Association and surface properties of tapered statistical copolymers of ethylene oxide and butylene oxide in water

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Ga-Er Yu, Dharmista Mistry, Sonia Ludhera, Frank Heatley, David Attwood and Colin Booth


Abstract

Two statistical copolymers of ethylene oxide (EO) and 1,2-butylene oxide (BO) of different compositions (80 and 60 mol% oxyethylene) were polymerised (anionic polymerisation with monofunctional initiation) to 100% conversion. Their molar masses (Mn≈5000 g mol-1) and molar mass distributions (Mw/Mn≈1.06) were similar. The disparity in reactivity ratios in the EO/BO copolymerisation resulted in pronounced composition drift along the chains (tapered statistical copolymers) giving them the character of diblock copolymers. The association behaviour of the copolymers in aqueous solution at 25°C was studied by dynamic and static light scattering and surface tension. It was confirmed that both formed micelles by a closed process. Surface activity, as measured by surface tension lowering, was superior to conventional EO/BO diblock copolymers with comparable micelle properties. Phase diagrams, determined over a wide concentration range (c⩽70 wt.%), showed regions of gel formation (liquid crystallinity) and clouding (phase separation).


References

  1. Y.-W. Yang, G. Brine, G.-E. Yu, F. Heatley, D. Attwood, C. Booth and M. Malmsten, Polymer, 1997, 38, 1659 CrossRef CAS.
  2. S. Dickson, G.-E. Yu, F. Heatley and C. Booth, Eur. Polym. J., 1993, 29, 281 CrossRef CAS.
  3. Y.-W. Yang, Z. Yang, Z.-K. Zhou, D. Attwood and C. Booth, Macromolecules, 1996, 29, 670 CrossRef CAS.
  4. Z. Yang, Y.-W. Yang, Z.-K. Zhou, D. Attwood and C. Booth, J. Chem. Soc., Faraday Trans., 1996, 92, 257 RSC.
  5. Z.-K. Zhou, Y.-W. Yang, C. Booth and B. Chu, Macromolecules, 1996, 29, 8357 CrossRef CAS.
  6. Y.-W. Yang, Z. Ali-Adib, N. B. McKeown, A. J. Ryan, D. Attwood and C. Booth, Langmuir, 1997, 13, 1860 CrossRef.
  7. G. Wanka, H. Hoffmann and W. Ulbricht, Macromolecules, 1994, 27, 4145 CrossRef.
  8. P. Alexandridis, J. F. Holzwarth and T. A. Hatton, Macromolecules, 1994, 27, 2414 CrossRef CAS.
  9. M. Almgren, W. Brown and S. Hvidt, Colloid Polym. Sci., 1995, 273, 2 CrossRef CAS.
  10. G.-E. Yu, H. Altinok, S. K. Nixon, C. Booth, P. Alexandridis and T. A. Hatton, Eur. Polym. J., 1997, 33, 673 CrossRef CAS.
  11. Y.-W. Yang, N.-J. Deng, G.-E. Yu, Z.-K. Zhou, D. Attwood and C. Booth, Langmuir, 1995, 11, 4703 CrossRef CAS.
  12. V. M. Nace, J. Am. Oil Chem. Soc., 1996, 73, 1 CrossRef CAS.
  13. G.-E. Yu, Y.-W. Yang, Z. Yang, D. Attwood, C. Booth and V. M. Nace, Langmuir, 1996, 12, 3404 CrossRef CAS.
  14. Nonionic Surfactants, Polyoxyalkylene Block Copolymers, ed. V. M. Nace, Surfactant Science Series Vol. 60, Marcel Dekker, New York, 1996 Search PubMed.
  15. A. D. Bedells, R. M. Arafeh, Z. Yang, D. Attwood, F. Heatley, J. C. Padget, C. Price and C. Booth, J. Chem. Soc., Faraday Trans., 1993, 89, 1235 RSC.
  16. H. Li, G.-E. Yu, C. Price, C. Booth, E. Hecht and H. Hoffmann, Macromolecules, 1997, 30, 1347 CrossRef CAS.
  17. F. Heatley, G.-E. Yu, W.-B. Sun, E. J. Pywell, R. H. Mobbs and C. Booth, Eur. Polym. J., 1990, 26, 583 CrossRef CAS.
  18. S. W. Provencher, Makromol. Chem., 1979, 180, 201 CrossRef CAS.
  19. D. E. Koppel, J. Chem. Phys., 1972, 57, 4814 CrossRef CAS.
  20. J. C. Brown and P. N. Pusey, J. Phys. D: Appl. Phys., 1974, 7, L31 Search PubMed.
  21. G.-E. Yu, Z.-K. Zhou, D. Attwood, C. Price, C. Booth, P. C. Griffiths and P. Stilbs, J. Chem. Soc., Faraday Trans., 1996, 92, 5021 RSC.
  22. D. Attwood and A. T. Florence, Surfactant Systems, Chapman and Hall, London, 1983, ch. 1 Search PubMed.
  23. G.-E. Yu, Z. Yang, D. Attwood, C. Price and C. Booth, Macromolecules, 1996, 29, 8479 CrossRef CAS.
  24. A. Vrij, J. Chem. Phys., 1978, 69, 1742 CrossRef CAS.
  25. N. F. Carnahan and K. E. Starling, J. Chem. Phys., 1969, 51, 635 CrossRef CAS.
  26. D. Attwood, J. H. Collett and C. J. Tait, Int. J. Pharm., 1985, 26, 25 CrossRef CAS.
  27. G.-E. Yu, Z. Yang, M. Ameri, D. Attwood, J. H. Collett, C. Price and C. Booth, J. Phys. Chem., Part B, 1997, 101, 4238 Search PubMed.
  28. D. Attwood and A. T. Florence, Surfactant Systems, Chapman and Hall, London, 1983, p. 101 Search PubMed.
  29. B. Chu and Z.-K. Zhou, in Nonionic Surfactants, Polyoxyalkylene Block Copolymers, ed. V. M. Nace, Surfactant Science Series Vol. 60, Marcel Dekker, New York, 1996, ch. 3 Search PubMed.
  30. C. Booth, G.-E. Yu and V. M. Nace, in Amphiphilic Block Copolymers: Self-Assembly and Applications, ed. P. Alexandridis and B. Lindman, Elsevier, Amsterdam, 1997 Search PubMed.
  31. S. Tanodekaew, N.-J. Deng, S. Smith, Y.-W. Yang, D. Attwood and C. Booth, J. Phys. Chem., 1993, 97, 11847 CrossRef CAS.
  32. N.-J. Deng, Y.-Z. Luo, S. Tanodekaew, N. Bingham, D. Attwood and C. Booth, J. Polym. Sci., Part B: Polym. Phys., 1995, 33, 1085 CrossRef CAS.
  33. J. A. Pople, I. W. Hamley, J. P. A. Fairclough, A. J. Ryan, B. U. Komanschek, A. J. Gleeson, G.-E. Yu and C. Booth, Macromolecules, in press Search PubMed.
  34. F. E. Bailey and R. W. Callard, J. Appl. Polym. Sci., 1959, 1, 56; 373.
  35. D. R. Beech and C. Booth, J. Polym. Sci., Polym. Phys. Ed., 1969, 7, 575 Search PubMed.
  36. M. J. Rosen, Surfactants and Interfacial Phenomena, John Wiley, New York, 2nd edn., 1989, p. 84 Search PubMed.
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