n+ (n = 1, 2, 3) with vinyl fluoride: polymerization initiated by C60ú3+



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Eur. J. Mass Spectrom. 5, 471 - 475 (1999)

Selected-ion flow tube studies of reactions of C60n+ (n = 1, 2, 3) with vinyl fluoride: polymerization initiated by C60ú3+

Yun Ling and Diethard K. Bohme*
Department of Chemistry and Centre for Research in Earth and Space Science, York University, Toronto, Ontario, Canada M3J 1P3

ABSTRACT:
Results are reported for kinetic measurements of reactions between the C60n+ cations C60"+, C602+ and C60"3+ and vinyl fluoride in the gas phase and comparisons are provided with the chemistry previously characterized with ethylene and vinyl chloride. The measurements were made at 294 ± 3 K and 0.35 ± 0.01 Torr of helium using the Selected-Ion Flow Tube (SIFT) technique. They show that, although C60"+ is unreactive and C602+ is barely reactive under these conditions, C60"3+ reacts rapidly with vinyl fluoride presumably to initiate vinyl polymerization in a manner similar to that we have proposed previously to occur with ethylene under similar operating conditions. Electron transfer competes with the initiation of the polymerization in both cases. Vinyl chloride, on the other hand, is unsuitable for cationic polymerization with C60"3+ as initiator because of the exclusive occurrence of electron transfer. The measurements have revealed, in a systematic way, the influence of the ionization energy of the vinyl monomer on the competition between electron transfer and initiation of vinyl polymerization by C60"3+ in the gas phase under SIFT conditions.

Keywords: fullerene cations, vinyl fluoride, ethylene, vinyl chloride, cationic polymerization, electron transfer, SIFT

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