactic acid) (PLLA). However, the thermal degradation kinetics of PLLA containing Sn have not yet clearly been established; in particular, whether the degradation mechanism is a 1st-order or a random reaction. To clarify the effects of residual Sn on PLLA pyrolysis, PLLA samples with different Sn contents from 20 to 607 ppm were prepared and subjected to pyrolysis analysed with pyrolysis-gas chromatography/mass spectroscopy (Py-GC/MS) and thermogravimetry (TG). The pyrolysis of PLLA Sn-607 (Sn content: 607 ppm) with Py-GC/MS in the temperature range of 40–400 °C selectively produced lactides. In contrast, the pyrolysis of PLLA Sn-20 (Sn content: 20 ppm) was accompanied by the production of cyclic oligomers. The dynamic pyrolysis of PLLA-Sn samples by TG clearly indicated that with an increase in Sn content there was a shift to a lower degradation temperature range and a decrease in activation energy Ea. The kinetic analysis of the dynamic pyrolysis data indicates that the Sn-catalyzed pyrolysis starts through a random degradation behaviour and then shifts to a zero-order weight loss as the main process. Three reactions were put forward as being possible mechanisms of the zero-order weight loss; one being an unzipping reaction accompanying a random transesterification, the other two being the Sn-catalyzed pseudo-selective and selective lactide elimination reactions from random positions on a polymer chain. The kinetic parameter values obtained could be adequately explained for each degradation process

Pyrolysis Kinetics of Poly(L-lactide) with Carboxyl and Calcium Salt End Structures

To clarify the pyrolysis mechanism of poly(L-lactide), which has been reported as complex, the thermal decomposition of carboxyl type and calcium ion end capped PLLA (PLLA-H and PLLA-Ca, respectively) was investigated by means of thermogravimetric analysis (TG), and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS). The TG data revealed that PLLA-Ca has a lower pyrolysis temperature (220~360°C) than that of carboxyl type PLLA-H (280~370°C). The apparent activation energy of the decomposition reaction was estimated from TG curves at different heating rates by plural methods to be 176 and 98 kJ mol-1 for PLLA-H and PLLA-Ca, respectively. Further kinetic studies indicated that PLLA-H degraded mainly through a random reaction with a pre-exponential factor A=2.0×1012 s-1, whereas PLLA-Ca degraded by way of a 1st-order reaction with A=8.4×105 s-1. Pyrolysis products of PLLA-H were composed of lactides and other cyclic oligomers, while the degradation products of PLLA-Ca were principally lactides. The main reaction pathway for PLLA-H pyrolysis was regarded as the random transesterification, whereas for PLLA-Ca pyrolysis the unzipping depolymerization process was dominant