Skip to main content
SpringerLink
Log in

Influence of the association of hydrophobic end groups on the temperature insensitivity of HEUR-thickened latex/Fe2O3/Zn3(PO4)2/BaSO4 suspensions

  • Published:
Journal of Coatings Technology and Research Aims and scope Submit manuscript

Abstract

Hydrophobically modified ethoxylated urethane (HEUR) with different structures was synthesized and confirmed by gel permeation chromatography, Fourier transform infrared spectroscopy and nuclear magnetic resonance (1H NMR). We propose the relationship between the temperature insensitivity model and the thickening mechanism of HEUR/latex/Fe2O3/Zn3(PO4)2/BaSO4 suspensions. Meanwhile, the temperature insensitivity of HEUR/C suspensions is the result of two main associations: intermolecular interactions bridging the hydrophobic tails of HEURs and the hydrophobic groups tightly adsorbing onto the latex particle surfaces. A smaller ratio of viscosity (Rv) at 1 s−1 from the steady state condition indicates the better temperature insensitivity of viscosity. The higher degree of crystallinity and rheological activation energy corresponds to a great extent with better temperature insensitivity due to stronger association. The temperature insensitivity is consistent with the longer hydrophobic chain, which was proven by hysteresis tests and oscillatory shear measurements. The storage stability was enhanced in the lockstep with a hydrophobic length of HEUR, which is consistent with the rougher surfaces of HEUR/C films. As an appealing method, the results are meaningful and instructive for coating storage and application.

Graphical abstract

An intermolecular network model of HEUR/C is presented, which suggests intermolecular associations in the bridging of hydrophobic tails and the hydrophobic groups adsorbing onto the latex particle surfaces. A temperature insensitivity mechanism model combined with rheology results and AFM is also proposed to clarify the relationship between temperature insensitivity and storage stability and the hydrophobic tail length.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

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

Similar content being viewed by others

References

  1. Uneyama, T, Suzuki, S, Watanabe, H, “Concentration Dependence of Rheological Properties of Telechelic Associative Polymer Solutions.” Phys. Rev. E, 86 (3–1) 031802 (2012)

    Article  Google Scholar 

  2. Tam, KC, Jenkins, RD, Winnik, MA, et al. “A Structural Model of Hydrophobically Modified Urethane−Ethoxylate (HEUR) Associative Polymers in Shear Flows.” Macromolecules, 31 (13) 4149–4159 (1998)

    Article  CAS  Google Scholar 

  3. Xie, A, Chen, H, Xu, C, et al. “Synthesis and Characterization of Waterborne Polyurethane Thickeners Based on Hyperbranched Polyester.” J. Coat. Technol. Res., 12 (2) 325–332 (2014)

    Article  Google Scholar 

  4. Sarrafi, M, Kaffashi, B, Barmar, M, “Study of the Simultaneous Effects of MMT Nanoclay and Hydrophobically Modified Ethoxylated Urethane (HEUR) on Viscoelastic and Steady Shear Properties of Water-Based Acrylic Resins.” J. Coat. Technol. Res., 10 (5) 727–731 (2013)

    Article  CAS  Google Scholar 

  5. Yin, W, Zeng, X, Li, H, et al. “Steady Rheological Behaviors of UV-Curable Waterborne Hyperbranched Polyurethane Acrylate Dispersions.” J. Coat. Technol. Res., 10 (1) 57–64 (2012)

    Article  Google Scholar 

  6. Suzuki, S, Uneyama, T, Inoue, T, et al. “Nonlinear Rheology of Telechelic Associative Polymer Networks: Shear Thickening and Thinning Behavior of Hydrophobically Modified Ethoxylated Urethane (HEUR) in Aqueous Solution.” Macromolecules, 45 (2) 888–898 (2012)

    Article  CAS  Google Scholar 

  7. Birjandi Nejad, H, Paczkowski, MA, Malajati, Y, Melkowits, RB, “Polyurethane Rheology Modifiers for Organic Compositions.” J. Appl. Polym. Sci., 135 46372 (2018)

    Article  Google Scholar 

  8. Bhavsar, RA, Nehete, KM, “Rheological Approach to Select most Suitable Associative Thickener for Water-Based Polymer Dispersions and Paints.” J. Coat. Technol. Res., 16 1089–1098 (2019)

    Article  CAS  Google Scholar 

  9. Xu, C, Chen, H, Xie, A, Chen, H, Zhou, Y, Li, Y, Yang, M, “Study on Associating Thickening Mechanism and Structure–Efficiency Relationship of Hyperbranched Waterborne Polyurethane.” Prog. Org. Coat., 92 73–79 (2016)

    Article  CAS  Google Scholar 

  10. Chatterjee, T, Nakatani, AI, Van Dyk, AK, “Shear-Dependent Interactions in Hydrophobically Modified Ethylene Oxide Urethane (HEUR) Based Rheology Modifier-Latex Suspensions: Part 1. Molecular Microstructure.” Macromolecules, 47 1155–1174 (2014)

    Article  CAS  Google Scholar 

  11. Yang, P, Bai, L, Wang, W, Rabasco, J, “Analysis of Hydrophobically Modified Ethylene Oxide Urethane Rheology Modifiers by Comprehensive Two Dimensional Liquid Chromatography.” J. Chromatogr. A, 1560 55–62 (2018)

    Article  CAS  Google Scholar 

  12. Ginzburg, VV, Chatterjee, T, Nakatani, AI, Van Dyk, AK, “Oscillatory and Steady Shear Rheology of Model Hydrophobically Modified Ethoxylated Urethane-Thickened Waterborne Paints.” Langmuir, 3 10993–11002 (2018)

    Article  Google Scholar 

  13. Horigome, M, Yada, M, Isoda, T, “Rheological Behavior of PMMA Powder/ Associating Polymer Suspensions.” Nihon Reoroji Gakk., 26 (3) 157–162 (1998)

    Article  CAS  Google Scholar 

  14. Liao, D, Dai, S, Tam, KC, “Influence of Anionic Surfactant on the Rheological properties of Hydrophobically Modified Polyethylene-Oxide/Cyclodextrin Inclusion Complexes.” J. Rheol., 53 (2) 293–308 (2009)

    Article  CAS  Google Scholar 

  15. Du, Z, Wang, F, Chang, X, Peng, J, Ren, B, “Influence of Substituted Structure of Percec-Type Mini-Dendritic End Groups on Aggregation and Rheology of Hydrophobically Modified Ethoxylated Urethanes (HEURs) in Aqueous Solution.” Polymer, 135 131–141 (2018)

    Article  CAS  Google Scholar 

  16. Wang, F, Peng, J, Dong, R, Chang, X, Ren, B, Tong, Z, “Highly Efficient Hydrophobically Modified Ethoxylated Urethanes (HEURs) End-Functionalized by Two-Tail Dendritic Hydrophobes: Synthesis, Solution Rheological Behavior and Thickening in Latex.” Colloid Surf. A., 502 114–120 (2016)

    Article  CAS  Google Scholar 

  17. Peng, J, Dong, R, Ren, B, Chang, X, Tong, Z, “Novel Hydrophobically Modified Ethoxylated Urethanes End-Capped by Percec-Type Alkyl Substituted Benzyl Alcohol Dendrons: Synthesis, Characterization, and Rheological Behavior.” Macromolecules, 47 5971–5981 (2014)

    Article  CAS  Google Scholar 

  18. Peng, J, Guan, T, Ren, B, “Study on Thickening Mechanism and Thickening Efficiency of Polyurethane Associated Thickener.” Guangdong Chemical Industry, 48 135-136+138 (2021)

    Google Scholar 

  19. Rubio-Hernández, FJ, López-Galbeño, A, Muñoz-Cabezas, AM, Ruiz-Martín, D, Gómez-Merino, AI, Páez-Flor, NM, Delgado-García, R, “Rheological Study of the Anatase/Latex Polystyrene System.” Rev. Mex. de Ing. Quim., 15 (2) 655–665 (2016)

    Article  Google Scholar 

  20. He, C, Zeng, J, Luo, Y, “Method for Preparing Waterborne Styrene-Acrylate Emulsion Used in Common Waterborne Metal Primer.” CN Patent 107698706 (2017)

  21. Xu, J, Koelling, KW, “Temperature Dependence of Rheological Behavior of a Metallic Automotive Waterborne Basecoat.” Prog. Org. Coat., 53 169–176 (2005)

    Article  CAS  Google Scholar 

  22. Matia-Merino, L, Goh, K, Singh, KTH, “A Natural Shear-Thickening Water-Soluble Polymer From the Fronds of The Black Tree Fern, Cyathea medullaris: Influence of Salt, pH and Temperature.” Carbohydr. Polym., 87 131–138 (2012)

    Article  CAS  Google Scholar 

  23. Annable, T, Buscall, R, Ettelaie, R, Whittlestone, D, “The Rheology of Solutions of Associating Polymers: Comparison of Experimental Behavior with Transient Network Theory.” J. Rheol., 37 (4) 695–726 (1993)

    Article  CAS  Google Scholar 

  24. Lu, M, Song, C, Wan, B, “Thixotropic Behavior of Hydrophobically Modified Ethoxylated Urethane-thickened Waterborne Latex.” Chem. J. Chinese Universities, 41 1108–1119 (2020)

    CAS  Google Scholar 

  25. Yan, G, “Rheopectical Properties of Nano-scale Calcium Carbonate Filled DOP Suspension.” China Powder Sci. Technol., 4 4 (2016)

    Google Scholar 

  26. Barnes, HA, “Thixotropy: A Review.” J. Non-Newtonian Fluid Mech., 70 (1) 1–33 (1997)

    Article  CAS  Google Scholar 

  27. Osterhold, M, “Rheological Methods for Characterising Modern Paint Systems.” Prog. Org. Coat., 40 131–137 (2000)

    Article  CAS  Google Scholar 

  28. Ferry, JD, Viscoelastic Properties of Polymers. Wiley, New York (1980)

    Google Scholar 

  29. Maghazechi, A, Nafchi, AM, Tan, TC, Seow, EK, Easa, AM, “Rheological Characterization of Coconut Cream Emulsion Using Steady-State Shear and Time-Dependent Modeling.” J. Food Eng., 306 110642 (2021)

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The financial support from the NSFC (51203050).

Author information

Authors and Affiliations

  1. School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200241, China

    Yating Lin & Chunmei Song

  2. Shanghai Synuo Chemical Technology Limited Company, Shanghai, 201600, China

    Xiong Xiao & Bo Wan

Authors
  1. Yating Lin
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Chunmei Song
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Xiong Xiao
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Bo Wan
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Chunmei Song.

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 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

Lin, Y., Song, C., Xiao, X. et al. Influence of the association of hydrophobic end groups on the temperature insensitivity of HEUR-thickened latex/Fe2O3/Zn3(PO4)2/BaSO4 suspensions. J Coat Technol Res 20, 587–601 (2023). https://doi.org/10.1007/s11998-022-00692-0

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11998-022-00692-0

Keywords

Search

Navigation