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Ionic Polymerizations and Related Processes pp 99–115Cite as

Rate Constants and Reactivity Ratios in Carbocationic Polymerizations

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Part of the book series: NATO Science 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.

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References

  1. Plesch, P.H. (1993) Prog. Reaction Kinetics 18, 1–62.

    CAS  Google Scholar 

  2. Charleux, B., Rives, A., Vairon, J.-P., and Matyjaszewski, K. (1996) Macromolecules 29, 5777–5783.

    Article  CAS  Google Scholar 

  3. Vairon, J.-P., Charleux, B., and Rives, A. (1996) Macromol. Symp. 107, 307–317.

    Article  CAS  Google Scholar 

  4. Vairon, J.-P., Rives, A., and Bunel, C. (1992) Makromol. Chem., Macromol. Symp. 60, 97–105.

    Article  CAS  Google Scholar 

  5. Mayr, H., Roth, M., and Lang, G. (1997) Cationic Polymerization, Fundamentals and Applications, ACS Symposium Series, Vol. 665, pp. 25–40.

    Article  CAS  Google Scholar 

  6. Roth, M. and Mayr, H. (1996) Macromolecules 29, 6104–6109.

    Article  CAS  Google Scholar 

  7. Wang, Y. and Dorfman, L.M. (1980) Macromolecules 13, 63–65.

    Article  CAS  Google Scholar 

  8. Dorfman, L.M., Sujdak, R.J., and Bockrath, B. (1976) Acc. Chem. Res. 9, 352–357.

    Article  CAS  Google Scholar 

  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. Mayr, H., Schneider, R., Schade, C., Bartl, J., and Bederke, R. (1990) J. Am. Chem. Soc. 112, 4446–4454.

    Article  CAS  Google Scholar 

  11. Mayr, H. (1990) Angew. Chem. 102, 1415–1428; Angew. Chem. Int. Ed. Engl. 29, 1371–1384.

    Google Scholar 

  12. Problems to define “stabilities” of carbocations have been discussed. See ref. [13], and refs. cited therein.

    Google Scholar 

  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. 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.

    Article  CAS  Google Scholar 

  15. 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.

    Article  Google Scholar 

  16. 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.

    Article  CAS  Google Scholar 

  17. 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.

    Article  CAS  Google Scholar 

  18. 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.

    Article  CAS  Google Scholar 

  19. 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.

    Article  CAS  Google Scholar 

  20. 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. Hering, N. (1996) Quantifizierung der Nucleophilie von Enaminen, Diploma thesis, Technische Hochschule Darmstadt.

    Google Scholar 

  22. Mayr, H. and Striepe, W. (1983) J. Org. Chem. 48, 1159–1165.

    Article  CAS  Google Scholar 

  23. Mayr, H. and Gorath, G. (1995) J. Am. Chem. Soc. 117, 7862–7868.

    Article  CAS  Google Scholar 

  24. 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.

    Chapter  Google Scholar 

  25. 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. Pross, A. and Shaik, S.S. (1982) J. Am. Chem. Soc. 104, 1129–1130.

    Article  CAS  Google Scholar 

  27. Brönsted, J.N. (1923) Recl. Tray. Chim. Pays-Bas 42, 718–728.

    Article  Google Scholar 

  28. Dau-Schmidt, J.-P. and Mayr, H. (1994) Chem. Ber. 127, 205–212.

    Article  CAS  Google Scholar 

  29. Mayr, H., Schneider, R., Irrgang, B., and Schade, C. (1990) J. Am. Chem. Soc. 112, 4454–4459.

    Article  CAS  Google Scholar 

  30. Mayr, H. and Patz, M. (1994) Angew. Chem. 106, 990–1010; Angew. Chem. Int. Ed. Engl. 33, 938–957.

    Google Scholar 

  31. Mayr, H., Kuhn, O., Gotta, M.F., and Patz, M. (1998) J. Phys. Org. Chem. 11, 642–654.

    Article  CAS  Google Scholar 

  32. Bartl, J., Steenken, S., and Mayr, H. (1991) J. Am. Chem. Soc. 113, 7710–7716.

    Article  CAS  Google Scholar 

  33. Burfeindt, J., Patz, M., Müller, M., and Mayr, H. (1998) J. Am. Chem. Soc. 120, 3629–3634.

    Article  CAS  Google Scholar 

  34. Roth, M., Schade, C., and Mayr, H. (1994) J. Org. Chem. 59, 169–172.

    Article  CAS  Google Scholar 

  35. Pock, R. and Mayr, H. (1986) Chem. Ber. 119, 2497–2509.

    Article  CAS  Google Scholar 

  36. Mayr, H. and Hartnagel, M. (1996) Liebigs Ann.,2015–2018.

    Google Scholar 

  37. Kennedy, J.P. and Marechal, E. (1982) Carbocationic Polymerization, Wiley, New York.

    Google Scholar 

  38. Olah, G.A. and Westerman, P.W. (1973) J. Am. Chem. Soc. 95, 7530–7531.

    Article  CAS  Google Scholar 

  39. Larsen, J.W., Bouis, P.A., and Riddle, C.A. (1980) J. Org. Chem. 45, 4969–4973.

    Article  CAS  Google Scholar 

  40. Roth, M. and Mayr, H. (1995) Angew. Chem. 107, 2428–2430; Angew. Chem. Int. Ed. Engl. 34, 2250–2252.

    Google Scholar 

  41. Mayr, H. and Ofial, A.R. (1997) Tetrahedron Lett. 38, 3503–3506.

    Article  CAS  Google Scholar 

  42. Henninger, J., Mayr, H., Patz, M., and Stanescu, M.D. (1995) Liebigs Ann., 2005–2009.

    Google Scholar 

  43. Mayr, H., Müller, K.-H.,Ofial, A.R., and Bühl, M. (1998) submitted.

    Google Scholar 

  44. Mayr, H., Henninger, J., and Siegmund, T. (1996) Res. Chem. Intermed. 22, 821–838.

    Article  CAS  Google Scholar 

  45. Mayr, H., Patz, M., Gotta, M.F., and Ofial, A.R. (1998) Pure Appl. Chem., in press.

    Google Scholar 

  46. 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 

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Author information

Authors and Affiliations

  1. Institut für Organische Chemie der Ludwig-Maximilians-Universität München, Karlstrasse 23, München, D-80333, Germany

    H. Mayr

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  1. H. Mayr
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Editors and Affiliations

  1. Department of Chemical and Biochemical Engineering, The University of Western Ontario, London, Ontario, Canada

    Judit E. Puskas , Armin Michel  & Shahzad Barghi ,  & 

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Mayr, H. (1999). Rate Constants and Reactivity Ratios in Carbocationic Polymerizations. In: Puskas, J.E., Michel, A., Barghi, S. (eds) Ionic Polymerizations and Related Processes. NATO Science Series, vol 359. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-4627-2_7

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  • DOI: https://doi.org/10.1007/978-94-011-4627-2_7

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-0-7923-5812-1

  • Online ISBN: 978-94-011-4627-2

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