Scalable, biologically sourced depolymerizable polydienes with intrinsically weakened carbon–carbon bonds

Hu, Qixuan [Purdue University, West Lafayette, IN (United States)] (ORCID:0000000325385261); Luo, Xuyi [Purdue University, West Lafayette, IN (United States)]; Ogunfowora, Lawal Adewale [Purdue University, West Lafayette, IN (United States)] (ORCID:0000000221043582); Athaley, Abhay [National Renewable Energy Laboratory (NREL), Golden, CO (United States); BOTTLE Consortium, Golden, CO (United States)]; DesVeaux, Jason S. [National Renewable Energy Laboratory (NREL), Golden, CO (United States); BOTTLE Consortium, Golden, CO (United States)] (ORCID:0000000179266327); Klein, Bruno C. [National Renewable Energy Laboratory (NREL), Golden, CO (United States); USDOE Agile BioFoundry, Emeryville, CA (United States)] (ORCID:000000033438253X); Xu, Shu [Argonne National Laboratory (ANL), Argonne, IL (United States); Northwestern University, Evanston, IL (United States). Argonne Institute of Science and Engineering (NAISE)] (ORCID:0000000227137897); Wu, Pengfei [Purdue University, West Lafayette, IN (United States)]; Wei, Zitang [Purdue University, West Lafayette, IN (United States)] (ORCID:0000000273910342); Lin, Chenjian [Purdue University, West Lafayette, IN (United States)] (ORCID:0000000288175133); Haraniya, Tejaswini [Purdue University, West Lafayette, IN (United States)]; Maiorano, Dominick [Purdue University, West Lafayette, IN (United States)]; Boudouris, Bryan [Purdue University, West Lafayette, IN (United States)] (ORCID:000000030428631X); Mei, Jianguo [Purdue University, West Lafayette, IN (United States)] (ORCID:0000000257432715); Urgun-Demirtas, Meltem [Argonne National Laboratory (ANL), Argonne, IL (United States)]; Beckham, Gregg T. [BOTTLE Consortium, Golden, CO (United States); USDOE Agile BioFoundry, Emeryville, CA (United States); National Renewable Energy Laboratory (NREL), Golden, CO (United States)] (ORCID:000000023480212X); Savoie, Brett M. [Purdue University, West Lafayette, IN (United States)] (ORCID:0000000270394039); Dou, Letian [Purdue University, West Lafayette, IN (United States)] (ORCID:0000000164118591)

doi:10.1038/s44286-025-00183-0

DOE OSTI · 2561256

Scalable, biologically sourced depolymerizable polydienes with intrinsically weakened carbon–carbon bonds

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Abstract

Currently, there are few examples of circularly recyclable polymers with all-carbon backbones, probably owing to the challenge of using selective C–C bond cleavage to efficiently produce monomers in recycling processes. Furthermore, here we demonstrate a series of biologically sourced polymuconate polymers synthesized via simple free-radical polymerization that exhibit intrinsically weakened C–C bonds and controlled chemical recycling to monomers. Modifying the side chains and copolymerization ratios allows a wide range of mechanical property tuning, achieving performances comparable to those of commercial plastics such as polystyrene, polymethyl methacrylate and polybutadiene. Techno-economic analysis and life cycle assessment for production at a scale of 100 kilotons per year show that the materials are currently slightly more expensive and environmentally intensive compared with conventional rubbers. However, use of recycled materials via depolymerization can greatly decrease the cost and environmental impacts of polymuconate production (for example, down to US$1.59 per kilogram) to outperform its commercial counterparts.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY 42 ENGINEERING Chemical engineering ENGINEERING,INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY Polymer synthesis Polymers bio-derived polymuconate (polyME) polymers c-c bond cleavage chemical recycling to monomer

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Hu, Qixuan [Purdue University, West Lafayette, IN (United States)] (ORCID:0000000325385261), Luo, Xuyi [Purdue University, West Lafayette, IN (United States)], Ogunfowora, Lawal Adewale [Purdue University, West Lafayette, IN (United States)] (ORCID:0000000221043582), Athaley, Abhay [National Renewable Energy Laboratory (NREL), Golden, CO (United States); BOTTLE Consortium, Golden, CO (United States)], DesVeaux, Jason S. [National Renewable Energy Laboratory (NREL), Golden, CO (United States); BOTTLE Consortium, Golden, CO (United States)] (ORCID:0000000179266327), Klein, Bruno C. [National Renewable Energy Laboratory (NREL), Golden, CO (United States); USDOE Agile BioFoundry, Emeryville, CA (United States)] (ORCID:000000033438253X), Xu, Shu [Argonne National Laboratory (ANL), Argonne, IL (United States); Northwestern University, Evanston, IL (United States). Argonne Institute of Science and Engineering (NAISE)] (ORCID:0000000227137897), Wu, Pengfei [Purdue University, West Lafayette, IN (United States)], Wei, Zitang [Purdue University, West Lafayette, IN (United States)] (ORCID:0000000273910342), Lin, Chenjian [Purdue University, West Lafayette, IN (United States)] (ORCID:0000000288175133), Haraniya, Tejaswini [Purdue University, West Lafayette, IN (United States)], Maiorano, Dominick [Purdue University, West Lafayette, IN (United States)], Boudouris, Bryan [Purdue University, West Lafayette, IN (United States)] (ORCID:000000030428631X), Mei, Jianguo [Purdue University, West Lafayette, IN (United States)] (ORCID:0000000257432715), Urgun-Demirtas, Meltem [Argonne National Laboratory (ANL), Argonne, IL (United States)], Beckham, Gregg T. [BOTTLE Consortium, Golden, CO (United States); USDOE Agile BioFoundry, Emeryville, CA (United States); National Renewable Energy Laboratory (NREL), Golden, CO (United States)] (ORCID:000000023480212X), Savoie, Brett M. [Purdue University, West Lafayette, IN (United States)] (ORCID:0000000270394039), Dou, Letian [Purdue University, West Lafayette, IN (United States)] (ORCID:0000000164118591). 2025-02-12. Scalable, biologically sourced depolymerizable polydienes with intrinsically weakened carbon–carbon bonds. https://doi.org/10.1038/s44286-025-00183-0

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