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Cationic olefin polymerization using alkyl halide alkylaluminum initiator systems

1. Reactivity studies
  • Joseph P. Kennedy
  • Prakash D. Trivedi
Conference paper
Part of the Advances in Polymer Science book series (POLYMER, volume 28)

Abstract

After a survey of pertinent earlier studies, isobutylene polymerizations have been carried out using t-BuX initiators, Me3Al, Et2AlX and EtAlCl2 coinitiators and MeX (X=Cl, Br, I) and n-pentane solvents in the range from −25° to −100°C. The effect of t-BuX, Me3Al, Et2AlX or EtAlCl2, MeX and temperature on polymerization rate has been determined. Polyisobutylene (PIB) yield, molecular weight and molecular weight distribution have been studied in detail. Initiator reactivity series have been established on the basis of polymerization rates, floor temperatures, PIB yields and initiator efficiencies. The effect of solvent on initiator reactivity order has been evaluated. These results have been explained considering details of initiation, which involves four steps: complexation, displacement, ionization and initiation. The absence of polymerization using MeI and MeBr (with Et2AlI system) has been interpreted in terms of propagation-inactive halonium ions.

Keywords

Polymerization Rate Reactivity Study Cationic Polymerization Initiator System Initiator Reactivity 
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.

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X. References

  1. 1).
    Kennedy, J. P., Trivedi, P. D.: Adv. Polymer Sci. 28, 31 (1978)Google Scholar
  2. 2).
    Kennedy, J. P.: Belgian Patent 663, 319 (April 30, 1965)Google Scholar
  3. 3).
    Kennedy, J. P., Melby, E. M.: J. Polymer Sci. 13, 29 (1975)Google Scholar
  4. 4).
    Kennedy, J. P., Smith, R. R.: Polymer Preprints 13 (2), 710 (1972)Google Scholar
  5. 5).
    Kennedy, J. P., Charles, J. J., Davidson, D. L.: Polymer Preprints 14 (2), 974 (1973)Google Scholar
  6. 6).
    Sigwalt, P., Palton, A., Miskovic, M.: J. Polymer Sci. C, 56, 13 (1976)Google Scholar
  7. 7).
    Vidal, A., Kennedy, J. P.: J. Polymer Sci. B, 14, 489 (1976)Google Scholar
  8. 8).
    Kennedy, J. P.: Inter. Symp. Macromol. Chem., Tokyo, Kyoto, Abstract 2.104 (1966)Google Scholar
  9. 9).
    Kennedy, J. P.: J. Polymer Sci. A-1, 6, 3139 (1968)CrossRefGoogle Scholar
  10. 10).
    Kennedy, J. P., Desai, N. V., Sivaram, S.: J. Am. Chem. Soc. 95, 6386 (1973)CrossRefGoogle Scholar
  11. 11).
    Kennedy, J. P., Rengachary, S.: Adv. in Polymer Sci. 14, 1 (1974)Google Scholar
  12. 12).
    Kennedy, J. P. in: Copolymerization. Chapter V, Ham, G. E. (ed.). New York: Wiley-Interscience Publ. 1964Google Scholar
  13. 13).
    Kraus, C. A.,: U. S. Patent 2,220, 930 (1940)Google Scholar
  14. 14).
    Kennedy, J. P., Gillham, J. K.: Adv. in Polymer Sci. 10, 1 (1972)CrossRefGoogle Scholar
  15. 15).
    Kennedy, J. P., Sivaram, S.: J. Macromol. Sci.-Chem. A7, 969 (1973)Google Scholar
  16. 16).
    Maslinska-Solich, J., Chmelir, M., Marek, M.: Collection Czechoslov. Chem. Commun. 34, 2611 (1969)Google Scholar
  17. 17).
    Priola, A., Cesca, S., Ferraris, G., Milanese, S. D., Boy, M. S., Giusti, P.: U. S. Patent 3,850, 894 (1974)Google Scholar
  18. 18).
    Priola, A., Cesca, S., Ferraris, G., Milanese, S. D.: U. S. Patent 3,850, 895 (1974)Google Scholar
  19. 19).
    Priola, A., Cesca, S., Ferraris, G., Milanese, S. D., Boy, M. B., Giusti, P.: U. S. Patent 3,850, 896 (1974)Google Scholar
  20. 20).
    Priola, A., Cesca, S., Ferraris, G., Milanese, S. D.: U. S. Patent 3,850, 897 (1974)Google Scholar
  21. 21).
    Priola, A., Ferraris, G., de Maina, M., Giusti, P.: Makromol. Chem. 176, 2271 (1975)CrossRefGoogle Scholar
  22. 22).
    Priola, A., Cesca, S., Ferraris, G., de Maina, M.: Makromol. Chem. 176, 2289 (1975)CrossRefGoogle Scholar
  23. 23).
    Giusti, P., Priola, A., Magagnini, P., Narducci, P.: Makromol. Chem. 176, 2303 (1975)CrossRefGoogle Scholar
  24. 24).
    Cesca, S., Giusti, P., Magagnini, P., Priola, A.: Makromol. Chem. 176, 2319 (1975)CrossRefGoogle Scholar
  25. 25).
    Cesca, S., Priola, A., Bruzzone, M., Ferraris, G., Giusti, P.: Makromol. Chem. 176, 2339 (1975)CrossRefGoogle Scholar
  26. 26).
    de Maina, M., Cesca, S., Giusti, P., Ferraris, G., Magagnini, P. L.: Makromol. Chem. 178, 2223 (1977)CrossRefGoogle Scholar
  27. 27).
    Magagnini, P. L., Cesca, S., Giusti, P., Priola, A., de Maina, M.: Makromol. Chem. 178, 2235 (1977)CrossRefGoogle Scholar
  28. 28).
    Flory, P. J.: J. Am. Chem. Soc. 65, 372 (1943)CrossRefGoogle Scholar
  29. 29).
    Kennedy, J. P.: Cationic polymerization of olefins: A critical inventory. New York: Wiley-Interscience Publ. 1975Google Scholar
  30. 30).
    Charadame, H., Sigwalt, P.: Compt. Rend. 259, 4273 (1964)Google Scholar
  31. 31).
    Kennedy, J. P., Langer, A. W.: Adv. in Polymer Sci. 3, 508 (1964)CrossRefGoogle Scholar
  32. 32).
    Kennedy, J. P., Sivaram, S.: J. Org. Chem. 38, 2262 (1973)CrossRefGoogle Scholar
  33. 33).
    Kennedy, J. P.: Brit. Patent 1,094, 728 (1965)Google Scholar
  34. 34).
    Kennedy, J. P., Trivedi, P. D.: Polymer Preprints 17 (2), 791 (1976)Google Scholar
  35. 35).
    Kennedy, J. P., Squires, R. G.: Polymer 6, 579 (1965)CrossRefGoogle Scholar
  36. 36).
    Pepper, D. C.: Quart. Rev. 8, 90 (1954)CrossRefGoogle Scholar
  37. 37).
    Sawada, H.: J. Macromol. Sci.-Revs. C7, 161 (1972)Google Scholar
  38. 38).
    Olah, G. A.: Halonium ions. New York: Wiley-Interscience Publ. 1975Google Scholar
  39. 39).
    Dahlig, W., Pasynkiewicz, S., Meszorer, L.: Roczniki Chem. 34, 1519 (1960)Google Scholar
  40. 40).
    Pasynkiewicz, S., Dahlig, W., Meszorer, L.: Roczniki Chem. 35, 1301 (1961)Google Scholar
  41. 41).
    Brown, H. C., Wallace, W. J.: J. Am. Chem. Soc. 75, 6279 (1953)CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 1978

Authors and Affiliations

  • Joseph P. Kennedy
    • 1
  • Prakash D. Trivedi
    • 1
  1. 1.Institute of polymer ScienceThe University of AkronAkronUSA

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