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Scalable and continuous access to pure cyclic polymers enabled by ‘quarantined’ heterogeneous catalysts

Nature Chemistry volume 14, pages 1242–1248 (2022)Cite this article

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A Publisher Correction to this article was published on 21 September 2022

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Abstract

Cyclic polymers are topologically interesting and envisioned as a lubricant material. However, scalable synthesis of pure cyclic polymers remains elusive. The most straightforward way is to recover a used catalyst after the synthesis of cyclic polymers and reuse it. Unfortunately, this is demanding because of the catalyst’s vulnerability and inseparability from polymers, which reduce the practicality of the process. Here we develop a continuous circular process, where polymerization, polymer separation and catalyst recovery happen in situ, to dispense a pure cyclic polymer after bulk ring-expansion metathesis polymerization of cyclopentene. It is enabled by introducing silica-supported ruthenium catalysts and newly designed glassware. Different depolymerization kinetics of the cyclic polymer from its linear analogue are also discussed. This process minimizes manual labour, maximizes the security of vulnerable catalysts and guarantees the purity of cyclic polymers, thereby showcasing a prototype of a scalable access to cyclic polymers with increased turnovers (≥415,000) of precious catalysts.

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Fig. 1: REMP and purification process for the preparation of cyclic polymers.
Fig. 2: REMP of CP with the immobilized ruthenium carbene catalysts.
Fig. 3: Importance of monomer purity for REMP.
Fig. 4: ‘Monomer in, Polymer out’.
Fig. 5: Distancing effect.
Fig. 6: Topology dependence of depolymerization.

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

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References

  1. González-Reyes, G. A., Bayo-Besteiro, S., Vich Llobet, J. & Añel, J. A. Environmental and economic constraints on the use of lubricant oils for wind and hydropower generation: the case of NATURGY. Sustainability 12, 4242 (2020).

    Article  Google Scholar 

  2. Wakiru, J., Pintelon, L., Muchiri, P. N., Chemweno, P. K. & Mburu, S. Towards an innovative lubricant condition monitoring strategy for maintenance of ageing multi-unit systems. Reliab. Eng. Syst. 204, 107200 (2020).

    Article  Google Scholar 

  3. Zolper, T. et al. Lubrication properties of polyalphaolefin and polysiloxane lubricants: molecular structure–tribology relationships. Tribol. Lett. 48, 355–365 (2012).

    CAS  Google Scholar 

  4. Greaves, M. Pressure viscosity coefficients and traction properties of synthetic lubricants for wind turbine gear systems. Lubr. Sci. 24, 75–83 (2012).

    Article  CAS  Google Scholar 

  5. Ray, S., Rao, P. V. C. & Choudary, N. V. Poly-α-olefin-based synthetic lubricants: a short review on various synthetic routes. Lubr. Sci. 24, 23–44 (2012).

    Article  CAS  Google Scholar 

  6. Martini, A., Ramasamy, U. S. & Len, M. Review of viscosity modifier lubricant additives. Tribol. Lett. 66, 58 (2018).

    Article  Google Scholar 

  7. Morgan, S., Ye, Z., Subramanian, R. & Zhu, S. Higher-molecular-weight hyperbranched polyethylenes containing crosslinking structures as lubricant viscosity-index improvers. Polym. Eng. Sci. 50, 911–918 (2010).

    Article  CAS  Google Scholar 

  8. Ver Strate, G. & Struglinski, M. J. in Polymers as Rheology Modifiers, ACS Symposium Series Vol. 462 (eds Schulz, D. N. & Glass, J. E.) Ch. 15 (American Chemical Society, 1991).

  9. Peterson, G. I. & Choi, T.-L. The influence of polymer architecture in polymer mechanochemistry. Chem. Commun. 57, 6465–6474 (2021).

    Article  CAS  Google Scholar 

  10. Lin, Y., Zhang, Y., Wang, Z. & Craig, S. L. Dynamic memory effects in the mechanochemistry of cyclic polymers. J. Am. Chem. Soc. 141, 10943–10947 (2019).

    Article  CAS  PubMed  Google Scholar 

  11. Bielawski, C. W., Benitez, D. & Grubbs, R. H. An ‘endless’ route to cyclic polymers. Science 297, 2041–2044 (2002).

    Article  CAS  PubMed  Google Scholar 

  12. Xia, Y. et al. Ring-expansion metathesis polymerization: catalyst-dependent polymerization profiles. J. Am. Chem. Soc. 131, 2670–2677 (2009).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  13. Boydston, A. J., Xia, Y., Kornfield, J. A., Gorodetskaya, I. A. & Grubbs, R. H. Cyclic ruthenium-alkylidene catalysts for ring-expansion metathesis polymerization. J. Am. Chem. Soc. 130, 12775–12782 (2008).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  14. Xia, Y., Boydston, A. J. & Grubbs, R. H. Synthesis and direct imaging of ultrahigh molecular weight cyclic brush polymers. Angew. Chem. Int. Ed. 50, 5882–5885 (2011).

    Article  CAS  Google Scholar 

  15. Boydston, A. J., Holcombe, T. W., Unruh, D. A., Fréchet, J. M. J. & Grubbs, R. H. A direct route to cyclic organic nanostructures via ring-expansion metathesis polymerization of a dendronized macromonomer. J. Am. Chem. Soc. 131, 5388–5389 (2009).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  16. Bielawski, C. W., Benitez, D. & Grubbs, R. H. Synthesis of cyclic polybutadiene via ring-opening metathesis polymerization: the importance of removing trace linear contaminants. J. Am. Chem. Soc. 125, 8424–8425 (2003).

    Article  CAS  PubMed  Google Scholar 

  17. Wang, T.-W., Huang, P.-R., Chow, J. L., Kaminsky, W. & Golder, M. R. A cyclic ruthenium benzylidene initiator platform enhances reactivity for ring-expansion metathesis polymerization. J. Am. Chem. Soc. 143, 7314–7319 (2021).

    Article  CAS  PubMed  Google Scholar 

  18. Miao, Z. et al. Cyclic polyacetylene. Nat. Chem. 13, 792–799 (2021).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  19. McGraw, M. L., Clarke, R. W. & Chen, E. Y. X. Synchronous control of chain length/sequence/topology for precision synthesis of cyclic block copolymers from monomer mixtures. J. Am. Chem. Soc. 143, 3318–3322 (2021).

    Article  CAS  PubMed  Google Scholar 

  20. Niu, W. et al. Polypropylene: now available without chain ends. Chem 5, 237–244 (2019).

    Article  CAS  Google Scholar 

  21. Roland, C. D., Li, H., Abboud, K. A., Wagener, K. B. & Veige, A. S. Cyclic polymers from alkynes. Nat. Chem. 8, 791–796 (2016).

    Article  CAS  PubMed  Google Scholar 

  22. Lidster, B. J. et al. Macrocyclic poly(p-phenylenevinylene)s by ring expansion metathesis polymerisation and their characterisation by single-molecule spectroscopy. Chem. Sci. 9, 2934–2941 (2018).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  23. Zhang, K., Lackey, M. A., Wu, Y. & Tew, G. N. Universal cyclic polymer templates. J. Am. Chem. Soc. 133, 6906–6909 (2011).

    Article  CAS  PubMed  Google Scholar 

  24. Edwards, J. P., Wolf, W. J. & Grubbs, R. H. The synthesis of cyclic polymers by olefin metathesis: achievements and challenges. J. Polym. Sci. A Polym. Chem. 57, 228–242 (2018).

    Article  Google Scholar 

  25. Chang, Y. A. & Waymouth, R. M. Recent progress on the synthesis of cyclic polymers via ring-expansion strategies. J. Polym. Sci. A Polym. Chem. 55, 2892–2902 (2017).

    Article  CAS  Google Scholar 

  26. Haque, F. M. & Grayson, S. M. The synthesis, properties and potential applications of cyclic polymers. Nat. Chem. 12, 433–444 (2020).

    Article  CAS  PubMed  Google Scholar 

  27. Golba, B., Benetti, E. M. & De Geest, B. G. Biomaterials applications of cyclic polymers. Biomaterials 267, 120468 (2021).

    Article  CAS  PubMed  Google Scholar 

  28. Miao, Z. et al. Semi-conducting cyclic copolymers of acetylene and propyne. React. Funct. Polym. 169, 105088 (2021).

    Article  CAS  Google Scholar 

  29. Tuba, R. Synthesis of cyclopolyolefins via ruthenium catalyzed ring-expansion metathesis polymerization. Pure Appl. Chem. 86, 1685–1693 (2014).

    Article  CAS  Google Scholar 

  30. Jawiczuk, M., Marczyk, A. & Trzaskowski, B. Decomposition of ruthenium olefin metathesis catalyst. Catalysts 10, 887 (2020).

    Article  CAS  Google Scholar 

  31. Allen, D. P., Van Wingerden, M. M. & Grubbs, R. H. Well-defined silica-supported olefin metathesis catalysts. Org. Lett. 11, 1261–1264 (2009).

    Article  CAS  PubMed  Google Scholar 

  32. Dewaele, A., Van Berlo, B., Dijkmans, J., Jacobs, P. A. & Sels, B. F. Immobilized Grubbs catalysts on mesoporous silica materials: insight into support characteristics and their impact on catalytic activity and product selectivity. Catal. Sci. Technol. 6, 2580–2597 (2016).

    Article  CAS  Google Scholar 

  33. Hejl, A., Scherman, O. A. & Grubbs, R. H. Ring-opening metathesis polymerization of functionalized low-strain monomers with ruthenium-based catalysts. Macromolecules 38, 7214–7218 (2005).

    Article  CAS  Google Scholar 

  34. Neary, W. J. & Kennemur, J. G. Polypentenamer renaissance: challenges and opportunities. ACS Macro Lett. 8, 46–56 (2019).

    Article  CAS  PubMed  Google Scholar 

  35. Tuba, R. & Grubbs, R. H. Ruthenium catalyzed equilibrium ring-opening metathesis polymerization of cyclopentene. Polym. Chem. 4, 3959–3962 (2013).

    Article  CAS  Google Scholar 

  36. Neary, W. J. & Kennemur, J. G. Variable temperature ROMP: leveraging low ring strain thermodynamics to achieve well-defined polypentenamers. Macromolecules 50, 4935–4941 (2017).

    Article  CAS  Google Scholar 

  37. Mulhearn, W. D. & Register, R. A. Synthesis of narrow-distribution, high-molecular-weight ROMP polycyclopentene via suppression of acyclic metathesis side reactions. ACS Macro Lett. 6, 112–116 (2017).

    Article  CAS  PubMed  Google Scholar 

  38. Lee, L.-B. W. & Register, R. A. Acyclic metathesis during ring-opening metathesis polymerization of cyclopentene. Polymer 45, 6479–6485 (2004).

    Article  CAS  Google Scholar 

  39. Ji, S., Hoye, T. R. & Macosko, C. W. Controlled synthesis of high molecular weight telechelic polybutadienes by ring-opening metathesis polymerization. Macromolecules 37, 5485–5489 (2004).

    Article  CAS  Google Scholar 

  40. Obligacion, J. V. & Chirik, P. J. Bis(imino)pyridine cobalt-catalyzed alkene isomerization–hydroboration: a strategy for remote hydrofunctionalization with terminal selectivity. J. Am. Chem. Soc. 135, 19107–19110 (2013).

    Article  CAS  PubMed  Google Scholar 

  41. Ulman, M. & Grubbs, R. H. Ruthenium carbene-based olefin metathesis initiators: catalyst decomposition and longevity. J. Org. Chem. 64, 7202–7207 (1999).

    Article  CAS  Google Scholar 

  42. Torre Iii, M., Mulhearn, W. D. & Register, R. A. Ring-opening metathesis copolymerization of cyclopentene above and below its equilibrium monomer concentration. Macromol. Chem. Phys. 219, 1800030 (2018).

    Article  Google Scholar 

  43. Szczepaniak, G., Kosiński, K. & Grela, K. Towards ‘cleaner’ olefin metathesis: tailoring the NHC ligand of second generation ruthenium catalysts to afford auxiliary traits. Green Chem. 16, 4474–4492 (2014).

    Article  CAS  Google Scholar 

  44. 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 

  45. Neary, W. J., Isais, T. A. & Kennemur, J. G. Depolymerization of bottlebrush polypentenamers and their macromolecular metamorphosis. J. Am. Chem. Soc. 141, 14220–14229 (2019).

    Article  CAS  PubMed  Google Scholar 

  46. Yuan, J., Giardino, G. J. & Niu, J. Metathesis cascade-triggered depolymerization of enyne self-immolative polymers. Angew. Chem. Int. Ed. 60, 24800–24805 (2021).

    Article  CAS  Google Scholar 

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Acknowledgements

R. H. Grubbs passed away on 19th December 2021 and was a corresponding author when the article was first submitted. This work is financially supported by the National Science Foundation (CHE#1807154) and the Creative Research Initiative Grant. N. Hart at Caltech Glass Shop is gratefully acknowledged for the glass blowing. S. Hwang at Caltech Solid State NMR Facility is thanked for the solid-state NMR. We thank NCIRF at Seoul National University for supporting headspace gas chromatography–mass spectrometry experiments. Y. Xu (Peking University), J. H. Ko (Caltech), J.-A. Song (Samsung), Y.-J. Jang (University of Minnesota) and D. Allen (Materia) are acknowledged for helpful discussions.

Author information

Author notes

  1. Ki-Young Yoon

    Present address: Ashland Specialty Ingredients, Bridgewater, NJ, USA

  2. Tae-Lim Choi

    Present address: Department of Materials, ETH Zürich, Zürich, Switzerland

  3. These authors contributed equally: Ki-Young Yoon, Jinkyung Noh, Quan Gan.

  4. Deceased: Robert H. Grubbs.

Authors and Affiliations

  1. Arnold and Mabel Beckman Laboratory of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA

    Ki-Young Yoon, Quan Gan, Julian P. Edwards & Robert H. Grubbs

  2. Department of Chemistry, Seoul National University, Seoul, Republic of Korea

    Jinkyung Noh & Tae-Lim Choi

  3. Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Budapest, Hungary

    Robert Tuba

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Contributions

R.H.G. and K.-Y.Y. conceived and designed the project. R.H.G. and T.-L.C. directed the project and provided valuable input. K.-Y.Y., Q.G. and J.P.E. synthesized the catalysts. K.-Y.Y. designed the glassware. K.-Y.Y. and Q.G. conducted polymer synthesis. K.-Y.Y., J.N. and Q.G. characterized the polymers. J.N. performed depolymerization experiments. R.T. demonstrated the heterogeneous cyclic polymer process. All authors analysed the data and discussed the results. K.-Y.Y. wrote the manuscript and then all authors reviewed and commented on it.

Corresponding author

Correspondence to Tae-Lim Choi.

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Nature Chemistry thanks Matthew Golder, Farihah Haque and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–11, Tables 1–6 and Sections 1–18.

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Data for plots (Fig. 3c,d).

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Data for plots (Fig. 4c,d).

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Yoon, KY., Noh, J., Gan, Q. et al. Scalable and continuous access to pure cyclic polymers enabled by ‘quarantined’ heterogeneous catalysts. Nat. Chem. 14, 1242–1248 (2022). https://doi.org/10.1038/s41557-022-01034-8

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