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Sustainable polyesters via direct functionalization of lignocellulosic sugars

Nature Chemistry volume 14, pages 976–984 (2022)Cite this article

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Abstract

The development of sustainable plastics from abundant renewable feedstocks has been limited by the complexity and efficiency of their production, as well as their lack of competitive material properties. Here we demonstrate the direct transformation of the hemicellulosic fraction of non-edible biomass into a tricyclic diester plastic precursor at 83% yield (95% from commercial xylose) during integrated plant fractionation with glyoxylic acid. Melt polycondensation of the resulting diester with a range of aliphatic diols led to amorphous polyesters (Mn = 30–60 kDa) with high glass transition temperatures (72–100 °C), tough mechanical properties (ultimate tensile strengths of 63–77 MPa, tensile moduli of 2,000–2,500 MPa and elongations at break of 50–80%) and strong gas barriers (oxygen transmission rates (100 µm) of 11–24 cc m−2 day−1 bar−1 and water vapour transmission rates (100 µm) of 25–36 g m−2 day−1) that could be processed by injection moulding, thermoforming, twin-screw extrusion and three-dimensional printing. Although standardized biodegradation studies still need to be performed, the inherently degradable nature of these materials facilitated their chemical recycling via methanolysis at 64 °C, and eventual depolymerization in room-temperature water.

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Fig. 1: Production of PAX polyesters directly from xylose or during integrated lignocellulosic biomass fractionation.
Fig. 2: Sankey diagram of the fractionation of birch wood with glyoxylic acid and the subsequent depolymerization and upgrading of the polysaccharide and lignin fractions.
Fig. 3: Properties of PAX polymers.
Fig. 4: Chemical recycling and hydrolytic stability studies.

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Data availability

All data needed to support the findings of this study are included in the main text or in the Supplementary Information. Crystallographic data for the structure reported in this Article have been deposited at the Cambridge Crystallographic Data Centre, under deposition no. CCDC 2121378 (1S-DMGX). Copies of the data can be obtained free of charge via ccdc.cam.ac.uk/structures/Search?ccdc=2121378. All of the data associated with the Article have been deposited38 with Zenodo at https://zenodo.org/record/6482769.

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Acknowledgements

This work was supported by the Swiss National Science Foundation (grant no. CRSII5_180258) and the National Competence Center Catalysis (grant no. 51NF40_180544), by the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant CATACOAT, no. 758653) and under a Marie Skłodowska-Curie grant agreement no. 945363, by the Swiss Competence Center for Energy Research: Biomass for a Swiss Energy Future through the Swiss Commission for Technology and Innovation (grant no. KTI.2014.0116) and by EPFL (partly through the Tech4Dev programme). We thank M. Studer from the Bern University of Applied Sciences (Switzerland) for providing various wood samples, IP-Suisse for providing corn cob samples, C. Wegmann for compositional analyses of the biomass feedstocks, M. Hannebelle and A. Gagliardi for assisting with the vacuum forming, F. Fadaei Tirani for crystal structure determination, S. Bertella for assistance with graphic design and illustrations, L. Blanchard for assistance with TGA measurements and A. Magrez for powder XRD measurements.

Author information

Authors and Affiliations

  1. Laboratory of Sustainable and Catalytic Processing (LPDC), Institute of Chemical Sciences and Engineering (ISIC), School of Basic Sciences (SB), École Polytechnique Fédérale de Lausanne (EPFL), Lausanne, Switzerland

    Lorenz P. Manker, Graham R. Dick, Maxime A. Hedou, Christèle Rayroud, Thibault Rambert, Marie J. Jones, Mariella Vieli & Jeremy S. Luterbacher

  2. Laboratory for Processing of Advanced Composites (LPAC), Institute of Materials (IMX), School of Engineering (STI), École Polytechnique Fédérale de Lausanne (EPFL), Lausanne, Switzerland

    Adrien Demongeot, Yves Leterrier & Véronique Michaud

  3. Industrial Process and Energy Systems Engineering (IPESE), École Polytechnique Fédérale de Lausanne (EPFL); EPFL Valais-Wallis, Sion, Switzerland

    Marie J. Jones & François Maréchal

  4. Institute for Chemistry of Renewable Resources, Department of Chemistry, University of Natural Resources and Life Sciences, Vienna, Austria

    Irina Sulaeva & Antje Potthast

  5. Wood K Plus – Competence Center for Wood Composites & Wood Chemistry, Kompetenzzentrum Holz GmbH, Linz, Austria

    Irina Sulaeva

  6. Institut des Matériaux and Institut des Sciences et Ingénierie Chimiques, Laboratoire des Polymères, École Polytechnique Fédérale de Lausanne (EPFL), Lausanne, Switzerland

    Harm-Anton Klok

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  1. Lorenz P. Manker
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Contributions

L.P.M. and J.S.L. conceived of the project and designed the research. L.P.M. performed most of the experiments and drafting of the manuscript. G.R.D. performed most of the biomass fractionation and lignin upgrading experiments and helped design syntheses. A.D. performed most of the material characterization experiments and was supervised by Y.L. and V.M. M.A.H., with the assistance of C.R., performed the catalyst optimization and some of the polymerization, purification and material characterization experiments. M.J.J. performed the life-cycle analysis, aided with the technoeconomic analysis and was supervised by F.M. T.R. performed the pretreatment experiments on the corn cob feedstock. I.S. performed gel permeation chromatography experiments supervised by A.P. M.V. performed injection moulding and tensile strength testing of the PAX samples. H.-A.K. helped design some of the polymerization and characterization experiments. All authors contributed to editing the manuscript.

Corresponding author

Correspondence to Jeremy S. Luterbacher.

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Competing interests

The authors declare the following competing financial interests. L.P.M., G.R.D. and J.S.L. are inventors on a European patent application (EP19203000.5) on methods for producing the renewable monomer and polymer described here. G.R.D. and J.S.L. are inventors on a European patent application (EP19202957.7) on methods for producing fragments of lignin with functional groups. J.S.L. is an inventor on a European patent application (EP16165180.7) on methods for producing lignin monomers from lignocellulosic biomass during biomass depolymerization. J.S.L. is a co-founder, and M.A.H. a shareholder, of Bloom Biorenewables Ltd, which is exploring commercial opportunities for aldehyde-stabilized lignin and aldehyde-protected xyloses. The remaining authors declare no competing interests.

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Extended data

Extended Data Fig. 1 Photos and process yields for production of PAX from commercial xylose.

Alternatively, production steps 3–5 can be replaced by directly precipitating DMGX from the crude esterification reaction (see Extended Data Fig. 4).

Extended Data Fig. 2 Characterization of the distilled DMGX (4-stereoisomer oil) used in polymerizations.

a, 1H NMR spectrum. b, 13C NMR spectrum. c, 2D HSQC NMR spectrum. d, GC chromatogram with percent abundance of each stereoisomer. e, GC-MS spectrum (combination of 4 stereoisomers). f, Photo of DMGX 4-stereoisomer oil. NMR spectrums were acquired in DMSO-d6 at 25 °C.

Extended Data Fig. 3 Characterization of the crystalline DMGX single isomer used in polymerizations.

a, 1H NMR spectrum. b, 13C NMR spectrum. c, 2D HSQC NMR spectrum. d, Crystal structure with probability ellipsoids. The structure was submitted to the Cambridge Crystallographic Data Centre (CCDC) with deposition number CCDC 2121378. e, DSC curve of crystalline DMGX (melting point was determined by maximum of the 1st derivative of DSC curve). f, Photo of DMGX single isomer crystals. NMR spectrums acquired in DMSO-d6 at 25 °C.

Extended Data Fig. 4 Recovery of DMGX via direct precipitation from the crude esterification mixture.

a, 1H NMR spectrum of the precipitate taken in DMSO-d6 at 25 °C. b, HSQC NMR spectrum of the precipitate taken in DMSO-d6 at 25 °C. c, Photo of DMGX precipitating from esterification mixture after chilling the mixture on ice. d, Photo of the precipitate after filtration from the mixture.

Extended Data Fig. 5 DMGX and PAX derived from lignocellulosic biomass.

a, 2D HSQC NMR of distilled DMGX produced from birch wood taken in DMSO-d6 at 25 °C. b, 2D HSQC NMR of crystalline DMGX single isomer produced from birch wood taken in CDCl3 at 25 °C. c, 2D HSQC NMR of 1S-PPTX produced using DMGX from birch wood taken in CDCl3 at 25 °C. d, DMA curves of 1S-PPTX polymers derived from xylose and from birch wood. Tan delta curves are dashed lines.

Extended Data Fig. 6 Minimum selling price of DMGX produced from commercial xylose under various economic scenarios.

Black dashed lines are mean prices for purified terephthalic acid and PLA grade lactic acid and shaded grey areas represent price ranges. IRR is internal rate of return.

Extended Data Fig. 7 Global warming potential of DGMX with various carbon sourcing scenarios.

(left) Using fossil based glyoxylic acid and natural gas heat and power, (middle) using glyoxylic acid from CO2 and natural gas heat and power, and (right) glyoxylic acid from CO2 with biomass burned for heat and power. The red dotted line corresponds to our calculated GWP of commercially available fossil-based purified terephthalic acid.

Extended Data Fig. 8 Supplemental properties of PAX polymers.

a, DMA curves for PAX polymers and PLA with heating ramps applied at 3 °C/min from -50 to 200 °C (shown from 50 °C). Tan delta curves are dashed lines. b, TGA curves with heating rate of 10 °C/min under nitrogen. Incomplete degradation of PAX polymers is attributed to the cyclic nature of the DMGX monomer which likely leads to formation of non-volatile chars in pyrolysis conditions. c, Stress-strain curves of injection-moulded PAX dog bone samples with PLA (NatureWorks 4032D) and PET (Terez 3200) curves for comparison. The displayed curves are from single representative samples but reported tensile data values are all averages of 3–5 samples. d, Full version of panel C with tabulated tensile values. e, DMA curves for pentanediol-based polymers with heating ramps applied at 3 °C/min from −50 to 200 °C (shown from 50 °C). Tan delta curves are dashed lines.

Extended Data Fig. 9 Hydrolytic stability of various PAX polymers in pH 7 phosphate buffer at 37 °C.

The hydrolytic studies were performed in the same manner as detailed in the Supplementary Information section 1.7.14. All polymer films had an initial starting number average molecular weight (Mn) of ~20 kDa. These experiments were performed in triplicate. Error bars represent standard errors.

Extended Data Fig. 10 2D HSQC NMR spectra of chemically-recycled monomers and plastic.

a, Recycled DMGX. b, Recycled 1,6-hexanediol. c, Original PHX used for chemical-recycling study. d, The final recycled PHX using the recycled DMGX and 1,6-hexanediol. NMRs were taken in d-DMSO at 25 °C for the monomers and CDCl3 at 25 °C for the polymers.

Supplementary information

Supplementary Information

Materials and Methods, text, Figs. 1–23, Tables 1–20 and references 38–75.

Supplementary Video 1

Timelapse video of tensile strength testing of the 4S-PHX injection-moulded dog bone.

Supplementary Data 1

The .zip file contains the .cif file of the 1S-DMGX monomer (CCDC reference 2121378), a PDF of the CheckCIF routine, and a Word document containing supporting crystallographic data.

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Manker, L.P., Dick, G.R., Demongeot, A. et al. Sustainable polyesters via direct functionalization of lignocellulosic sugars. Nat. Chem. 14, 976–984 (2022). https://doi.org/10.1038/s41557-022-00974-5

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