Free radical copolymerization of trifluoroethyl methacrylate with perfluoroalkyl ethyl acrylates for superhydrophobic coating application

  • Mei Hu
  • Yabin Zhang
  • Umair Azhar
  • Luqing Zhang
  • Zizhao Chen
  • Shuxiang Zhang
  • Chuanyong Zong


The chemical constitution is a critical factor to the surface properties and the applications of polymers. In this paper, the random copolymers of trifluoroethyl methacrylate (FMA) and perfluoroalkyl ethyl acrylate (TEAc-8) with different feed molar ratios were synthesized by radical solution polymerization. The chemical structures of copolymers [poly(FMA-co-TEAc-8)] were characterized by FTIR, 1H NMR and 19F NMR. Thermogravimetric analysis and differential scanning calorimetry were performed to analyze thermal properties of copolymer. These copolymers demonstrated good thermal stability and lower glass transition temperature (Tg) by introducing the flexible perfluoroalkyl ethyl acrylate with long side chain. At the same time, the surface hydrophobicity of the prepared copolymer coatings was significantly improved, and the water contact angles could be raised to 117° when the molar ratios of TEAc-8 increased to 80%. Furthermore, superhydrophobic coatings were fabricated simply based on organic/inorganic hybrid. The water contact angle and the contact angle hysteresis of the composite coatings higher than 150° and lower than 5°, respectively, were achieved with blending of 2 wt% nano-silica. These superhydrophobic hybrid coatings have superb potential for large-scale and practical applications in self-cleaning and corrosion prevention owing to their simplicity in preparation.


Solution copolymerization Organic/inorganic hybrid Superhydrophobicity 



Authors gratefully acknowledge the financial support from the National Science Foundation of China (21704033), Major Program of Shandong Province Natural Science Foundation (ZR2017ZC0529) and Key Research Program of Shandong Province (2018GGX102002).

Supplementary material

11998_2018_160_MOESM1_ESM.doc (2.9 mb)
Supplementary material 1 (DOC 3005 kb)


  1. 1.
    Bunn, CW, Howells, ER, “Structures of Molecules and Crystals of Fluoro-Carbons.” Nature, 174 549–551 (1954)CrossRefGoogle Scholar
  2. 2.
    Jeon, IY, Ju, MJ, Xu, J, Choi, HJ, Seo, JM, Kim, MJ, Choi, IT, Kim, HM, Kim, JC, Lee, JJ, Liu, HK, Kim, HK, Dou, S, Dai, L, Baek, JB, “Edge-Fluorinated Graphene Nanoplatelets as High Performance Electrodes for Dye-Sensitized Solar Cells and Lithium Ion Batteries.” Adv. Funct. Mater., 25 (8) 1170–1179 (2015)CrossRefGoogle Scholar
  3. 3.
    Lu, Y, Sathasivam, S, Song, J, Crick, CR, Carmalt, CJ, Parkin, IP, “Robust Self-Cleaning Surfaces that Function When Exposed to Either Air or Oil.” Science, 347 (6226) 1132–1135 (2015)CrossRefGoogle Scholar
  4. 4.
    Liu, Y, Khabashesku, VN, Halas, NJ, “Fluorinated Nanodiamond as a Wet Chemistry Precursor for Diamond Coatings Covalently Bonded to Glass Surface.” J. Am. Chem. Soc., 127 (11) 3712–3713 (2005)CrossRefGoogle Scholar
  5. 5.
    Weng, W, Pol, VG, Amine, K, “Ultrasound Assisted Design of Sulfur/Carbon Cathodes with Partially Fluorinated Ether Electrolytes for Highly Efficient Li/S Batteries.” Adv. Mater., 25 (11) 1608–1615 (2013)CrossRefGoogle Scholar
  6. 6.
    Zhang, P, Lv, FY, “A Review of the Recent Advances in Superhydrophobic Surfaces and the Emerging Energy-Related Applications.” Energy, 82 1068–1087 (2015)CrossRefGoogle Scholar
  7. 7.
    Purser, S, Moore, PR, Swallow, S, Gouverneur, V, “Fluorine in Medicinal Chemistry.” Chem. Soc. Rev., 37 (2) 320–330 (2008)CrossRefGoogle Scholar
  8. 8.
    Costa, JL, Joy, DC, Maher, DM, Kirk, KL, Hui, SW, “Fluorinated Molecule as a Tracer: Difluoroserotonin in Human Platelets Mapped by Electron Energy-Loss Spectroscopy.” Science, 200 (4341) 537–539 (1978)CrossRefGoogle Scholar
  9. 9.
    Watson, GS, Green, DW, Schwarzkopf, L, Li, X, Cribb, BW, Myhra, S, Watson, JA, “A Gecko Skin Micro/Nano Structure—A Low Adhesion, Superhydrophobic, Anti-wetting, Self-Cleaning, Biocompatible, Antibacterial Surface.” Acta Biomater., 21 109–122 (2015)CrossRefGoogle Scholar
  10. 10.
    Howarter, JA, Youngblood, JP, “Self-Cleaning and Anti-fog Surfaces via Stimuli-Responsive Polymer Brushes.” Adv. Mater., 19 (22) 3838–3843 (2007)CrossRefGoogle Scholar
  11. 11.
    Baradie, B, Shoichet, MS, “Novel Fluoro-Terpolymers for Coatings Applications.” Macromolecules, 38 (13) 5560–5568 (2005)CrossRefGoogle Scholar
  12. 12.
    Banerjee, S, Wehbi, M, Manseri, A, Mehdi, A, Alaaeddine, A, Hachem, A, Ameduri, B, “Poly(vinylidene fluoride) Containing Phosphonic Acid as Anticorrosion Coating for Steel.” ACS Appl. Mater. Interfaces, 9 (7) 6433–6443 (2017)CrossRefGoogle Scholar
  13. 13.
    Mohamed, AMA, Abdullah, AM, Younan, NA, “Corrosion Behavior of Superhydrophobic Surfaces: A Review.” Arab. J. Chem., 8 749–765 (2015)CrossRefGoogle Scholar
  14. 14.
    Zhang, DW, Wang, LT, Qian, HC, Li, XG, “Superhydrophobic Surfaces for Corrosion Protection: A Review of Recent Progresses and Future Directions.” J. Coat. Technol. Res., 13 (1) 11–29 (2016)CrossRefGoogle Scholar
  15. 15.
    Chu, ZL, Feng, YJ, Seeger, S, “Oil/Water Separation with Selective Superantiwetting/Superwetting Surface Materials.” Angew. Chem. Int. Ed., 54 2328–2338 (2015)CrossRefGoogle Scholar
  16. 16.
    Kreder, MJ, Alvarenga, J, Kim, P, Aizenberg, J, “Design of Anti-icing Surfaces: Smooth, Textured or Slippery?” Nat. Rev. Mater., 1 15003 (2016)CrossRefGoogle Scholar
  17. 17.
    Katano, Y, Tomono, H, Nakajima, T, “Surface Property of Polymer Films with Fluoroalkyl Side Chains.” Macromolecules, 27 (8) 2342–2344 (1994)CrossRefGoogle Scholar
  18. 18.
    Lehmler, HJ, Rao, VR, Nauduri, D, Vargo, JD, Parkin, S, “Synthesis and Structure of Environmentally Relevant Perfluorinated Sulfonamides.” J. Fluor. Chem., 128 (6) 595–607 (2007)CrossRefGoogle Scholar
  19. 19.
    Zhang, QH, Wang, QY, Zhan, XL, Chen, FQ, “Synthesis and Performance of Novel Fluorinated Acrylate Polymers: Preparation and Reactivity of Short Perfluoroalkyl Group Containing Monomers.” Ind. Eng. Chem. Res., 53 (19) 8026–8034 (2014)CrossRefGoogle Scholar
  20. 20.
    Honda, K, Morita, M, Otsuka, H, Takahara, A, “Molecular Aggregation Structure and Surface Properties of Poly(fluoroalkyl acrylate) Thin Films.” Macromolecules, 38 (13) 5699–5705 (2005)CrossRefGoogle Scholar
  21. 21.
    Yao, W, Li, Y, Huang, X, “Fluorinated Poly(meth)acrylate: Synthesis and Properties.” Polymer, 55 (24) 6197–6211 (2014)CrossRefGoogle Scholar
  22. 22.
    Banerjee, S, Tawade, BV, Ladmiral, V, Dupuy, LX, MacDonaldc, MP, Améduri, B, “Poly(fluoroacrylate)s with Tunable Surface Hydrophobicity via Radical Copolymerization of 2,2,2-Trifluoroethyl α-Fluoroacrylate and 2-(Trifluoromethyl)acrylic Acid.” Polym. Chem., 8 1978–1988 (2017)CrossRefGoogle Scholar
  23. 23.
    Li, K, Zeng, X, Laia, X, Chai, S, “Study on the Anti-abrasion Resistance of Superhydrophobic Coatings Based on Fluorine-containing Acrylates with Different T g and SiO2.” RSC Adv., 7 (75) 47738–47745 (2017)CrossRefGoogle Scholar
  24. 24.
    Chang, KC, Chen, YK, Chen, H, “Preparation of Superhydrophobic Silica-Based Films by Using Polyethylene Glycol and Tetraethoxysilane.” J. Appl. Polym. Sci., 105 (3) 1503–1510 (2007)CrossRefGoogle Scholar
  25. 25.
    Ha, JW, Park, IJ, Lee, SB, “Hydrophobicity and Sliding Behavior of Liquid Droplets on the Fluorinated Latex Films.” Macromolecules, 38 (3) 736–744 (2005)CrossRefGoogle Scholar
  26. 26.
    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, 43 (1) 454–460 (2009)CrossRefGoogle Scholar
  27. 27.
    Chen, Y, Chen, D, Ma, Y, Yang, W, “Multiple Levels Hydrophobic Modification of Polymeric Substrates by UV-Grafting Polymerization with FMA as Monomer.” J. Polym. Sci. Polym. Chem., 52 (8) 1059–1067 (2014)CrossRefGoogle Scholar
  28. 28.
    Yamada, B, Kontani, T, Yoshida, M, Otsu, T, “Determination of Absolute Rate Constants for Free Radical Polymerization of Ethyl α-Fluoroacrylate and Characterization of the Polymer.” J. Polym. Sci. Polym. Chem., 22 (10) 2381–2393 (1984)CrossRefGoogle Scholar
  29. 29.
    Zhang, S, Zhao, J, Chu, G, Zhang, L, Xu, A, Li, H, Geng, B, “Synthesis, Characterization and Properties of a Novel Fluorinated Methacrylate Polymer.” J. Fluor. Chem., 132 (11) 915–919 (2011)CrossRefGoogle Scholar
  30. 30.
    Zhou, D, Teng, H, Koike, K, Koike, Y, Okamoto, Y, “Copolymers of Methyl Methacrylate and Fluoroalkyl Methacrylates: Effects of Fluoroalkyl Groups on the Thermal and Optical Properties of the Copolymers.” J. Polym. Sci. Polym. Chem., 46 (11) 4748–4755 (2008)CrossRefGoogle Scholar
  31. 31.
    Alyamac, E, Soucek, MD, “Acrylate-Based Fluorinated Copolymers for High-Solids Coatings.” Prog. Org. Coat., 71 (3) 213–224 (2011)CrossRefGoogle Scholar
  32. 32.
    Xi, G, Fan, W, Wang, L, Liu, X, Endo, T, “Fabrication of Asymmetrically Superhydrophobic Cotton Fabrics via Mist Copolymerization of 2,2,2-Trifluoroethyl Methacrylate.” J. Polym. Sci. Polym. Chem., 53 (16) 1862–1871 (2015)CrossRefGoogle Scholar
  33. 33.
    Rodney, RJ, Grulke, EA, “Glass Transition Temperatures of Polymers.” In: Brandrup, J, Immergut, EH, Grulke, EA, Abe, A, Bloch, DR (eds.) Polymer Handbook, 4th edn., pp. 194–253. John Wiley & Sons, Inc., New York (1999)Google Scholar
  34. 34.
    Xu, A, Zhang, L, Ma, J, Ma, Y, Geng, B, Zhang, S, “Preparation and Surface Properties of Poly(2, 2, 2-trifluoroethyl methacrylate) Coatings Modified with Methyl Acrylate.” J. Coat. Technol. Res., 13 (5) 795–804 (2016)CrossRefGoogle Scholar
  35. 35.
    Morita, M, Ogisu, H, Kubo, M, “Surface Properties of Perfluoroalkylethyl Acrylate/n-alkyl Acrylate Copolymers.” J. Appl. Polym. Sci., 73 (9) 1741–1749 (1999)CrossRefGoogle Scholar
  36. 36.
    Ozbay, S, Erbil, HY, “Solution Copolymerization of Perfluoroalkyl Ethyl Methacrylate with Methyl Methacrylate and Butyl Acrylate: Synthesis and Surface Properties.” Colloids Surf. A Physicochem. Eng. Asp., 452 (20) 9–17 (2014)CrossRefGoogle Scholar
  37. 37.
    Malshe, VC, Sangaj, NS, “Fluorinated Acrylic Copolymers: Part I: Study of Clear Coatings.” Prog. Org. Coat., 53 (3) 207–211 (2005)CrossRefGoogle Scholar
  38. 38.
    Tsibouklis, J, Nevell, TG, “Ultra-Low Surface Energy Polymers: The Molecular Design Requirements.” Adv. Mater., 15 (7–8) 647–650 (2003)CrossRefGoogle Scholar
  39. 39.
    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, 31 (16) 4752–4760 (2015)CrossRefGoogle Scholar
  40. 40.
    Graham, P, Stone, M, Thorpe, A, Nevell, TG, Tsibouklis, J, “Fluoropolymers with Very Low Surface Energy Characteristics.” J. Fluor. Chem., 104 (1) 29–36 (2000)CrossRefGoogle Scholar
  41. 41.
    Imae, T, “Fluorinated Polymers.” Curr. Opin. Colloid Interface, 8 (3) 307–314 (2003)CrossRefGoogle Scholar
  42. 42.
    He, L, Liang, J, Zhao, X, Li, W, Luo, H, “Preparation and Comparative Evaluation of Well-Defined Fluorinated Acrylic Copolymer Latex and Solution for Ancient Stone Protection.” Prog. Org. Coat., 69 (4) 352–358 (2010)CrossRefGoogle Scholar
  43. 43.
    Pafiti, KS, Loizou, E, Patrickios, CS, Porcar, L, “End-Linked Semifluorinated Amphiphilic Polymer Conetworks: Synthesis by Sequential Reversible Addition-Fragmentation Chain Transfer Polymerization and Characterization.” Macromolecules, 43 (12) 5195–5204 (2010)CrossRefGoogle Scholar
  44. 44.
    Tongkhundam, Y, Sirivat, A, Brostow, W, “Tribological Properties of Perfluoralkylethyl Methacrylate-Polymethyl Methacrylate Copolymer Thin Films.” Polymer, 45 (26) 8731–8738 (2004)CrossRefGoogle Scholar
  45. 45.
    Borkar, S, Jankova, K, Siesler, HW, Hvilsted, S, “New Highly Fluorinated Styrene-Based Materials with Low Surface Energy Prepared by ATRP.” Macromolecules, 37 (3) 788–794 (2004)CrossRefGoogle Scholar
  46. 46.
    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.” ACS Appl. Mater. Interfaces, 8 (16) 10513–10523 (2016)CrossRefGoogle Scholar
  47. 47.
    Chee, KK, “Dependence of Glass Transition Temperature on Chain Flexibility and Intermolecular Interactions in Polymers.” J. Appl. Polym. Sci., 43 (6) 1205–1208 (1991)CrossRefGoogle Scholar
  48. 48.
    Choi, D, Yeom, EH, Park, M, Kim, JK, Kim, BC, “Preparation and Properties of Methyl Methacrylate and Fluoroacrylate Copolymers for Plastic Optical Fiber Cladding.” J. Appl. Polym. Sci., 93 (5) 2082–2089 (2004)CrossRefGoogle Scholar
  49. 49.
    Cengiz, U, Gengec, NA, Kaya, NU, Erbil, HY, Sarac, AS, “Mechanical and Thermal Properties of Perfluoroalkyl Ethyl Methacrylate-Methyl Methacrylate Statistical Copolymers Synthesized in Supercritical Carbon Dioxide.” J. Fluor. Chem., 132 (5) 348–355 (2011)CrossRefGoogle Scholar
  50. 50.
    Wu, DT, Fredrickson, GH, “Effect of Architecture in the Surface Segregation of Polymer Blends.” Macromolecules, 29 (24) 7919–7930 (1996)CrossRefGoogle Scholar
  51. 51.
    Saïdi, S, Guittard, F, Guimon, C, Géribaldi, S, “Synthesis and Characterization of Copolymers Based on Styrene and Partially Fluorinated Acrylates.” Eur. Polym. J., 42 (3) 702–710 (2006)CrossRefGoogle Scholar
  52. 52.
    Huang, Y, Hu, M, Yi, S, Liu, X, Li, H, Huang, C, Luo, Y, Li, Y, “Preparation and Characterization of Silica/Fluorinated Acrylate Copolymers Hybrid Films and the Investigation of Their Icephobicity.” Thin Solid Films, 520 (17) 5644–5651 (2012)CrossRefGoogle Scholar
  53. 53.
    Yoshimitsu, Z, Nakajima, A, Watanabe, T, Hashimoto, K, “Effects of Surface Structure on the Hydrophobicity and Sliding Behavior of Water Droplets.” Langmuir, 18 (15) 5818–5822 (2002)CrossRefGoogle Scholar
  54. 54.
    Martinelli, E, Galli, G, Krishnan, S, Paik, MY, Ober, CK, Fischer, DA, “New Poly(dimethylsiloxane)/Poly(perfluorooctylethyl acrylate) Block Copolymers: Structure and Order Across Multiple Length Scales in Thin Films.” J. Mater. Chem., 21 (39) 15357–15368 (2011)CrossRefGoogle Scholar
  55. 55.
    Gu, ZX, Cheng, J, Zhang, MZ, He, JL, Ni, PH, “Effect of Groups at A-Position and Side-Chain Structure of Comonomers on Surface Free Energy and Surface Reorganization of Fluorinated Methacrylate Copolymer.” Polymer, 114 79–87 (2017)CrossRefGoogle Scholar
  56. 56.
    Wang, ZF, Wang, ZG, “Synthesis of Cross-Linkable Fluorinated Core–shell Latex Nanoparticles and the Hydrophobic Stability of Films.” Polymer, 74 216–223 (2015)CrossRefGoogle Scholar
  57. 57.
    Yaobo Cheng, YB, Wang, ZG, “Fluorinated Poly(isobornyl methacrylate–co–butyl acrylate) Core–shell Latex Nanoparticles: Synthesis, Morphology and Wettability of Films.” Polymer, 54 3047–3054 (2013)CrossRefGoogle Scholar
  58. 58.
    Wang, ZG, Li, WJ, Zhao, XL, Zhu, DJ, You, J, “Self-Segregation Behavior of N-Ethyl-pentadecafluorooctanamide-Terminated Polybutylene Isophthalate and Its Effects on Film Morphology and Wettability.” J. Phys. Chem. B, 113 15204–15211 (2009)CrossRefGoogle Scholar
  59. 59.
    Tijing, LD, Woo, YC, Shim, WG, He, T, Choi, JS, Kim, SH, Shon, HK, “Superhydrophobic Nanofiber Membrane Containing Carbon Nanotubes for High-Performance Direct Contact Membrane Distillation.” J. Membrane. Sci., 502 158–170 (2016)CrossRefGoogle Scholar
  60. 60.
    Li, KQ, Zeng, XR, Li, HQ, Lai, XJ, “Fabrication and Characterization of Stable Superhydrophobic Fluorinated-Polyacrylate/Silica Hybrid Coating.” Appl. Surf. Sci., 298 214–220 (2014)CrossRefGoogle Scholar

Copyright information

© American Coatings Association 2018

Authors and Affiliations

  1. 1.Shandong Provincial Key Laboratory of Fluorine Chemistry and Chemical Materials, School of Chemistry and Chemical Engineering, Shandong Engineering Research Center for Fluorinated MaterialUniversity of JinanJinanChina

Personalised recommendations