The use of chain extenders as processing aids in the valorization of single-use polylactide (PLA) products by rotomolding

Abstract

Biodegradable plastics in single-use products have increased in popularity as a way to reduce the negative environmental impact of conventional plastics and meet the tightening law regulations. However, their recyclability needs to be assessed, as the environmental behavior of single-use plastics, even if compostable, is not negligible. Polylactide (PLA) is susceptible to thermal, oxidative, hydrolytic, and mechanical degradation during reprocessing, so the conditions of such cycles must be accurately controlled. The necessity of using additives to reduce such degradations during rotational molding, a process with long cycle times and oxidizing atmosphere, has been demonstrated. Chain extenders based on a carbodiimide (Bioadimide® 100 - KI), a methylene diphenyl diisocyanate (MDI), and a polystyrene-acrylic copolymer (Joncryl® ADR-4368c - J) have been added to post-consumer PLA wastes. It has been demonstrated that these three chain extenders enabled obtaining a higher molecular weight of the reprocessed polymer, compared to the ∼50% reduction for the neat PLA. The use of carbodiimide yielded the most similar performance to that of unprocessed raw material. All samples provided adequate thermal stability and processing parameters for the rotational molding. Carbodiimide is considered the most efficient additive, as it increases the molecular mass of the polymer as it remains unchanged after processing. Similarly, KI-modified PLA rheological behavior remains unchanged after processing, which means this compound can reduce thermooxidative and hydrolytic degradation reactions. Thus contributing to the achievement of improved processability and better performance; in particular, impact strength increased from 1.06 ± 0.56 for PLA to 8.12 ± 2.28 kJ/m2 for KI-modified PLA, and toughness of 5.36 ± 1.61 to 61.49 ± 8.01 J/mm3, respectively, leading to rotomolded items without structural defects. On the opposite, the use of Joncryl® and MDI led to structural defects in the rotomolded parts despite a higher molecular weight of the polymer, which resulted in poor mechanical properties, although better than PLA without any additive. All three chain extenders resulted in an amorphous PLA structure with increased glass transition temperature and improved thermal stability, which correlated with the reduced emissions of volatile compounds compared to neat recycled PLA. The presented findings significantly contribute to a better understanding of PLA and its modifications at a molecular scale required for its efficient and possibly environmentally burden-free reprocessing. Gathered knowledge will be crucial for optimizing its environmental performance and widening its applications, particularly in a process with long cycle times and oxidative character, such as rotational molding.