Abstract
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 CO(2) (ScCO(2)) 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 ScCO(2) at an optimal molar ratio of CO(2)/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 ScCO(2) 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 CO(2) 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 ScCO(2). It should be expected to achieve an efficient and high-yield depolymerization process of wasted polyesters assisted with ScCO(2) at a relatively low temperature.