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-2_H_-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. Access through your institution

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EXTRA-HEAVY OLEFINS FROM CARBON MONOXIDE AND WATER Article Open access 03 April 2023 OVERCOMING THE LOW REACTIVITY OF BIOBASED, SECONDARY DIOLS IN POLYESTER SYNTHESIS Article Open access 30

November 2022 BIFUNCTIONAL AND RECYCLABLE POLYESTERS BY CHEMOSELECTIVE RING-OPENING POLYMERIZATION OF A Δ-LACTONE DERIVED FROM CO2 AND BUTADIENE Article Open access 08 October 2024 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 * Omae, I.

Recent developments in carbon dioxide utilization for the production of organic chemicals. _Coord. Chem. Rev._ 256, 1384–1405 (2012). Article  CAS  Google Scholar  * Sakakura, T., Choi, J.

C. & Yasuda, H. Transformation of carbon dioxide. _Chem. Rev._ 107, 2365–2387 (2007). Article  CAS  PubMed  Google Scholar  * 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). Article  CAS  PubMed  Google Scholar  * Artz, J. et

al. Sustainable conversion of carbon dioxide: an integrated review of catalysis and life cycle assessment. _Chem. Rev._ 118, 434–504 (2018). Article  CAS  PubMed  Google Scholar  * 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). Article  CAS  Google

Scholar  * 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). Article  CAS  Google

Scholar  * Zhu, Y., Romain, C. & Williams, C. K. Sustainable polymers from renewable resources. _Nature_ 540, 354–362 (2016). Article  CAS  PubMed  Google Scholar  * 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). Article  CAS 

Google Scholar  * 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). Article  CAS  Google Scholar  * 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). Article  CAS  Google Scholar  *

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). Article

  CAS  Google Scholar  * Behr, A. & Juszak, K. D. Palladium-catalyzed reaction of butadiene and carbon dioxide. _J. Organomet. Chem._ 255, 263–268 (1983). Article  CAS  Google Scholar  *

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). Article  CAS  Google Scholar  * 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). Article  CAS  Google Scholar  * 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). Article  CAS  Google Scholar  * Behr, A. & Henze, G. Use of carbon dioxide in chemical syntheses via a lactone intermediate.

_Green Chem._ 13, 25–39 (2011). Article  CAS  Google Scholar  * 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). Article  CAS  Google Scholar  * 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). Article  CAS  Google Scholar  * 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). Article  CAS

  Google Scholar  * Schneiderman, D. K. & Hillmyer, M. A. Aliphatic polyester block polymer design. _Macromolecules_ 49, 2419–2428 (2016). Article  CAS  Google Scholar  * Olsén, P.,

Odelius, K. & Albertsson, A. C. Thermodynamic presynthetic considerations for ring-opening polymerization. _Biomacromolecules_ 17, 699–709 (2016). Article  PubMed  PubMed Central  CAS 

Google Scholar  * Wheeler, O. H. & Granell, E. E. Solvolysis of substituted γ-butrolactones and δ-valerolactones. _J. Org. Chem._ 701, 1959–1961 (1964). Google Scholar  * Nakano, R.,

Ito, S. & Nozaki, K. Copolymerization of carbon dioxide and butadiene via a lactone intermediate. _Nat. Chem._ 6, 325–331 (2014). Article  CAS  PubMed  Google Scholar  * 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). Article  CAS  PubMed  Google Scholar  * 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). Article  CAS  PubMed  Google Scholar  * Yue, S. et al. Ring-opening polymerization of CO2-based disubstituted δ-valerolactone toward sustainable

functional polyesters. _ACS Macro Lett._ 10, 1055–1060 (2021). Article  CAS  PubMed  Google Scholar  * 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  * 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  * Behr, A. & Brehme, V. A. Bimetallic-catalyzed reduction of carboxylic acids and lactones to alcohols and diols. _Adv. Synth. Catal._ 344, 525–532 (2002). Article  CAS  Google

Scholar  * 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). Article 

CAS  Google Scholar  * 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). Article  CAS  Google Scholar  * 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). Article  CAS  Google Scholar  * Dove, A. P. Organic

catalysis for ring-opening polymerization. _ACS Macro Lett._ 1, 1409–1412 (2012). Article  CAS  PubMed  Google Scholar  * Thomas, C. & Bibal, B. Hydrogen-bonding organocatalysts for

ring-opening polymerization. _Green Chem._ 16, 1687–1699 (2014). Article  CAS  Google Scholar  * 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). Article  CAS  PubMed  Google Scholar  * 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). Article  CAS  PubMed  Google Scholar  * Simón, L. & Goodman, J. M. The mechanism of TBD-catalyzed ring-opening polymerization of cyclic

esters. _J. Org. Chem._ 72, 9656–9662 (2007). Article  PubMed  CAS  Google Scholar  * Whelan, D. in _Brydson’s Plastic Mater_ials 8th edn (ed. Gilbert, M.) Ch. 24 (Butterworth-Heinemann,

2017). * 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). Article  CAS  PubMed  Google Scholar  * Lin, B. & Waymouth, R. M. Urea anions: simple, fast and selective catalysts for ring-opening

polymerizations. _J. Am. Chem. Soc._ 139, 1645–1652 (2017). Article  CAS  PubMed  Google Scholar  * Anslyn, E. V. & Dougherty, D. A. in _Modern Physical Organic Chemistry_ Ch. 2

(University Science Books, 2006). * Hong, M. & Chen, E. Y. X. Future directions for sustainable polymers. _Trends Chem._ 1, 148–151 (2019). Article  CAS  Google Scholar  * Tang, X. &

Chen, E. Y. X. Toward infinitely recyclable plastics derived from renewable cyclic esters. _Chem_ 5, 284–312 (2019). Article  CAS  Google Scholar  * Fagnani, D. E. et al. 100th anniversary

of macromolecular science viewpoint: redefining sustainable polymers. _ACS Macro Lett._ 10, 41–53 (2021). Article  CAS  PubMed  Google Scholar  * 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). Article  CAS  Google Scholar  * 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). Article  CAS  PubMed  Google Scholar  * 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  * OECD. _Test No. 301_: _Ready Biodegradability_, _OECD Guidelines for the Testing of Chemicals_ Section 3 (OECD, 1992).

* 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).

Article  CAS  PubMed  Google Scholar  * 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  * 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). Article  CAS  PubMed  Google Scholar  * Campos, L. M. et al. Development of thermal and

photochemical strategies for thiol-ene click polymer functionalization. _Macromolecules_ 41, 7063–7070 (2008). Article  CAS  Google Scholar  * Hauenstein, O., Agarwal, S. & Greiner, A.

Bio-based polycarbonate as synthetic toolbox. _Nat. Commun._ 7, 11862 (2016). Article  CAS  PubMed  PubMed Central  Google Scholar  * 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). Article  CAS  Google

Scholar  * 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). Article  CAS  Google Scholar  * Huang, K. S. et al. Recent advances in antimicrobial polymers:

a mini-review. _Int. J. Mol. Sci._ 17, 1578–1592 (2016). Article  PubMed Central  CAS  Google Scholar  * 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  * 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). Article  CAS  Google Scholar  * Robert, T. & Friebel, S. Itaconic

acid—a versatile building block for renewable polyesters with enhanced functionality. _Green Chem._ 18, 2922–2934 (2016). Article  CAS  Google Scholar  * 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). Article 

CAS  Google Scholar  * 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).

Article  CAS  Google Scholar  * Mango, L. A. & Lenz, R. W. Hydrogenation of unsaturated polymers with diimide. _Die Makromol. Chem._ 163, 13–36 (1973). Article  CAS  Google Scholar  *

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 Download references 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). AUTHOR INFORMATION AUTHORS AND AFFILIATIONS * Department of Chemistry, University of Minnesota – Twin Cities, Minneapolis, MN, USA Rachel M. Rapagnani, Rachel J. Dunscomb &

 Ian A. Tonks * Department of Chemistry, Purdue University, West Lafayette, IN, USA Alexandra A. Fresh Authors * Rachel M. Rapagnani View author publications You can also search for this

author inPubMed Google Scholar * Rachel J. Dunscomb View author publications You can also search for this author inPubMed Google Scholar * Alexandra A. Fresh View author publications You can

also search for this author inPubMed Google Scholar * Ian A. Tonks View author publications You can also search for this author inPubMed Google Scholar CONTRIBUTIONS 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. CORRESPONDING AUTHOR Correspondence to

Ian A. Tonks. ETHICS DECLARATIONS COMPETING INTERESTS 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. PEER REVIEW PEER REVIEW INFORMATION _Nature

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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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