3299-24-9Relevant articles and documents
Kinetics and mechanism of the thermal gas-phase oxidation of perfluorobutene-2 in presence of trifluoromethyl hypofluorite
Romano, Rosana M.,Della Vedova, Carlos O.,Czarnowski, Joanna
, p. 532 - 541 (2003)
The oxidation of perfluorobutene-2 (C4F8) initiated by trifluoromethyl hypofluorite (CF3OF) in presence of O2 has been studied at 323.1, 332.6, 342.5, and 352.0 K, using a conventional static system. The initial pressure of CF3OF was varied between 4.8 and 23.6 Torr, that of C4F8 between 48.7 and 302.4 Torr, and that of O2 between 51.5 and 270.4 Torr. Several runs were made in presence of 325.5-451.2 Torr of N2. The main products were COF2, CF3C(O)F, and CF3OC(O)F. Small amounts of compound containing -CF(CF3)-O-C(O)CF3 group were also formed, as detected by 13C NMR spectroscopy. The oxidation is a homogeneous short-chain reaction, attaining, at the pressure of O2 used, the pseudo-zero-order condition with respect to O2 as reactant. The reaction is independent of the total pressure. Its basic steps are as follows: the thermal generation of CF3O radicals by the abstraction of fluorine atom of CF3OF by C4F8, the addition of CF3O to the alkene, the formation of perfluoroalkoxy radicals RO in presence of O2, and the decomposition of these radicals via the C-C bond scission, giving products containing -C(O)F end group and reforming RO and CF3O radicals. The mechanism consistent with experimental results is postulated.
TFE-based thermoprocessable copolymers
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Page/Page column 4, (2008/06/13)
TFE-based thermoprocessable copolymers having the following composition, expressed in percentage by moles on the total of the monomers: A) from 0.01 to 15% of the monomer of formula: [in-line-formulae]CF2═CFOCF2OCF3??(a); [/in-line-formulae] A1) tetrafluoroethylene from 99.99 to 85%; optionally B) one or more (per)fluorinated comonomers having at least one unsaturation of ethylene type, different from TFE; the sum of the molar percentages A)+B) being such as to give polymers showing at least one melting peak at the thermogravimetric analysis (DSC).
Kinetics and Mechanism of the Thermal Reaction between Perfluorobutene-2 and Trifluoromethylhypofluorite
Santos Afonso, M. dos,Schumacher, H. J.
, p. 15 - 24 (2007/10/02)
The kinetics of the thermal reaction between CF3OF and C4F8 have been investigated in the range of 30 deg C to 90 deg C.It was found to be a homogeneous chain reaction of moderate length.The main product is CF3CF(OCF3)CF2CF3, accompanied by small amounts of C8F18, CF3OOCF3 and CF3CF(OCF3)CF(OCF3)CF3 in constant ratio.Traces of (CF3CF(OCF3)CFCF3)2 are also formed.Inert gases and reaction products have no influence on the reaction, whereas small amounts of oxygen change its course.Under conditions in which / > 1, the reaction follows a second order rate expressi on - = k.The following mechanism explains the experimental results .The chain length ν = /2 is found to be ν = 19+/-3 in the range 32 deg C to 92 deg C, the rate constant of the starting reaction k1 = (5.34+/-0.30)106exp(-13.9 kcal*mol-1/RT)l*mol-1*s-1. - Keywords: Kinetics / Thermal reaction / Perfluorobutene-2 / Trifluoromethylhypofluorite / Perfluoroalkyl radicals