Revisiting living and apparently living carbocationic polymerizations

P Sigwalt; J.-P. Vairon

doi:10.14314/polimery.2014.038

Published : 2014-01-30

Vol. 59 No. 1 (2014)

Revisiting living and apparently living carbocationic polymerizations

P Sigwalt J.-P. Vairon

DOI: https://doi.org/10.14314/polimery.2014.038

Abstract

This short review aims at reconsidering the behaviours of a few vinyl monomers (isobutylvinylether, p-methylstyrene, p-methoxystyrene, indene and 2,4,6-trimethylstyrene) well identified as leading to different levels of living character during their cationic polymerization. These polymerizations agree well with the general scheme of dormant-active equilibrium of propagating species. The available data, and particularly that from of our Paris group, are summed up and discussed in terms of cation stability and of absence (or non-detection) of transfer depending on the conditions of polymerization (nature of the monomer, initiating system, temperature, medium, range of considered Mn, etc.). This living situation allows the estimation of the absolute kp± (propagation rate constant) for the considered monomers, either via the determination of the concentration of active ionic species (ISC — ionic species concentration method) or via the capping method (diffusion clock or DC method). A discrepancy still persists between the two approaches as the DC method leads to kp ± which are 105 times larger. Furthermore the capping rate constants kc± and the corresponding kp± obtained through the DC method have led to the conclusion that the effect of a monomer substituent on the reactivity of carbocation is much larger than the effect on the reactivity of the corresponding monomer. But, from the kp± values obtained by the ISC method and from the reactivity ratios in copolymerization of the styrenic monomers, we concluded that there could be an approximate compensation between carbocation and monomer reactivities.

Keywords

living polymerization ; carbocationic polymerization ; propagation rate constant ; carbocation reactivity polimeryzacja żyjąca ; polimeryzacja karbokationowa ; stała szybkości propagacji ; reaktywność karbokationu

Details

References

Statistics

Authors

Download files

PDF

Zasady cytowania

Sigwalt, P., & Vairon, J.-P. (2014). Revisiting living and apparently living carbocationic polymerizations. Polimery, 59(1), 38–48. https://doi.org/10.14314/polimery.2014.038

References

Sawamoto M.: Makromol. Chem. Macromol. Symp. 1994, 85, 33.

[2] Faust R., Kennedy J. P.: J. Polym. Sci. A 1987, 25,1847.

[3] Kennedy J. P., Ivan B.: «Designed Polymers by Carbocationic Macromolecular Engineering: Theory and Practice», Hanser Munich, NewYork 1992.

[4] Sigwalt P.: Makromol. Chem. Macromol. Symp. 1991, 47, 178.

[5] Thomas L., Polton A., Tardi M., Sigwalt P.: Macromolecules 1993, 26, 4075.

[6] a) Thomas L., Polton A., Tardi M., Sigwalt P.: Macromolecules 1992, 25(22), 5886. b) Thomas L. Polton A. Tardi M., Sigwalt P.: Macromolecules 1995, 28(7), 2105.

[7] Aoshima S., Higashimura T.: Macromolecules 1989, 22, 1009.

[8] Leleu J. M., Tardi M., Polton A., Sigwalt P.: Makromol. Chem. Macromol. Symp. 1991, 47, 253.

[9] Aoshima S. et al.: Polym. Bull. 1986, 15, 417.

[10] Granier L. et al.: 1987, unpublished results.

[11] Leleu J. M., Bernardo V., Tardi M., Polton A., Sigwalt P.: Polym. Int. 1995, 37, 219.

[12] Tazi M., Tardi M., Polton A., Sigwalt P.: Europ. Pol. J. 1986, 22, 451.

[13] Taxi M., Tardi M., Polton A., Sigwalt P.: British Polym. J. 1987, 19, 369.

[14] Sigwalt P., Polton A., Tardi, M.: J. Macromol. Sci. 1994, A 31(8), 953.

[15] Sigwalt P.: Makromol. Chem. Macromol. Symp. 1998, 132, 127.

[16] Penczek S.: Makromol. Chem. Rapid Comm. 1992, 13(3), 147.

[17] Moreau M., Ouragi M., Benaboura A., Sigwalt P.: IUPAC Symp. on Ionic Polymerizations, Boston 2003.

[18] a) De Sorgo M., Pepper D. C., Szwarc M.: J. Chem. Soc. Chem. Com. 1973, 419, DOI: 10.1039/C39730000419. b) Kunitake T., Takarabe T.: J. Polym. Sci. Symp. 1976, 56, 33. c) Vairon J. P., Rives A., Bunel C.: Makromol. Chem. Macromol. Symp. 1992, 60, 97. d) Vairon J. P., Charleux B., Moreau M.: NATO Science Series, Kluver 1999, 359, 177.

[19] Rives A.: PhD Thesis, University P. and M. Curie, Paris 1994.

[20] a) Charleux B. Rives A., Vairon J. P., Matyjaszewski K.: Macromolecules 1996, 29(18), 5777. b) Charleux B., Rives A., Vairon J. P., Matyjaszewski K.: Macromolecules 1998, 31(8), 2403.

[21] De P., Faust R.: Macromolecules 2005, 38(13), 5498.

[22] De P., Faust R., Schimmel H., Ofial A. R., Mayr H.: Macromolecules 2004, 37(12), 4422.

[23] De P., Faust R.: Macromolecules 2004, 37(24), 9290.

[24] Sigwalt P., Moreau M.: Prog. Polym. Sci. 2006, 31, 44.

[25] Sigwalt P., Moreau M.: J. Polym. Sci. A 2010, 48, 2666.

[26] Sigwalt P., Moreau M., Polton A.: Macromol. Symp. 2002, 183, 43.

[27] Tsunogae Y., Majoros I., Kennedy J. P.: J. Macromol. Sci. Pure Appl. Chem. 1993, A30(4), 253.

[28] Cotrel R., Sauvet G., Vairon J. P., Sigwalt P.: Macromolecules 1976, 9(6), 931.

[29] Sauvet G., Moreau M., Sigwalt P.: Makromol. Chem. Macromol. Symp. 1986, 3, 33.

[30] Sawamoto M., Higashimura T.: Macromolecules 1978, 11(2), 328.

[31] Sawamoto M., Higashimura T.: Macromolecules 1978, 11(3), 501.

[32] Higashimura T., Sawamoto M.: Polym. Bull. (Berlin), 1978, 1, 11—15.

[33] Sawamoto M., Higashimura T.: Macromolecules 1979, 12(4), 581.

[34] McClelland R. A., Chan C., Cozens F., Modro A., Steenken S.:. Angew. Chem. Int. Ed. Engl. 1991, 30(10), 1337.

[35] De P., Faust R.: Macromolecules 2004, 37(21), 7930.

[36] Faust R., Kennedy J. P.: Polym. Bull. (Berlin) 1988, 19, 35.

[37] Vairon J. P., Moreau M., Charleux B., Cretol R., Faust R.: Macromol. Symp. 2002, 183, 43.

[38] De P., Sipos L., Faust R., Moreau M., Charleux B., Vairon J. P.: Macromolecules, 2005, 38(1), 41.

[39] Schimmel H.: «Dissertation» Ludwig-Maximilians-Universität, München 2000.

[40] Müller A. H. E., Litvinenko G., Yan D.: Macromolecules 1996, 29(7), 2339.

[41] Mayr H., Ofial A. R., Schimmel H.: Macromolecules 2005, 38(1), 33.

[42] Storey R. F., Donnalley A. B.: Macromolecules 1999, 32(21), 7003.

[43] Puskas J. E., Kaszas G., Litt M.: Macromolecules 1991, 24(19), 5278.

[44] Kolishetti N., Faust R.: Macromolecules 2008, 41(11), 3842.

[45] Dimitrov P., Faust R.: Macromolecules 2010, 43(4), 1724.

[46] Sigwalt P., Moreau N.: Macromol. Symp. 2011, 308, 49.

[47] a) Matyjaszewski K., Sigwalt P.: Polym. Int. 1994, 35, 1. b) Matyjaszewski K., Pugh C. In: «Carbocationic polymerizations, mechanisms, synthesis, and applications» (Ed., Matyjaszewski K.), New York, DekkerMPress 1996, p. 223.

[48] Bkouche-Waksman I., Sigwalt P.: Compt. Rend. 1962, 255, 680.

[49] Givehchi M., Polton A., Tardi M., Moreau M., Sigwalt P., Vairon J. P.: Macromol. Symp. 2000, 157(1), 77.

Google Scholar

Altmetric indicators

Citing articles via

Statistics

Total abstract views : 0

PDF Downloads : 0

P Sigwalt sigwaltpierre@gmail.com

Affiliation
Laboratoire de Chimie des Polymeres, UMR7610, Université P. et M. Curie, 4 place Jussieu, 75252 Paris

J.-P. Vairon

Affiliation
Laboratoire de Chimie des Polymeres, UMR7610, Université P. et M. Curie, 4 place Jussieu, 75252 Paris