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Syneresis and rheology mechanisms of a latex-HEUR associative thickener system

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Abstract

This study focuses on the phase behavior, rheology, and interactions of polymer latex particles and a hydrophobically modified ethoxylated urethane (HEUR) associative thickener in water. At constant 0.25 latex particle volume fraction, increasing HEUR caused stable, followed by phase separated (syneresis), and stable mixtures as HEUR concentration increased from 0% to 2.0% (by weight) in the latex-thickener aqueous mixture. The mixtures that underwent syneresis were flocculated. The relationship between the flocculation behavior and the composition of the latex-HEUR mixtures is consistent with previous work reported by other investigators. However, detailed rheological data on systems like these that have undergone syneresis have not been reported. This paper presents detailed viscosity vs shear rate data and correlates viscosity trends with the both flocculation and syneresis behavior. The stable latex-HEUR mixtures at low HEUR levels show Newtonian or shear-thinning viscosity with well-defined low-shear Newtonian plateaus. As HEUR level is increased to levels at which syneresis is observed, erratic rheological profiles with shear thinning as well as thickening are observed. This type of shear thickening has been attributed to bridging flocculation by other investigators. When HEUR level is further increased to levels at which no syneresis is observed, low-shear Newtonian plateaus re-appeared, albeit at higher viscosities. Detailed analysis of syneresis and shear-thickening behavior of a latex-HEUR mixture containing 0.5% (by weight) HEUR showed two shear-thickening regions, one between 0.1 and 0.5 s−1 shear rate range and another between 30 and 100 s−1 shear rate range. Molecular weight distribution (MWD) of the HEUR thickener indicates that the two shear-thickening regions are related to the bi-modal nature of the thickener’s MWD.

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References

  1. Kostansek, E, “Using Dispersion/Flocculation Phase Diagrams to Visualize Interactions of Associative Polymers, Latexes, and Surfactants.” J. Coat. Technol., 75 1–8 (2003)

    Article  Google Scholar 

  2. Glass, JE, “A Perspective on the History of and Current Research in Surfactant-Modified, Water-Soluble Polymers.” J. Coat. Technol., 73 (913) 79–98 (2001)

    Article  Google Scholar 

  3. Thibeault, T, Sperry, PR, Schaller, EJ, “Effect of Surfactants and Cosolvents on the Behavior of Associative Thickeners in Latex Systems, Chapter 20.” In: Glass, JE (ed.) Water Soluble Polymers: Beauty with Performance, Advances in Chemistry Series 213. American Chemical Society, Washington, DC (1986)

    Google Scholar 

  4. Glass, JE, Fernando, RH, Egland-Jongewaard, SK, Brown, RG, “The Influence of Associative Thickeners on Coating Performance: Part I. Small-Particle, all Acrylic Latex Studies.” J. Oil Colour Chem. Assoc., 67 (10) 256–261 (1984)

    Google Scholar 

  5. Yekta, A, Duhamel, J, Adiwijaja, H, Brochard, P, Winnik, MA, “Association Structure of Telechelic Associative Thickeners in Water.” Langmuir, 4 881–883 (1993)

    Article  Google Scholar 

  6. Hulden, M, “Hydrophobically Modified Urethane-Ethoxylate (HEUR) Associative Thickeners 1. Rheology of Aqueous Solutions and Interactions with Surfactants.” Colloid. Surf. A: Physiochem. Eng. Aspects, 82 263–277 (1994)

    Article  Google Scholar 

  7. Mahli, DM, Steffenhagen, MJ, Xing, L, Glass, JE, “Surfactant Behavior and its Influence on the Viscosity of Associative Thickeners Solutions, Thickened Latex Dispersions, and Waterborne Latex Coatings.” J. Coat. Technol., 75 (938) 39–51 (2003)

    Article  Google Scholar 

  8. Chen, M, Wetzel, WH, Ma, Z, Glass, JE, “Unifying Model for Understanding HEUR Associative Thickener Influences on Waterborne Coatings: I. HEUR Interactions with a Small Particle Latex.” J. Coat. Technol., 69 (867) 73–80 (1997)

    Article  Google Scholar 

  9. Dai, S, Tam, KC, Jenkins, RD, “Microstructure of Dilute Telechelic Associative Polymer in Sodium Dodecyl Sulfate Solutions.” Macromolecules, 34 4673–4675 (2001)

    Article  Google Scholar 

  10. Annable, T, Buscall, R, Ettelaie, R, Shepherd, P, Whittlestone, D, “Influence of Surfactants on the Rheology of Associating Polymers in Solution.” Langmuir, 10 1060–1070 (1994)

    Article  Google Scholar 

  11. Wang, Y, Winnick, M, “Onset of Aggregation for Water-Soluble Polymeric Associative Thickeners: A Fluorescence Study.” Langmuir, 6 (9) 1437–1439 (1990)

    Article  Google Scholar 

  12. Jenkins, RD, Bassett, DR, “Synergistic Interactions Among Associative Polymers and Surfactants.” In: Asua, JM (ed.) Polymeric Dispersions: Principles and Applications (NATO Science Series E), pp. 477–495. Springer, Dordrecht (1997)

    Chapter  Google Scholar 

  13. Pham, QT, Russel, WB, Lau, W, “The Effects of Adsorbed Layers and Solution Polymer on the Viscosity of Dispersions Containing Associative Polymers.” J. Rheol., 42 (1) 159–176 (1998)

    Article  Google Scholar 

  14. Saucy, D, “Avoiding Viscosity Loss on Tinting.” Paint Coat. Ind., 24 2–5 (2008)

    Google Scholar 

  15. Herrick, DJ, Boke, JW, Htet, MY, Fernando, RH, “The Effects of Color Concentrates on the Rheology of Tint Bases.” JCT CoatingsTech, 10 34–40 (2013)

    Google Scholar 

  16. Schaller, EJ, Sperry, PR, “Associative Thickeners.” In: Calbo, LJ (ed.) Handbook of Coatings Additives, Vol. 2, pp. 105–163. Marcel Dekker, New York (1987)

    Google Scholar 

  17. Karunasena, A, Glass, JE, “Interactions in Associative Thickener/220 nm Methyl Methacrylate Latex Dispersions.” Progr. Org. Coat., 17 301–320 (1989)

    Article  Google Scholar 

  18. Ma, Z, Lundburg, DJ, Roberts, S, Glass, JE, “Phase Behaviors and Film Properties of Dispersions and Coatings Containing Associative and Conventional Thickeners.” J. Appl. Polym. Sci., 49 1509–1527 (1993)

    Article  Google Scholar 

  19. Iler, RK, “Relation of Particle Size of Colloidal Silica to the Amount of a Cationic Polymer Required for Flocculation and Surface Coverage.” J. Colloid Interface Sci., 37 364 (1971)

    Article  Google Scholar 

  20. Bharti, B, Meissner, J, Klapp, SHL, Findenegg, GH, “Bridging Interactions of Proteins with Silica Nanoparticles: The Influence of pH, Ionic Strength and Protein Concentration.” Soft Matter, 10 718–728 (2014)

    Article  Google Scholar 

  21. Otsubo, Y, “A Nonlinear Elastic Model for Shear Thickening of Suspensions Flocculated by Reversible Bridging.” Langmuir, 15 1960–1965 (1999)

    Article  Google Scholar 

  22. Fleer, GL, Lyklema, J, “Polymer Adsorption and its Effect on the Stability of Hydrophobic Colloids. II. The Flocculation Process as Studied with the Silver Iodide-Polyvinyl Alcohol System.” J. Colloid Interface Sci., 46 1 (1974)

    Article  Google Scholar 

  23. Richey, B, Kirk, AB, Eisenhart, EK, Fitzwater, S, Hook, J, “Interactions of Associative Thickeners with Paint Compositions as Studied by the Use of Fluorescently Labeled Model Thickener.” J. Coat. Technol., 63 (798) 31–40 (1991)

    Google Scholar 

  24. Xu, B, Yekta, A, Winnik, MA, “Viscoelastic Properties in Water of Comb Associative Polymers Based on Poly(Ethylene oxide).” Langmuir, 13 6903–6911 (1997)

    Article  Google Scholar 

  25. Wagner, NJ, Brady, JF, “Shear Thickening in Colloidal Dispersions.” Phys. Today, 62 27 (2009)

    Article  Google Scholar 

  26. Metzner, AB, Whitlock, M, “Flow Behavior of Concentrated (Dilatant) Suspensions.” Trans. Soc. Rheol., 2 239–254 (1958)

    Article  Google Scholar 

  27. Boersma, WH, Laven, J, Stein, HN, “Shear Thickening (Dilatancy) in Concentrated Dispersions.” AIChE J., 36 (3) 321 (1990)

    Article  Google Scholar 

  28. Ma, SX, Cooper, SL, “Shear-Thickening in Aqueous Solutions of Hydrocarbon End-Capped Poly(Ethylene oxide).” Macromolecules, 34 3294–3301 (2001)

    Article  Google Scholar 

  29. Manion, SJ, Johnson, LL, Fernando, RH, “Shear-Thickening in Aqueous Surfactant-Associative Thickener Mixtures.” J.Coat. Technol. Res., 8 (3) 299–309 (2011)

    Article  Google Scholar 

  30. Beshah, K, Izmitli, A, Van Dyk, AK, Rabasco, JJ, Bohling, J, “Diffusion-Weighted PFGNMR Study of Molecular Level Interactions of Loops and Direct Bridges of HEURs on Latex Particles.” Macromolecules, 46 2216–2227 (2013)

    Article  Google Scholar 

  31. Bell, TJ, Fernando, RH, Ness, J, Street, C, Booth, K, Korenkiewicz, S, “Dispersion Phase Diagrams for HEUR-Thickened Acrylic Paint Systems.” JCT CoatingsTech, 12 32–39 (2015)

    Google Scholar 

  32. May, R, Kaczmarski, JP, Glass, JE, “Influence of Molecular Weight Distributions on HEUR Aqueous Solution Rheology.” Macromolecules, 29 4745–4753 (1996)

    Article  Google Scholar 

Download references

Acknowledgments

Several student authors of this work acknowledge the financial support provided through Cal Poly’s Bill Moore and Arthur C Edwards Endowments. One of the students (T. J. Bell) received financial and facility support through a graduate internship at Valspar Corporation R&D Center, and his work with Valspar scientists inspired the current study. All remaining students utilized the facilities of Cal Poly’s Kenneth N. Edwards Western Coatings Technology Center for their work.

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Authors and Affiliations

  1. Polymers and Coatings Program, Department of Chemistry and Biochemistry, California Polytechnic State University, San Luis Obispo, CA, USA

    Franceska A. Santos, Tyler J. Bell, Alexandra R. Stevenson, Dana J. Christensen, Michaela R. Pfau, Brendan Q. Nghiem, Christopher R. Kasprzak, Travis B. Smith & Raymond H. Fernando

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  1. Franceska A. Santos
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  2. Tyler J. Bell
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  3. Alexandra R. Stevenson
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  4. Dana J. Christensen
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  5. Michaela R. Pfau
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  6. Brendan Q. Nghiem
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  7. Christopher R. Kasprzak
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  8. Travis B. Smith
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  9. Raymond H. Fernando
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Correspondence to Raymond H. Fernando.

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Santos, F.A., Bell, T.J., Stevenson, A.R. et al. Syneresis and rheology mechanisms of a latex-HEUR associative thickener system. J Coat Technol Res 14, 57–67 (2017). https://doi.org/10.1007/s11998-016-9829-x

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