Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Chemical recycling of a lignin-based non-isocyanate polyurethane foam

Abstract

The crisis of plastic waste in the environment calls for new polymers that are designed specifically for recycling at the end of their life. Lignin, which is present in approximately 15–40% of woody biomass, is an attractive biobased source for polymers given its aromatic nature. However, the use of lignin in polymers is complicated by its own reactivity and heterogeneous structure, factors that also create difficulties for designing end-of-life solutions for lignin-based polymers. Here we demonstrate a chemical recycling technique that prevents the loss of functionality to lignin and produces a recycled precursor capable of entering back into the synthetic sequence for non-isocyanate polyurethane foams. This technique enables the depolymerization of the polymer and isolation of lignin with enhanced solubility and hydroxyl content so that it can be reused in second-generation polymers. Detailed structural analysis of lignin after chemical recycling reveals the insertion of ethylene glycol in the side-chain region during a high-pressure hydrolysis recycling procedure. The closed-loop recycling process for the lignin-derived non-isocyanate polyurethane foam demonstrates a pathway towards a circular economy.

This is a preview of subscription content, access via your institution

Access options

Buy this article

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Chemical recycling scheme.
Fig. 2: Recycled lignin yield and solubility.
Fig. 3: 31P NMR spectroscopy of raw Kraft lignin and recycled lignin.
Fig. 4: 2D HSQC NMR of control reactions and recycled lignin.
Fig. 5: Comparison of first- and second-generation CC lignin and NIPU foams.

Similar content being viewed by others

Data availability

Additional data that support the findings of this study are available from the corresponding author upon request.

References

  1. Jambeck, J. Plastic waste inputs from land into the ocean. Science 347, 768–771 (2015).

    Article  CAS  Google Scholar 

  2. Rillig, M. C. Microplastic in terrestrial ecosystems and the soil? Environ. Sci. Technol. 46, 6453–6454 (2012).

    Article  CAS  Google Scholar 

  3. Vanholme, R. et al. Metabolic engineering of novel lignin in biomass crops. N. Phytol. 196, 978–1000 (2012).

    Article  CAS  Google Scholar 

  4. Upton, B. M. & Kasko, A. M. Strategies for the conversion of lignin to high-value polymeric materials: review and perspective. Chem. Rev. 116, 2275–2306 (2016).

    Article  CAS  Google Scholar 

  5. Duval, A. & Lawoko, M. A review on lignin-based polymeric, micro- and nano-structured materials. React. Funct. Polym. 85, 78–96 (2014).

    Article  CAS  Google Scholar 

  6. Sternberg, J., Sequerth, O. & Pilla, S. Green chemistry design in polymers derived from lignin: review and perspective. Prog. Polym. Sci. 113, 101344 (2021).

    Article  CAS  Google Scholar 

  7. Karunarathna, M. S., Lauer, M. K., Thiounn, T., Smith, R. C. & Tennyson, A. G. Valorisation of waste to yield recyclable composites of elemental sulfur and lignin. J. Mater. Chem. A 7, 15683–15690 (2019).

    Article  CAS  Google Scholar 

  8. Buono, P., Duval, A., Averous, L. & Habibi, Y. Thermally healable and remendable lignin-based materials through Diels–Alder click polymerization. Polym. J. 133, 78–88 (2017).

    Article  CAS  Google Scholar 

  9. Xu, Y., Odelius, K. & Hakkarainen, M. Recyclable and flexible polyester thermosets derived from microwave-processed lignin. ACS Appl. Polym. Mater. 2, 1917–1924 (2020).

    Article  CAS  Google Scholar 

  10. Deuss, P. J. et al. Aromatic monomers by in situ conversion of reactive intermediates in the acid-catalyzed depolymerization of lignin. J. Am. Chem. Soc. 137, 7456–7467 (2015).

    Article  CAS  Google Scholar 

  11. Shuai, L. et al. Formaldehyde stabilization facilitates lignin monomer production during biomass depolymerization. Science 354, 329–333 (2016).

    Article  CAS  Google Scholar 

  12. Lancefield, C. S., Panovic, I., Deuss, P. J., Barta, K. & Westwood, N. J. Pre-treatment of lignocellulosic feedstocks using biorenewable alcohols: towards complete biomass valorisation. Green. Chem. 19, 202–214 (2017).

    Article  CAS  Google Scholar 

  13. Deuss, P. J. et al. Phenolic acetals from lignins of varying compositions: Via iron(iii) triflate catalysed depolymerisation. Green Chem. 19, 2774–2782 (2017).

    Article  CAS  Google Scholar 

  14. Lancefield, C. S., Wienk, H. L. J., Boelens, R., Weckhuysen, B. M. & Bruijnincx, P. C. A. Chemical science identification of a diagnostic structural motif reveals a new reaction intermediate and condensation pathway in Kraft lignin formation. Chem. Sci. 9, 6317–6454 (2018).

    Article  Google Scholar 

  15. Bauer, S., Sorek, H., Mitchell, V. D., Ibáñez, A. B. & Wemmer, D. E. Characterization of Miscanthus giganteus lignin isolated by ethanol Organosolv process under reflux condition. J. Agric. Food Chem. 60, 8203–8212 (2012).

    Article  CAS  Google Scholar 

  16. Sternberg, J. & Pilla, S. Materials for the biorefinery: high bio-content, shape memory Kraft lignin-derived non-isocyanate polyurethane foams using a non-toxic protocol. Green Chem. 20, 6922–6935 (2020).

    Article  Google Scholar 

  17. Collins, M. N. et al. Valorization of lignin in polymer and composite systems for advanced engineering applications—a review. Int. J. Biol. Macromol. 131, 828–849 (2019).

    Article  CAS  Google Scholar 

  18. Suhas Carrot, P. J. M. & Ribeiro Carrott, M. M. L. Lignin—from natural adsorbent to activated carbon: a review. Bioresour. Technol. 98, 2301–2312 (2007).

    Article  Google Scholar 

  19. Culebras, M. et al. Bio-derived carbon nanofibres from lignin as high-performance Li-ion anode materials. ChemSusChem 12, 4516–4521 (2019).

    Article  CAS  Google Scholar 

  20. Motokucho, S., Nakayama, Y., Morikawa, H. & Nakatani, H. Environment-friendly chemical recycling of aliphatic polyurethanes by hydrolysis in a CO2 –water system. J. Appl. Polym. Sci. 135, 45897 (2018).

    Article  Google Scholar 

  21. Motokucho, S., Yamaguchi, A., Nakayama, Y., Morikawa, H. & Nakatani, H. Hydrolysis of aromatic polyurethane in water under high pressure of CO2. J. Polym. Sci. A 55, 2004–2010 (2017).

    Article  CAS  Google Scholar 

  22. Simón, D., Borreguero, A. M., de Lucas, A. & Rodríguez, J. F. Glycolysis of viscoelastic flexible polyurethane foam wastes. Polym. Degrad. Stab. 116, 23–35 (2015).

    Article  Google Scholar 

  23. Trajano, H. L. et al. The fate of lignin during hydrothermal pretreatment. Biotechnol. Biofuels 6, 110 (2013).

    Article  CAS  Google Scholar 

  24. Chakar, F. S. & Ragauskas, A. J. Review of current and future softwood Kraft lignin process chemistry. Ind. Crops Prod. 20, 131–141 (2004).

    Article  CAS  Google Scholar 

  25. Granata, A. & Argyropoulos, D. S. 2-Chloro-4,4,5,5-tetramethyl-1,3>2-dioxaphospholane, a reagent for the accurate determination of the uncondensed and condensed phenolic moieties in lignins. J. Agric. Food Chem. 43, 1538–1544 (1995).

    Article  CAS  Google Scholar 

  26. Hu, Z., Du, X., Liu, J., Chang, H. & Jameel, H. Structural characterization of pine Kraft lignin: BioChoice lignin vs Indulin AT. J. Wood Chem. Technol. 36, 432–446 (2016).

    Article  CAS  Google Scholar 

  27. Gierer, J. Chemical aspects of Kraft pulping. Wood Sci. Technol. 14, 241–266 (1980).

    Article  CAS  Google Scholar 

  28. Gierer, J. Chemistry of delignification. Wood Sci. Technol. 20, 1–33 (1986).

    Article  CAS  Google Scholar 

  29. Cornille, A., Dworakowska, S., Bogdal, D., Boutevin, B. & Caillol, S. A new way of creating cellular polyurethane materials: NIPU foams. Eur. Polym. J. 66, 129–138 (2015).

    Article  CAS  Google Scholar 

  30. Tran, F., Lancefield, C. S., Kamer, P. C. J., Lebl, T. & Westwood, N. J. Selective modification of the β–β linkage in DDQ-treated Kraft lignin analysed by 2D NMR spectroscopy. Green Chem. 17, 244–249 (2014).

    Article  Google Scholar 

Download references

Acknowledgements

We thank O. Sequerth, L. Slann and A. Devol of Clemson University for their support during this project. Research was supported by the Department of Energy, Basic Energy Sciences, award no. DE-SC0021367 (chemical recycling and characterization), by Sonoco FRESH initiative at Clemson University (NIPU synthesis) and as part of the AIM for Composites, an Energy Frontier Research Center funded by the US Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), under award no. DE-SC0023389 (NMR studies). In addition, S.P. acknowledges the Robert Patrick Jenkins Professorship. J.S. acknowledges graduate fellowship support through Cooper-Standard, Draexlmaier and Sonoco foundations.

Author information

Authors and Affiliations

Authors

Contributions

J.S. and S.P. contributed jointly to this paper. S.P. conceptualized the scope of the study and guided the research progress and manuscript editing. J.S. completed the experimental design, characterization of materials and manuscript writing.

Corresponding author

Correspondence to Srikanth Pilla.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Sustainability thanks Maurice Collins and the other, anonymous, reviewers for their contribution to the peer review of this work.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Figs. 1–7, Tables 1–5 and Notes 1–3.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Sternberg, J., Pilla, S. Chemical recycling of a lignin-based non-isocyanate polyurethane foam. Nat Sustain 6, 316–324 (2023). https://doi.org/10.1038/s41893-022-01022-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41893-022-01022-3

This article is cited by

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing