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Synthesis of discrete oligoethylenes towards chemically recyclable polyolefins

Nature Synthesis (2026)Cite this article

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Abstract

Polyethylene-like materials consist of long-chain oligoethylene blocks and chemically cleavable linkages, providing a promising alternative to chemically inert polyethylene while retaining comparable properties. Larger and uniform chain lengths of oligoethylene blocks are preferred to retain polyethylene crystallinity; however, the efficient synthesis of uniform ultralong oligoethylenes with guaranteed purity remains challenging. Here we report the precision synthesis of uniform oligoethylenes of up to 576 carbon atoms based on the Julia–Kocienski reaction. Using these as building blocks, a series of high-density polyethylene-like materials with regularly distributed ester linkages were developed. The oligoethylene with 126 carbon atoms readily affords remarkable thermal (Tm ≈ 130 °C) and mechanical properties. Due to the uniformity of oligoethylene blocks, closed-loop chemical recyclability of high-density polyethylene-like materials is possible for at least five cycles, excluding compositional heterogeneity and batch-to-batch fluctuation. Our strategy for constructing uniform oligoethylenes with exceptionally high chain lengths is interesting for new-generation recyclable materials.

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Fig. 1: Precision synthesis of discrete oligoethylene precursors.
Fig. 2: Synthesis of discrete oligoethylene precursors via iterative J–K reactions.
Fig. 3: Characterization of discrete oligoethylene precursors.
Fig. 4: Characterization of discrete unsaturated ultralong diols and diesters.
Fig. 5: Synthesis and characterization of discrete unsaturated oligopropylene (oPn+1) and oligo(1,4-isoprene) (oIpn).
Fig. 6: Preparation and characterization for ester-containing HDPE-like materials.
Fig. 7: Chemical recycling of ester-containing HDPE-like materials and characterization of recycled HDPE-like materials.

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The data supporting the findings of this study are freely available in the paper and its Supplementary Information.

References

  1. Martín, A. J., Mondelli, C., Jaydev, S. D. & Pérez-Ramírez, J. Catalytic processing of plastic waste on the rise. Chem 7, 1487–1533 (2021).

    Article  Google Scholar 

  2. 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 

  3. Jehanno, C. et al. Critical advances and future opportunities in upcycling commodity polymers. Nature 603, 803–814 (2022).

    Article  PubMed  CAS  Google Scholar 

  4. Wang, X.-Y., Gao, Y. & Tang, Y. Sustainable developments in polyolefin chemistry: progress, challenges, and outlook. Prog. Polym. Sci. 143, 2023–101713(2023).

    Article  Google Scholar 

  5. Eck, M. & Mecking, S. Closed-loop recyclable and nonpersistent polyethylene-like polyesters. Acc. Chem. Res. 57, 971–980 (2024).

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  6. Schwab, S. T., Baur, M., Nelson, T. F. & Mecking, S. Synthesis and deconstruction of polyethylene-type materials. Chem. Rev. 124, 2327–2351 (2024).

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  7. Lefay, C. & Guillaneuf, Y. Recyclable/degradable materials via the insertion of labile/cleavable bonds using a comonomer approach. Prog. Polym. Sci. 147, 101764 (2023).

    Article  CAS  Google Scholar 

  8. Song, L. et al. Ultra-strong long-chain polyamide elastomers with programmable supramolecular interactions and oriented crystalline microstructures. Nat. Commun. 10, 1315 (2019).

    Article  PubMed  PubMed Central  Google Scholar 

  9. Baur, M., Lin, F., Morgen, T. O., Odenwald, L. & Mecking, S. Polyethylene materials with in-chain ketones from nonalternating catalytic copolymerization. Science 374, 604–607 (2021).

    Article  PubMed  CAS  Google Scholar 

  10. Kocen, A. L., Cui, S., Lin, T. W., LaPointe, A. M. & Coates, G. W. Chemically recyclable ester-linked polypropylene. J. Am. Chem. Soc. 144, 12613–12618 (2022).

    Article  PubMed  CAS  Google Scholar 

  11. Arroyave, A. et al. Catalytic chemical recycling of post-consumer polyethylene. J. Am. Chem. Soc. 144, 23280–23285 (2022).

    Article  PubMed  CAS  Google Scholar 

  12. Xia, Y., Yue, X., Sun, Y., Zhang, C. & Zhang, X. Chemically recyclable polyethylene-like sulfur-containing plastics from sustainable feedstocks. Angew. Chem. Int. Ed. 62, e202219251 (2023).

    Article  CAS  Google Scholar 

  13. Parke, S. M., Lopez, J. C., Cui, S., LaPointe, A. M. & Coates, G. W. Polyethylene incorporating Diels–Alder comonomers: a ‘trojan horse’ strategy for chemically recyclable polyolefins. Angew. Chem. Int. Ed. 62, e202301927 (2023).

    Article  CAS  Google Scholar 

  14. Johnson, A. M. & Johnson, J. A. Thermally robust yet deconstructable and chemically recyclable high-density polyethylene (HDPE)-like materials based on Si–O bonds. Angew. Chem. Int. Ed. 62, e202315085 (2023).

    Article  CAS  Google Scholar 

  15. Eck, M. et al. Biodegradable high-density polyethylene-like material. Angew. Chem. Int. Ed. 62, e202213438 (2023).

    Article  CAS  Google Scholar 

  16. Zhao, Y. et al. Chemically recyclable polyolefin-like multiblock polymers. Science 382, 310–314 (2023).

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  17. Zhou, L. et al. Chemically circular, mechanically tough, and melt-processable polyhydroxyalkanoates. Science 380, 64–69 (2023).

    Article  PubMed  CAS  Google Scholar 

  18. Cheng, C. et al. Polymers from plant oils linked by siloxane bonds for programmed depolymerization. J. Am. Chem. Soc. 146, 12645–12655 (2024).

    Article  PubMed  CAS  Google Scholar 

  19. Jang, Y. J., Nguyen, S. & Hillmyer, M. A. Chemically recyclable linear and branched polyethylenes synthesized from stoichiometrically self-balanced telechelic polyethylenes. J. Am. Chem. Soc. 146, 4771–4782 (2024).

    Article  PubMed  CAS  Google Scholar 

  20. Han, X. W. et al. Circular olefin copolymers made de novo from ethylene and α-olefins. Nat. Commun. 15, 1462 (2024).

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  21. Nan, T. et al. Installing a trigger to upcycle high-density polyethylene. J. Am. Chem. Soc. 146, 27794–27801 (2024).

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  22. Yu, Z. et al. Synthesis of telechelic isotactic polypropylenes for circular polypropylene-like materials via chain transfer polymerization. J. Am. Chem. Soc. 147, 3931–3936 (2025).

    Article  PubMed  CAS  Google Scholar 

  23. Liu, X. 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).

    Article  PubMed  Google Scholar 

  24. Ortmann, P., Heckler, I. & Mecking, S. Physical properties and hydrolytic degradability of polyethylene-like polyacetals and polycarbonates. Green Chem. 16, 1816–1827 (2014).

    Article  CAS  Google Scholar 

  25. Pepels, M. P. F., Govaert, L. E. & Duchateau, R. Influence of the main-chain configuration on the mechanical properties of linear aliphatic polyesters. Macromolecules 48, 5845–5854 (2015).

    Article  CAS  Google Scholar 

  26. Zhang, X., Zuo, X., Ortmann, P., Mecking, S. & Alamo, R. G. Crystallization of long-spaced precision polyacetals I: Melting and recrystallization of rapidly formed crystallites. Macromolecules 52, 4934–4948 (2019).

    Article  CAS  Google Scholar 

  27. Marxsen, S. F., Häußler, M., Mecking, S. & Alamo, R. G. Unlayered–layered crystal transition in recyclable long-spaced aliphatic polyesters. ACS Appl. Polym. Mater. 3, 5243–5256 (2021).

    Article  CAS  Google Scholar 

  28. Flores, I. et al. Unexpected structural properties in the saturation region of the odd–even effects in aliphatic polyethers: Influence of crystallization conditions. Macromolecules 55, 584–594 (2022).

    Article  CAS  Google Scholar 

  29. Marxsen, S. F., Häußler, M., Eck, M., Mecking, S. & Alamo, R. G. Effect of CH2 run length on the crystallization kinetics of sustainable long-spaced aliphatic polyesters. Polymer 282, 126181 (2023).

    Article  CAS  Google Scholar 

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

    Article  PubMed  Google Scholar 

  31. Stempfle, F., Ortmann, P. & Mecking, S. Long-chain aliphatic polymers to bridge the gap between semicrystalline polyolefins and traditional polycondensates. Chem. Rev. 116, 4597–4641 (2016).

    Article  PubMed  CAS  Google Scholar 

  32. Witt, T., Haussler, M., Kulpa, S. & Mecking, S. Chain multiplication of fatty acids to precise telechelic polyethylene. Angew. Chem. Int. Ed. 56, 7589–7594 (2017).

    Article  CAS  Google Scholar 

  33. Yan, T. & Guironnet, D. Synthesis of telechelic polyolefins. Polym. Chem. 12, 5126–5138 (2021).

    Article  CAS  Google Scholar 

  34. Paynter, O. I., Simmonds, D. J. & Whiting, M. C. The synthesis of long-chain unbranched aliphatic-compounds by molecular doubling. J. Chem. Soc. Chem. Commun. 1165–1166 (1982).

  35. Ungar, G., Stejny, J., Keller, A., Bidd, I. & Whiting, M. C. The crystallization of ultralong normal paraffins—the onset of chain folding. Science 229, 386–389 (1985).

    Article  PubMed  CAS  Google Scholar 

  36. Bidd, I. W., M. C. The synthesis of pure normal-paraffins with chain-lengths between one and 400. J. Chem. Soc. Chem. Commun. 543–544 (1985).

  37. Bidd, I., Holdup, D. W. & Whiting, M. C. Studies on the synthesis of linear aliphatic compounds. Part 3 The synthesis of paraffins with very long chains. J. Chem. Soc. Perkin Trans. 1, 2455–2463 (1987).

    Article  Google Scholar 

  38. Ando, K. & Takama, D. Stereoselective synthesis of trisubstituted (Z)-alkenes from ketones via the Julia–Kocienski olefination using 1-methyl- and 1-tert-butyl-1H-tetrazol-5-yl alkyl sulfones. Org. Lett. 22, 6907–6910 (2020).

    Article  PubMed  CAS  Google Scholar 

  39. Rinu, P. X. T., Radhika, S. & Anilkumar, G. Recent applications and trends in the Julia–Kocienski olefination. ChemistrySelect 7, e202200760 (2022).

    Article  CAS  Google Scholar 

  40. Liu, Y., Tan, R., Wu, H., Dong, X.-H. & Zhang, Z. Quantitative understanding of phase segregation behaviors by precisely building discrete oligo-ester-b-oligo-olefin block copolymers. Sci. China Chem. 67, 1008–1016 (2023).

    Article  Google Scholar 

  41. Wallace, D. C. Mitochondria and cancer. Nat. Rev. Cancer 12, 685–698 (2012).

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  42. Sheldon, R. A. Organic synthesis—past, present and future. Chem. Ind. 23, 903–906 (1992).

    Google Scholar 

  43. Sheldon, R. A. Catalysis and pollution prevention. Chem. Ind. 1, 12–15 (1997).

    Google Scholar 

  44. Constable, D. J. C., Curzons, A. D. & Cunningham, V. L. Metrics to ‘green’ chemistry—which are the best?. Green Chem. 4, 521–527 (2002).

    Article  CAS  Google Scholar 

  45. Sheldon, R. A. The E factor: fifteen years on. Green Chem. 9, 1273–1283 (2007).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Natural Science Foundation of China (22431010, 21925107, 52233009, 52021002), the Basic Research Program of Jiangsu (BK20243006) and the Collaborative Innovation Center of Suzhou Nano Science and Technology.

Author information

Author notes

  1. These authors contributed equally: Rui Tan, Yanru An, Yuxin Liu.

Authors and Affiliations

  1. College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, China

    Rui Tan, Yanru An, Yuxin Liu, Xiaojie Yang, Qinmeng Zhong, Xinyue Yan, Yuxiao Hu, Xiaoman Huang, Gefei Wang & Zhengbiao Zhang

  2. Department of Polymer Science and Engineering, Hefei National Laboratory of Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, China

    Minglong Chen, Jie Cen, Jinming Hu & Shiyong Liu

  3. State Key Laboratory of Radiation Medicine and Protection, Soochow University, Suzhou, China

    Zhengbiao Zhang

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Contributions

R.T., S.L. and Z.Z. conceived and designed the project. Y.L, X. Yang and R.T. synthesized and characterized discrete oligoethylenes, oligopropylenes and oligoisoprenes. R.T. and Y.A. synthesized and characterized discrete diols and diesters. Y.A. synthesized and characterized PE-n materials. X. Yan, Y.H., M.C., J.C., X.H. and G.W. contributed to data analysis and interpretation. R.T., J.H., S.L. and Z.Z. wrote the manuscript. R.T., S.L. and Z.Z. supervised the research. All authors discussed the results and provided critical feedback on the final manuscript.

Corresponding authors

Correspondence to Rui Tan, Shiyong Liu or Zhengbiao Zhang.

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Nature Synthesis thanks Christophe M. Thomas and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alexandra Groves, in collaboration with the Nature Synthesis team.

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Extended data

Extended Data Fig. 1 Model J-K reaction of decanal with 1-phenyl-1H-tetrazol-5-yl decyl sulfone.

a, Schematic of the model reaction. b, Screening of reaction conditions for the model reaction. Optimized standard condition: C10-CHO (1.0 equiv.) and C10-SO2PT (1.1 equiv.) were dissolved in dry THF. LiHDMS (1 M in THF) was added dropwise into the mixture in three portions (1.1 equiv. for 30 min; 0.5 equiv. for 30 min; 0.5 equiv. for 1 h) under argon at −20 °C. c, TLC analysis (petroleum ether/ethyl acetate, 9:1 v/v) of C10-CHO, 1-bromodecane, and C10-SO2PT. The results highlight the marked enhancement in polarity of long-chain alkanes with incorporation of highly polar tetrazole groups. d, TLC analysis (petroleum ether/ethyl acetate, 9:1 v/v) of J-K reaction between C10-CHO and C10-SO2PT under optimized condition. CHO, C10-CHO; PTO, C10-SO2PT; R, reaction solution. The reaction is completed within 30 min, demonstrating the remarkable efficiency of J-K reaction. Distinct Rf values between the substrates (C10-CHO and C10-SO2PT) and product (E/Z-C20) further underscore the critical role of highly polar tetrazole groups in facilitating the separation process. e, Quantitative 13C-NMR spectrum (CDCl3, 75 MHz, 25 °C) of C20. This result reveals an E-selectivity (in E/Z 66:34) of J-K reaction under standard condition. f, ESI-MS analysis of C20.

Source data

Extended Data Fig. 2 Characterization of HO-C18-OH and heterobifunctional precursors.

a, Quantitative 13C-NMR spectrum (CDCl3, 25 °C) of HO-C18-OH. This result reveals an E-selectivity (in E/Z 85:15) for the self-metathesis reaction. b, ESI-MS analysis of AT-C18-SO2PT. The absence of any homologues with varying carbon atom numbers confirms the high purity of the product. c, Large-scale preparation of AT-C18-SPT ( ~ 100 g per batch). d, Large-scale preparation of AT-C36-SPT ( ~ 50 g per batch). Approximately 50 g of AT-C36-SPT was obtained per batch, highlighting the scalability of this approach.

Source data

Extended Data Fig. 3 TLC analysis of the Julia-Kocienski reaction of AT-C36 -SO2PT and CHO-C36-SPT.

a, Schematic of the J-K reaction between AT-C36-SO2PT and CHO-C36-SPT. Reaction condition: AT-C36-SO2PT (1.0 equiv.) and CHO-C36-SPT (1.1 equiv.) were dissolved in dry THF. LiHDMS (1 M in THF) was added dropwise into the mixture in three portions (1.1 equiv. for 30 min; 0.5 equiv. for 30 min; 0.5 equiv. for 1 h) under argon at −20 °C. b-d, TLC analysis (petroleum ether/ethyl acetate, 9:1 v/v) at 30 min (b), 1 h (c), 12 h (d). PTO, AT-C36-SO2PT; CHO, CHO-C36-SPT; R, the reaction solution; M, the mixture of AT-C36-SO2PT, CHO-C36-SPT, and reaction solution. TLC analysis revealed complete conversion within 1 h, highlighting the high efficiency of the J-K reaction. The substantial polarity difference between the product (AT-C72-PT) and the substrates (AT-C36-SO2PT and CHO-C36-SPT) underscores the critical role of highly polar tetrazole groups in enhancing the polarity of long-chain alkanes.

Extended Data Fig. 4 Properties of recycled PE-126.

a, Comparison of SEC profiles of original and recycled PE-126. b, Comparison of WAXS profiles of original and recycled PE-126. The red solid curves represent the recycled PE-126, and the black dashed curves represent the original PE-126.

Source data

Extended Data Fig. 5 E-factor analysis of Julia-Kocienski reaction-based iterative exponential growth approach.

a, E-factor analysis of reaction intermediates and orthogonal monomers without and with solvent recovery. b, Mass distributions of raw materials, reagents, solvents, and final products used for the synthesis of reaction intermediates and orthogonal monomers. c, E-factor analysis of discrete AT-C36-SPT, AT-C36-SO2PT, and AT-C72-SPT without and with solvent recovery. d, Mass distributions of raw materials, reagents, solvents, and final products used for iterative synthesis of discrete AT-C36-SPT, AT-C36-SO2PT, and AT-C72-SPT. e, E-factor analysis of discrete oligoethylene blocks without and with solvent recovery.

Source data

Extended Data Fig. 6 E-factor analysis for J-K reaction-based bidirectional iterative growth approach.

a, E-factors for the synthesis of discrete TBDMSO-C90-OTBDMS, HO-C90-OH, CHO-C90-CHO, and MeOOC-C90-COOMe without or with solvent recovery. b, Mass distributions of raw materials, reagents, solvents, and final products used for the iterative synthesis of discrete TBDMSO-C90-OTBDMS, HO-C90-OH, CHO-C90-CHO, and MeOOC-C90-COOMe. c, E-factors for the synthesis of discrete ultralong diols (HO-Cn-OH, n = 54 and 126) and diesters (MeOOC-Cn-COOMe, n = 54 and 126) without or with solvent recovery.

Source data

Extended Data Table 1 Molecular parameters of discrete unsaturated telechelic oligoethylenes
Full size table
Extended Data Table 2 Thermal properties of PE-n and commercial HDPE
Full size table

Supplementary information

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Tan, R., An, Y., Liu, Y. et al. Synthesis of discrete oligoethylenes towards chemically recyclable polyolefins. Nat. Synth (2026). https://doi.org/10.1038/s44160-025-00955-9

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