Long-Term Thermal Stabilization of Poly(Lactic Acid).

To use polylactic acid in demanding technical applications, sufficient long-term thermal stability is required. In this work, the thermal aging of polylactic acid (PLA) in the solid phase at 100 °C and 150 °C is investigated. PLA has only limited aging stability without the addition of stabilizers. Therefore, the degradation mechanism in thermal aging was subsequently investigated in more detail to identify a suitable stabilization strategy. Investigations using nuclear magnetic resonance spectroscopy showed that, contrary to expectations, even under thermal aging conditions, hydrolytic degradation rather than oxidative degradation is the primary degradation mechanism. This was further confirmed by the investigation of suitable stabilizers. While the addition of phenols, phosphites and thioethers as antioxidants leads only to a limited improvement in aging stability, the addition of an additive composition to provide hydrolytic stabilization results in extended durability. Efficient compositions consist of an aziridine-based hydrolysis inhibitor and a hydrotalcite co-stabilizer. At an aging temperature of 100 °C, the time until significant polymer chain degradation occurs is extended from approx. 500 h for unstabilized polylactic acid to over 2000 h for stabilized polylactic acid.

Enhancing the Hydrolytic Stability of Poly(lactic acid) Using Novel Stabilizer Combinations.

Commercially available poly(lactic acid) exhibits poor hydrolytic stability, which makes it impossible for use in durable applications. Therefore, a novel hydrolysis inhibitor based on an aziridine derivative as well as a novel stabilizer composition, containing an aziridine derivative and an acid scavenger, were investigated to improve the hydrolytic stability. To evaluate the stabilizing effect, the melt volume rate (MVR) and molecular weight were monitored during an accelerated hydrolytic aging in water at elevated temperatures. Temperatures were selected according to the glass transition temperature (~60 °C) of PLA. It was shown that the novel hydrolysis inhibitor as well as the novel stabilizer composition exhibited excellent performance during hydrolytic aging, exceeding commercially available alternatives, e.g., polymeric carbodiimides. A molecular weight analysis resulted in a molecular weight decrease of only 10% during approximately 850 h and up to 20% after 1200 h of hydrolytic aging, whereas poly(lactic acid) stabilized with a commercial polycarbodiimide revealed comparable molecular weight reductions after only 300 h. Furthermore, the stabilization mechanism of the aziridine derivative alone, as well as in the synergistic combination with the acid scavenger (calcium hydrotalcite), was investigated using nuclear magnetic resonance (NMR) spectroscopy. In addition to an improved hydrolytic stability, the thermal properties were also enhanced compared to polymeric carbodiimides.