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Catalytic closed-loop recycling of polyethylene-like materials produced by acceptorless dehydrogenative polymerization of bio-derived diols

Nature Chemistry volume 17, pages 500–506 (2025)Cite this article

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Abstract

Petroleum-derived polyolefins exhibit diverse properties and are the most important and largest volume class of plastics. However, polyolefins are difficult to efficiently recycle or break down and are now a persistent global contaminant. Broadly replacing polyolefins with bio-derived and degradable polyethylene-like materials is an important yet challenging endeavour towards sustainable plastics. Here we report a solution for circular bio-based polyethylene-like materials synthesized by acceptorless dehydrogenative polymerization from linear and branched diols and their catalytic closed-loop recycling. The polymerization and depolymerization processes utilize earth-abundant manganese complexes as catalysts. These materials exhibit a wide range of mechanical properties, encompassing thermoplastics to plastomers to elastomers. The branched diols, produced through a thiol–ene click reaction, can be polymerized to plastics with significantly enhanced tensile properties, toughness and adhesive properties. These materials could be depolymerized back to monomers through hydrogenation and were separatable with a monomer recovery of up to 99%, unaffected by the presence of dyes and additives. Overall, this system establishes a route to more sustainable plastics.

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Fig. 1: Overview of the catalytic closed-loop recycling of PE-like materials with tunable properties from polymerization of bio-based linear and branched diols.
Fig. 2: Properties of the polymers are modulated over diverse regimes.
Fig. 3: Catalytic recycling of PE-like materials.

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Data availability

Full experimental details and the summary of the data supporting the findings of this study are available within the article and its Supplementary Information. Owing to the large number of raw data files, they are available from the corresponding author on reasonable request. Source data are provided with this paper.

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Acknowledgements

We thank Z. Zhang for insightful discussions throughout the lap-shear adhesion testing. This work was supported by the National Institutes of Health under award no. R35GM144356 and RePLACE (Redesigning Polymers to Leverage a Circular Economy) funded by the Office of Science of the US Department of Energy through award no. DE-SC0022290. Funding for N.A.R. and J.M. was provided in part by the US Department of Energy, Office of Energy Efficiency and Renewable Energy, Advanced Manufacturing Office (AMO) and Bioenergy Technologies Office (BETO). This work was performed as part of the BOTTLE Consortium and was supported by AMO and BETO under contract no. DE-AC36-08GO28308 with the National Renewable Energy Laboratory, operated by Alliance for Sustainable Energy, LLC. We thank the Analytical Resources Core (RRID: SCR_021759) and the SAMD Core (RRID: SCR_022002) at Colorado State University for instrument access and training. G.M.M. acknowledges support from The Camille & Henry Dreyfus Foundation through a Camille Dreyfus Teacher-Scholar Award and the Dr. Robert Williams Professorship in Organic Chemistry at Colorado State University.

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Author notes

  1. These authors contributed equally: Xin Liu, Zhitao Hu.

Authors and Affiliations

  1. Department of Chemistry, Colorado State University, Fort Collins, CO, USA

    Xin Liu, Zhitao Hu, Katherine L. Harry & Garret M. Miyake

  2. School of Materials Science and Engineering, Colorado State University, Fort Collins, CO, USA

    Emma M. Rettner & Garret M. Miyake

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

    Joel Miscall & Nicholas A. Rorrer

  4. BOTTLE Consortium, Golden, CO, USA

    Joel Miscall & Nicholas A. Rorrer

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Contributions

X.L., Z.H. and G.M.M. conceived the idea. X.L. and Z.H. designed and conducted the experiments and analysed results. X.L., Z.H., E.M.R., J.M. and N.A.R. performed characterization and analysed results. X.L. and K.L.H synthesized the required complexes. X.L. wrote the initial paper and supplementary materials. All authors read and edited the paper. G.M.M. directed the project.

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Correspondence to Garret M. Miyake.

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Nature Chemistry thanks Georgina Gregory, Benjamin McDonald, Christophe Thomas and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Liu, X., Hu, Z., Rettner, E.M. et al. Catalytic closed-loop recycling of polyethylene-like materials produced by acceptorless dehydrogenative polymerization of bio-derived diols. Nat. Chem. 17, 500–506 (2025). https://doi.org/10.1038/s41557-025-01753-8

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