Selected-Ion Flow Tube Studies of Reactions of C 60 n + ( n = 1,2,3) with Vinyl Fluoride: Polymerization Initiated by C 60 •3+

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.