UV-curable waterborne polyurethane dispersions modified with a trimethoxysilane end-capping agent and edge-hydroxylated boron nitride

  • Huixiang Liu
  • Hong Zhang
  • Chaohua Peng
  • Shufan Ren
  • Conghui Yuan
  • Weiang Luo
  • Guorong Chen
  • Fuqiang HeEmail author
  • Lizong DaiEmail author


In this study, waterborne polyurethane (WPU) dispersions were prepared using a trimethoxysilane end-capping agent (DAA-GPTMS) derived from diallylamine (DAA), (3-glycidoxypropyl)methyldiethoxysilane (GPTMS) and modified with edge-hydroxylated boron nitride (hBN-OH) nanosheets. The WPU films containing DAA-GPTMS possessed remarkable hydrophobicity and favorable water repellency, attaining a contact angle of 101.2° and a 52% decrease in water absorption relative to those of the pure WPU. When the contents of DAA-GPTMS and hBN-OH were 7.5 wt% and 0.2 wt%, respectively, the synergetic effect between the DAA-GPTMS and the hBN-OH nanosheets greatly enhanced the physical and mechanical properties of the nanocomposite films, i.e., the stress doubled and the Young’s modulus increased by fivefold compared to those of pure WPU. Embedding 0.2 wt% of the hBN-OH nanosheets in the WPU coatings resulted in a lower corrosion current density (1.0 × 10−10 A cm−2) and more positive corrosion potential (− 0.63 V). The results demonstrate that WPU/hBN-OH nanocomposite coatings possess great potential for corrosion protection.


Waterborne polyurethane Trimethoxysilane end-capping agent Boron nitride nanosheets UV-curable 



This work was supported by the National Natural Science Foundation of China (U1805253, 51673161); Scientific and Technological Innovation Platform of Fujian Province (2014H2006).

Supplementary material

11998_2019_232_MOESM1_ESM.docx (664 kb)
Supplementary material 1 (DOCX 663 kb)


  1. 1.
    Krol, P, “Synthesis Methods, Chemical Structures and Phase Structures of Linear Polyurethanes. Properties and Applications of Linear Polyurethanes in Polyurethane Elastomers, Copolymers and Ionomers.” Prog. Mater. Sci., 52 915–1015 (2007)CrossRefGoogle Scholar
  2. 2.
    Liu, H, Li, C, Sun, XS, “Soy-Oil-Based Waterborne Polyurethane Improved Wet Strength of Soy Protein Adhesives on Wood.” Int. J. Adhes. Adhes., 73 66–74 (2017)CrossRefGoogle Scholar
  3. 3.
    Zhou, X, Li, Y, Fang, C, Li, S, Cheng, Y, Lei, W, Meng, X, “Recent Advances in Synthesis of Waterborne Polyurethane and Their Application in Water-Based Ink: A Review.” J. Mater. Sci. Technol., 31 708–722 (2015)CrossRefGoogle Scholar
  4. 4.
    Noreen, A, Zia, KM, Zuber, M, Tabasum, S, Saif, MJ, “Recent Trends in Environmentally Friendly Water-Borne Polyurethane Coatings: A Review.” Korean J. Chem. Eng., 33 388–400 (2015)CrossRefGoogle Scholar
  5. 5.
    Madbouly, SA, Otaigbe, JU, “Nanostructured Polyurethane/POSS Hybrid Aqueous Dispersions Prepared by Homogeneous Solution Polymerization.” Macromolecules, 39 4144–4151 (2006)CrossRefGoogle Scholar
  6. 6.
    Chattopadhyay, DK, Raju, KVSN, “Structural Engineering of Polyurethane Coatings for High Performance Applications.” Prog. Polym. Sci., 32 352–418 (2007)CrossRefGoogle Scholar
  7. 7.
    Liu, Y, Ding, T, Meng, Q, Dong, B, Cao, L, Gao, R, “Preparation of Stable Superamphiphobic Surfaces on X80 Pipeline Steel Substrates.” RSC Adv., 6 91669–91678 (2016)CrossRefGoogle Scholar
  8. 8.
    Ellinas, K, Pujari, SP, Dragatogiannis, DA, Charitidis, CA, Gogolides, E, “Plasma Micro-Nanotextured, Scratch, Water and Hexadecane Resistant, Superhydrophobic, and Superamphiphobic Polymeric Surfaces with Perfluorinated Monolayers.” ACS Appl. Mater. Interfaces, 6 6510–6524 (2014)CrossRefGoogle Scholar
  9. 9.
    Wu, ZF, Wang, H, Tian, X, Xue, M, Ding, X, Ye, X, Cui, Z, “Surface and Mechanical Properties of Hydrophobic Silica Contained Hybrid Films of Waterborne Polyurethane and Fluorinated Polymethacrylate.” Polymer, 55 187–194 (2014)CrossRefGoogle Scholar
  10. 10.
    Tan, J, Liu, W, Wang, Z, “Preparation and Performance of Waterborne UV-Curable Polyurethane Containing Long Fluorinated Side Chains.” J. Appl. Polym. Sci., 134 44506 (2017)Google Scholar
  11. 11.
    Zheng, G, Lu, M, Rui, X, Shao, B, “Surface and Bulk Properties of Waterborne Polyurethane Modified with Fluorinated Siloxane.” J. Appl. Polym. Sci., 135 46473 (2018)CrossRefGoogle Scholar
  12. 12.
    Ji, X, Wang, H, Ma, X, Hou, C, Ma, G, “Progress in Polydimethylsiloxane-Modified Waterborne Polyurethanes.” RSC Adv., 7 34086–34095 (2017)CrossRefGoogle Scholar
  13. 13.
    Zhang, S, Chen, Z, Guo, M, Zhao, J, Liu, X, “Waterborne UV-Curable Polycarbonate Polyurethane Nanocomposite Based on Polydimethylsiloxane and Colloidal Silica with Enhanced Mechanical and Surface Properties.” RSC Adv., 4 30938–30947 (2014)CrossRefGoogle Scholar
  14. 14.
    Ge, Z, Luo, Y, “Synthesis and Characterization of Siloxane-Modified Two-Component Waterborne Polyurethane.” Prog. Org. Coat., 76 1522–1526 (2013)CrossRefGoogle Scholar
  15. 15.
    Li, Q, Guo, L, Qiu, T, Xiao, W, Du, D, Li, X, “Synthesis of Waterborne Polyurethane Containing Alkoxysilane Side Groups and the Properties of the Hybrid Coating Films.” Appl. Surf. Sci., 377 66–74 (2016)CrossRefGoogle Scholar
  16. 16.
    Xu, H, Qiu, F, Wang, Y, Wu, W, Yang, D, Guo, Q, “UV-Curable Waterborne Polyurethane-Acrylate: Preparation, Characterization and Properties.” Prog. Org. Coat., 73 47–53 (2012)CrossRefGoogle Scholar
  17. 17.
    Yuan, C, Wang, M, Li, H, Wang, Z, “Preparation and Properties of UV-Curable Waterborne Polyurethane-Acrylate Emulsion.” J. Appl. Polym. Sci., 134 45208 (2017)CrossRefGoogle Scholar
  18. 18.
    Liu, X, Zhang, Q, Huang, C, Li, H, Wang, H, Hu, M, “UV-Curable Coating Crosslinked by a Novel Hyperbranched Polyurethane Acrylate with Excellent Mechanical Properties and Hardness.” RSC Adv., 6 107942–107950 (2016)CrossRefGoogle Scholar
  19. 19.
    Zhang, S, Chen, Z, Guo, M, Bai, H, Liu, X, “Synthesis and Characterization of Waterborne UV-Curable Polyurethane Modified with Side-Chain Triethoxysilane and Colloidal Silica.” Colloids Surf. A: Physicochem. Eng. Aspects, 468 1–9 (2015)CrossRefGoogle Scholar
  20. 20.
    Christopher, G, Anbu Kulandainathan, M, Harichandran, G, “Comparative Study of Effect of Corrosion on Mild Steel with Waterborne Polyurethane Dispersion Containing Graphene Oxide Versus Carbon Black Nanocomposites.” Prog. Org. Coat., 89 199–211 (2015)CrossRefGoogle Scholar
  21. 21.
    Hu, L, Jiang, P, Zhang, P, Bian, G, Xia, J, “Amine-Graphene Oxide/Waterborne Polyurethane Nanocomposites: Effects of Different Amine Modifiers on Physical Properties.” J. Mater. Sci., 51 8296–8309 (2016)CrossRefGoogle Scholar
  22. 22.
    Feng, J, Wang, X, Guo, P, Wang, Y, Luo, X, “Mechanical Properties and Wear Resistance of Sulfonated Graphene/Waterborne Polyurethane Composites Prepared by In Situ Method.” Polymers, 10 75 (2018)CrossRefGoogle Scholar
  23. 23.
    Kim, YJ, Kim, BK, “Synthesis and Properties of Silanized Waterborne Polyurethane/Graphene Nanocomposites.” Colloid. Polym. Sci., 292 51–58 (2014)CrossRefGoogle Scholar
  24. 24.
    Cui, C, Lim, ATO, Huang, J, “A Cautionary Note on Graphene Anti-corrosion Coatings.” Nat. Nanotechnol., 12 834–835 (2017)CrossRefGoogle Scholar
  25. 25.
    Schriver, M, Regan, W, Gannett, WJ, Zaniewski, AM, Crommie, MF, Zettl, A, “Graphene as a Long-Term Metal Oxidation Barrier: Worse Than Nothing.” ACS Nano., 7 5763–5768 (2013)CrossRefGoogle Scholar
  26. 26.
    Liu, J, Kutty, RG, Zheng, Q, Eswariah, V, Sreejith, S, Liu, Z, “Hexagonal Boron Nitride Nanosheets as High-Performance Binder-Free Fire-Resistant Wood Coatings.” Small, 13 1602456 (2016)CrossRefGoogle Scholar
  27. 27.
    Cho, DH, Kim, JS, Kwon, SH, Lee, C, Lee, YZ, “Evaluation of Hexagonal Boron Nitride Nano-Sheets as a Lubricant Additive in Water.” Wear, 302 981–986 (2013)CrossRefGoogle Scholar
  28. 28.
    Shen, L, Zhao, Y, Wang, Y, Song, R, Yao, Q, Chen, S, Chai, Y, “A Long-Term Corrosion Barrier with an Insulating Boron Nitride Monolayer.” J. Mater. Chem. A, 4 5044–5050 (2016)CrossRefGoogle Scholar
  29. 29.
    Zhang, C, He, Y, Zhan, Y, Zhang, L, Shi, H, Xu, Z, “Poly(dopamine) Assisted Epoxy Functionalization of Hexagonal Boron Nitride for Enhancement of Epoxy Resin Anticorrosion Performance: Epoxy Resin Anticorrosion Performance.” Polym. Adv. Technol., 28 214–221 (2017)CrossRefGoogle Scholar
  30. 30.
    Cui, M, Ren, S, Qin, S, Xue, Q, Zhao, H, Wang, L, “Non-covalent Functionalized Hexagonal Boron Nitride Nanoplatelets to Improve Corrosion and Wear Resistance of Epoxy Coatings.” RSC Adv., 7 44043–44053 (2017)CrossRefGoogle Scholar
  31. 31.
    Husain, E, Narayanan, TN, Taha-Tijerina, JJ, Vinod, S, Vajtai, R, Ajayan, PM, “Marine Corrosion Protective Coatings of Hexagonal Boron Nitride Thin Films on Stainless Steel.” ACS Appl. Mater. Inter., 5 4129–4135 (2013)CrossRefGoogle Scholar
  32. 32.
    Zhao, H, Ding, J, Yu, H, “Efficient Exfoliation and Dispersion of hBN Nanoplatelets: Advanced Application on Waterborne Anticorrosion Coatings.” New J. Chem., 42 14433–14443 (2018)CrossRefGoogle Scholar
  33. 33.
    Stengl, V, Henych, J, Kormunda, M, “Self-Assembled BN and BCN Quantum Dots Obtained from High Intensity Ultrasound Exfoliated Nanosheets.” Sci. Adv. Mater., 6 1106–1116 (2014)CrossRefGoogle Scholar
  34. 34.
    Camurlu, HE, Mathur, S, Arslan, O, Akarsu, E, “Modification of Hexagonal Boron Nitride Nanoparticles with Fluorosilane.” Ceram. Inter., 42 6312–6318 (2016)CrossRefGoogle Scholar
  35. 35.
    Xiao, F, Naficy, S, Casillas, G, Khan, MH, Katkus, T, Jiang, L, Liu, H, Li, H, Huang, Z, “Edge-Hydroxylated Boron Nitride Nanosheets as an Effective Additive to Improve the Thermal Response of Hydrogels.” Adv. Mater., 27 7196–7203 (2015)CrossRefGoogle Scholar
  36. 36.
    ISO 14896: 2009 Polyurethane Raw Materials—Determination of Isocyanate Content.Google Scholar
  37. 37.
    ISO 2409: 2013 Paints and Varnishes—Cross-Cut Test.Google Scholar
  38. 38.
    ISO 15184: 2012 Paints and Varnishes—Determination of Film Hardness by Pencil Test.Google Scholar
  39. 39.
    Xu, GW, Waterborne Polyurethane Materials. Chemical Industry Press, Beijing (2006)Google Scholar
  40. 40.
    Li, J, Cui, J, Yang, J, Li, Y, Qiu, H, Yang, J, “Reinforcement of Graphene and its Derivatives on the Anticorrosive Properties of Waterborne Polyurethane Coatings.” Compos. Sci. Technol., 129 30–37 (2016)CrossRefGoogle Scholar
  41. 41.
    Li, J, Gan, L, Liu, Y, Mateti, S, Lei, W, Chen, Y, Yang, J, “Boron Nitride Nanosheets Reinforced Waterborne Polyurethane Coatings for Improving Corrosion Resistance and Antifriction Properties.” Eur. Polym. J., 104 57–63 (2018)CrossRefGoogle Scholar

Copyright information

© American Coatings Association 2019

Authors and Affiliations

  1. 1.Fujian Provincial Key Laboratory of Fire Retardant Materials, College of MaterialsXiamen UniversityXiamenPeople’s Republic of China
  2. 2.School of Civil Engineering and ArchitectureXiamen University of TechnologyXiamenPeople’s Republic of China

Personalised recommendations