The propagation rate-constants in cationic polymerisations

  • P. H. Plesch
Conference paper
Part of the Advances in Polymer Science book series (POLYMER, volume 8)


An observer who is accustomed to the relative clarity and simplicity of radical and anionic polymerisations and the abundance of information about them might suggest that “Much Ado about Nothing” would be an appropriate sub-title to this article. The fact is indeed that in the field of cationic polymerisation there are still only very few rate-constants which can be regarded as well substantiated. In this situation we have deliberately refrained here from quoting and criticising in detail each and every claim to have measured a rateconstant. Instead, we thought it more useful to explore the origins of the present unsatisfactory position, and to indicate some guide-lines which will help in the planning of future researches.

It now appears that much more careful thought is required in the selection of systems which may offer the prospect of yielding unambiguous results. In particular, the choice of solvent and initiator must be considered very carefully, and features such as mechanisms of initiation, catalyst efficiency, nature of end-groups, and the internal order of reactions need to be explored much more thoroughly than has been customary in the past. Too much effort has been wasted by ignoring the precept: “First the Chemistry, then the Kinetics”.


Vinyl Ether Cyclic Ether Paired Cation Ethylene Dichloride Methylene Dichloride 
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.
    Bauer, R. F., LaFlair, R. T., Russell, K. E.: Can. J. Chem. 48, 1251 (1970).CrossRefGoogle Scholar
  2. 2.
    From Greek enioi = several, eidos = form or image; monoeidic = one form; dieidic = two forms.Google Scholar
  3. 3.
    Gandini, A., Plesch, P. H.: S. C. I. Monograph No. 20, p. 107, (1966).Google Scholar
  4. 4.
    Plesch, P. H.: Pure Appl. Chem. 12, 117 (1966).CrossRefGoogle Scholar
  5. 5a.
    Szwarc, M.: Carbanions, Living Polymers, and Electron-Transfer Processes: New York: Interscience 1968.Google Scholar
  6. 5b.
    — Adv. Chem. Ser. 91, 263 (1969).Google Scholar
  7. 5c.
    Plesch, P. H.: Progr. High Polymers, Vol. II, 137–288. Robb, J. C., Peaker, F. W., (Eds.), London: Iliffe Books 1968.Google Scholar
  8. 6.
    Longworth W. R., Mason, C. P.: J. Chem. Soc. (A), 1164 (1966).Google Scholar
  9. 7.
    Kalfoglou, N., Szwarc, M.: J. Phys. Chem. 72, 2233 (1968).CrossRefGoogle Scholar
  10. 8.
    Lee, W. Y., Treloar, F. E.: J. Phys. Chem. 73, 2458 (1969).CrossRefGoogle Scholar
  11. 9.
    Ledwith, A.: Adv. Chem. Ser., No. 91, 317 (1969).CrossRefGoogle Scholar
  12. 10.
    Jones, F. R., Plesch, P. H.: Chem. Commun. 1018 (1970).Google Scholar
  13. 11.
    — Chem. Commun., 1231 (1969).Google Scholar
  14. 12.
    — Chem. Commun., 1230 (1969).Google Scholar
  15. 13.
    Bawn, C. E. H., Fitzsimmons, C., Ledwith, A.: Proc. Chem. Soc. 391 (1964).Google Scholar
  16. 14.
    Bonin, M. A., Busler, W. R., Williams Ff.: J. Am. Chem. Soc. 87, 199 (1965).CrossRefGoogle Scholar
  17. 15.
    Williams, Ff., Hayashi, Kanae, Ueno, K., Hayashi, Koichiro, Okamura, S.: Trans. Faraday Soc. 63, 1501 (1967).CrossRefGoogle Scholar
  18. 16.
    Ueno, K., Hayashi, K., Okamura, S.: J. Macromol. Sci. (Chem.). A 2, 209 (1968).CrossRefGoogle Scholar
  19. 17.
    Goethals, W. J., Drijvers, W.: Makromol. Chem. 136, 73 (1970).CrossRefGoogle Scholar
  20. 18.
    Penczek, St., Kubisa, P.: Symp. on Macromols. Budapest, Paper 2/12 (1969).Google Scholar
  21. 19.
    Penczek, St., Kubisa, P.: Makromol. Chem. 130, 186 (1969).CrossRefGoogle Scholar
  22. 20.
    Plesch, P. H., Westermann, P. H.: to be published; Westermann, P. H.: Ph. D. Thesis, Keele (1967).Google Scholar
  23. 21.
    Saegusa, T., Matsumoto, S., Hashimoto, Y.: Polymer J. 1, 31 (1970), and earlier papers.CrossRefGoogle Scholar
  24. 22.
    Jaacks, V., Boehlke, K., Eberius, E.: Makromol. Chem. 118, 354 (1968).CrossRefGoogle Scholar
  25. 23.
    Pepper, D. C., et al.: Proc. Roy. Soc. A. 263, 58, 63, 75, 82 (1961).Google Scholar
  26. 24.
    Ikeda, K., Higashimura, T., Okamura, S.: Chem. High Polymers (Japan) 26, 364 (1969).Google Scholar
  27. 25.
    Pepper, D. C., Reilly, P. J.: J. Polymer Sci. 58, 639 (1962).CrossRefGoogle Scholar
  28. 26.
    — Proc. Roy. Soc. A. 291, 41 (1966).Google Scholar
  29. 27.
    Darcy, L. E., Millrine, P., Pepper, D. C.: Chem. Commun. 1441 (1968).Google Scholar
  30. 28.
    MacCarthy, B., Millrine, W. P., Pepper, D. C.: Chem. Commun. 1442 (1968).Google Scholar
  31. 29.
    Gandini, A., Plesch, P. H.: Proc. Chem. Soc. 240 (1964).Google Scholar
  32. 30.
    — J. Polymer Sci. B. 3, 127 (1965).CrossRefGoogle Scholar
  33. 31.
    — J. Chem. Soc. 4826 (1965).Google Scholar
  34. 32.
    — European Polymer J. 4, 55 (1968).CrossRefGoogle Scholar
  35. 33.
    Bertoli, V., Plesch, P. H.: J. Chem. Soc. (B) 1500 (1968).Google Scholar
  36. 34.
    Mathias, E., Plesch, P. H.: to be published; Mathias, E.: Ph. D. Thesis, Keele (1970).Google Scholar
  37. 35.
    Evans, A. G., Polanyi, M.: J. Chem. Soc. 252 (1947).Google Scholar
  38. 36.
    Plesch, P. H., Westermann, P. H.: J. Polymer Sci. C. 16, 3837 (1968).Google Scholar
  39. 37.
    — Polymer 10, 105 (1969).CrossRefGoogle Scholar
  40. 38.
    Goethals, E. J.: to be published; quoted by permission.Google Scholar

Copyright information

© Springer-Verlag 1971

Authors and Affiliations

  • P. H. Plesch
    • 1
  1. 1.Chemistry DepartmentUniversity of KeeleNorth StaffordshireEngland

Personalised recommendations