Abstract
For the first time, propagation rate coefficients, k(p,COPO) , for the copolymerizations of vinylidene fluoride and hexafluoropropene have been determined. The kinetic data was determined via pulsed-laser polymerization in conjunction with polymer analysis via size-exclusion chromatography, the PLP-SEC technique. The experiments were carried out in homogeneous phase with supercritical CO(2) as solvent for temperatures ranging from 45 to 90 °C. Absolute polymer molecular weights were calculated on the basis of experimentally determined Mark-Houwink constants. The Arrhenius parameters of k(p,COPO) vary significantly compared with ethene, which is explained by the high electronegativity of fluorine and less intra- and intermolecular interactions between the partially fluorinated macroradicals.
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