Synergistic dual catalytic system and kinetics for the alcoholysis of poly(lactic acid)

Plastic pollution is a global issue that is approaching crisis levels as plastic production is projected to reach 1.1 GT annually by 2050. The bioplastic industry along with a circular production economy are solutions to this problem. One promising bioplastic polylactic acid (PLA) has mechanical properties comparable to polystyrene (PS), so it could replace PS in its applications as a more environmentally sustainable material. However, since the bioplastic PLA also suffers from long biodegradation times in the environment, to ensure that it does not add to the current pollution problem, it should instead be chemically recycled. In this work, PLA was chemically recycled via alcoholysis, using either methanol or ethanol to generate the value-added products methyl lactate and ethyl lactate respectively. Two catalysts, zinc acetate dihydrate (ZnAc) and 4-(dimethylamino)pyridine (DMAP), were tested both individually and in mixtures. A synergistic effect was exhibited on the reaction rate when both catalysts were used in an equal ratio. The methanolysis reaction was determined to be two-step, with the activation energy estimated to be 73 kJ mol ⁻¹ for the first step and 40.16 kJ mol ⁻¹ for the second step. Both catalysts are cheap and commercially available, their synergistic effect could be exploited for large-scale PLA recycling.