The thermolysis of cyclic diethylketone triperoxide (3,3,6,6,9,2,4,5,7, DEKTP) and cyclic pinacolone diperoxide (3,6-diterbutyl-3,6-dimethyl-1,2,4,5-tetraoxacyclohexane , PDP) were studied in neat N,N-dimetyhlformamide (DMF) and in binary mixtures DMF/Ionic Liquid (1-butyl-3-methylimidazolium tetrafluoroborate, [BMIM + ][BF 4 -]). The activation parameters for the decomposition of both peroxides in DMF, correspond to a process of homolytic cleavage of one O-O bond, generating a biradical in the initial step of radical mechanism. The rate constant values (k d ) are higher for reactions performed in mixtures. A gradual increase of [BMIM + ][BF 4 -]in the reaction media generate higher k d for both peroxides (i. e. k d, DEKTP in DMF/[BMIM + ][BF 4 -] 4.0 mol L -1 is 3.3 times greater than the k d obtained for the mixture with a concentration 1.0 mol L -1 , under the same experimental conditions). The increase in decomposition rate can be associated to a more solvated and stabilized transition state when the ionic liquid is part of the reaction medium.
1‐Butyl‐3‐methylimidazolium tetrafluoroborate ([BMIM][BF4]) was used as a solvent during the methyl methacrylate polymerization, in a temperature range of 110 to 130°C, employing two multifunctional cyclic peroxides as initiators, the pinacolone diperoxide and the diethylketone triperoxide, and results were compared with those obtained in N,N‐dimethylformamide (DMF) as a solvent under the same reaction conditions. The polymerization rate was approximately four times faster in [BMIM][BF4] than in DMF, and this behavior is supported by the higher decomposition rate constants calculated for both initiators in pure ionic liquid in comparison with those calculated in DMF. The average molecular weights values were nearly three times lower in DMF than in the ionic liquid, and this is explained by the reduction in the propagation activation energy in the presence of the ionic liquid.
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