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Unified model of association-induced lower critical solution temperature phase separation and its application to solutions of telechelic poly(ethylene oxide) and of telechelic poly(N-isopropylacrylamide) in water

J. Chem. Phys. 125, 244902 (2006); doi:10.1063/1.2400230

Published 26 December 2006

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Yukinori Okada and Fumihiko Tanaka
Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Kyoto 615-8510, Japan

Piotr Kujawa and Françoise M. Winnik
Department of Chemistry, University of Montréal, CP 6128, Succursale Centre Ville, Montréal, Quebec H3C 3J7, Canada and Faculty of Pharmacy, University of Montréal, CP 6128, Succursale Centre Ville, Montréal, Quebec H3C 3J7, Canada
The authors present a model describing the coexistence of hydrophobic association and phase separation with lower critical solution temperature (LCST) in aqueous solutions of polymers carrying short hydrophobic chains at both chain ends (telechelic associating polymers). The LCST of these solutions is found to decrease along the sol/gel transition curve as a result of both end-chain association (association-induced phase separation) and direct hydrophobic interaction of the end chains with water. The authors relate the magnitude of the LCST decrease to a hydration cooperativity parameter sigma. The LCST decreases substantially (~100  K) in the case of random hydration (sigma=1), whereas only a small shift (~5–10  K) occurs in the case of cooperative hydration (sigma=0.3). The molecular weight dependence of the LCST drop is studied in detail in each case. The results are compared with experimental observations of the cloud points of telechelic poly(ethylene oxide) solutions, in which random hydration predominates, and of telechelic poly(N-isopropylacrylamide) solutions, in which cooperative hydration prevails. ©2006 American Institute of Physics
History: Received 29 September 2006; accepted 27 October 2006; published 26 December 2006
Permalink: http://link.aip.org/link/?JCPSA6/125/244902/1
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KEYWORDS and PACS

Keywords
PACS
  • 64.75.+g
    Solubility, segregation, and mixing; phase separation
  • 82.30.Nr
    Association, addition, insertion, cluster formation (chemical reactions)
  • 82.70.Gg
    Gels and sols
  • 61.25.Hq
    Structure of macromolecular and polymer solutions, and polymer melts; swelling
  • 61.20.Qg
    Structure of associated liquids including electrolytes, molten salts, etc
  • YEAR: 2006

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PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
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REFERENCES (43)
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  1. G. N. Malcolm and J. S. Rowlinson, Trans. Faraday Soc. 53, 921 (1953).
  2. S. Saeki, N. Kuwahara, M. Nakata, and M. Kaneko, Polymer 17, 685 (1976).
  3. Y. C. Bae, S. M. Lambert, D. S. Soane, and J. M. Prausnitz, Macromolecules 24, 4403 (1991).
  4. R. L. Cook, H. E. King, and D. G. Peiffer, Phys. Rev. Lett. 69, 3072 (1992).
  5. A. Matsuyama and F. Tanaka, Phys. Rev. Lett. 65, 341 (1990).
  6. K. Tasaki, J. Am. Chem. Soc. 118, 8459 (1996).
  7. M. Heskins and J. E. Guillet, J. Macromol. Sci., Chem. A2, 1441 (1968).
  8. S. Fujishige, K. Kubota, and I. Ando, J. Phys. Chem. 93, 3311 (1989).
  9. F. Afroze, E. Nies, and H. Berghmans, J. Mol. Struct. 554, 55 (2000).
  10. R. G. de Azevedo, L. P. N. Rebelo, A. M. Ramos, J. Szydlowski, H. C. de Sousa, and J. Klein, Fluid Phase Equilib. 185, 189 (2001).
  11. L. P. N. Rebelo, Z. P. Visak, H. C. de Sousa, J. Szydlowski, R. G. de Azevedo, A. M. Ramos, V. Najdanovic-Visak, M. N. da Ponte, and J. Klein, Macromolecules 35, 1887 (2002).
  12. A. Milewska, J. Szydlowski, and L. P. N. Rebelo, J. Polym. Sci., Part B: Polym. Phys. Ed. 41, 1219 (2003).
  13. Y. Okada and F. Tanaka, Macromolecules 38, 4465 (2005).
  14. T. Annable, R. Buscall, R. Ettelaie, and D. Whittlestone, J. Rheol. 37, 695 (1993).
  15. T. Annable, R. Buscall, R. Ettelaie, P. Shepherd, and D. Whittlestone, Langmuir 10, 1060 (1994).
  16. B. Rao, Y. Uemura, L. Dyke, and P. M. Macdonald, Macromolecules 28, 531 (1995).
  17. E. Alami, M. Almgren, W. Brown, and J. Francois, Macromolecules 29, 2229 (1996).
  18. E. Alami, M. Almgren, and W. Brown, Macromolecules 29, 5026 (1996).
  19. B. Xu, A. Yekta, and M. A. Winnik, Langmuir 13, 6903 (1997).
  20. K. C. Tam, R. D. Jenkins, M. A. Winnik, and D. R. Bassett, Macromolecules 31, 4149 (1998).
  21. F. Tanaka and W. H. Stockmayer, Macromolecules 27, 3943 (1994).
  22. F. Tanaka, in Molecular Gels, edited by G. Weiss and P. Terech (Kluwer Academic, London, 2004), Chap. 1.
  23. C. Tanford, The Hydrophobic Effects (Wiley, New York, 1980).
  24. E. Alami, M. Rawiso, F. Isel, G. Beinert, W. Binana-Limbele, and J. François, Adv. Chem. Ser. 248, 343 (1996).
  25. P. Kujawa, F. Segui, S. Shaban, C. Diab, Y. Okada, F. Tanaka, and F. M. Winnik, Macromolecules 39, 341 (2006).
  26. P. Kujawa, F. Tanaka, and F. M. Winnik, Macromolecules 39, 3048 (2006).
  27. F. Tanaka and M. Ishida, J. Chem. Soc., Faraday Trans. 91, 2663 (1995).
  28. P. J. Flory, J. Chem. Phys. 10, 51 (1942).
  29. P. J. Flory, Principles of Polymer Chemistry (Cornell University Press, Ithaca, NY, 1953), Chap. XII.
  30. K. Fukui and T. Yamabe, Bull. Chem. Soc. Jpn. 40, 2052 (1967).
  31. R. Motokawa, K. Morishita, S. Koizumi, T. Nakahira, and M. Annaka, Macromolecules 38, 5748 (2005).
  32. V. Degiorgio, in Physics of Amphiphiles: Micelles, Vesicles and Microemulsions, edited by V. Dergiogio and M. Corti (North-Holland, Amsterdam, 1985), Chap. V.
  33. S. Shirai and Y. Einaga, Polym. J. (Tokyo, Jpn.) 37, 913 (2005).
  34. F. Lafleche, D. Durand, and T. Nicolai, Macromolecules 36, 1331 (2003).
  35. W. H. Stockmayer, J. Chem. Phys. 11, 45 (1943);
    36. 12, 125 (1944).
  36. P. J. Flory, J. Am. Chem. Soc. 63, 3091 (1941);
    37. 63, 3096 (1941).
  37. R. M. Ziff and G. Stell, J. Chem. Phys. 73, 3492 (1980).
  38. A similar combinational method was employed by one of the authors to study partition functions of helical polymers whose helices are induced by hydrogen-bonded chiral side groups [F. Tanaka, Macromolecules 37, 605 (2004)].
  39. B. H. Zimm and J. K. Bragg, J. Chem. Phys. 31, 526 (1959).
  40. A. R. Schultz and P. J. Flory, J. Am. Chem. Soc. 74, 4760 (1952).
  41. F. Tanaka and T. Koga, Comput. Theor. Polym. Sci. 10, 259 (2000).
  42. S. Koizumi, M. Monkenbusch, D. Richter, D. Schwahn, and B. Farago, J. Chem. Phys. 121, 12721 (2004).
  43. R. Motokawa, S. Koizumi, F. M. Winnik, and F. Tanaka (unpublished).

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