Kinetics of Radical Polymerization of Perfluoropropylvinyl Ether in the Presence of p-Perfluorotoluylic Acid Peroxide at High Pressures

The kinetics of radical polymerization of perfluoropropylvinyl ether (PFPE) was investigated in the presence of a radical initiator at pressures of 264–1056 MPa and temperatures of 323–368 K. Activation energies were determined at different pressures: at P = 10.56 kbar E_act = 135.4 kJ/mol (32.4 kcal/mol), at P =7.04 kbar E_act = 108.3 kJ/mol (25.9 kcal/mol). The activation volume of the total polymerization rate ΔV₀^≠ = –14.6 cm³/mol was determined at T = 353 K. The activation energies of the material initiation were calculated at different pressures [at P = 10.56 kbar, E_i = 123.3 kJ/mol (29.5 kcal/mol), at P = 7.04 kbar, E_i = 88.3 kJ/mol (21.1 kcal/mol)].