This study provides insight into the accelerated hydrolysis of polyester PLA through the addition of phosphites based on pentaerythritol. To control hydrolysis and ensure processing stability, different types of phosphites and combinations of phosphites with acid scavengers were studied. Therefore, commercially available PLA was compounded with selected additives on a twin-screw extruder, and hydrolysis experiments were performed at 23 °C, 35 °C and 58 °C in deionized water. Hydrolysis of PLA was evaluated by the melt volume rate (MVR) and size-exclusion chromatography (SEC). For example, after 4 days of water storage at 58 °C, the number average molecular weight of the PLA comparison sample was reduced by 31.3%, whereas PLA compounded with 0.8% phosphite P1 had a 57.7% lower molecular weight. The results are in good agreement with the expected and tested stability against hydrolysis of the investigated phosphite structures. ³¹P-NMR spectroscopy was utilized to elucidate the hydrolysis of phosphites in the presence of lactic acid. With the addition of phosphites based on pentaerythritol, the hydrolysis rate can be enhanced, and faster biodegradation behavior of biodegradable polyesters is expected. Accelerated biodegradation is beneficial for reducing the residence time of polymers in composting facilities or during home composting and as litter or microplastic residues.

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.

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.

Antioxidants (AOs) from natural resources are an attractive research area, as petroleum-based products can be replaced in polymer stabilization. Therefore, novel esters based on the p-hydroxycinnamic acids p-coumaric acid, ferulic acid and sinapic acid were synthesized and their structure properties relationships were investigated. The structures of the novel bio-based antioxidants were verified using NMR and Fourier-transform infrared (FTIR) spectrometry. The high thermal stability above 280 °C and, therefore, their suitability as potential plastic stabilizers were shown using thermal gravimetric analysis (TGA). The radical scavenging activity of the synthesized esters was evaluated by using the 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay. Stabilization performance was evaluated in polypropylene (PP) using extended extrusion experiments, oxidation induction time (OIT) measurements and accelerated heat aging. In particular, the sinapic acid derivative provides a processing stability of PP being superior to the commercial state-of-the-art stabilizer octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

This study provides insight into the causes of inferior long-term stability of nanocomposites based on organic layered silicates (OLSs) used for cable mantles. A hierarchy was established by analyzing bentonite products and their respective polyolefin nanocomposites. Thermogravimetric analysis (TGA), X-ray diffraction (XRD), gas adsorption, energy-dispersive spectroscopy (SEM-EDX), and infrared spectroscopy (IR) provided evidence for the adsorption of stabilizers onto the filler surface and thus their reduction in activity, promoting polymer oxidation. This behavior corresponds to the specific surface area of the incorporated OLS. Therefore, it can be stated that gas adsorption and XRD are especially useful for the evaluation of long-term photostability. It was revealed that photocatalytically active iron is of secondary importance since iron-rich bentonites still formed the most stable nanocomposite. This also applies to the Hofmann elimination products of the modifying agent, where higher contents do not accelerate the degradation process. No elimination products could be traced within the composites. Due to the polymer-filler interface being essential for long-term photostability, prior analysis of the filler surface properties can be used to estimate the stability of the respective nanocomposite as a rationale for product selection in the early stages of development. The reasons identified in this work for decreasing the long-term photostability of OLS nanocomposites compared with unfilled formulations is an important step toward increasing their stability.