Photo-initiated solvent-mediated depolymerization of consumer poly(methyl methacrylate) without chlorinated reagents

Jonathan T Husband; Gavin Irvine; Callum R. Morris; Andrea Folli; Matthew G. Davidson; Simon J. Freakley

doi:10.1038/s41467-025-67997-7

Photo-initiated solvent-mediated depolymerization of consumer poly(methyl methacrylate) without chlorinated reagents

Jonathan T Husband, Gavin Irvine, Callum R. Morris, Andrea Folli, Matthew G. Davidson, Simon J. Freakley

Research output: Contribution to journal › Article › peer-review

Abstract

The chemical recycling of commodity acrylic polymers, such as the transparent thermoplastic polymethyl methacrylate (PMMA), typically requires temperatures of 350-400°C. Herein, we report chemical recycling back to monomers for PMMA between 120-180°C, through UV illumination under oxygen-free conditions. We have achieved gram-scale degradation of consumer plastic with >95% conversion, yielding >70% monomer, which can be readily repolymerized. The process proceeds even at high concentrations (>1 M) and depends strongly on solvent choice: aromatic solvents like dichlorobenzene and diphenyl ether maximize conversion. In contrast to a concurrently published study, we report that chlorine radicals are not required for depolymerization; however, when present, they react with the unzipping chain to form chlorine-functionalized PMMA which can be upcycled through derivatization. In more sustainable non-chlorinated solvents such as benzonitrile, minimal termination by radicals enables complete unzipping. These findings demonstrate a low-temperature, scalable route for the chemical recycling of PMMA, offering alternative pathways for plastic circularity.

Original language	English
Article number	1235
Journal	Nature Communications
Volume	17
Issue number	1
Early online date	28 Jan 2026
DOIs	https://doi.org/10.1038/s41467-025-67997-7
Publication status	Published - 2 Feb 2026

Data Availability Statement

All experimental and spectroscopic results are available in the Supplementary Information, including tabulation of all reactions performed. All data are available from the corresponding authors upon request.

Funding

This work was financially supported by the Research England Development Fund and EPSRC grant number EP/Z532782/1 [Innovation Centre for Applied Sustainable Technologies (iCAST) to MGD, SF, JH and GI and Sustainable Chemicals and Materials Manufacturing Hub (SCHEMA) to MGD, respectively]. The team and facilities at the Innovation Center for Sustainable Technologies (iCAST) and the Institute of Sustainability and Climate Change (ISCC) at the University of Bath are thanked for hosting and supporting the research program. Dr Alexander J. Cresswell, Dr Tim Woodman and Dr Martin Levere of the University of Bath and the research facilities at the University of Bath ( https://doi.org/10.15125/mx6j-3r54 ) are thanked for their technical provision, support, and assistance throughout this work. This work was financially supported by the Research England Development Fund and EPSRC grant number EP/Z532782/1 [Innovation Centre for Applied Sustainable Technologies (iCAST) to MGD, SF, JH and GI and Sustainable Chemicals and Materials Manufacturing Hub (SCHEMA) to MGD, respectively]. The team and facilities at the Innovation Center for Sustainable Technologies (iCAST) and the Institute of Sustainability and Climate Change (ISCC) at the University of Bath are thanked for hosting and supporting the research program. Dr Alexander J. Cresswell, Dr Tim Woodman and Dr Martin Levere of the University of Bath and the research facilities at the University of Bath (https://doi.org/10.15125/mx6j-3r54) are thanked for their technical provision, support, and assistance throughout this work.

Funders	Funder number
Engineering and Physical Sciences Research Council	EP/Z532782/1

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title = "Photo-initiated solvent-mediated depolymerization of consumer poly(methyl methacrylate) without chlorinated reagents",

abstract = "The chemical recycling of commodity acrylic polymers, such as the transparent thermoplastic polymethyl methacrylate (PMMA), typically requires temperatures of 350-400°C. Herein, we report chemical recycling back to monomers for PMMA between 120-180°C, through UV illumination under oxygen-free conditions. We have achieved gram-scale degradation of consumer plastic with >95\% conversion, yielding >70\% monomer, which can be readily repolymerized. The process proceeds even at high concentrations (>1 M) and depends strongly on solvent choice: aromatic solvents like dichlorobenzene and diphenyl ether maximize conversion. In contrast to a concurrently published study, we report that chlorine radicals are not required for depolymerization; however, when present, they react with the unzipping chain to form chlorine-functionalized PMMA which can be upcycled through derivatization. In more sustainable non-chlorinated solvents such as benzonitrile, minimal termination by radicals enables complete unzipping. These findings demonstrate a low-temperature, scalable route for the chemical recycling of PMMA, offering alternative pathways for plastic circularity. ",

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Photo-initiated solvent-mediated depolymerization of consumer poly(methyl methacrylate) without chlorinated reagents

Abstract

Data Availability Statement

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