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A kinetic model for the redox-initiated radical telomerization of vinyl acetate activated by microwave irradiation is presented. Four approaches based on the “microwave” or “thermal” effects were used to study the cases under microwave irradiation. One of the models assumes microwave-induced generation of radicals from monomer. The second model considers higher reaction temperatures than those reported in the experiments. The third model assumes that microwave radiation affects specifically catalyst-involved reactions. The fourth model is a combination of the second and third ones. The kinetic model captures well the effect of initiator, catalyst and solvent contents, as well as absence or presence of microwave irradiation, on polymerization rate and molecular weight development. Limiting monomer conversions and fairly constant values of number average molecular weight and molar mass dispersity were predicted by the model, which agrees with experimental observations. [ABSTRACT FROM PUBLISHER]

Abstract: Polymerization of vinyl acetate (VAc) was carried out with four different cyclometalated ruthenium(II) catalysts, using CCl4 as initiator under conventional heating and microwave irradiation. The thermo-polymerizations were solvent-dependent and proceeded to limited conversions without control. Only the polymerization in DMSO mediated by [Ru(η6-C6H6)(C6H4-2-CH2NMe2)(MeCN)]PF6 (1) showed dependence of the molecular weights on conversion. Besides, this complex was the only one active under microwave irradiation. The microwave assisted polymerization was much faster than that under conventional heating, maintaining an increase of the molecular weights with conversion. The chain extensions were quite successful under both conventional heating and microwave irradiation, confirming the participation of ATRP mechanism. The complex 1 was active in atom transfer radical addition of CCl3Br to VAc substrate providing the adduct in high yield. Mechanistic studies demonstrated the importance of the presence of a labile benzene ligand to increase the catalytic activity of the ruthenium complexes. [Copyright &y& Elsevier]