Abstract
In the cationic polymerization of vinyl and cyclic monomers containing heteroatoms there is a possibility of simultaneous presence of carbenium and onium ions being in dynamic equilibrium, e.g.,
Fragment containing the heteroatom X can either come from macromolecule or from monomer itself. Polymerization of cyclic acetals, for which intra- and inter-molecular formation of onium ions has been discussed in detail, was modelled by systems involving both carbenium and oxonium ions, separately observed by 1H NMR. Application of dynamic 1H NMR allowed the rate constants involving both kinds of ions to be determined, and showed, that, at least in the polymerization of 1,3-dioxolane, the macrooxonium ions dominate in the chain growth.
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K. Hiraoka and P. Kebarle, J. Am. Chem. Soc., 99, 360 (1977).
S. Slomkowski and S. Penczek, J. Chem. Soc., Perkin Trans., 2, 1718 (1974).
S. Penczek, Macromol. Chem., 175, 1217 (1974).
E. M. Arnett, in “Progress in Physical Organic Chemistry,” Vol. 1, S. G. Cohen, A. Streitwieser, Jr., and R. W. Taft, Ed., Interscience Publishers, New York, N. Y., and London, 1963, p 223.
M. Bjorøy, B. B. Saunders, S. Esperas, and J. Songstad, Phosphorus, 83 (1976).
K. Brzezinska, W. Chwialkowska, P. Kubisa, K. Matyjaszewski, and S. Penczek, Makromol. Chem., 178, 2491 (1977).
K. Matyjaszewski, P. Kubisa, and S. Penczek, Preprints, IUPAC 26th International Symposium on Macromolecules, Mainz, September 17—21, 1979, I, 161.
V. M. DePalma, Y. Wang, and L. M. Dorfman, J. Am. Chem. Soc., 100, 5416 (1978).
L. M. Dorfman, Y. Wang, H.-Y. Wang, and R. J. Sujdak, Faraday Discuss. Chem. Soc., No. 63, 149 (1977).
C. B. Kim and K. T. Leffek, Can J. Chem., 53, 3408 (1975).
G. A. Olah, J. Sommer, and E. Namanworth, J. Am. Chem. Soc., 89, 3576 (1967).
R. J. Sujdak, R. L. Jones, and L. M. Dorfman, J. Am. Chem. Soc., 98, 4875 (1976).
H. Meerwein, V. Hederich, H. Morschel, and K. Wunderlich, Annalen, 635, 1 (1960).
S. Slomkowski and S. Penczek, Chem. Commun., 1347 (1970).
Z. Jedlinski, J. Lukaszczyk, J. Dudek, and M. Gibas, Makromolecules, 9, 621 (1976).
Kabir-ud-Din and P. H. Plesch, J. Chem. Soc., Perkin Trans., 2, 937 (1978).
F. Afshar-Taromi, M. Scheer, P. Rempp, and E. Franta, Macromol. Chem., 179, 849 (1978).
R. Szymanski and S. Penczek, in preparation.
M. Szwarc, “Ions and Ion Pairs in Ionic Polymerization” in “Ions and Ion Pairs in Organic Reactions,” Vol. 2, M. Szwarc, Ed., Wiley-Interscience, New York, N.Y., London, Sydney, and Toronto, 1974, p 375.
S. Penczek and K. Matyjaszewski, J. Polym. Sci., Polym. Symp., 56, 255 (1976).
G. Binsch, “Band-Shape Analysis” in “Dynamic Nuclear Magnetic Resonance Spectroscopy,” L. M. Jackman and F. A. Cotton, Ed., Academic Press, New York, N.Y., San Francisco, and London, 1975, p 50.
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Penczek, S., Szymanski, R. The Carbenium Ion–Onium Ion Equilibria in Cationic Polymerization. Polym J 12, 617–628 (1980). https://doi.org/10.1295/polymj.12.617
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DOI: https://doi.org/10.1295/polymj.12.617