Skip to main content
SpringerLink
Log in

Effect of Steric Hindrance on the Aggregation Behavior of Cationic Silicone Surfactants in Aqueous Solutions

  • Published:
Journal of Solution Chemistry Aims and scope Submit manuscript

Abstract

To study the effect of steric hindrance on the surface activities and thermodynamics of cationic silicone surfactants, the adsorption and aggregation behavior of cationic silicone surfactants with different siloxane hydrophobic groups and headgroups, bis(trimethylsiloxy)methylsilylpropylpyridinium chloride (Si3pyrCl), N,N,N-triethyl-3-[tri(trimethylsiloxy)]silylpropylammonium chloride (Si4AEtCl), and 3-[tri(vinyldimethylsiloxy)methyl]silylpropylpyridinium chloride (Vi–Si4pyrCl), were investigated by surface tension, electrical conductivity, DLS, TEM, and 2D NOESY NMR measurements. All the three cationic silicone surfactants have excellent surface activity. Owing to the steric hindrance of hydrophobic groups and headgroups, the CMC values increase following the order Vi–Si4pyrCl < Si4AEtCl < Si3pyrCl. The micellization process of Si3pyrCl and Si4AEtCl in aqueous solution is enthalpy-driven, while Vi–Si4pyrCl is entropy-driven at low temperature and enthalpy-driven at high temperature and the degree of counterion binding of Vi–Si4pyrCl increases as the temperature increases, caused by the intermolecular interaction between the pyridinium group and vinyldimethylsiloxy hydrophobic region of the micelles. Moreover, the results obtained in this paper can be useful in understanding the structure-properties relationship of cationic silicone surfactants and the design of novel silicone surfactants.

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

Access this article

Log in via an institution

Subscribe and save

Springer+ Basic
$34.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or eBook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

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

Similar content being viewed by others

References

  1. Hill, R.M.: Silicone Surfactants. Marcel Dekker, New York (1999)

    Google Scholar 

  2. Hill, R.M.: Silicone surfactants—new development. Curr. Opin. Colloids Interface Sci. 7, 255–261 (2002)

    Article  CAS  Google Scholar 

  3. Wang, G., Zhu, Y.Y., Zhai, Y.H., Wang, W.X., Du, Z.P., Qin, J.Q.: Polyglycerol modified polysiloxane surfactants: their adsorption and aggregation behavior in aqueous solution. J. Ind. Eng. Chem. 47, 121–127 (2017)

    Article  CAS  Google Scholar 

  4. Bao, Y., Guo, J., Ma, J.Z., Liu, P., Kang, Q.L., Zhang, J.: Cationic silicon-based gemini surfactants: effect of hydrophobic chains on surface activity, physic-chemical properties and aggregation behaviors. J. Ind. Eng. Chem. 53, 51–61 (2017)

    Article  CAS  Google Scholar 

  5. Xu, A.W., Yu, J.C., Cai, Y.P., Zhang, H.X., Zhang, L.Z.: The preparation of a highly ordered long-range lamellar silica structure with large interlayer spacings. Chem. Commun. 15, 1614–1615 (2002)

    Article  CAS  Google Scholar 

  6. Sun, B., Guo, C.Y., Yao, Y., Che, S.: Functional group-template integrated ABC copolymer silicone surfactant directing for highly hydrophobic mesoporous silica. J. Mater. Chem. 22, 19076–19080 (2012)

    Article  CAS  Google Scholar 

  7. Tan, J.L., Xiong, X.M., He, Z.Y., Cao, F., Sun, D.S.: Aggregation behavior of polyether based siloxane surfactants in aqueous solutions: effect of alkyl groups and steric hindrance. J. Phys. Chem. B 123, 1390–1399 (2019)

    Article  CAS  PubMed  Google Scholar 

  8. Fang, P.X., Bai, Y.Y., Ma, X.Y., Tai, X.M., Wang, W.X., Wang, G.Y.: Novel coal and siloxane based surfactants: bola polysiloxanes modified with butynediol-ethoxylate and their properties. J. Ind. Eng. Chem. 59, 208–217 (2018)

    Article  CAS  Google Scholar 

  9. Soni, S.S., Sastry, N.V., Joshi, J.V., Seth, E., Goyal, P.S.: Study on the effects of nonelectrolyte additives on the phase, thermodynamics, and structural changes in micelles of silicone surfactants in aqueous solutions from surface activity, small angle neutron scattering, and viscosity measurements. Langmuir 19, 6668–6677 (2003)

    Article  CAS  Google Scholar 

  10. Gentle, T.E., Snow, S.A.: Adsorption of small silicone polyether surfactants at the airwater interface. Langmuir 11, 2905–2910 (1995)

    Article  CAS  Google Scholar 

  11. Kanner, B., Reid, W.G., Petersen, I.H.: Synthesis and properties of siloxane–polyether copolymer surfactants. I&EC Prod. Res. Dev. 6, 88–92 (1967)

    Article  CAS  Google Scholar 

  12. Snow, S.A., Fenton, W.N., Owen, M.J.: Synthesis and characterization of zwitterionic silicone sulfobetaine surfactants. Langmuir 6, 385–391 (1990)

    Article  CAS  Google Scholar 

  13. Kunieda, K., Uddin, M.H., Horii, M., Furukawa, H., Harashima, A.: Effect of hydrophilic- and hydrophobic-chain lengths on the phase behavior of A–B type silicone surfactants in water. J. Phys. Chem. B 105, 5419–5426 (2001)

    Article  CAS  Google Scholar 

  14. Czajka, A., Hill, C., Peach, J., Pegg, J.C., Grillo, I., Guittard, F., Rogers, S.E., Sagisaka, M., Eastoe, J.: Trimethylsilyl hedgehogs: a novel class of super-efficient hydrocarbon surfactants. Phys. Chem. Chem. Phys. 19, 23869–23877 (2017)

    Article  CAS  PubMed  Google Scholar 

  15. Du, Z.P., Li, E., Cao, Y., Li, X., Wang, G.: Synthesis of trisiloxane-tailed surface active ionic liquids and their aggregation behavior in aqueous solution. Colloids Surf. A 441, 744–751 (2014)

    Article  CAS  Google Scholar 

  16. Wang, G.Y., Li, X., Du, Z.P., Li, E.Z., Li, P.: Butynediol-ethoxylate based trisiloxane: structural characterization and physico-chemical properties in water. J. Mol. Liq. 197, 197–203 (2014)

    Article  CAS  Google Scholar 

  17. Han, F., Zhang, G.Y.: New family of Gemini surfactants with glucosamide-based trisiloxane. Colloids Surf. A 237, 79–85 (2004)

    Article  CAS  Google Scholar 

  18. Frampton, M.B., Marquardt, D., Letofsky-Papst, I., Pabst, G., Zelisko, P.M.: Analysis of trisiloxane phosphocholine bilayers. Langmuir 33, 4948–4953 (2017)

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  19. Zhao, X.H., Liang, W.P., An, D., Ye, Z.W.: Synthesis and properties of tetrasiloxane Gemini imidazolium surfactants. Colloid Polym. Sci. 294, 491–500 (2016)

    Article  CAS  Google Scholar 

  20. Tan, J.L., Ma, D.P., Feng, S.Y., Zhang, C.Q.: Effect of headgroups on the aggregation behavior of cationic silicone surfactants in aqueous solution. Colloids Surf. A 417, 146–153 (2013)

    Article  CAS  Google Scholar 

  21. Tan, J.L., Zhao, P.J., Ma, D.P., Feng, S.Y., Zhang, C.Q.: Effect of hydrophobic chains on the aggregation behavior of cationic silicone surfactants in aqueous solution. Colloid Polym. Sci. 291, 1487–1494 (2013)

    Article  CAS  Google Scholar 

  22. Fang, L.Y., Tan, J.L., Zheng, Y., Li, H.N., Li, C.W., Feng, S.Y.: Effect of organic salts on the aggregation behavior of tri-(trimethylsiloxy)silylpropylpyridinium chloride in aqueous solution. Colloids Surf. A 509, 48–55 (2016)

    Article  CAS  Google Scholar 

  23. Czajka, A., Hazell, G., Eastoe, J.: Surfactants at the design limit. Langmuir 31, 8205–8217 (2015)

    Article  CAS  PubMed  Google Scholar 

  24. Qin, J.Q., Du, Z.P., Ma, X.Y., Zhu, Y.Y., Wang, G.Y.: Effect of siloxane backbone length on butynediol-ethoxylate based polysiloxanes. J. Mol. Liq. 214, 54–58 (2016)

    Article  CAS  Google Scholar 

  25. Hao, C., Cui, Y., Yang, P., Zhang, H., Mao, D., Cui, X., Li, J.: Effect of siloxane spacer length on organosilicon bi-quaternary ammonium amphiphiles. Colloids Surf. B 128, 528–536 (2015)

    Article  CAS  Google Scholar 

  26. Zhang, S.H., Yan, H., Zhao, M.W., Zheng, L.Q.: Aggregation behavior of gemini pyrrolidine-based ionic liquids 1,1′-(butane-1,4-diyl)bis(1-alkylpyrrolidinium) bromide ([Cnpy-4-Cnpy][Br2]) in aqueous solution. J. Colloid Interface Sci. 372, 52–57 (2012)

    Article  CAS  PubMed  Google Scholar 

  27. Shi, L.J., Li, N., Yan, H., Gao, Y.A., Zheng, L.Q.: Aggregation behavior of long-chain N-aryl imidazolium bromide in aqueous solution. Langmuir 27, 1618–1625 (2011)

    Article  CAS  PubMed  Google Scholar 

  28. Dong, B., Zhao, X.Y., Zheng, L.Q., Zhang, J., Li, N., Inoue, T.: Aggregation behavior of long-chain imidazolium ionic liquids in aqueous solution: micellization and characterization of micelle microenvironment. Colloids Surf. A 317, 666–672 (2008)

    Article  CAS  Google Scholar 

  29. Vekariya, R.L., Kumar, N.S.: Micellization behaviour of surface active N-alkyl pyridinium dodecylsulphate task-specific ionic liquids in aqueous solutions. Colloids Surf. A 529, 203–209 (2017)

    Article  CAS  Google Scholar 

  30. Rosen, M.J.: Surfactants and Interfacial Phenomena. Wiley, New York (1989)

    Google Scholar 

  31. Zhang, Q., Gao, Z.N., Xu, F., Tai, S.X.: Effect of hydrocarbon structure of the headgroup on the thermodynamic properties of micellization of cationic gemini surfactants: an electrical conductivity study. J. Colloid Interface Sci. 371, 73–81 (2012)

    Article  CAS  PubMed  Google Scholar 

  32. Gao, Y.A., Li, N., Li, X.W., Zhang, S.H., Zheng, L.Q., Bai, X.T., Yu, L.: Microstructures of micellar aggregations formed within 1-butyl-3-methylimidazol-ium type ionic liquids. J. Phys. Chem. B 113, 123–130 (2009)

    Article  CAS  PubMed  Google Scholar 

  33. Nusselder, J.J.H., Engerts, J.B.F.N.: Toward a better understanding of the driving force for micelle formation and micellar growth. J. Colloid Interface Sci. 148, 353–361 (1992)

    Article  CAS  Google Scholar 

  34. Buckingham, S.A., Garvey, C.J., Warr, G.G.: Effect of head-group size on micellization and phase behavior in quaternary ammonium surfactant systems. J. Phys. Chem. 97, 10236–10244 (1993)

    Article  CAS  Google Scholar 

  35. Miki, K., Westh, P., Nishikawa, K., Koga, Y.: Effect of an “ionic liquid” cation, 1-butyl-3-methylimidazolium, on the molecular organization of H2O. J. Phys. Chem. B 109, 9014–9019 (2005)

    Article  CAS  PubMed  Google Scholar 

  36. Wang, G.Y., Zhu, Y.Y., Zhai, Y.H., Wang, W.X., Du, Z.P., Qin, J.Q.: Polyglycerol modified polysiloxane surfactants: their adsorption and aggregation behavior in aqueous solution. J. Ind. Eng. Chem. 47, 121–127 (2017)

    Article  CAS  Google Scholar 

  37. Yoshimura, T., Ohno, A., Esumi, K.: Equilibrium and dynamic surface tension properties of partially fluorinated quaternary ammonium salt gemini surfactants. Langmuir 22, 4643–4648 (2006)

    Article  CAS  PubMed  Google Scholar 

  38. Li, P., Wang, W.X., Du, Z.P., Wang, G.Y., Li, E.Z., Li, X.: Adsorption and aggregation behavior of surface active trisiloxane room-temperature ionic liquids. Colloids Surf. A 450, 52–58 (2014)

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We gratefully acknowledge the financial support from the National Natural Science Foundation of China (Nos. 21563016 and 21862009).

Author information

Authors and Affiliations

  1. School of Chemical and Environmental Engineering, Jiujiang University, Jiujiang, 332005, China

    Jinglin Tan, Ziyan He, Yongxiang Miao & Dezhi Zhou

  2. Jiangxi Province Engineering Research Center of Ecological Chemical Industry, Jiujiang, 332005, China

    Jinglin Tan & Dezhi Zhou

Authors
  1. Jinglin Tan
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Ziyan He
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yongxiang Miao
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Dezhi Zhou
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Jinglin Tan or Dezhi Zhou.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Tan, J., He, Z., Miao, Y. et al. Effect of Steric Hindrance on the Aggregation Behavior of Cationic Silicone Surfactants in Aqueous Solutions. J Solution Chem 48, 891–904 (2019). https://doi.org/10.1007/s10953-019-00888-w

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10953-019-00888-w

Keywords

Search

Navigation