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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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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.

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Correspondence to Tae-Lim Choi.

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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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