Abstract
Condensation thermoplastics have become ubiquitous. The emergence of chemical upcycling could transform them into valuable feedstocks for chemical manufacturing at their end-of-life. However, current solvolysis processes suffer equilibrium limitations due to the liberation of reactive byproducts. We report a carbonate interchange deconstruction (CID) methodology for poly(ethylene terephthalate) (PET), where carbonates act as both latent nucleophiles and byproduct sequestering agents. High product selectivity (>95%) is achieved regardless of the targeted terephthalate product, originating from removal of ethylene glycol from the reaction equilibrium via its conversion into various oligoethers. CID is robust to the impurities present in post-consumer waste plastics and significantly reduces solvent demand, with just 10 mL of dimethyl carbonate successfully converting ca. 5 g of mixed PET waste into highly pure dimethyl terephthalate in excellent isolated yield (92%). CID opens a new upcycling paradigm wherein CO2 , embedded in carbonates, is leveraged to choreograph the selectivity of an otherwise equilibrium-controlled polymer upcycling process.
| Original language | English |
|---|---|
| Pages (from-to) | 15124-15134 |
| Number of pages | 11 |
| Journal | Green Chemistry |
| Volume | 27 |
| Issue number | 47 |
| DOIs | |
| State | Published - Dec 21 2025 |
Funding
The authors thank Dr Ilja Popovs and Dr Jared Bowman for invaluable discussion. This research was primarily supported by the US Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division. GC-MS characterization was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science program. DFT calculations were performed at the Center for Nanophase Materials Sciences, a US Department of Energy Office of Science User Facility operated at Oak Ridge National Laboratory. This manuscript has been authored by UT-Battelle LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( https://energy.gov/downloads/doe-public-access-plan ).