The kinetic features of vinylidene fluoride (VDF) radical polymerization in solution, initiated by bis(4-t-butylcyclohexyl)peroxydicarbonate, have been investigated in three different solvents (acetone, ethyl acetate and methyl acetate) under homogeneous conditions. Many significant deviations of the dependence of the polymerization rate on the 'ideal' 1.0 and 0.5 exponent values of monomer and initiator concentrations, respectively, are indicative of anomalous kinetic behaviours linked to concurrent reactions, which are operative during such polymerization. The complexity of the kinetic behaviour prevents, inter alia, the correct evaluation of chain transfer constants to the solvents from kinetic data. 19F nuclear magnetic resonance spectroscopy has been used in order to get full microstructural characterization of the low-molar-mass poly(vinylidene fluoride) (PVDF) synthesized under the above conditions. Both chain transfer constants to the solvent and extent of chain inversions in PVDF have been evaluated by this technique.
Посилання на статтю:
Synthesis and microstructural characterization of low-molar-mass poly(vinylidene fluoride) / Saverio Russo*, Kunj Beharit and Shan Chengji and Maurizio Pianca, Emma Barchiesi and Giovanni Moggi // Polymer. – 1993. – Vol 34. – P. 4777-4781.