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Tunable and recyclable polyesters from CO2 and butadiene

Abstract

Carbon dioxide is inexpensive and abundant, and its prevalence as waste makes it attractive as a sustainable chemical feedstock. Although there are examples of copolymerizations of CO2 with high-energy monomers, the direct copolymerization of CO2 with olefins has not been reported. Here an alternative route to functionalizable, recyclable polyesters derived from CO2, butadiene and hydrogen via an intermediary lactone, 3-ethyl-6-vinyltetrahydro-2H-pyran-2-one, is described. Catalytic ring-opening polymerization of the lactone by 1,5,7-triazabicyclo[4.4.0]dec-5-ene yields polyesters with molar masses up to 13.6 kg mol−1 and pendent vinyl side chains that can undergo post-polymerization functionalization. The polymer has a low ceiling temperature of 138 °C, allowing for facile chemical recycling, and is inherently biodegradable under aerobic aqueous conditions (OECD-301B protocol). These results show that a well-defined polyester can be derived from CO2, olefins and hydrogen, expanding access to new polymer feedstocks that were once considered unfeasible.

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Fig. 1: EVP is a promising platform chemical derived from the telomerization of CO2 and butadiene that is underutilized in polymer synthesis.
Fig. 2: Synthesis and thermodynamic comparisons.
Fig. 3: Molecular weight studies of EtVP polymerization.
Fig. 4: The cistrans interconversion of EtVP via α-epimerization.
Fig. 5: Recycling and degradation of poly(EtVP).
Fig. 6: Post-polymerization modification of poly(EtVP).

Data availability

All primary data files63 are available free of charge from the Data Repository for the University of Minnesota at https://doi.org/10.13020/sy3d-cf59.

References

  1. Omae, I. Recent developments in carbon dioxide utilization for the production of organic chemicals. Coord. Chem. Rev. 256, 1384–1405 (2012).

    CAS  Article  Google Scholar 

  2. Sakakura, T., Choi, J. C. & Yasuda, H. Transformation of carbon dioxide. Chem. Rev. 107, 2365–2387 (2007).

    CAS  PubMed  Article  Google Scholar 

  3. Grignard, B., Gennen, S., Jérôme, C., Kleij, A. W. & Detrembleur, C. Advances in the use of CO2 as a renewable feedstock for the synthesis of polymers. Chem. Soc. Rev. 48, 4466–4514 (2019).

    CAS  PubMed  Article  Google Scholar 

  4. Artz, J. et al. Sustainable conversion of carbon dioxide: an integrated review of catalysis and life cycle assessment. Chem. Rev. 118, 434–504 (2018).

    CAS  PubMed  Article  Google Scholar 

  5. Dabral, S. & Schaub, T. The use of carbon dioxide (CO2) as a building block in organic synthesis from an industrial perspective. Adv. Synth. Catal. 361, 223–246 (2019).

    CAS  Article  Google Scholar 

  6. Khoo, R. S. H., Luo, H.-K., Braunstein, P. & Hor, T. S. A. Transformation of CO2 to value-added materials. J. Mol. Eng. Mater. 3, 1540007 (2015).

    CAS  Article  Google Scholar 

  7. Zhu, Y., Romain, C. & Williams, C. K. Sustainable polymers from renewable resources. Nature 540, 354–362 (2016).

    CAS  PubMed  Article  Google Scholar 

  8. Price, C. J., Jesse, B., Reich, E. & Miller, S. A. Thermodynamic and kinetic considerations in the copolymerization of ethylene and carbon dioxide. Macromolecules 39, 2751–2756 (2006).

    CAS  Article  Google Scholar 

  9. Musco, A., Perego, C. & Tartiari, V. Telomerization reactions of butadiene and CO2 catalyzed by phosphine Pd(0) complexes: (E)−2-ethylideneheptden-5-olide and octadienyl esters of 2-ethylidenehepta-4,6-dienoic acid. Inorg. Chim. Acta 28, L147–L148 (1978).

    CAS  Article  Google Scholar 

  10. Inoue, Y., Sasaki, Y. & Hashimoto, H. Incorporation of CO2 in butadiene dimerization catalyzed by palladium complexes. Formation of 2-ethylidene-5-hepten-4-olide. Bull. Chem. Soc. Jpn 51, 2375–2378 (1978).

    CAS  Article  Google Scholar 

  11. Braunstein, P., Matt, D. & Nobel, D. Carbon dioxide activation and catalytic lactone synthesis by telomerization of butadiene and CO2. J. Am. Chem. Soc. 110, 3207–3212 (1988).

    CAS  Article  Google Scholar 

  12. Behr, A. & Juszak, K. D. Palladium-catalyzed reaction of butadiene and carbon dioxide. J. Organomet. Chem. 255, 263–268 (1983).

    CAS  Article  Google Scholar 

  13. Sharif, M., Jackstell, R., Dastgir, S., Al-Shihi, B. & Beller, M. Efficient and selective palladium-catalyzed telomerization of 1,3-butadiene with carbon dioxide. ChemCatChem 9, 542–546 (2017).

    CAS  Article  Google Scholar 

  14. Balbino, J. M., Dupont, J. & Bayón, J. C. Telomerization of 1,3-butadiene with carbon dioxide: a highly efficient process for δ-lactone generation. ChemCatChem 10, 206–210 (2018).

    CAS  Article  Google Scholar 

  15. Song, J. et al. Selective synthesis of δ-lactone via palladium nanoparticles-catalyzed telomerization of CO2 with 1,3-butadiene. Tetrahedron Lett. 57, 3163–3166 (2016).

    CAS  Article  Google Scholar 

  16. Behr, A. & Henze, G. Use of carbon dioxide in chemical syntheses via a lactone intermediate. Green Chem. 13, 25–39 (2011).

    CAS  Article  Google Scholar 

  17. Haack, V., Dinjus, E. & Pitter, S. Synthesis of polymers with an intact lactone ring structure in the main chain. Angew. Makromol. Chem. 257, 19–22 (1998).

    CAS  Article  Google Scholar 

  18. Hardouin Duparc, V., Shakaroun, R. M., Slawinski, M., Carpentier, J. F. & Guillaume, S. M. Ring-opening (co)polymerization of six-membered substituted ë-valerolactones with alkali metal alkoxides. Eur. Polym. J. 134, 109858 (2020).

    CAS  Article  Google Scholar 

  19. Sajjad, H., Prebihalo, E. A., Tolman, W. B. & Reineke, T. M. Ring opening polymerization of β-acetoxy-δ-methylvalerolactone, a triacetic acid lactone derivative. Polym. Chem. 12, 6724–6730 (2021).

    CAS  Article  Google Scholar 

  20. Schneiderman, D. K. & Hillmyer, M. A. Aliphatic polyester block polymer design. Macromolecules 49, 2419–2428 (2016).

    CAS  Article  Google Scholar 

  21. Olsén, P., Odelius, K. & Albertsson, A. C. Thermodynamic presynthetic considerations for ring-opening polymerization. Biomacromolecules 17, 699–709 (2016).

    PubMed  PubMed Central  Article  CAS  Google Scholar 

  22. Wheeler, O. H. & Granell, E. E. Solvolysis of substituted γ-butrolactones and δ-valerolactones. J. Org. Chem. 701, 1959–1961 (1964).

    Google Scholar 

  23. Nakano, R., Ito, S. & Nozaki, K. Copolymerization of carbon dioxide and butadiene via a lactone intermediate. Nat. Chem. 6, 325–331 (2014).

    CAS  PubMed  Article  Google Scholar 

  24. Tang, S., Zhao, Y. & Nozaki, K. Accessing divergent main-chain-functionalized polyethylenes via copolymerization of ethylene with a CO2/butadiene-derived lactone. J. Am. Chem. Soc. 143, 17953–17957 (2021).

    CAS  PubMed  Article  Google Scholar 

  25. Liu, M., Sun, Y., Liang, Y. & Lin, B. L. Highly efficient synthesis of functionalizable polymers from a CO2/1,3-butadiene-derived lactone. ACS Macro Lett. 6, 1373–1378 (2017).

    CAS  PubMed  Article  Google Scholar 

  26. Yue, S. et al. Ring-opening polymerization of CO2-based disubstituted δ-valerolactone toward sustainable functional polyesters. ACS Macro Lett. 10, 1055–1060 (2021).

    CAS  PubMed  Article  Google Scholar 

  27. Espinosa, L. D. G., Williams-Pavlantos, K., Turney, K. M., Wesdemiotis, C. & Eagan, J. M. Degradable polymer structures from carbon dioxide and butadiene. ACS Macro Lett. 10, 1254–1259 (2021).

    Article  CAS  Google Scholar 

  28. Sugiura, M., Sato, N., Kotani, S. & Nakajima, M. Lewis base-catalyzed conjugate reduction and reductive aldol reaction of α,β-unsaturated ketones using trichlorosilane. Chem. Commun. 2, 4309–4311 (2008).

    Article  CAS  Google Scholar 

  29. Behr, A. & Brehme, V. A. Bimetallic-catalyzed reduction of carboxylic acids and lactones to alcohols and diols. Adv. Synth. Catal. 344, 525–532 (2002).

    CAS  Article  Google Scholar 

  30. Hudlicky, T., Sinai-Zingde, G. & Natchus, M. G. Selective reduction of α,β-unsaturated esters in the presence of olefins. Tetrahedron Lett. 28, 5287–5290 (1987).

    CAS  Article  Google Scholar 

  31. Makiguchi, K., Satoh, T. & Kakuchi, T. Diphenyl phosphate as an efficient cationic organocatalyst for controlled/living ring-opening polymerization of δ-valerolactone and ε-caprolactone. Macromolecules 44, 1999–2005 (2011).

    CAS  Article  Google Scholar 

  32. Delcroix, D. et al. Phosphoric and phosphoramidic acids as bifunctional catalysts for the ring-opening polymerization of ε-caprolactone: a combined experimental and theoretical study. Polym. Chem. 2, 2249–2256 (2011).

    CAS  Article  Google Scholar 

  33. Dove, A. P. Organic catalysis for ring-opening polymerization. ACS Macro Lett. 1, 1409–1412 (2012).

    CAS  PubMed  Article  Google Scholar 

  34. Thomas, C. & Bibal, B. Hydrogen-bonding organocatalysts for ring-opening polymerization. Green Chem. 16, 1687–1699 (2014).

    CAS  Article  Google Scholar 

  35. Chuma, A. et al. The reaction mechanism for the organocatalytic ring-opening polymerization of l-lactide using a guanidine-based catalyst: hydrogen-bonded or covalently bound? J. Am. Chem. Soc. 130, 6749–6754 (2008).

    CAS  PubMed  Article  Google Scholar 

  36. Pratt, R. C., Lohmeijer, B. G. G., Long, D. A., Waymouth, R. M. & Hedrick, J. L. Triazabicyclodecene: a simple bifunctional organocatalyst for acyl transfer and ring-opening polymerization of cyclic esters. J. Am. Chem. Soc. 128, 4556–4557 (2006).

    CAS  PubMed  Article  Google Scholar 

  37. Simón, L. & Goodman, J. M. The mechanism of TBD-catalyzed ring-opening polymerization of cyclic esters. J. Org. Chem. 72, 9656–9662 (2007).

    PubMed  Article  CAS  Google Scholar 

  38. Whelan, D. in Brydson’s Plastic Materials 8th edn (ed. Gilbert, M.) Ch. 24 (Butterworth-Heinemann, 2017).

  39. Wanamaker, C. L., O’Leary, L. E., Lynd, N. A., Hillmyer, M. A. & Tolman, W. B. Renewable-resource thermoplastic elastomers based on polylactide and polymenthide. Biomacromolecules 8, 3634–3640 (2007).

    CAS  PubMed  Article  Google Scholar 

  40. Lin, B. & Waymouth, R. M. Urea anions: simple, fast and selective catalysts for ring-opening polymerizations. J. Am. Chem. Soc. 139, 1645–1652 (2017).

    CAS  PubMed  Article  Google Scholar 

  41. Anslyn, E. V. & Dougherty, D. A. in Modern Physical Organic Chemistry Ch. 2 (University Science Books, 2006).

  42. Hong, M. & Chen, E. Y. X. Future directions for sustainable polymers. Trends Chem. 1, 148–151 (2019).

    CAS  Article  Google Scholar 

  43. Tang, X. & Chen, E. Y. X. Toward infinitely recyclable plastics derived from renewable cyclic esters. Chem 5, 284–312 (2019).

    CAS  Article  Google Scholar 

  44. Fagnani, D. E. et al. 100th anniversary of macromolecular science viewpoint: redefining sustainable polymers. ACS Macro Lett. 10, 41–53 (2021).

    CAS  PubMed  Article  Google Scholar 

  45. Darensbourg, D. J., Wei, S.-H., Yeung, A. D. & Chadwick Ellis, W. An efficient method of depolymerization of poly(cyclopentene carbonate) to its comonomers: cyclopentene oxide and carbon dioxide. Macromolecules 46, 5850–5855 (2013).

    CAS  Article  Google Scholar 

  46. Zhu, J. B., Watson, E. M., Tang, J. & Chen, E. Y. X. A synthetic polymer system with repeatable chemical recyclability. Science 360, 398–403 (2018).

    CAS  PubMed  Article  Google Scholar 

  47. Abel, B. A., Snyder, R. L. & Coates, G. W. Chemically recyclable thermoplastics from reversible-deactivation polymerization of cyclic acetals. Science 789, 783–789 (2021).

    Article  CAS  Google Scholar 

  48. OECD. Test No. 301: Ready Biodegradability, OECD Guidelines for the Testing of Chemicals Section 3 (OECD, 1992).

  49. Ditzler, R. A. J. & Zhukhovitskiy, A. V. Sigmatropic rearrangements of polymer backbones: vinyl polymers from polyesters in one step. J. Am. Chem. Soc. 143, 20326–20331 (2021).

    CAS  PubMed  Article  Google Scholar 

  50. Rieger, J. et al. Versatile functionalization and grafting of poly(ε-caprolactone) by Michael-type addition. Chem. Commun. 2005, 274–276 (2005).

    Article  Google Scholar 

  51. Tang, X. et al. The quest for converting biorenewable bifunctional α-methylene-γ-butyrolactone into degradable and recyclable polyester: controlling vinyl-addition/ring-opening/cross-linking pathways. J. Am. Chem. Soc. 138, 14326–14337 (2016).

    CAS  PubMed  Article  Google Scholar 

  52. Campos, L. M. et al. Development of thermal and photochemical strategies for thiol-ene click polymer functionalization. Macromolecules 41, 7063–7070 (2008).

    CAS  Article  Google Scholar 

  53. Hauenstein, O., Agarwal, S. & Greiner, A. Bio-based polycarbonate as synthetic toolbox. Nat. Commun. 7, 11862 (2016).

    CAS  PubMed  PubMed Central  Article  Google Scholar 

  54. Chanda, S. & Ramakrishnan, S. Poly(alkylene itaconate)s – an interesting class of polyesters with periodically located exo-chain double bonds susceptible to Michael addition. Polym. Chem. 6, 2108–2114 (2015).

    CAS  Article  Google Scholar 

  55. Ohsawa, S., Morino, K., Sudo, A. & Endo, T. Synthesis of a reactive polyester bearing α,β-unsaturated ketone groups by anionic alternating copolymerization of epoxide and bicyclic bis(γ-butyrolactone) bearing isopropenyl group. Macromolecules 44, 1814–1820 (2011).

    CAS  Article  Google Scholar 

  56. Huang, K. S. et al. Recent advances in antimicrobial polymers: a mini-review. Int. J. Mol. Sci. 17, 1578–1592 (2016).

    PubMed Central  Article  CAS  Google Scholar 

  57. Șucu, T. & Shaver, M. P. Inherently degradable cross-linked polyesters and polycarbonates: resins to be cheerful. Polym. Chem. 11, 6397–6421 (2020).

    Article  Google Scholar 

  58. Brutman, J. P., De Hoe, G. X., Schneiderman, D. K., Le, T. N. & Hillmyer, M. A. Renewable, degradable and chemically recyclable cross-linked elastomers. Ind. Eng. Chem. Res. 55, 11097–11106 (2016).

    CAS  Article  Google Scholar 

  59. Robert, T. & Friebel, S. Itaconic acid—a versatile building block for renewable polyesters with enhanced functionality. Green Chem. 18, 2922–2934 (2016).

    CAS  Article  Google Scholar 

  60. Fournier, L., Rivera Mirabal, D. M. & Hillmyer, M. A. Toward sustainable elastomers from the grafting-through polymerization of lactone-containing polyester macromonomers. Macromolecules 55, 1003–1014 (2022).

    CAS  Article  Google Scholar 

  61. Huang, J. et al. DAB-Pd-MAH: a versatile Pd(0) source for precatalyst formation, reaction screening and preparative-scale synthesis. ACS Catal. 11, 5636–5646 (2021).

    CAS  Article  Google Scholar 

  62. Mango, L. A. & Lenz, R. W. Hydrogenation of unsaturated polymers with diimide. Die Makromol. Chem. 163, 13–36 (1973).

    CAS  Article  Google Scholar 

  63. Rapagnani, R. M., Dunscomb, R. J., Fresh, A. A. & Tonks, I. A. Supporting data for tunable and recyclable polyesters from CO2 and butadiene (Data Repository for the University of Minnesota, 2021); https://doi.org/10.13020/sy3d-cf59

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Acknowledgements

The funding for this work was provided by the NSF Center for Sustainable Polymers (no. CHE-1901635 to I.A.T.) at the University of Minnesota. Instrumentation for the University of Minnesota Chemistry NMR facility was supported by a grant through the National Institutes of Health (no. S10OD011952).

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R.M.R., R.J.D. and A.A.F. designed and performed all experiments and carried out data analysis. I.A.T. directed the research. R.M.R. and I.A.T. prepared the manuscript.

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Correspondence to Ian A. Tonks.

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I.A.T. and R.M.R. are co-inventors on a provisional US patent covering the methods of polymerization and composition of matter presented in this work, filed through the University of Minnesota (application no. 63/156,135). R.J.D. and A.A.F. declare no competing interests.

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Materials and Methods, Supplementary text, Figs. 1 to 35, Tables 1 to 5, references, OECD-301B report from Situ Biosciences

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Rapagnani, R.M., Dunscomb, R.J., Fresh, A.A. et al. Tunable and recyclable polyesters from CO2 and butadiene. Nat. Chem. 14, 877–883 (2022). https://doi.org/10.1038/s41557-022-00969-2

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