Selected-ion flow tube studies of reactions of C-60(n+) (n=1, 2, 3) with vinyl fluoride: polymerization initiated by C-60(center dot 3+) (a)

Results are reported for kinetic measurements of reactions between the C-60 (n+) cations C-60(.+), C-60(2+) and C-60(. 3+) and vinyl fluoride in the ga s phase and comparisons are provided with the chemistry previously characte rized 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 (S IFT) technique. They show that, although C-60(.+) unreactive and C-60(2+) i s barely reactive under these conditions, C-60(. 3+) reacts rapidly with vi nyl fluoride presumably to initiate vinyl polymerization in a manner simila r 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 unsuit able for cationic polymerization with C-60(. 3+) as initiator because of th e 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 viny l polymerization by C-60(. 3+) in the gas phase under SIFT conditions.