Synthesis and properties of fluorinated non-isocyanate polyurethanes coatings with good hydrophobic and oleophobic properties

  • Zhijun Wu
  • Liuyan Tang
  • Jingtao Dai
  • Jinqing QuEmail author


To improve the chemical resistance of non-isocyanate polyurethane (NIPU), two kinds of diglycidyl ether, bisphenol AF (E-AF) and perfluorooctyl glycidyl ether (PFGE), were selected to synthesize two different cyclic carbonates, bisphenol AF (EC-AF) and perfluorooctyl cyclic carbonate (PFGC), respectively. These cyclic carbonates were successfully used to prepare fluorine-containing non-isocyanate polyurethane coatings. The effects of PFGC amounts on the properties of NIPU were studied, and it was found that the contact angles of water, diiodomethane, and hexadecane were increased with the addition of PFGC and up to 106.7°, 80.2°, and 72.7°, respectively, whereas the pendulum hardness of NIPU coatings relatively decreased with the increase in PFGC contents. The NIPU coatings exhibited excellent flexibility, adhesion, and impact resistance. They also displayed good thermal stability with 5% weight loss temperature (T5%) ranging from 249 to 271°C. Moreover, these coatings possessed very low water uptake, excellent hydrophobic/oleophobic properties, and corrosion resistance properties.


Hydrophobic and oleophobic properties Corrosion resistance Cyclic carbonate Non-isocyanate polyurethane (NIPU) Coatings 



This work was financially supported by the National Natural Science Foundation of China (No. 21878109), and the Science and Technology Program of Guangdong Province, China (Nos. 2015A010105010, 2015B090925006, 2016B090930005, and 2016B030302004).


  1. 1.
    Chattopadhyay, DK, Raju, KVSN, “Structural Engineering of Polyurethane Coatings for High Performance Applications.” Prog. Polym. Sci., 32 (3) 352–418 (2007)CrossRefGoogle Scholar
  2. 2.
    Chattopadhyay, DK, Webster, DC, “Thermal Stability and Flame Retardancy of Polyurethanes.” Prog. Polym. Sci., 34 (10) 1068–1133 (2009)CrossRefGoogle Scholar
  3. 3.
    Etienne, D, Jean-Pierre, P, Bernard, B, François, G, “On the Versatility of Urethane/Urea Bonds: Reversibility, Blocked Isocyanate, and Non-isocyanate Polyurethane.” Chem. Rev., 113 (1) 80–118 (2013)CrossRefGoogle Scholar
  4. 4.
    Zhang, C, Garrison, TF, Madbouly, SA, Kessler, MR, “Recent Advances in Vegetable Oil-Based Polymers and Their Composites.” Prog. Polym. Sci., 71 (1) 91–143 (2017)CrossRefGoogle Scholar
  5. 5.
    Cornille, A, Auvergne, R, Figovsky, O, Boutevin, B, Caillol, S, “A Perspective Approach to Sustainable Routes for Non-isocyanate Polyurethanes.” Eur. Polym. J., 87 (1) 535–552 (2017)CrossRefGoogle Scholar
  6. 6.
    Grignard, B, Thomassin, JM, Gennen, S, Poussard, L, Bonnaud, L, Raquez, JM, Dubois, P, Tran, MP, Park, CB, Jerome, C, “CO2-Blown Microcellular Non-isocyanate Polyurethane (NIPU) Foams: From Bio- and CO2-Sourced Monomers to Potentially Thermal Insulating Materials.” Green Chem., 18 (7) 2206–2215 (2016)CrossRefGoogle Scholar
  7. 7.
    Maisonneuve, L, Lamarzelle, O, Rix, E, Grau, E, Cramail, H, “Isocyanate-Free Routes to Polyurethanes and Poly(Hydroxy Urethane)s.” Chem. Rev., 115 (22) 12407–12439 (2015)CrossRefGoogle Scholar
  8. 8.
    Hannes, B, Maria, F, Moritz, BH, Rolf, M, “Isocyanate- and Phosgene-Free Routes to Polyfunctional Cyclic Carbonates and Green Polyurethanes by Fixation of Carbon Dioxide.” Macromol. Rapid Commun., 35 (14) 1238–1254 (2014)CrossRefGoogle Scholar
  9. 9.
    Caillol, S, Dolci, E, Fouquay, S, Boutevin, B, Simon, F, Michaud, G, “Remendable Thermosetting Polymers for Isocyanate-Free Adhesives: A Preliminary Study.” Polym. Chem., 6 (45) 7851–7861 (2015)CrossRefGoogle Scholar
  10. 10.
    Blain, M, Jean-Gérard, L, Rémi, A, Benazet, D, Caillol, S, Andrioletti, B, “Rational Investigations in the Ring Opening of Cyclic Carbonates by Amines.” Green Chem., 16 (9) 4286–4291 (2014)CrossRefGoogle Scholar
  11. 11.
    Lambeth, RH, Henderson, TJ, “Organocatalytic Synthesis of (Poly)Hydroxyurethanes from Cyclic Carbonates and Amines.” Polymer, 54 (21) 5568–5573 (2013)CrossRefGoogle Scholar
  12. 12.
    Tomita, H, Sanda, F, Endo, T, “Model Reaction for the Synthesis of Polyhydroxyurethanes from Cyclic Carbonates with Amines: Substituent Effect on the Reactivity and Selectivity of Ring-Opening Direction in the Reaction of Five-Membered Cyclic Carbonates with Amine.” J. Polym. Sci. Pol. Chem., 39 (21) 3678–3685 (2001)CrossRefGoogle Scholar
  13. 13.
    He, Y, Keul, H, Möller, M, “Synthesis, Characterization, and Application of a Bifunctional Coupler Containing a Five- and a Six-Membered Ring Carbonate.” React. Funct. Polym., 71 (2) 175–186 (2011)CrossRefGoogle Scholar
  14. 14.
    Bähr, M, Bitto, A, Mülhaupt, R, “Cyclic Limonene Dicarbonate as a New Monomer for Non-isocyanate Oligo- and Polyurethanes (NIPU) Based Upon Terpenes.” Green Chem., 14 (5) 1447–1454 (2012)CrossRefGoogle Scholar
  15. 15.
    Zhang, L, Luo, X, Qin, Y, Li, Y, “A Novel 2,5-Furandicarboxylic Acid-Based Bis(Cyclic Carbonate) for the Synthesis of Biobased Non-isocyanate Polyurethanes.” RSC Adv., 7 (1) 37–46 (2016)CrossRefGoogle Scholar
  16. 16.
    Fleischer, M, Blattmann, H, Mülhaupt, R, “Glycerol-, Pentaerythritol- and Trimethylolpropane-Based Polyurethanes and Their Cellulose Carbonate Composites Prepared via the Non-isocyanate Route with Catalytic Carbon Dioxide Fixation.” Green Chem., 15 (4) 934–942 (2013)CrossRefGoogle Scholar
  17. 17.
    Liu, G, Wu, G, Chen, J, Huo, S, Jin, C, Kong, Z, “Synthesis and Properties of POSS-Containing Gallic Acid-Based Non-isocyanate Polyurethanes Coatings.” Polym. Degrad. Stab., 121 247–252 (2015)CrossRefGoogle Scholar
  18. 18.
    Liu, G, Wu, G, Chen, J, Kong, Z, “Synthesis, Modification and Properties of Rosin-Based Non-isocyanate Polyurethanes Coatings.” Prog. Org. Coat., 101 461–467 (2016)CrossRefGoogle Scholar
  19. 19.
    Blattmann, H, Mülhaupt, R, “Multifunctional β-Amino Alcohols as Bio-Based Amine Curing Agents for the Isocyanate- and Phosgene-Free Synthesis of 100% Bio-Based Polyhydroxyurethane Thermosets.” Green Chem., 18 (8) 2406–2415 (2016)CrossRefGoogle Scholar
  20. 20.
    Blattmann, H, Mülhaupt, R, “Multifunctional POSS Cyclic Carbonates and Non-isocyanate Polyhydroxyurethane Hybrid Materials.” Macromolecules, 49 (3) 742–751 (2016)CrossRefGoogle Scholar
  21. 21.
    Wu, Z, Cai, W, Chen, R, Qu, J, “Synthesis and Properties of Ambient-Curable Non-isocyanate Polyurethanes.” Prog. Org. Coat., 119 116–122 (2018)CrossRefGoogle Scholar
  22. 22.
    Wu, Z, Dai, J, Tang, L, Qu, J, “Sorbitol-Based Aqueous Cyclic Carbonate Dispersion for Waterborne Nonisocyanate Polyurethane Coatings via an Environment-Friendly Route.” J. Coat. Technol. Res.
  23. 23.
    Danielle, M, Muhammad, R, Grozea, CM, Guojun, L, Yu, W, Alison, C, Martin, W, “Clear Antismudge Unimolecular Coatings of Diblock Copolymers on Glass Plates.” ACS Appl. Mater. Inter., 6 (23) 21435–21445 (2014)CrossRefGoogle Scholar
  24. 24.
    Darmanin, T, Guittard, F, “Superoleophobic Surfaces with Short Fluorinated Chains?” Soft Matter, 9 (25) 5982–5990 (2013)CrossRefGoogle Scholar
  25. 25.
    Martinelli, E, Fantoni, C, Gallot, B, Glisenti, A, Galli, G, “Polystyrene–Polyperfluorooctylethyl Acrylate Diblock Copolymers: The Effect of Dilution of the Fluorinated Mesogenic Chains on Bulk and Surface Properties.” Macromol Sym., 296 (1) 294–302 (2010)CrossRefGoogle Scholar
  26. 26.
    Trombetta, T, Iengo, P, Turri, S, “Fluorinated Segmented Polyurethane Anionomers for Water–Oil Repellent Surface Treatments of Cellulosic Substrates.” J Appl. Polym. Sci., 98 (3) 1364–1372 (2010)CrossRefGoogle Scholar
  27. 27.
    Zhao, X, Ding, J, Ye, L, “Structure and Solvent-Resistant Property of Fluorinated Polyurethane Elastomer.” J. Fluor. Chem., 159 38–47 (2014)CrossRefGoogle Scholar
  28. 28.
    Shin, MS, Lee, YH, Rahman, MM, Kim, HD, “Synthesis and Properties of Waterborne Fluorinated Polyurethane-Acrylate Using a Solvent-/Emulsifier-Free Method.” Polymer, 54 (18) 4873–4882 (2013)CrossRefGoogle Scholar

Copyright information

© American Coatings Association 2019

Authors and Affiliations

  • Zhijun Wu
    • 1
  • Liuyan Tang
    • 1
  • Jingtao Dai
    • 1
  • Jinqing Qu
    • 1
    Email author
  1. 1.School of Chemistry and Chemical EngineeringSouth China University of TechnologyGuangzhouPeople’s Republic of China

Personalised recommendations