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

Nature Chemical Engineering volume 2, pages 130–141 (2025)Cite this article

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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. 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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Fig. 1: Overview of chemically recyclable polyME prepared from free radical polymerization, including its microstructure and impact on depolymerization.
Fig. 2: Properties of polyME homopolymers and copolymers with their laboratory scalability and processing.
Fig. 3: Chemical recycling of polyMEs.
Fig. 4: TEA and LCA of polyME-Et production and recycling.

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All data supporting the findings of this study are included in the article and its Supplementary Information. Source data are provided with this paper.

References

  1. Zhu, Y., Romain, C. & Williams, C. K. Sustainable polymers from renewable resources. Nature 540, 354–362 (2016).

    Article  CAS  PubMed  Google Scholar 

  2. Hong, M. & Chen, E. Y. X. Chemically recyclable polymers: a circular economy approach to sustainability. Green Chem. 19, 3692–3706 (2017).

    Article  CAS  Google Scholar 

  3. Coates, G. W. & Getzler, Y. D. Y. L. Chemical recycling to monomer for an ideal, circular polymer economy. Nat. Rev. Mater. 5, 501–516 (2020).

    Article  CAS  Google Scholar 

  4. Cywar, R. M., Rorrer, N. A., Hoyt, C. B., Beckham, G. T. & Chen, E. Y. X. Bio-based polymers with performance-advantaged properties. Nat. Rev. Mater. 7, 83–103 (2022).

    Article  CAS  Google Scholar 

  5. Bachmann, M. et al. Towards circular plastics within planetary boundaries. Nat. Sustain. 6, 599–610 (2023).

    Article  Google Scholar 

  6. Zhang, F. et al. Polyethylene upcycling to long-chain alkylaromatics by tandem hydrogenolysis/aromatization. Science 370, 437–441 (2020).

    Article  CAS  PubMed  Google Scholar 

  7. Tennakoon, A. et al. Catalytic upcycling of high-density polyethylene via a processive mechanism. Nat. Catal. 3, 893–901 (2020).

    Article  CAS  Google Scholar 

  8. Rorrer, J. E., Troyano-Valls, C., Beckham, G. T. & Román-Leshkov, Y. Hydrogenolysis of polypropylene and mixed polyolefin plastic waste over Ru/C to produce liquid alkanes. ACS Sustain. Chem. Eng. 9, 11661–11666 (2021).

    Article  CAS  Google Scholar 

  9. Dong, Q. et al. Depolymerization of plastics by means of electrified spatiotemporal heating. Nature 616, 488–494 (2023).

    Article  CAS  PubMed  Google Scholar 

  10. Zhu, J. B., Watson, E. M., Tang, J. & Chen, E. Y. X. A synthetic polymer system with repeatable chemical recyclability. Science 360, 398–403 (2018).

    Article  CAS  PubMed  Google Scholar 

  11. Lillie, L. M., Tolman, W. B. & Reineke, T. M. Degradable and renewably-sourced poly(ester-thioethers) by photo-initiated thiol-ene polymerization. Polym. Chem. 9, 3272–3278 (2018).

    Article  CAS  Google Scholar 

  12. Christensen, P. R., Scheuermann, A. M., Loeffler, K. E. & Helms, B. A. Closed-loop recycling of plastics enabled by dynamic covalent diketoenamine bonds. Nat. Chem. 11, 442–448 (2019).

    Article  CAS  PubMed  Google Scholar 

  13. Häußler, M., Eck, M., Rothauer, D. & Mecking, S. Closed-loop recycling of polyethylene-like materials. Nature 590, 423–427 (2021).

    Article  PubMed  Google Scholar 

  14. Zhang, Z., Shi, C., Scoti, M., Tang, X. & Chen, E. Y. X. Alternating isotactic polyhydroxyalkanoates via site- and stereoselective polymerization of unsymmetrical diolides. J. Am. Chem. Soc. 144, 20016–20024 (2022).

    Article  CAS  PubMed  Google Scholar 

  15. Cywar, R. M. et al. Redesigned hybrid nylons with optical clarity and chemical recyclability. J. Am. Chem. Soc. 144, 5366–5376 (2022).

    Article  CAS  PubMed  Google Scholar 

  16. Zhang, X., Guo, W., Zhang, C. & Zhang, X. A recyclable polyester library from reversible alternating copolymerization of aldehyde and cyclic anhydride. Nat. Commun. 14, 5423 (2023).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  17. Zhang, Z. et al. Strong and tough supramolecular covalent adaptable networks with room-temperature closed-loop recyclability. Adv. Mater., https://doi.org/10.1002/adma.202208619 (2023).

    Article  PubMed  PubMed Central  Google Scholar 

  18. Monfette, S. & Fogg, D. E. Equilibrium ring-closing metathesis. Chem. Rev. 109, 3783–3816 (2009).

    Article  CAS  PubMed  Google Scholar 

  19. Sathe, D. et al. Olefin metathesis-based chemically recyclable polymers enabled by fused-ring monomers. Nat. Chem. 13, 743–750 (2021).

    Article  CAS  PubMed  Google Scholar 

  20. Bywater, S. & Black, P. E. Thermal depolymerization of polymethyl methacrylate and poly-α-methylstyrene in solution in various solvents. J. Phys. Chem. 69, 2967–2970 (1965).

    Article  CAS  Google Scholar 

  21. Ye, L., Liu, M., Huang, Y., Zhang, Z. & Yang, J. Effects of molecular weight on thermal degradation of poly(α-methyl styrene) in nitrogen. J. Macromol. Sci. Part B 54, 1479–1494 (2015).

    Article  CAS  Google Scholar 

  22. Allen, F. H. et al. Tables of bond lengths determined by x-ray and neutron diffraction. Part 1. Bond lengths in organic compounds. J. Chem. Soc. Perkin Trans. https://doi.org/10.1039/P298700000S1 (1987).

    Article  Google Scholar 

  23. Zavitsas, A. A. The relation between bond lengths and dissociation energies of carbon-carbon bonds. J. Phys. Chem. A 107, 897–898 (2003).

    Article  CAS  Google Scholar 

  24. Luo, X. et al. Circularly recyclable polymers featuring topochemically weakened carbon–carbon bonds. J. Am. Chem. Soc. 144, 16588–16597 (2022).

    Article  CAS  PubMed  Google Scholar 

  25. Marsh, R. D. L. & Blanshard, J. M. V. The application of polymer crystal growth theory to the kinetics of formation of the B-amylose polymorph in a 50% wheat-starch gel. Carbohydr. Polym. 9, 301–317 (1988).

    Article  CAS  Google Scholar 

  26. Matsumoto, A. Stereospecific polymerization of 1,3-diene monomers in the crystalline state. Prog. React. Kinet. Mech. 26, 59–110 (2001).

    Article  CAS  Google Scholar 

  27. Matsumoto, A. Polymer structure control based on crystal engineering for materials design.Polymer J. 35, 93–121 (2003).

    Article  CAS  Google Scholar 

  28. Mon, Y. & Matsumoto, A. Molecular stacking and photoreactions of fluorine-substituted benzyl muconates in the crystals. Cryst. Growth Des. 7, 377–385 (2007).

    Article  Google Scholar 

  29. Biradha, K. & Santra, R. Crystal engineering of topochemical solid state reactionsns. Chem. Soc. Rev. 42, 950–967 (2013).

    Article  CAS  PubMed  Google Scholar 

  30. Agbolaghi, S., Abbaspoor, S. & Abbasi, F. A comprehensive review on polymer single crystals—from fundamental concepts to applications. Prog. Polym. Sci. 81, 22–79 (2018).

    Article  CAS  Google Scholar 

  31. Saeed, M. H. et al. Recent advances in the polymer dispersed liquid crystal composite and its applications. Molecules 25, 1–22 (2020).

    Article  Google Scholar 

  32. Hema, K. et al. Topochemical polymerizations for the solid-state synthesis of organic polymers. Chem. Soc. Rev. 50, 4062–4099 (2021).

    Article  CAS  PubMed  Google Scholar 

  33. Zia, K. M., Akram, N., Tabasum, S., Noreen, A. & Akbar, M. U. in Processing Technology for Bio-Based Polymers (eds Zia, K. M. et al.) 29–61 (Elsevier, 2021); https://doi.org/10.1016/B978-0-323-85772-7.00005-7

  34. Morris, B. A. in The Science and Technology of Flexible Packaging 2nd edn (ed. Morris, B. A.) Ch. 4, 85–138 (William Andrew Publishing, 2022); https://doi.org/10.1016/B978-0-323-85435-1.00017-X

  35. Itoh, T., Nomura, S. & Uno, T. Topochemical polymerization of 7,7,8,8-tetrakis(methoxycarbonyl)quinodimethane. Angew. Chem. Int. Ed. 41, 4306–4309 (2002).

  36. Matsumoto, A. et al. Crystal engineering for topochemical polymerization of muconic esters using halogen–halogen and CH/π interactions as weak intermolecular interactions. J. Am. Chem. Soc. 124, 8891–8902 (2002).

    Article  CAS  PubMed  Google Scholar 

  37. Matsumoto, A., Tanaka, T. & Oka, K. Stereospecific radical polymerization of substituted benzyl muconates in the solid state under topochemical control. Synthesis https://doi.org/10.1055/s-2005-865320 (2005).

  38. Matsumoto, A., Furukawa, D., Mori, Y., Tanaka, T. & Oka, K. Change in crystal structure and polymerization reactivity for the solid-state polymerization of muconic esters. Cryst. Growth Des. 7, 1078–1085 (2007).

    Article  CAS  Google Scholar 

  39. Dou, L. et al. Single-crystal linear polymers through visible light-triggered topochemical quantitative polymerization. Science 343, 272–277 (2014).

    Article  CAS  PubMed  Google Scholar 

  40. Wei, Z. et al. Side-chain control of topochemical polymer single crystals with tunable elastic modulus. Angew. Chem. Int. Ed. 61, e202213840 (2022).

    Article  CAS  Google Scholar 

  41. Quintens, G., Vrijsen, J. H., Adriaensens, P., Vanderzande, D. & Junkers, T. Muconic acid esters as bio-based acrylate mimics. Polym. Chem. 10, 5555–5563 (2019).

    Article  CAS  Google Scholar 

  42. Dardé, T., Diomar, É., Schultze, X. & Taton, D. An expedient route to bio-based polyacrylate alternatives with inherent post-chemical modification and degradation capabilities by organic catalysis for polymerization of muconate esters. Angew. Chem. Int. Ed. 63, e202411249 (2024).

  43. Li, T. et al. Chain flexibility and glass transition temperatures of poly(n-alkyl (meth)acrylate)s: implications of tacticity and chain dynamics. Polymer 213, 123207 (2021).

    Article  CAS  Google Scholar 

  44. Hendrich, M. & Vana, P. Tuning the mechanical properties of multiblock copolymers generated by polyfunctional RAFT agents. Macromol. Mater. Eng. 302, 1700018 (2017).

    Article  Google Scholar 

  45. Draths, K. M. & Frost, J. W. Environmentally compatible synthesis of adipic acid from D-glucose. J. Am. Chem. Soc. 116, 399–400 (1994).

    Article  CAS  Google Scholar 

  46. Vardon, D. R. et al. Adipic acid production from lignin. Energy Environ. Sci. 8, 617–628 (2015).

    Article  CAS  Google Scholar 

  47. Shanks, B. H. & Keeling, P. L. Bioprivileged molecules: creating value from biomass. Green Chem. 19, 3177–3185 (2017).

    Article  CAS  Google Scholar 

  48. Sullivan, K. P. et al. Mixed plastics waste valorization through tandem chemical oxidation and biological funneling. Science 378, 207–211 (2022).

    Article  CAS  PubMed  Google Scholar 

  49. Settle, A. E. et al. Iodine-catalyzed isomerization of dimethyl muconate. ChemSusChem 11, 1768–1780 (2018).

    Article  CAS  PubMed  Google Scholar 

  50. Nicholson, S. R. et al. The critical role of process analysis in chemical recycling and upcycling of waste plastics. Annu. Rev. Chem. Biomol. Eng. 13, 301–324 (2022).

    Article  CAS  PubMed  Google Scholar 

  51. Mokwatlo, S. C. et al. Bioprocess development and scale-up for cis,cis-muconic acid production from glucose and xylose by Pseudomonas putida. Green Chem. 26, 10152–10167 (2024).

    Article  CAS  Google Scholar 

  52. Nicholson, S. R., Rorrer, N. A., Carpenter, A. C. & Beckham, G. T. Manufacturing energy and greenhouse gas emissions associated with plastics consumption. Joule 5, 673–686 (2021).

    Article  CAS  Google Scholar 

  53. Taylor, B. PureCycle Ironton plant up and running. recyclingtoday https://www.recyclingtoday.com/news/purecycle-polyproylene-plastic-recycling-ohio-facility-maintenance-running/#:~:text=At%20full%20capacity%20%2Cpure%20Cycle%20expects,of%20PP%20resin%20per%20year (2023).

  54. Kingsport, Tennessee, site. Eastman https://www.eastman.com/en/sustainability/environmental/circularity/site-locations/tennessee-site#:~:text=Located at Eastman’sKingsport%2CTenn,recyclingfacilitiesintheworld (2024).

  55. Singh, A. et al. Techno-economic, life-cycle, and socioeconomic impact analysis of enzymatic recycling of poly(ethylene terephthalate). Joule 5, 2479–2503 (2021).

    Article  CAS  Google Scholar 

  56. Milbrandt, A., Coney, K., Badgett, A. & Beckham, G. T. Quantification and evaluation of plastic waste in the United States. Resour. Conserv. Recycl. 183, 1–16 (2022).

    Article  Google Scholar 

  57. Frisch, M. J. et al. Gaussian 16 (Gaussian, 2016).

  58. Haynes, W. M. CRC Handbook of Chemistry and Physics (CRC Press, 2016); https://doi.org/10.1201/9781315380476

  59. Grimme, S. Exploration of chemical compound, conformer, and reaction space with meta-dynamics simulations based on tight-binding quantum chemical calculations. J. Chem. Theory Comput. 15, 2847–2862 (2019).

    Article  CAS  PubMed  Google Scholar 

  60. Lin, Y.-S., Li, G.-D., Mao, S.-P. & Chai, J.-D. Long-range corrected hybrid density functionals with improved dispersion corrections. J. Chem. Theory Comput. 9, 263–272 (2013).

    Article  CAS  PubMed  Google Scholar 

  61. Weigend, F. & Ahlrichs, R. Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: design and assessment of accuracy. Phys. Chem. Chem. Phys. 7, 3297–3305 (2005).

    Article  CAS  PubMed  Google Scholar 

  62. Zhao, Q. & Savoie, B. M. Algorithmic explorations of unimolecular and bimolecular reaction spaces. Angew. Chem. Int. Ed. 61, e202210693 (2022).

    Article  CAS  Google Scholar 

  63. ISO 14851 Determination of the Ultimate Aerobic Biodegradability of Plastic Materials in an Aqueous Medium—Method by Measuring the Oxygen Demand in a Closed Respirometer (International Organization for Standardization, 2019).

  64. ASTM D5988 Standard Test Method for Determining Aerobic Biodegradation of Plastic Materials in Soil (ASTM International, 2018).

  65. Hanes, R. J. & Carpenter, A. Evaluating opportunities to improve material and energy impacts in commodity supply chains. Environ. Syst. Decis. 37, 6–12 (2017).

    Article  Google Scholar 

  66. U.S. Life Cycle Inventory Database (National Renewable Energy Laboratory, 2022).

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Acknowledgements

This work is supported primarily by Ralph W. and Grace M. Showalter Research Trust and Charles Davidson Rising Star Startup Fund of Purdue University. The work performed by L.A.O. and B.M.S. was supported by the Office of Naval Research through the Energetic Materials Program (MURI grant number N00014-21-1-2476, program manager C. Stoltz). This work was authored in part by the National Renewable Energy Laboratory, operated by Alliance for Sustainable Energy, LLC, for the US Department of Energy (DOE) under contract no. DE-AC36-08GO28308. Funding was provided to A.A., J.S.D., G.T.B., S.X. and U.D.M. by the US Department of Energy, Office of Energy Efficiency and Renewable Energy, Advanced Materials and Manufacturing Technologies Office (AMMTO) and Bioenergy Technologies Office (BETO). This work was performed as part of the BOTTLE Consortium and was supported by AMMTO and BETO under contract no. DE-AC36-08GO28308 with the National Renewable Energy Laboratory, operated by Alliance for Sustainable Energy, LLC and under contract no. DE-AC02-06CH11357 with the Argonne National Laboratory, operated by UChicago Argonne, LLC.. Funding for B.C.K. and G.T.B. was provided by the US Department of Energy Office of Energy Efficiency and Renewable Energy Bioenergy Technologies Office (BETO) for the Agile BioFoundry. The views expressed in the Article do not necessarily represent the views of the DOE or the US Government. 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 work, or allow others to do so, for US Government purposes. We thank I. Burch and L. Franquilino for the help with synthesis and mechanical testing; respectively. We thank C. Mokwatlo, C. Kneucker, C. Singer, V. Sànchez i Nogué, R. Lyons, M. Baker, D. Salvachúa, Y. Chen, L. Stanley, J. Miscall and T. Uekert for production and purification of the muconic acid.

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  1. These authors contributed equally: Qixuan Hu, Xuyi Luo.

Authors and Affiliations

  1. Davidson School of Chemical Engineering, Purdue University, West Lafayette, IN, USA

    Qixuan Hu, Xuyi Luo, Pengfei Wu, Zitang Wei, Chenjian Lin, Tejaswini Haraniya, Dominick Maiorano, Bryan Boudouris, Brett M. Savoie & Letian Dou

  2. Department of Chemistry, Purdue University, West Lafayette, IN, USA

    Lawal Adewale Ogunfowora, Bryan Boudouris, Jianguo Mei & Letian Dou

  3. Catalytic Carbon Transformation and Scale-Up Center, National Renewable Energy Laboratory, Golden, CO, USA

    Abhay Athaley, Jason S. DesVeaux & Bruno C. Klein

  4. BOTTLE Consortium, Golden, CO, USA

    Abhay Athaley, Jason S. DesVeaux & Gregg T. Beckham

  5. Agile BioFoundry, Emeryville, CA, USA

    Bruno C. Klein & Gregg T. Beckham

  6. Argonne National Laboratory, Applied Materials Division, Lemont, IL, USA

    Shu Xu & Meltem Urgun-Demirtas

  7. Northwestern Argonne Institute of Science and Engineering, Evanston, IL, USA

    Shu Xu

  8. Renewable Resources and Enabling Sciences Center, National Renewable Energy Laboratory, Golden, CO, USA

    Gregg T. Beckham

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Contributions

The project was designed by L.D. Q.H. and X.L. contributed equally to this work. Q.H. and X.L. carried out material synthesis, characterized recyclability and depolymerization kinetics, and conducted ultrasonication processing and hot solvent processing. L.A.O. conducted calculations on carbon–carbon bond dissociation energies and other simulations. Q.H. carried out mechanical tests of the polymer materials. Q.H. carried out the 3D-printing demonstration of the extruded polymer filaments and injection molding of the toy sample. A.A., J.S.D. and B.C.K. conducted TEA and LCA. S.X. performed the biodegradation test of polymer samples. T.H. and D.M. helped with material synthesis and depolymerization study. L.D., Q.H. and X.L. wrote the paper with contributions from all authors. P.W., Z.W., C.L., B.B., J.M., M.U.-D., G.T.B. and B.M.S. discussed the data interpretation and commented on the paper.

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Correspondence to Gregg T. Beckham, Brett M. Savoie or Letian Dou.

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Hu, Q., Luo, X., Ogunfowora, L.A. et al. Scalable, biologically sourced depolymerizable polydienes with intrinsically weakened carbon–carbon bonds. Nat Chem Eng 2, 130–141 (2025). https://doi.org/10.1038/s44286-025-00183-0

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