Journal of Solution Chemistry

, Volume 47, Issue 9, pp 1539–1552 | Cite as

Solvation Behaviors of Poly(acrylic acid) in Mixed Solvents of 2-Butoxyethanol + Water

  • Zhiyun Chen
  • Sihan Yu
  • Doudou Liu
  • Shaoxiong Shi
  • Weiguo ShenEmail author


Poly(acrylic acid) (PAA) is a well known weak polyelectrolyte in water but little is known about the solvation behavior of PAA in the mixtures of alcohol + water. In this study, the solvation behavior of PAA in the mixed solvents composed of 2-butoxyethanol (2BE) + water were investigated by measurements of volumetric properties, electrical conductivity, resonance light scattering and dynamic light scattering. All the measured experimental properties showed extrema or abrupt changes at a 2BE mole fraction of about 0.017 in 2BE + water. This may be explained by the formation of aggregates of 2BE and water, which is a poor solvent for PAA and results in cononsolvency of PAA in the mixture of the two good solvents, 2BE and water. We found that the volumetric property is sensitive to the occurrence of the specific aggregate of 2BE and water and the interactions in the complex fluid mixtures.


Volumetric property 2-Butoxyethanol Poly(acrylic acid) Cononsolvency 



This work was supported by the National Natural Science Foundation of China (Projects 21403067 and 21373085).

Supplementary material

10953_2018_809_MOESM1_ESM.docx (107 kb)
Supplementary material 1 (DOCX 106 kb)


  1. 1.
    Subramanian, D., Boughter, C.T., Klauda, J.B., Hammouda, B., Anisimov, M.A.: Mesoscale inhomogeneities in aqueous solutions of small amphiphilic molecules. Faraday Discuss. 167, 217–238 (2013)CrossRefGoogle Scholar
  2. 2.
    Zemánková, K., Troncoso, J., Cerdeiriña, C.A., Romaní, L.: Generality of hydrophobic phenomena for aqueous solutions of amphiphiles. Chem. Phys. Lett. 640, 184–187 (2015)CrossRefGoogle Scholar
  3. 3.
    Indra, S., Biswas, R.: Heterogeneity in (2-butoxyethanol + water) mixtures: hydrophobicity-induced aggregation or criticality-driven concentration fluctuations? J. Chem. Phys. 142, 204501 (2015)CrossRefGoogle Scholar
  4. 4.
    Roux, G., Perron, G., Desnoyers, J.E.: Model systems for hydrophobic interactions: volumes and heat capacities of n-alkoxyethanols in water. J. Solution Chem. 7, 639–654 (1978)CrossRefGoogle Scholar
  5. 5.
    Chiou, D.R., Chen, S.Y., Chen, L.J.: Density, viscosity and refractive index for water + 2-butoxyethanol and + 2-(2-butoxyethoxy)ethanol at various temperatures. J. Chem. Eng. Data 55, 1012–1016 (2010)CrossRefGoogle Scholar
  6. 6.
    Douhéret, G., Pal, A.: Dielectric constants and densities of aqueous mixtures of 2-alkoxyethanols at 25 °C. J. Chem. Eng. Data 33, 40–43 (1988)CrossRefGoogle Scholar
  7. 7.
    Douhéret, G., Davis, M.I., Reis, J.C.R., Fjellanger, I.J., Vaage, M.B., Høiland, H.: Aggregative processes in aqueous solutions of isomeric 2-butoxyethanols at 298.15 K. Phys. Chem. Chem. Phys. 4, 6034–6042 (2002)CrossRefGoogle Scholar
  8. 8.
    Elizalde, F., Gracia, J., Costas, M.: Effect of aggregates in bulk and surface properties. Surface tension, foam stability and heat capacities for 2-butoxyethanol + water. J. Phys. Chem. 92, 3565–3568 (1988)CrossRefGoogle Scholar
  9. 9.
    D’Angelo, M., Onori, G., Santucci, A.: Study of aggregation of n-butoxyethanol in water by compressibility and surface tension measurements. Chem. Phys. Lett. 220, 59–63 (1994)CrossRefGoogle Scholar
  10. 10.
    Lara, J., Desnoyers, J.E.: Isentropic compressibilities of alcohol–water mixtures at 25 °C. J. Solution Chem. 10, 465–478 (1981)CrossRefGoogle Scholar
  11. 11.
    Kato, S., Jobe, D., Rao, N.P., Ho, C.H., Verrall, R.E.: Ultrasonic relaxation studies of 2-butoxyethanol–water and 2-butoxyethanol–water–cetyltrimethylammonium bromide solutions as a function of composition. J. Phys. Chem. 90, 4167–4174 (1986)CrossRefGoogle Scholar
  12. 12.
    Koga, Y.: Vapor pressures of aqueous 2-butoxyethanol solutions at 25 °C: transitions in mixing scheme. J. Phys. Chem. 95, 4119–4126 (1991)CrossRefGoogle Scholar
  13. 13.
    Koga, Y., Westh, P., Moriya, Y., Kawasaki, K., Atake, T.: High temperature end of the so-called “Koga Line”: anomalies in temperature derivatives of heat capacities. J. Phys. Chem. B 113, 5885–5890 (2009)CrossRefGoogle Scholar
  14. 14.
    Vollmer, D., Vollmer, J., Wagner, A.J.: Oscillatory kinetics of phase separation in a binary mixture under constant heating. Phys. Chem. Chem. Phys. 4, 1380–1385 (2002)CrossRefGoogle Scholar
  15. 15.
    Mallamace, F., Micali, N., D’Arrigo, G.: Dynamical effects of supramolecular aggregates in water–butoxyethanol mixtures studied by viscosity measurements. Phys. Rev. A 44, 6652–6658 (1991)CrossRefGoogle Scholar
  16. 16.
    Yoshida, K., Baluja, S., Inaba, A., Koga, Y.: Acceleration of the effect of solute on the entropy–volume cross fluctuation density in aqueous 2-butoxyethanol, 1-propanol, and glycerol: the fourth derivative of Gibbs energy. J. Chem. Phys. 134, 214502 (2011)CrossRefGoogle Scholar
  17. 17.
    Micali, N., Trusso, S., Vasi, C., Mallamace, F., Lombardo, D.: Rotational dynamics of water molecules in a water–short-chain-nonionic-amphiphile mixture: depolarized light scattering. Phys. Rev. E 51, 2349–2355 (1995)CrossRefGoogle Scholar
  18. 18.
    Ito, N., Saito, K., Kato, T., Fujiyama, T.: Observation of mutual diffusion coefficients and cooperative motions in binary solutions of t-butyl alcohol–water and 2-butoxyethanol–water. Bull. Chem. Soc. Jpn. 54, 991–997 (1981)CrossRefGoogle Scholar
  19. 19.
    Bender, T.M., Pecora, R.: Dynamic light scattering measurements of mutual diffusion coefficients of water-rich 2-butoxyethanol/water systems. J. Phys. Chem. 92, 1675–1677 (1988)CrossRefGoogle Scholar
  20. 20.
    Troncoso, J., Zemánková, K., Jover, A.: Dynamic light scattering study of aggregation in aqueous solutions of five amphiphiles. J. Mol. Liq. 241, 525–529 (2017)CrossRefGoogle Scholar
  21. 21.
    D’Arrigo, G., Giordano, R., Teixeira, J.: Small-angle neutron scattering studies of aqueous solutions of short-chain amphiphiles. Eur. Phys. J. E 10, 135–142 (2003)CrossRefGoogle Scholar
  22. 22.
    Koehler, R.D., Schubert, K.V., Strey, R., Kaler, E.W.: The Lifshitz line in binary systems: structures in water/C4E1 mixtures. J. Chem. Phys. 101, 10843–10849 (1994)CrossRefGoogle Scholar
  23. 23.
    Gupta, R., Patey, G.N.: Association and microheterogeneity in aqueous 2-butoxyethanol solutions. J. Phys. Chem. B 115, 15323–15331 (2011)CrossRefGoogle Scholar
  24. 24.
    Pattenaude, S.R., Rankin, B.M., Mochizuki, K., Ben-Amotz, D.: Water-mediated aggregation of 2-butoxyethanol. Phys. Chem. Chem. Phys. 18, 24937–24943 (2016)CrossRefGoogle Scholar
  25. 25.
    Bennes, R., Douillard, J.M., Privat, M., Tenebre, L.: An ellipsometric study of the liquid–vapor interface of a binary system near its lower consolute solution temperature: water–2-butoxyethanol. J. Phys. Chem. 89, 1822–1825 (1985)CrossRefGoogle Scholar
  26. 26.
    Toyouchi, S., Kajimoto, S., Barzan, D., Kiel, A., Enderlein, J., Fukumura, H., Herten, D.P.: Observation of unusual molecular diffusion behaviour below the lower critical solution temperature of water/2-butoxyethanol mixtures by using fluorescence correlation spectroscopy. Chem. Phys. Chem. 15, 3832–3838 (2014)CrossRefGoogle Scholar
  27. 27.
    Perera, A., Mazighi, R., Kežić, B.: Fluctuations and micro-heterogeneity in aqueous mixtures. J. Chem. Phys. 136, 174516 (2012)CrossRefGoogle Scholar
  28. 28.
    Cowie, J.M.G., Mohsin, M.A., McEwen, I.J.: Alcohol–water cosolvent systems for poly(methyl methacrylate). Polymer 28, 1569–1572 (1987)CrossRefGoogle Scholar
  29. 29.
    Pica, A., Graziano, G.: An alternative explanation of the cononsolvency of poly(N-isopropylacrylamide) in water–methanol solutions. Phys. Chem. Chem. Phys. 18, 25601–25608 (2016)CrossRefGoogle Scholar
  30. 30.
    Zhang, G.Z., Wu, C.: Reentrant coil-to-globule-to-coil transition of a single linear homopolymer chain in a water/methanol mixture. Phys. Rev. Lett. 86, 822–825 (2001)CrossRefGoogle Scholar
  31. 31.
    Walter, J., Sehrt, J., Vrabec, J., Hasse, H.: Molecular dynamics and experimental study of conformation change of poly(N-isopropylacrylamide) hydrogels in mixtures of water and methanol. J. Phys. Chem. B 116, 5251–5259 (2012)CrossRefGoogle Scholar
  32. 32.
    Cai, J.L., Bo, S.Q., Cheng, R.S.: Division of the concentration ranges of polyelectrolyte solutions. Acta Polym. Sin. 5, 625–627 (2004)Google Scholar
  33. 33.
    Molisso, A., Mangiapia, G., D’Errico, G., Sartorio, R.: Interaction of poly(vinyl alcohol) with poly(acrylic acid) and with sodium polyacrylate in aqueous solutions: a volumetric study at 25 °C. J. Solution Chem. 39, 1627–1635 (2010)CrossRefGoogle Scholar
  34. 34.
    Philippova, O.E., Hourdet, D., Audebert, R., Khokhlov, A.R.: pH-responsive gels of hydrophobically modified poly(acrylic acid). Macromolecules 30, 8278–8285 (1997)CrossRefGoogle Scholar
  35. 35.
    Li, Y.B., Chen, X.D., Zhang, M.Q., Luo, W.A., Yang, J., Zhu, F.M.: Macromolecular aggregation of aqueous polyacrylic acid in the presence of surfactants revealed by resonance Rayleigh scattering. Macromolecules 41, 4873–4880 (2008)CrossRefGoogle Scholar
  36. 36.
    Fitzgerald, D.: Technical assessment of the Anton Paar DMA 5000 density meter. H&D Fitzgerald Ltd., St Asaph (2000)Google Scholar
  37. 37.
    Pasternack, R.F., Bustamante, C., Collings, P.J., Giannetto, A., Gibbs, E.J.: Porphyrin assemblies on DNA as studied by a resonance light-scattering technique. J. Am. Chem. Soc. 115, 5393–5399 (1993)CrossRefGoogle Scholar
  38. 38.
    Dondos, A., Tsitsilianis, C., Staikos, G.: Viscometric study of aggregation phenomena in polymer dilute solutions and determination of the critical concentration c **. Polymer 30, 1690–1694 (1989)CrossRefGoogle Scholar
  39. 39.
    Wandrey, C.: Concentration regimes in polyelectrolyte solutions. Langmuir 15, 4069–4075 (1999)CrossRefGoogle Scholar
  40. 40.
    Friedman, S., Caillé, A., Daoust, H.: Apparent molal volume of poly(acrylic acid) in aqueous solution. Macromolecules 3, 700–702 (1970)CrossRefGoogle Scholar
  41. 41.
    Tondre, C., Zana, R.: Apparent molal volumes of polyelectrolytes in aqueous solutions. J. Phys. Chem. 76, 3451–3459 (1972)CrossRefGoogle Scholar
  42. 42.
    Ise, N., Okubo, T.: The partial molal volume of polyelectrolytes. J. Am. Chem. Soc. 90, 4527–4533 (1968)CrossRefGoogle Scholar
  43. 43.
    Škerjanc, J.: Volume change on dilution and on protonation of polycarboxylates in aqueous solutions. J. Phys. Chem. 82, 2313–2316 (1978)CrossRefGoogle Scholar
  44. 44.
    Du, C.F., He, W., Yin, T.X., Shen, W.G.: Volumetric properties of water/AOT/isooctane microemulsions. Langmuir 30, 15135–15142 (2014)CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  • Zhiyun Chen
    • 1
  • Sihan Yu
    • 1
  • Doudou Liu
    • 1
  • Shaoxiong Shi
    • 1
  • Weiguo Shen
    • 1
    • 2
    Email author
  1. 1.School of Chemistry and Molecular EngineeringEast China University of Science and TechnologyShanghaiChina
  2. 2.Department of ChemistryLanzhou UniversityLanzhouChina

Personalised recommendations