Abstract
The kinetics of the thermal polymerization of perfluoromethylvinyl ether (PFMVE) is studied at pressures of 3–13 kbar (300–1300 MPa) and temperatures of 80–260°C. The activation energy (Eact = (76 ± 3) kJ/mol) and activation volume (ΔV0⪼ = −(27 ± 2) cm3/mol) for the overall polymerization rate are determined. The inhibition method is used to estimate the activation energy of thermal initiation (Ein = (79.9 ± 3) kJ/mol). The quantity Ep − (1/2)Et was calculated to be 36.6 ± 3 kJ/mol. The limiting polymerization temperature was evaluated: Tlim = (180 ± 3)°C. A mechanism of PFMVE polymerization is proposed on the assumption that the reaction is bimolecular.
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