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.

  • Original Article
  • Published:

Development of water/oil repellent and heat-resistant aromatic poly(ether ketone)s bearing 3,5-(C4F9)2C6H3 groups at both ends

Polymer Journal volume 57, pages 745–759 (2025)Cite this article

Subjects

Abstract

Three types of polyketones with different numbers of 3,5-(C4F9)2C6H3 groups at both ends were successfully synthesized. The resulting polyketones are soluble in typical organic solvents such as THF, CHCl3, and NMP. These materials exhibit good thermal stability above 519 °C (Td10) and high glass transition temperatures (Tg) above 221 °C. Furthermore, these polyketones have excellent water/oil repellency. Notably, the polyketone with ten C4F9 groups at each polymer end has a lower surface tension than PTFE (Polytetrafluoroethylene). XPS (X-ray Photoelectron Spectroscopy) measurements revealed that the increase in the water/oil repellency of the polyketones was due to the localization of terminal C4F9 groups on the film surface.

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

Access options

Buy this article

  • Purchase on SpringerLink
  • Instant access to the full article PDF.

USD 39.95

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

Fig. 1
Scheme 1
Scheme 2
Fig. 2
Fig. 3
Scheme 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10

Similar content being viewed by others

References

  1. Ohkubo Y, Tsuji I, Onishi S, Ogawa K. Preparation and characterization of super-hydrophobic and oleophobic surface. J Mater Sci 2010;45:4963–69.

    Article  CAS  Google Scholar 

  2. Hsieh C, Chang B, Lin J. Improvement of water and oil repellency on wood substrates by using fluorinated silica nanocoating. Appl Surf Sci. 2011;257:7997–8002.

    Article  CAS  Google Scholar 

  3. Tsuji I, Ohkubo Y, Ogawa K. Study on super-hydrophobic and oleophobic surfaces prepared by chemical adsorption technique. Jpn J Appl Phys 2009;48:040205.

    Article  Google Scholar 

  4. Chakounte RGM, Jolibois J, Kappertz O, Chambers J, Weis H, Wiame H, Viol W. Water and oil repellent coating on fabric using hollow cathode PECVD. Surf Coat Technol. 2022;446:128816.

    Article  Google Scholar 

  5. Shiraki Y, Yokoyama H. Novel hydrophobic and oleophobic surfaces using polyurethane with hydrogenated polyisoprene soft segment. Mater Today Commun. 2020;24:1012.

    Google Scholar 

  6. Zhao S, Chen L, Zhang C, Hasi QM, Zhang L, Luo X, Li A. Functional oil-repellent photothermal materials based on nickel foam for efficient solar steam generation. Sol Energy Mater Sol Cells. 2020;214:110574.

    Article  CAS  Google Scholar 

  7. Hayn RA, Owens JR, Boyer SA, McDonald RS, Lee HJ. Preparation of highly hydrophobic and oleophobic textile surfaces using microwave-promoted silane coupling. J Mater Sci 2011;46:2503–9.

    Article  CAS  Google Scholar 

  8. Shohbuke E, Kobayashi Y, Okubayashi S. Effects of acrylate monomers containing alkyl groups on water and oil repellent treatments of polyester fabrics. Colloids Surf A: Physicochem Eng Asp. 2021;631:127632.

    Article  CAS  Google Scholar 

  9. Sun Y, Zhao X, Liu R, Chen G, Zhou X. Synthesis and characterization of fluorinated polyacrylate as water and oil repellent and soil release finishing agent for polyester fabric. Prog Org Coat. 2018;123:306–13.

    Article  CAS  Google Scholar 

  10. Honda K, Morita M, Otsuka H, Takahara A. Molecular aggregation structure and surface properties of Poly(fluoroalkyl acrylate) thin films. Macromolecules. 2005;38:5699–705.

    Article  CAS  Google Scholar 

  11. Honda K, Morita M, Sakata O, Sasaki S, Takahara A. Effect of surface molecular aggregation state and surface molecular motion on wetting behavior of water on Poly(fluoroalkyl methacrylate) thin films. Macromolecules. 2010;43:454–60.

    Article  CAS  Google Scholar 

  12. Zhao Z, Li P, Li Y, Wang S. Durable thermal fluid super-repellency of elastic fluorine-modified SiO2@sponge composite aerogel. Chem Eng J. 2023;454:140247.

    Article  CAS  Google Scholar 

  13. Shao J, Sheng W, Wang C, Ye Y. Solvent-free fabrication of tough self-crosslinkable short-fluorinated copolymer nanocoatings for ultradurable superhydrophobic fabrics. Chem Eng J. 2021;416:128043.

    Article  CAS  Google Scholar 

  14. Chaudhuri A, Maity J. Durable hydrophobic polymer coating on silk surface by surfactant-aided fluoro-monomer polymerization through admicellar technique. Mater Today: Proc. 2023;73:567–75.

    CAS  Google Scholar 

  15. Chen S, Xiang B, Chen S, Zou X, Zhou Y, Hou J. Synthesis and surface characterization of self-assembled monolayers of thiazoles incorporating hydrocarbon and fluorocarbon chains on copper substrates. Appl Surf Sci. 2018;456:25–36.

    Article  CAS  Google Scholar 

  16. Kim BG, Sohn EH, Cho K, Lee JC. Semifluorinated side group poly(oxyethylene) derivatives having extremely low surface energy: Synthesis, characterization, and surface properties. Eur Polym J. 2008;44:2912–9.

    Article  CAS  Google Scholar 

  17. Cai L, Dai L, Yuan Y, Liu A, Li Z. Synthesis of novel polymethacrylates with siloxyl bridging perfluoroalkyl side-chains for hydrophobic application on cotton fabrics. Appl Surf Sci. 2016;371:453–67.

    Article  CAS  Google Scholar 

  18. Shirai T, Fukumoto H, Kanno Y, Kubota T, Agou T. Synthesis, structure, and surface properties of Poly(meth)acrylates bearing a vinylene-bridged fluoroalkyl side chain. Polymer. 2021;217:123478.

    Article  CAS  Google Scholar 

  19. Maeyama K, Tagata Y, Yonezawa N. 2,2’ -Bis(4-benzoylphenoxy)biphenyl: A novel efficient acyl-acceptant monomer yielding wholly aromatic polyketones via Friedel–crafts type polymerization with Arenedicarbonyl chloride. Polym J. 2004;36:146–50.

    Article  CAS  Google Scholar 

  20. Maeyama K, Ogura K, Okamoto A, Ogino K, Saito H, Yonezawa N. Nickel complex-mediated synthesis of optically active wholly aromatic polyketones bearing 2,2’-Dimethoxy-1,10-binaphthyl-6,6’-ene Units. Polym J. 2005;37:736–41.

    Article  CAS  Google Scholar 

  21. Maeyama K, Hikiji I, Ogura K, Okamoto A, Ogino K, Saito H, Yonezawa N. Synthesis of optically active aromatic Poly(ether ketone)s via nucleophilic aromatic substitution polymerization. Polym J. 2005;37:707–10.

    Article  CAS  Google Scholar 

  22. Hasegawa M, Ishigami T, Ishii J, Sugiura K, Fujii M. Solution-processable transparent polyimides with low coefficients of thermal expansion and self-orientation behavior induced by solution casting. Eur Polym J. 2013;49:3657–72.

    Article  CAS  Google Scholar 

  23. Hasegawa M, Hirano D, Fujii M, Haga M, Takezawa E, Yamaguchi S, Ishikawa A, Kagayama T. Solution-Processable colorless polyimides derived from hydrogenated pyromellitic dianhydride with controlled steric structure. J Polym Sci A: Polym Chem. 2013;51:575–92.

    Article  CAS  Google Scholar 

  24. Zhang C, He X, Lu Q. Polyimide films with ultralow dielectric loss for 5G applications: Influence and mechanism of ester groups in molecular chains. Eur Polym J. 2023;200:112544.

    Article  CAS  Google Scholar 

  25. Sun Y, Zhang X, Ma C, Guo N, Liu Y, Liu J, Xie H. Fluorine-containing triblock copolymers as solid-state polymer electrolytes for lithium metal batteries. J Power Sources. 2021;516:230686.

    Article  CAS  Google Scholar 

  26. Katano Y, Tomono H, Nakajima T. Surface property of polymer films with fluoroalkyl side chains. Macromolecules. 1994;27:2342–4.

    Article  CAS  Google Scholar 

  27. Miranda DA, Benskin JP, Awad R, Lepoint G, Leonel J, Hatje V. Bioaccumulation of Per- and polyfluoroalkyl substances (PFASs) in a tropical estuarine food web. Sci Total Environ. 2021;754:142146.

    Article  CAS  PubMed  Google Scholar 

  28. Worley RP, Moorea SM, Bruce C, Tierney BC, Ye X, Calafat AM, Campbell S, Woudneh MB, Fisherd J. Per- and polyfluoroalkyl substances in human serum and urine samples from a residentially exposed community. Environ Int. 2017;106:135–43.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  29. Boone JS, Vigo C, Boone T, Byrne C, Ferrario J, Benson R, Donohue J, Simmons JE, Kolpin DW, Furlong ET, Glassmeyer ST. Per- and polyfluoroalkyl substances in source and treated drinking waters of the United States. Sci Total Environ. 2019;653:359–69.

    Article  CAS  PubMed  Google Scholar 

  30. Giesy JP, Kannan K. Perfluorochemical surfactants in the environment. Environ Sci Technol. 2002;36:147A–152A.

    Article  Google Scholar 

  31. Wen W, Xi X, Zhou D, Wang H, Zhai Y, Lin H, Chen J, Hu D. Bioconcentration and tissue distribution of shorter and longer chain perfluoroalkyl acids (PFAAs) in zebrafish (Danio rerio): Effects of perfluorinated carbon chain length and zebrafish protein content. Environ Pollut. 2019;249:277–85.

    Article  CAS  PubMed  Google Scholar 

  32. Li W, Liu X, Mao H, Wang S. Concentration, distribution, and bioconcentration of short- and long-chain perfluoroalkyl substances in the water, suspended particulate matter, and surface sediment of a typical semi-enclosed bay. Sci Total Environ. 2023;890:164416.

    Article  CAS  PubMed  Google Scholar 

  33. Jiang J, Zhang G, Wang Q, Zhang Q, Zhan X, Chen F. Novel fluorinated polymers containing short perfluorobutyl side chains and their super wetting performance on diverse substrates. Mater Interfaces. 2016;8:10513–10523.

    Article  CAS  Google Scholar 

  34. Barmentlo SH, Stel JM, Doorn MV, Eschauzier C, Voogt PD, Kraak MHS. Acute and chronic toxicity of short chained perfluoroalkyl substances to Daphnia magna. Environ Pollut. 2015;198:47–53.

    Article  CAS  PubMed  Google Scholar 

  35. Wu X, Cao J, Zheng S, Cao Z. Hierarchical surface structure and performance of fluorinated copolymer films derived from side chain structure and α-position substitution of fluorinated monomeric units. Prog Org Coat. 2023;181:107605.

    Article  CAS  Google Scholar 

  36. Dong Q, Fu Y, Wang H, Bai W, Bai R. Design and synthesis of high-performance polymers with short perfluoroalkyl side groups using an environmentally friendly solvent. Eur Polym J. 2121;142:110131.

    Article  Google Scholar 

  37. Song L, Wang R, Niu K, Liu Y, Kou J, Song H, Zhang J, Wang Q. Design, synthesis, characterization, and surface activities of comb-like polymeric fluorinated surfactants with short fluoroalkyl chains. Colloids Surf A. 2021;609:125666.

    Article  CAS  Google Scholar 

  38. Qiu X, Li J, Gu J, Xie R, Yan X, Qi D Novel self-cross-linking fluorinated polyacrylate latex films with short chain perfluoroalkyl group: Surface free energy and surface reorganization. React Funct Polym. 2022;172105185.

  39. Hisa T, Kanno Y, Shirai T, Oshiki T, Mizuhata Y, Tokitoh N, Fukumoto H, Agou T. Synthesis and characterization of a polystyrene-type polymer bearing a cyclic perfluoroalkylene group. Polymer. 2023;265:125588.

    Article  CAS  Google Scholar 

  40. Konta H, Maeyama K. Synthesis of organosoluble aromatic poly(ether ketone)s with short perfuoroalkyl groups in the side chains. Polym Bull. 2024;81:12555–73.

    Article  CAS  Google Scholar 

  41. Zhang Q, Wang Q, Jiang J, Zhan X, Chen F. Microphase structure, crystallization behavior, and wettability properties of novel fluorinated copolymers poly(perfluoroalkyl acrylate-co-stearyl acrylate) containing short perfluorohexyl chains. Langmuir. 2015;31:4752–4760.

    Article  CAS  PubMed  Google Scholar 

  42. Wei L, Demir T, Grant A, Tsukruk V, Brown PJ, Luzinov I. Attainment of water and oil repellency for engineering thermoplastics without long-chain perfluoroalkyls: perfluoropolyether-based triblock polyester additives. Langmuir. 2018;34:12934–12946.

    Article  CAS  PubMed  Google Scholar 

  43. Pilati F, Toselli M, Re A, Bottino FA, Pollicino A, Recca A. Surface investigation by ESCA of Poly(ethylene terephthalate)-Perfluoro polyether block copolymers. Macromolecules. 1990;23:348–50.

    Article  CAS  Google Scholar 

  44. El-Shehawy AA, Yokoyama H, Sugiyama K, Hirao A. Precise synthesis of novel chain-end-functionalized polystyrenes with a definite number of perfluorooctyl groups and their surface characterization. Macromolecules. 2005;38:8285–99.

    Article  CAS  Google Scholar 

  45. Sugiyama K, Hirao A, Nakahama S. Synthesis of end-functionalized polymer by means of living anionic polymerization, 7. Reaction of anionic living polymers with perfluoroalkyl halides. Macromol Chem Phys 1996;197:3149–65.

    Article  CAS  Google Scholar 

  46. Walters KB, Schwark DW, Hirt DE. Surface characterization of linear low-density polyethylene films modified with fluorinated additives. Langmuir. 2003;19:5851–60.

    Article  CAS  Google Scholar 

  47. Tanaka K, Kawaguchi D, Yokoe Y, Kajiyama T. Surface segregation of chain ends in a,ω-fluoroalkyl-terminated polystyrenes films. Polymer. 2003;44:4171–7.

    Article  CAS  Google Scholar 

  48. Zhao C, Xue D, Jia Z, Wang C, Xiao J. Methanol-promoted borylation of arylamines: a simple and green synthetic method to arylboronic acids and arylboronates. Synlett. 2014;25:1577–84.

    Article  Google Scholar 

  49. Chavez AD, Evans AM, Flanders NC, Bisbey RP, Vitaku E, Chen LX, Dichtel WR. Equilibration of Imine-linked polymers to hexagonal macrocycles driven by self-assembly. Chem Eur J 2018;24:3989–93.

    Article  CAS  PubMed  Google Scholar 

  50. Nicholls TP, Robertson JC, Gardiner MG, Bissember AC. Identifying the potential of pulsed irradiation in synthesis: copper-photocatalysed C–F functionalization. Chem Comm 2018;54:4589–92.

    Article  CAS  PubMed  Google Scholar 

  51. Ishihara K, Kondo S, Yamamoto H. 3,5-Bis(perfluorodecyl)phenylboronic Acid as an Easily Recyclable Direct Amide Condensation Catalyst. Synlett. 2001;9:1371–4.

    Article  Google Scholar 

  52. Teng R, Wang H, Qu M, Zhou G. Synthesis of Amorphous Poly (aryl ether ketone) resin and its anti-irradiation properties under Gamma Ray. ChemistrySelect. 2023;8:e202204784.

    Article  CAS  Google Scholar 

  53. Owens DK, Wendt RC. Estimation of the surface free energy of polymers. J Appl Polym Sci. 1969;13:1741–7.

    Article  CAS  Google Scholar 

  54. Owens DK. Some thermodynamic aspects of polymer adhesion. J Appl Polym Sci. 1970;14:1725–30.

    Article  CAS  Google Scholar 

  55. Fox HW, Zisman WA. The spreading of liquids on low energy surfaces. I. Polytetrafluoroethylene. J Colloid Sci. 1950;5:514–31.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Organic Material Science, Yamagata University, 4-3-16 Jonan, Yonezawa, Yamagata, Japan

    Haruki Konta & Katsuya Maeyama

Authors
  1. Haruki Konta
    View author publications

    Search author on:PubMed Google Scholar

  2. Katsuya Maeyama
    View author publications

    Search author on:PubMed Google Scholar

Corresponding author

Correspondence to Katsuya Maeyama.

Ethics declarations

Conflict of interest

The author declares no competing interests.

Additional information

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

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

Konta, H., Maeyama, K. Development of water/oil repellent and heat-resistant aromatic poly(ether ketone)s bearing 3,5-(C4F9)2C6H3 groups at both ends. Polym J 57, 745–759 (2025). https://doi.org/10.1038/s41428-025-01029-5

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Version of record:

  • Issue date:

  • DOI: https://doi.org/10.1038/s41428-025-01029-5

Search

Advanced search

Quick links