Degradation kinetics of polyethylene terephthalate in supercritical methanol

Abstract

Abstract Degradation of polyethylene terephthalate (PET) in supercritical methanol was investigated to develop a chemical recycling process for waste plastics. Continuous kinetics analysis was applied to the experimental data. A batch reactor was used at 573 K under the estimated pressure of 20 MPa for a reaction time of 2–120 min. PET decomposed to its monomers, dimethyl terephthalate (DMT), and ethylene glycol (EG), by methanolysis in supercritical methanol. PET with a weight‐average molecular weight of about 47,000 was converted to oligomer with that of 3,000 in 300 s and with that of 1,000 in 600 s. The largest yield of DMT was 80 mol % at 7,200 s and that of EG was 60 mol % at 3,600 s. Reaction products were analyzed with size exclusion chromatography, gas chromatography‐mass spectrometry, and reversed phase liquid chromatography. The molecular‐weight distribution (MWD) of the products was obtained as a function of reaction time. The yields of monomer components of the decomposition products, including byproducts, were measured. Continuous kinetics theory was developed to analyze the decomposition behavior. The theory includes MWD change of polymer by random and specific scissions and secondary reactions for monomer components. Change of MWD and monomers as a function of time was simulated by the continuous kinetics.