Not Cutting Corners: Bioderived Triggers Driving Oxidative Main Chain Scission of Poly(ethylene terephthalate)
About 20–34 billion poly(ethylene terephthalate) (PET) bottles from the beverage industry leak into aquatic ecosystems annually, necessitating the development of urgent strategies to treat waterborne plastic pollution. Inspired by the scalability of water disinfection infrastructure and protocols, we present a dual depolymerization approach relying on oxidation, followed by hydrolysis. Incorporating bioderived monounsaturated C18 diacid (C18:1-DA) counits at low dosages (2–5%) in the PET backbone overcomes the diffusional limitations of depolymerizing PET in the solid state by suppressing the glass transition temperature of the copolymer by 20 °C. Cryomilled C18:1-PET powder suspended in an oxidant-loaded alkaline slurry underwent bulk depolymerization to oligomers at 80–100 °C via oxidative scissions at the internally located unsaturations. In contrast, conventional PET undergoes only minor end-chain scission under mild alkaline conditions. These oligomers are suitable for low-energy repolymerization or facile solvolysis to monomers. A permanganate-periodate oxidant couple demonstrated successful oxidation through the bulk of the polymer, which subsequently was hydrolyzed to monomers. Furthermore, this model system serves as a proxy for ozonolysis, followed by mild hydrolysis to reduce the energetics of alkaline hydrolysis. This integrated oxidation–hydrolysis strategy paves the way for the industrial adoption of cleaner, advanced oxidation processes, such as ozonolysis for plastic pretreatment, further enabling commercialized chemical recycling of unsaturation-containing polyesters.
- Research Organization:
- Iowa State University, Ames, IA (United States)
- Sponsoring Organization:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Bioenergy Technologies Office (BETO)
- Grant/Contract Number:
- EE0009294
- OSTI ID:
- 2507338
- Journal Information:
- ACS Sustainable Chemistry & Engineering, Journal Name: ACS Sustainable Chemistry & Engineering Journal Issue: 52 Vol. 12; ISSN 2168-0485
- Publisher:
- American Chemical Society (ACS)Copyright Statement
- Country of Publication:
- United States
- Language:
- English
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