Reaction Pathway Analysis of PET Deconstruction via Methanolysis and Tertiary Amine Catalysts.

Polyethylene terephthalate (PET) is a type of polymer frequently used in plastic packaging that significantly adds the amount of plastic waste found in landfills. One of the ways to recover valuable raw materials from postconsumer plastic is by depolymerizing PET into its monomeric constituents, which are dimethyl terephthalate (DMT) and ethylene glycol. PET depolymerization is often done in methanolysis with the help of acidic or base catalysts. Tertiary amine is one of the most attractive base catalysts for PET depolymerization in methanolysis since it does not lead to the generation of potentially environmentally harmful waste, unlike metal-based catalysts. However, the mechanism by which tertiary amines catalyze PET depolymerization in methanolysis remains unexplored. Developing a detailed mechanistic understanding of this process is important for improving plastic upcycling since it opens the possibility of employing various cheaper and more environmentally friendly reaction conditions. Using density functional theory and transition state analysis, we show that in the presence of tertiary amine catalysts, methanolysis of PET consists of multiple discrete-step reactions rather than a single concerted step. Furthermore, by comparing our calculations to recent experimental results, we were able to rationalize the DMT yield from the depolymerization process by relating it to charge polarization within tertiary amine catalysts, thus opening a pathway to identify atomic descriptors for future catalyst design.