More Efficient Chemical Recycling of Poly(Ethylene Terephthalate) by Intercepting Intermediates

The research presented in this paper offers insight into the availability of intermediates in the depolymerization of polyethylene terephthalate (PET) to be used as feedstock to create value‐added products. Monitoring the dispersity, molecular weight, end groups, and crystallinity of reaction intermediates during the heterogeneous depolymerization of PET offers insight into the mechanism by which the polymer chains evolve during the reaction. Our results show dispersity decreases and crystallinity increases while the yield of insoluble PET remains high early in the reaction. Our interpretation of this data depicts a mechanism where chain scission targets amorphous tie chains between crystalline phases. Targeting the tie‐chains lowers the Mn of the polymer without changing the amount of recovered polymer flake. Chain scission of tie‐chains and isolating highly crystalline PET lowers the dispersity (Đ) of the polymer chains, as the size of the crystalline lamellae guides the molecular weight of the depolymerized oligomers. When sufficient end groups of PET chains are converted to alcohol groups, the PET flakes break apart into highly crystalline and less disperse polymer. Our results also demonstrate that the oligomeric depolymerization intermediates are readily repolymerized, offering new opportunities to chemically recycle PET more effectively and efficiently, from both an energy and purification standpoint. To understand the chain evolution of polyethylene terephthalate (PET) during depolymerization, the molecular weights, yield, and percent crystallinity of the PET oligomers isolated were monitored as a function of time during glycolysis. The results show that the depolymerization forms oligomers as intermediates in the chain scission process that can be isolated and used as feedstocks in further reaction or repolymerized.