Synergistic Surface Activities and Phase Behavior in Mixtures of a Diglyceryl Cationic Surfactant and a Conventional Anionic Surfactant

디글리세릴계 양이온계면활성제와 일반 음이온계면활성제 혼합물에서의 계면활성 상승효과와 상거동

  • 최정진 ((주) LG생활건강 기술연구원) ;
  • 조완구 (전주대학교 대체의학대학 건강자원학부) ;
  • 랑문정 (배재대학교 분자과학부)
  • Received : 2008.04.11
  • Accepted : 2008.05.31
  • Published : 2008.08.31

Abstract

In general, anionic and cationic surfactants are incompatible because their mixtures form insoluble complexes and precipitate in the water. There are, however, some equimolar complexes of anionic and cationic surfactant that are soluble and behave like regular surfactants, specifically like nonionic surfactants, thus named pseudo-nonionic surfactant complexes. Pseudo-nonionic complexes are more effective and efficient in surface activities than their ionic surfactant components as shown by their equilibrium and dynamic surface tensions. They pack at the interface more than their ionic components. When a novel cationic surfactant, diglyceryl dodecyl dimethyl ammonium chloride(DGDAC), having the polyhydroxyl group at the hydrophilic head group, was mixed with a conventional anionic surfactant (sodium dodecyl sulfate; SDS) at equimolar ratio, we found that the aqueous equimolar mixture showed strong positive synergism in which molecular interaction parameter ${\beta}^M$ was very low, -17.2. According to the studies of equilibrium phase behavior and microscopy, this mixed system could form homogenous solutions containing vesicles.

일반적으로 음이온계면활성제와 양이온계면활성제는 수용액상에서 침전하는 불용성복합물을 형성하기 때문에 상용성이 좋지 않다. 하지만 경우에 따라서 일부 음이온계면활성제와 양이온계면활성제의 1:1 molar complex (catanionic surfactant)는물에용해하면서비이온계면활성제와같이행동하기때문에유사비이온계면활성제복합물(pseudo-nonionic surfactant complex)이라고 부른다. 유사비이온계면활성제복합물은 일반적인 이온성계면활성제에 비해 보다 용이하게 계면에 배열되기 때문에 평형 및 동적 표면장력에서 우수한 계면활성효과를 나타낸다. 계면활성제의 친수성 head group에 polyhydroxyl group을 가진 디글리세릴계 양이온계면활성제인 diglyceryl dodecyl dimethyl ammonium chloride(DGDAC)과 음이온계면활성제 sodium dodecyl sulfate(SDS)를 1:1 molar ratio로 수용액상에서 혼합하였을 경우 molecular interaction parameter ${\beta}^M$가 -17.2로 매우 강한 positive synergism을 보였으며. 평형 상거동과 현미경에 의한 실험결과는 이 DGDAC와 SDS의 혼합수용액은 single phase의 vesicle을 형성함을 알 수 있었다.

Keywords

Acknowledgement

Supported by : 배재대학교

References

  1. Holmberg, K. (Ed.), Handbook of Applied Surface and Colloid Chemistry, John Wiley & Sons, New York, NY(2002)
  2. Meyer, D., Surfactant Science and Technology, 3rd ed., John Wiley & Sons, Hoboken, NJ(2006)
  3. Rang, M. J. (Ed.), Recent Trend on Colloid and Surface Chemistry, Korean Federation of Science and Technology Societies and Korean Society of Industrial and Engineering Chemistry(2007)
  4. Scamehorn, J. F. (Ed.), Phenomena in Mixed Surfactant Systems, ACS Symposium Series 311, American Chemical Society, Washington, DC(1986)
  5. Holland, P. M. and Rubingh, D. M., Mixed Surfactant Systems, ACS Symposium Series 501. American Chemical Society, Washington, DC(1992)
  6. Ogino, K. and Abe, M., Mixed Surfactant Systems, Surfactant Science Series Vol. 46, Marcel Dekker, New York, NY(1993)
  7. Khan, A. and Marques, E., "Catanionic Surfactants," In Specialist Surfactants, Robb, I.D.(Ed.), Blackies Academic and Professional, London, 37-80(1997)
  8. Abe, M. and Scamehorn, J. F., Mixed Surfactant Systems, 2nd ed., Surfactant Science Series Vol. 124, Marcel Dekker, New York, NY(2004)
  9. Dixit, S. G. and Naik, P., "Cationic and Anionic Surfactant Interaction," in P. Somasundaran(Ed.), Encyclopedia of Surface and Colloid Science, 2nd ed., Taylor & Francis, Boca Raton, FL, 1190-1198(2006)
  10. Rosen, M. J., "Molecular Interactions and Synergism in Mixtures of Two Surfactants," Surfactants and Interfacial Phenomena, 3rd ed., John Wiley & Sons, Hoboken, NJ, 379-414(2004)
  11. Frese, C., Rupport, S., Schmidt-Lewerkuhne, H., Wittern, K. P., Eggers, R., Fainerman, V. B. and Miller, R., J. Colloid and Inter. Sci., 267(2), 475-482(2003) https://doi.org/10.1016/S0021-9797(03)00614-3
  12. Fainerman, V. B. and Lucassen-Reynols, E. H., Adv. Colloid Interface Sci., 96(1-3), 295-323(2002) https://doi.org/10.1016/S0001-8686(01)00086-0
  13. Stellner, K. L., Amante, J. C. and Harwell, J. H., "Precipitation Phenomenon in Mixtures of Anionic and Cationic Surfactants in aqueous Solutions," J. Colloid Interface Sci., 123(1), 186-200(1988) https://doi.org/10.1016/0021-9797(88)90235-4
  14. Amante, J. C., Scamehorn, J. F. and Harwell, J. H., "Precipitation of Mixtures of Anionic and Cationic Surfactants," J. Colloid Interface Sci., 144(1), 243-253(1991) https://doi.org/10.1016/0021-9797(91)90255-7
  15. Hreczuch, W., G. Bekierz, and J. Szymanowski, "Homologue Distribution of Alcohol Ethoxylates," Tenside, Surfactants, Detergents, 32(1), 55-60(1995)
  16. Mehreteab, A. and Lorest, F., "Anionic/Cationic Surfactant Mixtures," US patent No. 5472455(1995)
  17. Mehreteab, A. and Lorest, F., "Anionic/Cationic Surfactant Mixtures," US patent No. 5441541(1995)
  18. Singh, A. P., "Detergent Compositions," US patent No. 6555513(2003)
  19. Singh, A. P., "Detergent Compositions," US patent No. 6608016(2003)
  20. Levitt, M. D., Los, T. J., Besse, M. E., Hei, R. D., Hoyt, J. D., O'Connor, C. and Man, V. F., "Composition and Method for Road-Film Removal," US Patent 6864220(2005)
  21. Tsuchiya, K., Ishikake, J., Kim, T. S., Ohkubo, T., Sakai, H. and Abe, M., "Phase Behavior of Mixed Solution of a Glycerin-modified Cationic Surfactant and an Anionic Surfactant," J. Colloid Interface Sci., 312(1), 139-145(2007) https://doi.org/10.1016/j.jcis.2006.07.075
  22. Cho, W. G. and Choi, J. J., "Synthesis and Evaluation of N-(2,3-dihydroxypropyl)-N,N-dimethyldodecane-1-amine Chloride," J. Korean Oil Chemists Society, 25(1), 23-31(2008)
  23. Mekuro, K., Progress and Practice in Colloid Science, Nikko Chemical, 100(1987)
  24. Rubingh, D. N., in K. L. Mittal (Ed.), Solution Chemistry of Surfactants, Vol.1, Plenum, New York, NY, 337-354(1979)
  25. Jiang, R., Zhao, J. and Ma, Y., Colloids Surf. A, 289(1-3), 233-236(2006) https://doi.org/10.1016/j.colsurfa.2005.10.098
  26. Jiang, R., Zhao, J. and Ma, Y., J. Colloid and Inter. Sci., 297(2), 412-418(2006) https://doi.org/10.1016/j.jcis.2005.10.066
  27. Frese, C., Rupport, S., Schmidt-Lewerkuhne, H., Wittern, K. P., Eggers, R., Fainerman, V. B. and Miller, R., Colloids and Surfaces A, 239(1-3), 33-40(2004) https://doi.org/10.1016/j.colsurfa.2003.11.033
  28. Frese, C., Rupport, S., Schmidt-Lewerkuhne, H., Wittern, K. P., Eggers, R., Fainerman, V. B. and Miller, R., J. Colloid and Inter. Sci., 267(2), 475-482(2003) https://doi.org/10.1016/S0021-9797(03)00614-3
  29. Kumar, A., Alami, E., Homberg, K., Seredyuk, V. and Menger, F. M., Colloids and Surfaces A, 228(1-3), 197-207(2003) https://doi.org/10.1016/S0927-7757(03)00300-5
  30. Rosen, M. J. and Gao, T., "Dynamic Surface Tension of Aqueous Surfactant Solutions," J. Colloid Interface Sci., 173(1), 42-48(1995) https://doi.org/10.1006/jcis.1995.1294
  31. Fainerman, V. D., Makievski, A. V. and Miller, R., "The Analysis of Dynamic Surface Tension of Sodium Alkyl Sulphate Solutions, Based on Asymptotic Equations of Adsorption Kinetic Theory," Colloids and Surfaces A, 87(1), 61-75(1994) https://doi.org/10.1016/0927-7757(94)02747-1
  32. Reid, R. C., Prausnitz, J. M. and Poling, B. E., The Properties of Gases and Liquids, 4th ed., McGraw-Hill, New York, NY, 597(1987)
  33. Patist, A., Chhabra, V., Pagidipati, R., Shah, R. and Shah, D. O., Langmuir, 13(3), 432-434(1997) https://doi.org/10.1021/la960838t
  34. Kaler, E. W., Murthy, A. K., Rodriguez, B. E. and Zasadzinski, J. A. N., "Spontaneous Vesicle Formation in Aqueous Mixtures of Single-tailed Surfactants," Science, 245(4924), 1371-1374(1989) https://doi.org/10.1126/science.2781283
  35. Israelachvili, J., Intermolecular and Surface Forces, 2nd ed., Academic Press, San Diego, 380-382(1992)
  36. Jung, H. T., Coldren, B., Zasadzinski, J. A., Lampietro, J. and Kaler, E. W., "The Origins of Stability of Spontaneous Vesicles," PNAS, 98(4), 1353-1357(2001)
  37. Kaler, E. W., Herrington, K. L., Murthy, A. K. and Zasadzinski, J. A. N., "Phase Behavior and Structures of Mixtures of Anionic and Cationic Surfactants," J. Phys. Chem., 96(16), 6698-6707(1992) https://doi.org/10.1021/j100195a033