Rate Constants and Reactivity Ratios in Carbocationic Polymerizations

  • H. Mayr
Chapter
Part of the NATO Science Series book series (NSSE, volume 359)

Abstract

Rate constants for the reactions of carbocations with substituted ethylenes can be determined when the reactions terminate at the [1:1]-product stage. Correlation equations are presented which allow one to derive rate constants for these reactions from the electrophilicity parameters (E) of the carbocations and the nucleophilicity (N) and slope parameters (s) of the yn-systems. Since the slope s is usually close to 1, initiation and propagation rate constants of carbocationic polymerizations can be estimated from the data presented in Schemes 7–11. The special features of fast reactions (e.g., propagations), which do not have enthalpic barriers, are discussed.

Keywords

Vinyl Ether Cationic Polymerization Enol Ether Terminal Double Bond Alkyl Chloride 
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.
This is a preview of subscription content, log in to check access.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    Plesch, P.H. (1993) Prog. Reaction Kinetics 18, 1–62.Google Scholar
  2. 2.
    Charleux, B., Rives, A., Vairon, J.-P., and Matyjaszewski, K. (1996) Macromolecules 29, 5777–5783.CrossRefGoogle Scholar
  3. 3.
    Vairon, J.-P., Charleux, B., and Rives, A. (1996) Macromol. Symp. 107, 307–317.CrossRefGoogle Scholar
  4. 4.
    Vairon, J.-P., Rives, A., and Bunel, C. (1992) Makromol. Chem., Macromol. Symp. 60, 97–105.CrossRefGoogle Scholar
  5. 5.
    Mayr, H., Roth, M., and Lang, G. (1997) Cationic Polymerization, Fundamentals and Applications, ACS Symposium Series, Vol. 665, pp. 25–40.CrossRefGoogle Scholar
  6. 6.
    Roth, M. and Mayr, H. (1996) Macromolecules 29, 6104–6109.CrossRefGoogle Scholar
  7. 7.
    Wang, Y. and Dorfman, L.M. (1980) Macromolecules 13, 63–65.CrossRefGoogle Scholar
  8. 8.
    Dorfman, L.M., Sujdak, R.J., and Bockrath, B. (1976) Acc. Chem. Res. 9, 352–357.CrossRefGoogle Scholar
  9. 9.
    Schneider, R., Grabis, U., and Mayr, H. (1986) Angew. Chem. 98, 94–95; Angew. Chem. Int. Ed. Engl. 25, 89–90.Google Scholar
  10. 10.
    Mayr, H., Schneider, R., Schade, C., Bartl, J., and Bederke, R. (1990) J. Am. Chem. Soc. 112, 4446–4454.CrossRefGoogle Scholar
  11. 11.
    Mayr, H. (1990) Angew. Chem. 102, 1415–1428; Angew. Chem. Int. Ed. Engl. 29, 1371–1384.Google Scholar
  12. 12.
    Problems to define “stabilities” of carbocations have been discussed. See ref. [13], and refs. cited therein.Google Scholar
  13. 13.
    Mayr, H. (1996) Fundamentals of the reactions of carbocations with nucleophiles, in Matyjaszewski, K. (ed.), Cationic Polymerization: Mechanisms, Synthesis and Applications, Marcel Dekker, New York, pp. 51–136.Google Scholar
  14. 14a).
    Hadjikyriacou, S., Fodor, Z., and Faust, R. (1995) Synthetic applications of nonpolymerizable monomers in living cationic polymerization: Functional polyisobutylenes by end-quenching, J. Macromol. Sci., Pure Appl. Chem. A32, 1137–1153.CrossRefGoogle Scholar
  15. 14b).
    Roth, M., Mayr, H., and Faust, R. (1996) Examination of models for carbocationic polymerization: The influence of chain length on carbocation reactivities, Macromolecules 29, 6110–6113.CrossRefGoogle Scholar
  16. 14c).
    Fodor, Z. and Faust, R. (1994) Living carbocationic polymerization of p-methylstyrene and sequential block copolymerization of isobutylene with pmethylstyrene, J. Macromol. Sci., Pure Appl. Chem. A31, 1985–2000.CrossRefGoogle Scholar
  17. 14d).
    Li, D. and Faust, R. (1995) Polyisobutylene-based thermoplastic elastomers. 3. Synthesis, characterization, and properties of poly(a-methylstyrene-b-isobutylene-b-a-methylstyrene) triblock copolymers, Macromolecules 28, 4893–4898.CrossRefGoogle Scholar
  18. 14e).
    Hadjikyriacou, S. and Faust, R. (1995) Living carbocationic homopolymerization of isobutyl vinyl ether and sequential block copolymerization of isobutylene with isobutyl vinyl ether. Synthesis and mechanistic studies, Macromolecules 28, 7893–7900.CrossRefGoogle Scholar
  19. 14f).
    Hadjikyriacou, S. and Faust, R. (1996) Amphiphilic block copolymers by sequential living cationic polymerization: Synthesis and characterization of poly(isobutylene-b-methyl vinyl ether), Macromolecules 29, 5261–5267.CrossRefGoogle Scholar
  20. 14g).
    Schlaad, H., Erentova, K., Faust, R., Charleux, B., Moreau, M., Vairon, J.-P., and Mayr, H. (1998) Kinetic study on the capping reaction of living polyisobutylene with 1,1-diphenylethylene. 1. Effect of temperature and comparison to the model compound 2-chloro-2,4,4-trimethylpentane, Macromolecules,in print.Google Scholar
  21. 15.
    Hering, N. (1996) Quantifizierung der Nucleophilie von Enaminen, Diploma thesis, Technische Hochschule Darmstadt.Google Scholar
  22. 16.
    Mayr, H. and Striepe, W. (1983) J. Org. Chem. 48, 1159–1165.CrossRefGoogle Scholar
  23. 17.
    Mayr, H. and Gorath, G. (1995) J. Am. Chem. Soc. 117, 7862–7868.CrossRefGoogle Scholar
  24. 18.
    Mayr, H. (1989) in Schinzer, D. (ed.), Selectivities in Lewis Acid-Promoted Reactions, NATO ASI Series C, Vol. 289, Kluwer Academic Publishers, Dordrecht, pp. 21–36.CrossRefGoogle Scholar
  25. 19.
    Mayr, H., Schade, C., Rubow, M., and Schneider, R. (1987) Angew. Chem. 99, 1059–1060; Angew. Chem. Int. Ed. Engl. 26, 1029–1030.Google Scholar
  26. 20.
    Pross, A. and Shaik, S.S. (1982) J. Am. Chem. Soc. 104, 1129–1130.CrossRefGoogle Scholar
  27. 21.
    Brönsted, J.N. (1923) Recl. Tray. Chim. Pays-Bas 42, 718–728.CrossRefGoogle Scholar
  28. 22.
    Dau-Schmidt, J.-P. and Mayr, H. (1994) Chem. Ber. 127, 205–212.CrossRefGoogle Scholar
  29. 23.
    Mayr, H., Schneider, R., Irrgang, B., and Schade, C. (1990) J. Am. Chem. Soc. 112, 4454–4459.CrossRefGoogle Scholar
  30. 24.
    Mayr, H. and Patz, M. (1994) Angew. Chem. 106, 990–1010; Angew. Chem. Int. Ed. Engl. 33, 938–957.Google Scholar
  31. 25.
    Mayr, H., Kuhn, O., Gotta, M.F., and Patz, M. (1998) J. Phys. Org. Chem. 11, 642–654.CrossRefGoogle Scholar
  32. 26.
    Bartl, J., Steenken, S., and Mayr, H. (1991) J. Am. Chem. Soc. 113, 7710–7716.CrossRefGoogle Scholar
  33. 27.
    Burfeindt, J., Patz, M., Müller, M., and Mayr, H. (1998) J. Am. Chem. Soc. 120, 3629–3634.CrossRefGoogle Scholar
  34. 28.
    Roth, M., Schade, C., and Mayr, H. (1994) J. Org. Chem. 59, 169–172.CrossRefGoogle Scholar
  35. 29.
    Pock, R. and Mayr, H. (1986) Chem. Ber. 119, 2497–2509.CrossRefGoogle Scholar
  36. 30.
    Mayr, H. and Hartnagel, M. (1996) Liebigs Ann.,2015–2018.Google Scholar
  37. 31.
    Kennedy, J.P. and Marechal, E. (1982) Carbocationic Polymerization, Wiley, New York.Google Scholar
  38. 32.
    Olah, G.A. and Westerman, P.W. (1973) J. Am. Chem. Soc. 95, 7530–7531.CrossRefGoogle Scholar
  39. 33.
    Larsen, J.W., Bouis, P.A., and Riddle, C.A. (1980) J. Org. Chem. 45, 4969–4973.CrossRefGoogle Scholar
  40. 34.
    Roth, M. and Mayr, H. (1995) Angew. Chem. 107, 2428–2430; Angew. Chem. Int. Ed. Engl. 34, 2250–2252.Google Scholar
  41. 35.
    Mayr, H. and Ofial, A.R. (1997) Tetrahedron Lett. 38, 3503–3506.CrossRefGoogle Scholar
  42. 36.
    Henninger, J., Mayr, H., Patz, M., and Stanescu, M.D. (1995) Liebigs Ann., 2005–2009.Google Scholar
  43. 37.
    Mayr, H., Müller, K.-H.,Ofial, A.R., and Bühl, M. (1998) submitted.Google Scholar
  44. 38.
    Mayr, H., Henninger, J., and Siegmund, T. (1996) Res. Chem. Intermed. 22, 821–838.CrossRefGoogle Scholar
  45. 39.
    Mayr, H., Patz, M., Gotta, M.F., and Ofial, A.R. (1998) Pure Appl. Chem., in press.Google Scholar
  46. 40.
    Patz, M., Mayr, H., Bartl, J., and Steenken, S. (1995) Angew. Chem. 107, 519–521; Angew. Chem. Int. Ed. Engl. 34, 490–492.Google Scholar

Copyright information

© Springer Science+Business Media Dordrecht 1999

Authors and Affiliations

  • H. Mayr
    • 1
  1. 1.Institut für Organische Chemie der Ludwig-Maximilians-Universität MünchenMünchenGermany

Personalised recommendations