Efficient Alcoholysis of Poly(ethylene terephthalate) by Using Supercritical Carbon Dioxide as a Green Solvent

In order to reduce the environmental impact of poly(ethylene terephthalate) (PET) plastic waste, supercritical fluids were used to facilitate effective recovery via improved solvent effects. This work focuses on the mechanisms of supercritical CO₂ (ScCO₂) during the alcoholysis processing of PET using systematic experiments and molecular dynamics (MD) simulations. The results of the alcoholysis experiment indicated that PET chips can be completely depolymerized within only an hour at 473 K assisted with ScCO₂ at an optimal molar ratio of CO₂/ethanol of 0.2. Random scission of PET dominates the early stage of the depolymerization reaction process, while specific scission dominates the following stage. Correspondingly, molecular dynamics (MD) simulations revealed that the solubilization and self-diffusion properties of ScCO₂ facilitate the transportation of alcohol molecules into the bulk phase of PET, which leads to an accelerated diffusion of both oligomers and small molecules in the system. However, the presence of excessive CO₂ has a negative impact on depolymerization by weakening the hydrogen bonding between polyester chain segments and ethanol, as well as decreasing the swelling degree of PET. These data provide a deep understanding of PET degradation by alcohols and the enhancement of ScCO₂. It should be expected to achieve an efficient and high-yield depolymerization process of wasted polyesters assisted with ScCO₂ at a relatively low temperature.