Micellization of Ionic Block Copolymers in Three Dimensions

  • M. Moffitt
  • L. Zhang
  • K. Khougaz
  • A. Eisenberg
Part of the NATO ASI Series book series (NSSE, volume 327)


The self-assembly of block copolymers in selective solvents has become a topic of considerable interest to a growing number of research groups. Analogous to the association of surfactants in solution, the formation of spherical and non-spherical aggregates of block copolymers is a phenomenon of both academic and industrial relevance, attracting the efforts of theorists and experimentalists alike. The diverse range of studies in this area of colloidal science is described in several review articles [1–3].


Block Copolymer Reverse Micelle Block Length Aggregation Number Ionic Core 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Tuzar, Z., Kratochvil, P. (1976) Block an Graft Copolymer Micelles in Solution, In Advances in Colloid and Interface Science, vol.6, 201–232CrossRefGoogle Scholar
  2. 2.
    Price, C. (1982) Colloidal Developments in Block Copolymers, In Developments in Block Copolymers— 1; Goodman, I., Ed.; Elsevier App. Sc. Pub. U.K, 39–79.Google Scholar
  3. 3.
    Tuzar, Z., Kratochvil, P (1993) Micelles of Block and Graft Copolymers in Solution In Surface and Colloid Science; Matijevic, E., Ed.; Plenum Press. New York,1–83.CrossRefGoogle Scholar
  4. 4.
    Selb, J. and Gallot, Y. (1980) Copolymers with Polyvinylpyridinium Blocks or Grafts: Synthesis and Properties in Solution, In Polymeric Amines and Ammonium Salts. Goethals, E.J. Ed., Pergamon Press: New York, 205–218.Google Scholar
  5. 5.
    Selb, J and Gallot, Y. (1985) Ionic Block Copolymers, In Development in Block Copolymers; Goodman, I., Ed.; Elsevier Applied Science: London, U.K., vol 2, 27–96.Google Scholar
  6. 6.
    Jalal, N. and Duplessix, R. (1988) Aggregation of Monocarboxylic Chains by Neutralization: Neutron and X-Ray Scattering, J. Phys. France 49, 1775–1783.CrossRefGoogle Scholar
  7. 7a.
    Davidson, N.S., Fetters, L.J., Funk, W.G., Graessley, W.W., Hadjichristidis, N.(1988) Association Behavior in End-Functionalized Polymers. 1. Dilute Solution Properties of Polyisoprenes with Amine and Zwitterion End Groups, Macromolecules 21, 112–121.CrossRefGoogle Scholar
  8. 7b.
    Pispas, S. and Hadjichristidis, N.1994 Macromolecules 27, 1891-.Google Scholar
  9. 7c.
    Pispas, S., Hadjichristidis, N., Mays, J.M. (1994) Macromolecules 27, 6307.CrossRefGoogle Scholar
  10. 8.
    Zhong, X.F. and Eisenberg, A. (1994) Aggregation and Critical Micellization Behavior of Carboxylate-Terminated Monochelic Polystyrene, Macromolecules 27, 1751–1758.CrossRefGoogle Scholar
  11. 9.
    Zhong, X.F.X and Eisenberg, A.(1994) Synthesis and Characterization of 1,2 Dicarboxyethyl-Terminated Polystyrene, Macromolecules 27, 4914–4918.CrossRefGoogle Scholar
  12. 10.
    Gao, Z., Varshney, S.K., Wong, S. and Eisenberg, A. (1994) Block Copolymer “Crew-Cut” Micelles in Water, Macromolecules 27, 7923–7927.CrossRefGoogle Scholar
  13. 11.
    Zhang, L., Barlow, R.J. and Eisenberg, A. Scaling Relations and Coronal Dimensions in Aqueous Block Polyelectrolyte Micelles, Macromolecules, accepted for publication.Google Scholar
  14. 12.
    Zhang, L. and Eisenberg, A. Phase Behavior of “Crew-Cut” Micelle Formation in Solutions of Polystyrene-b-Poly(acrylic acid), paper in preparation.Google Scholar
  15. 13a.
    Zhang, L. and Eisenberg, A.(1995) Multiple Morphologies of “Crew-Cut” Aggregates of Polystyrene-fc-Poly(acylic acid) Block Copolymers, Science 268, 1728–1731.CrossRefGoogle Scholar
  16. 13b.
    b. Zhang, L. and Eisenberg, A. Chracteristics and Multiple Morphologies of “Crew-Cut” Micelle-like Aggregates of Polystyrene-b-Poly(acylic acid) Block Copolymers in Solution, paper in preparation.Google Scholar
  17. 14.
    Eisenberg, A. and Rinaudo, M. (1990) Polyelectrolytes and Ionomers, Polymer Bulletin 24, 671.CrossRefGoogle Scholar
  18. 15.
    Price, C. and Chan, E.K.M. and Stubbersfield, R.B. (1987) The Effect of Block Length on the Thermodynamic Stability of Micelles Formed by Polystyrene-block-Polyisoprene Copolymers in n-Hexadecane, Eur. Poly, J. 23, 649–651.CrossRefGoogle Scholar
  19. 16.
    Myers, D. (1988) Surfactant Science and Technology, VCH publishers; N.Y.Google Scholar
  20. 17.
    Wilhelm, M, Zhao, C.L., Wang, Y., Xu, R., Winnik, M.A., Mura, J.L., Riess, G., and Croucher, M.D. (1991) Poly(styrene ethylene oxide) Block Copolymer Micelle Formation in Water: A Fluorescence Probe Study, Macromolecules 24, 1033–1040.CrossRefGoogle Scholar
  21. 18.
    Nicolas, C.V., Luo, Y.Z., Deng, N.J., Attwood, D., Collet, J.H., Price, C, and Booth, C. (1993) Effect of Chain Length on the Micellization and Gelation of Block Copoly(oxyethylene/oxybutylene/oxyethylene) EmBnEm, Polymer 34, 138–144.CrossRefGoogle Scholar
  22. 19.
    Astafieva, I., Zhong, X.F. and Eisenberg, A. (1993) Critical Micellization Phenomena in Block Polyelectrolyte Solutions, Macromolecules 26, 7339–7352.CrossRefGoogle Scholar
  23. 20.
    Khougaz, K., Gao, Z., and Eisenberg, A.(1994) Determination of the Critical Micelle Concentration of Block Copolymer Micelles by Static Light Scattering, Macromolecules 27, 6341–6346.Google Scholar
  24. 21.
    Clarke, C., Lennox, B. and Eisenberg, A. 1995 Micellization of Block Copolymers in Two Dimensions, see subsequent chapter.Google Scholar
  25. 22.
    Ishizu, K., Kashi, Y., Fukutomi, T. and Kakurai, T. (1982) Synthesis of AB and BAB Poly(styrene-&-4-vinylpyridine) and Solution Properties of Their Quaternized Compounds., Makromol Chem 183, 3099–3107.CrossRefGoogle Scholar
  26. 23.
    Zhou, Z., Peiffer, D.J. and Chu, B. (1994) Light Scattering Studies of Block Ionomer Aggregation Characteristics in Nonpolar Sovents, Macromolecules 27, 1428–1433.CrossRefGoogle Scholar
  27. 24.
    Desjardins, A. and Eisenberg, A. (1991) Colloidal Properties of Block Ionomers. Characterization of Reverse Micelles of Styrene-b-Metal Methacrylate Diblocks by Size Exclusion Chromatography, Macromolecules 24, 5779–5790.Google Scholar
  28. 25.
    Desjardins, A., van de Ven, T.G.M. and Eisenberg, A. (1992) Colloidal Properties of Block Ionomers 2. Characterization of Reverse Micelles of Styrene-b-Methacrylic Acid and Styrene-b-Metal Methacrylate Diblocks by Dynamic Light Scattering, Macromolecules 25, 2412–2421.CrossRefGoogle Scholar
  29. 26.
    Nguyen, D., Williams, C.E. and Eisenberg, A. (1994) Block Ionomer Micelles in Solution 1. Characterization of Ionic Cores by Small-Angle X-ray Scattering, Macromolecules 27, 5090–5093.CrossRefGoogle Scholar
  30. 27.
    Halperin, A. (1989) Polymeric Micelles: A Star Model, Macromolecules 20, 2943–2946.CrossRefGoogle Scholar
  31. 28.
    Nguyen, D., Williams, C.E. and Eisenberg, A., results to be published.Google Scholar
  32. 30.
    Gao, Z., Desjardins, A. and Eisenberg, A. 1992 Solubilization Equilibria of Water in Nonaqueous Solutions of Block Ionomer Reverse Micelles: An NMR Study, Macromolecules 25, 1300–1303.CrossRefGoogle Scholar
  33. 29.
    Gao, Z., Zhong, X.F. and Eisenberg, A. (1994) Chain Dynamics in Coronas of Ionomer Aggregates, Macromolecules 27, 794–802.CrossRefGoogle Scholar
  34. 31.
    Khougaz, K., Gao, Z. and Eisenberg, A. Distribution of Water in Reverse Micellar Solutions of AOT XANDXBlock Copolymers Ionomers in Toluene-d8, paper in preparation.Google Scholar
  35. 32a.
    Moffitt, M., McMahon, L., Pessel, V. and Eisenberg, A. 1995 Size Control of Nanoparticles in Semiconductor-Polymer Composites. 2. Control via Sizes of Spherical Ionic Microdomains in Styrene-Based Diblock Ionomers, Chemistry of Materials, in pressGoogle Scholar
  36. 32b.
    Moffitt, M. and Eisenberg, A. (1995) Size Control of Nanoparticles in Semiconductor-Polymer Composites. 1. Control via Multiplet Aggregation Numbers in Styrene-Based Random Ionomers, Chemistry of Materials, in press.Google Scholar
  37. 33.
    Morishima, Y., Hashimoto, T., Itoh, Y., Kamachi, M., and Nozakura, S.-I. (1982) Syntheses of Amphiphilic Block Copolymers. Block Copolymers of Methacrylic Acid and p-N,N-dimethylaminostyrene, J. Polym Sci., Polym. Chem Ed. 20, 299–310.CrossRefGoogle Scholar
  38. 34.
    Morishima, Y., Itoh, Y., Hashimoto, T., and Nozakura, S.-I. (1982) Amphiphilic Block Copolymer of 9-Vinylphenanthrene and Methacrylic Acid: Fluorescence Quenching of Phenanthrene Residue in Aqueous Media, J. Polym. Sci., Polym. Chem. Ed. 20, 2007–2017.CrossRefGoogle Scholar
  39. 35.
    Valint, P.L. and Bock, J. (1988) Synthesis and Characterization of Hydrophobically Associating Block Polymers, Macromolecules 21, 175–179.CrossRefGoogle Scholar
  40. 36.
    Cao, T., Munk, P., Ramireddy, C., Tuzar, Z., and Webber, S.E. (1991) Fluorescence Studies of Amphiphilic Poly(methacrylic acid)-block-Polystyrene-block-Poly(methacrylic acid) Micelles, Macromolecules 24, 6300–6305.CrossRefGoogle Scholar
  41. 37.
    Kiserov, D., Prochazka, K., Ramireddy, C., Tuzar, Z., Munk, P., and Webber, S.E. (1992) Fluorimetric and Quasi-Elastic Light Sattering Study of the Solubilization of Nonpolar Low-Molar Mass Compounds into Water-Soluble Block-Copolymer Micelles, Macromolecules 25, 461–469.CrossRefGoogle Scholar
  42. 38.
    Astafieva., I., Khougaz, K., and Eisenberg, A. Micellization in Block Polyelectrolyte Solutions. II. Fluorescence Study on the cmc as a Function of Soluble Block Length and Salt Concentration, Submitted for publication in Macromolecules Google Scholar
  43. 39.
    Khougaz, K., Astafieva., I., and Eisenberg, A. Micellization in Block Polyelectrolyte Solutions. Ill Static Light Scattering Characterization, Submitted for publication in Macromolecules Google Scholar
  44. 40.
    Dan, N. and Tirrell, M. (1993) Self-Assembly of Block Copolymers with a Strongly Charged and a Hydrophobic Block in a Selective, Polar Solvent. Micelles and Adsorbed Layers, Macromolecules 26, 4310.CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 1996

Authors and Affiliations

  • M. Moffitt
    • 1
  • L. Zhang
    • 1
  • K. Khougaz
    • 1
  • A. Eisenberg
    • 1
  1. 1.Department of ChemistryMcGill UniversityMontrealCanada

Personalised recommendations