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Renewable and safer bisphenol A substitutes enabled by selective zeolite alkylation

Nature Sustainability volume 6, pages 1693–1704 (2023)Cite this article

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Abstract

Bisphenol A (BPA) is an industrial chemical that has been used for the manufacturing of polycarbonate plastics, epoxy resins and other consumer products, including food contact materials and dental resins. However, its petrochemical origin and adverse health effects, such as xeno-oestrogenic activity (EA), pose a challenge for sustainability. Here we show a green synthetic pathway towards genuinely sustainable BPA alternatives from a renewable lignin source. At the heart of this production route is a selective alkylation reaction between bio-based arene (for example, guaiacol) and alkene (for example, isoeugenol) molecules, catalysed by a recyclable zeolite catalyst H-USY. Zeolite catalysis favours regioselectivity and prompts higher reaction rate and chemoselectivity, enabling high yields of bisguaiacols. The synthesized bisguaiacols can be valorized into high-molecular-weight thermoplastic and thermosetting polymers with promising thermophysical properties, showcasing their potential as BPA replacements. This work progresses beyond the state of the art by demonstrating that renewability is not only a goal but also a means for safer chemicals.

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Fig. 1: The sustainable advantages of the proposed bisguaiacol process versus the current industrial bisphenol process.
Fig. 2: Product distributions.
Fig. 3: Kinetic analyses of p,p’-2a and α-3a formation by confined H-USY and unconfined H2SO4 catalysis.
Fig. 4: Key physical and thermal properties of bisguaiacol monomers and polymers.
Fig. 5: In vitro hERα activity of p,p’-bisguaiacols and p,p’-bisphenols.

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Data availability

The data that support the findings of this study are reported within the Article and its Supplementary Information, and are available from the corresponding author upon request.

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Acknowledgements

B.F.S. thanks the KU Leuven industrial research fund (C32/18/021 to L.T. and S.-F.K.). This work was performed in the framework of the Catalisti Cluster cSBO project PADDL, with the financial support of VLAIO HBC.2019.0118, within the iBOF programme Next-BIOREF project 20-VLIR-iBOF-026 (T.H., G.P. and H.W.) and the EOS project BIOFACT 30902231 (E.C.). I.B. and M.E. were supported by Research Foundation Flanders project G089016N of the Free University of Brussels (VUB). We thank D. Kerstens for the zeolite characterization and B. Van Meerbeek of the department BIOMAT at KU Leuven for help with the Vickers hardness tests (KU Leuven infrastructure funding KA/20/079).

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  1. These authors contributed equally: Laura Trullemans, Steven-Friso Koelewijn.

Authors and Affiliations

  1. Department of Microbial and Molecular Systems (M2S), Centre for Sustainable Catalysis and Engineering (CSCE), KU Leuven, Heverlee, Belgium

    Laura Trullemans, Steven-Friso Koelewijn, Elias Cooreman, Tessy Hendrickx, Gert Preegel, Joost Van Aelst, Michiel Dusselier & Bert F. Sels

  2. Department of Analytical, Environmental and Geo-Chemistry, Vrije Universiteit Brussel, Ixelles, Belgium

    Imke Boonen & Marc Elskens

  3. Unit Health, Flemish Institute for Technological Research (VITO), Mol, Belgium

    Hilda Witters

  4. Department of Chemical Engineering, Soft Matter, Rheology and Technology (SMaRT), KU Leuven, Heverlee, Belgium

    Peter Van Puyvelde

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Contributions

S.-F.K., L.T. and B.F.S. conceived and directed the project. S.-F.K. and L.T. carried out key experiments and wrote the manuscript. G.P. synthesized the polycarbonates. I.B. and M.E. performed the CALUX bioassay. T.H. and H.W. performed the MELN bioassay. H.W., I.B. and M.E. performed the in vitro EA screenings. E.C. and J.V.A. carried out the adapted RCF experiments. P.V.P. contributed to the screening and analysis of thermal properties and M.D. to the kinetic experimental design. All authors discussed the results and commented on the manuscript.

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Correspondence to Steven-Friso Koelewijn or Bert F. Sels.

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Competing interests

Patent applications (WO/2018/134427, WO/2019/002503) are pending or granted for inventors S.-F.K. and B.F.S. (US/EP/CN). The remaining authors declare no competing interests.

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Nature Sustainability thanks Guoyong Song and Bert M. Weckhuysen for their contribution to the peer review of this work.

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Trullemans, L., Koelewijn, SF., Boonen, I. et al. Renewable and safer bisphenol A substitutes enabled by selective zeolite alkylation. Nat Sustain 6, 1693–1704 (2023). https://doi.org/10.1038/s41893-023-01201-w

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