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Controlled anionic polymerization mediated by carbon dioxide

Nature Chemistry volume 17, pages 1076–1082 (2025)Cite this article

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Abstract

Anionic polymerizations of vinyl monomers are powerful synthetic platforms for making well-defined materials. However, these reactions are extremely sensitive to moisture and oxygen, require the use of highly purified reagents, must be run at low temperatures, and use hazardous and difficult-to-handle alkyl lithium initiators. Together, these drawbacks limit the practicality of these polymerizations and impede their widespread usage. On this basis, the development of a user-friendly anionic polymerization process for methacrylates is a grand challenge. Here we report an anionic polymerization of methacrylates mediated by CO2 that can be run at elevated temperatures and uses an easy-to-handle solid initiator. The reversible addition of CO2 to the enolate chain end efficiently tempers the reactivity of the anion, giving polymers with narrow molar mass distributions and excellent molecular weight targeting at elevated temperatures. Our scalable and more user-friendly CO2-mediated method improves the accessibility and safety of anionic polymerizations and facilitates the production of a variety of polymeric materials.

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Fig. 1: Development of a more user-friendly anionic polymerization.
Fig. 2: CO2-mediated anionic polymerization of methacrylates.
Fig. 3: CMAP with initiator 7.
Fig. 4: Chain-end manipulation and monomer scope overview.

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Data availability

All of the data that support the findings of this study are available in the main text or Supplementary Information. 1H and 13C NMR files and text files of GPC chromatograms, in situ CO2 evolution traces, and MALDI-TOF MS spectra have been deposited in eCommons (Cornell’s Digital Repository) at https://doi.org/10.7298/s733-8m37 (ref. 53). Source data are provided with this paper.

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Acknowledgements

We thank G. Coates for use of the GPC system with an ultraviolet detector and J. Koehl for sample preparation and analysis. We thank E. Stache for use of the GPC system with N,N-dimethylacetamide as the eluent and C. Preston for sample preparation and analysis. This work was supported by the National Science Foundation (grant number CHE 2203758 to B.P.F., P.E.J. and A.D.E.), National Science Foundation Graduate Research Fellowship Program (grant number DGE 2139899 to P.E.J.) and Cornell College of Arts and Sciences Klarman Postdoctoral Fellowship (to A.D.E.). This work made use of the Cornell University NMR Facility, which is supported in part by the National Science Foundation through MRI award CHE-1531632. This work made use of the Cornell Center for Materials Research, supported by the Materials Research Science and Engineering Centers programme DMR-1120296. The funders had no role in study design, data collection and analysis, decision to publish or preparation of the manuscript.

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  1. Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY, USA

    Paige E. Jacky, Alexandra D. Easley & Brett P. Fors

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  1. Paige E. Jacky
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  2. Alexandra D. Easley
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Contributions

P.E.J., A.D.E. and B.P.F. designed the experiments and prepared the paper. P.E.J. and A.D.E. conducted and analysed the experiments.

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Correspondence to Brett P. Fors.

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Competing interests

On 3 March 2025, B.P.F. and P.E.J. filed a patent application (US Patent application number 63/765,983; ‘Vinyl polymers, methods of making same, and uses thereof’) on technology related to the processes described in this article. The other author declares no competing interests.

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Supplementary Methods, Figs. 1–78, Tables 1–10 and References.

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Numerical data for the plots in Fig. 3b–d.

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Jacky, P.E., Easley, A.D. & Fors, B.P. Controlled anionic polymerization mediated by carbon dioxide. Nat. Chem. 17, 1076–1082 (2025). https://doi.org/10.1038/s41557-025-01819-7

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