Mechanochemical pathway for converting fluoropolymers to fluorochemicals

Masashi Hattori; Debarshi Saha; Muhamad Zulfaqar Bacho; Norio Shibata

doi:10.1038/s41557-025-01855-3

journal article Jun 27, 2025

Mechanochemical pathway for converting fluoropolymers to fluorochemicals

Masashi Hattori

Debarshi Saha

Muhamad Zulfaqar Bacho

Norio Shibata

Nature Chemistry Vol. 17 No. 10 pp. 1480-1487 · Springer Science and Business Media LLC

View at Publisher Save 10.1038/s41557-025-01855-3

Topics

No keywords indexed for this article. Browse by subject →

References

39

[1]

Britton, R. et al. Contemporary synthetic strategies in organofluorine chemistry. Nat. Rev. Methods Primers 1, 47 (2021). 10.1038/s43586-021-00042-1

[2]

Current Contributions of Organofluorine Compounds to the Agrochemical Industry

Yuta Ogawa, Etsuko Tokunaga, Osamu Kobayashi et al.

iScience 2020 10.1016/j.isci.2020.101467

[3]

Contribution of Organofluorine Compounds to Pharmaceuticals

Munenori Inoue, Yuji Sumii, Norio Shibata

ACS Omega 2020 10.1021/acsomega.0c00830

[4]

Martinelli, L. & Nikel, P. I. Breaking the state-of-the-art in the chemical industry with new-to-nature products via synthetic microbiology. Microb. Biotechnol. 12, 187–190 (2019). 10.1111/1751-7915.13372

[5]

Per- and polyfluoroalkyl substances in the environment

Marina G. Evich, Mary J. B. Davis, James P. McCord et al.

Science 2022 10.1126/science.abg9065

[6]

Battye, N. et al. Mechanochemical degradation of per- and polyfluoroalkyl substances in soil using an industrial-scale horizontal ball mill with comparisons of key operational metrics. Sci. Total Environ. 928, 172274 (2024). 10.1016/j.scitotenv.2024.172274

[7]

Trang, B. et al. Low-temperature mineralization of perfluorocarboxylic acids. Science 377, 839–845 (2022). 10.1126/science.abm8868

[8]

Shintani, M. et al. Decomposition of perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) by mechanochemical methods. Chem. Eng. J. 34, 539–544 (2008).

[9]

Roesch, P., Vogel, C. & Simon, F.-G. Reductive defluorination and mechanochemical decomposition of per- and polyfluoroalkyl substances (PFASs): from present knowledge to future remediation concepts. Int. J. Environ. Res. Public Health 17, 7242 (2020). 10.3390/ijerph17197242

[10]

Aigueperse, J. et al. Ullmann’s Encyclopedia of Industrial Chemistry 11–307 (Wiley, 2000).

[11]

Hydrogen Fluoride and its Solutions.

J. H. Simons

Chemical Reviews 1931 10.1021/cr60030a004

[12]

Khandelwal, M., Pemawat, G. & Khangarot, R. K. Recent developments in nucleophilic fluorination with potassium kluoride (KF): a review. Asian J. Org. Chem. 11, 1–17 (2022).

[13]

Tsuneizumi, T. & Yoshio, K. Method for producing anhydrous potassium fluoride for synthesis of organofluorine compounds. Japanese patent JPH046104A (1990).

[14]

Ameduri, B. Fluoropolymers: a special class of per- and polyfluoroalkyl substances (PFASs) essential for our daily life. J. Fluor. Chem. 267, 110117 (2023). 10.1016/j.jfluchem.2023.110117

[15]

A critical review of the application of polymer of low concern and regulatory criteria to fluoropolymers

Barbara J Henry, Joseph P Carlin, Jon A Hammerschmidt et al.

Integrated Environmental Assessment and Management 2018 10.1002/ieam.4035

[16]

Puts, G. J., Crouse, P. & Ameduri, B. Polytetrafluoroethylene: synthesis and characterization of the original extreme polymer. Chem. Rev. 119, 1763–1805 (2019). 10.1021/acs.chemrev.8b00458

[17]

A comprehensive review on fundamental properties and applications of poly(vinylidene fluoride) (PVDF)

Pooja Saxena, Prashant Shukla

Advanced Composites and Hybrid Materials 2021 10.1007/s42114-021-00217-0

[18]

Zou, G. et al. Mild reduction route to PTFE degradation at low temperature. Chem. Lett. 33, 1150–1151 (2004). 10.1246/cl.2004.1150

[19]

Veiga, A. G. et al. Reprocessed poly(vinylidene fluoride): a comparative approach for mechanical recycling purposes. Mater. Today Commun. 25, 101269 (2020). 10.1016/j.mtcomm.2020.101269

[20]

Marshall, J. E. et al. On the solubility and stability of polyvinylidene fluoride. Polymers 13, 1354–1385 (2021). 10.3390/polym13091354

[21]

Zhang, Q., Lu, J., Saito, F. & Baron, M. Mechanochemical solid-phase reaction between polyvinylidene fluoride and sodium hydroxide. J. Appl. Polym. Sci. 81, 2249–2252 (2001). 10.1002/app.1663

[22]

Alchikh, M., Fond, C., re, Y. F. & Pelletier, H. Mechanochemical degradation of poly(vinyl fluoride) by sodium hydroxide measured by microindentation. J. Mater. Sci. 45, 2311–2316 (2010). 10.1007/s10853-009-4193-1

[23]

Kise, H., Ogata, H. & Nakata, M. Chemical dehydrofluorination and electrical conductivity of poly(viny1idene fluoride) films. Die Angew. Makro. Chemie 168, 205–216 (1989). 10.1002/apmc.1989.051680117

[24]

Ross, G. J., Watts, J. F., Hilla, M. P. & Morrissey, P. Surface modification of poly(vinylidene fluoride) by alkaline treatment: the degradation mechanism. Polymer 41, 1685–1696 (2000). 10.1016/s0032-3861(99)00343-2

[25]

Sharma, J., Totee, C., Kulshrestha, V. & Ameduri, B. Spectroscopic evidence and mechanistic insights on dehydrofluorination of PVDF in alkaline medium. Eur. Polym. J. 201, 112580 (2023). 10.1016/j.eurpolymj.2023.112580

[26]

Morita, Y. et al. Fluorine recovery through alkaline defluorination of polyvinylidene fluoride. J. Mater. Cycles Waste Manag. 26, 669–678 (2024). 10.1007/s10163-023-01749-x

[27]

Fluorochemicals from fluorspar via a phosphate-enabled mechanochemical process that bypasses HF

Calum Patel, Emy André-Joyaux, Jamie A. Leitch et al.

Science 2023 10.1126/science.adi1557

[28]

Sheldon, D. J., Parr, J. M. & Crimmin, M. R. Room temperature defluorination of poly(tetrafluoroethylene) by a magnesium reagent. J. Am. Chem. Soc. 145, 10486–10490 (2023). 10.1021/jacs.3c02526

[29]

Bare, G. A. L. Synthesis of sulfonyl fluorides using direct chloride/fluoride exchange in potassium fluoride and water/acetone. J. Org. Chem. 88, 4761–4764 (2023). 10.1021/acs.joc.2c02630

[30]

Nielsen, M. K., Ugaz, C. R., Li, W. & Doyle, A. G. PyFluor: a low-cost, stable, and selective deoxyfluorination reagent. J. Am. Chem. Soc. 137, 9571–9574 (2015). 10.1021/jacs.5b06307

[31]

Gao, H., Guo, L., Zhu, Y., Yang, C. & Xia, W. Visible-light-induced dehydrogenative amidation of aldehydes enabled by iron salts. Chem. Commun. 59, 2771–2774 (2023). 10.1039/d2cc06507j

[32]

Bertrand, X., Chabaud, L., Aissaoui, D., Col, O. M. & Paquin, J.-F. Improved conditions for the synthesis of tertiary fluorides using a KF/H2SO4 combination. J. Fluor. Chem. 279, 110338 (2024). 10.1016/j.jfluchem.2024.110338

[33]

Kosobokov, M. et al. Importance of a fluorine substituent for the preparation of meta- and para-pentafluoro-λ6-sulfanyl-substituted pyridines. Angew. Chem. Int. Ed. 55, 10781–10785 (2016). 10.1002/anie.201605008

[34]

Kaspar, P. et al. Case study of polyvinylidene fluoride doping by carbon nanotubes. Materials 14, 1428 (2021). 10.3390/ma14061428

[35]

Elashmawi, I. S. & Gaabour, L. H. Raman, morphology and electrical behavior of nanocomposites based on PEO/PVDF with multi-walled carbon nanotubes. Results Phys. 5, 105–110 (2015). 10.1016/j.rinp.2015.04.005

[36]

Veres, M., Toth, S. & Koos, M. New aspects of Raman scattering in carbon-based amorphous materials. Diam. Relat. Mater. 17, 1692–1696 (2008). 10.1016/j.diamond.2008.01.110

[37]

Marton, M. et al. Raman spectroscopy of amorphous carbon prepared by pulsed arc discharge in various gas mixtures. J. Spectrosc. 2013, 467079 (2013). 10.1155/2013/467079

[38]

Hong, S. H. & Winter, J. Micro-Raman spectroscopy on α-C:H nanoparticles. J. Appl. Phys. 98, 124304–124315 (2005). 10.1063/1.2142078

[39]

Yang, L. et al. Phosphate-enabled mechanochemical PFAS destruction for fluoride reuse. Nature 640, 100–106 (2025). 10.1038/s41586-025-08698-5

Metrics

24

Citations

39

References

Details

Published: Jun 27, 2025
Vol/Issue: 17(10)
Pages: 1480-1487
License: View

Authors

M

Masashi Hattori

Laboratory for Materials and Structures, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan

D

Debarshi Saha

M

Muhamad Zulfaqar Bacho

N

Norio Shibata

Funding

MEXT | JST | Core Research for Evolutional Science and Technology Award: JPMJCR21L1

Cite This Article

Masashi Hattori, Debarshi Saha, Muhamad Zulfaqar Bacho, et al. (2025). Mechanochemical pathway for converting fluoropolymers to fluorochemicals. Nature Chemistry, 17(10), 1480-1487. https://doi.org/10.1038/s41557-025-01855-3

Mechanochemical pathway for converting fluoropolymers to fluorochemicals

You May Also Like