Thermal Decomposition Reaction of Acetone Triperoxide in Toluene Solution

Eyler, Gladys N.; Mateo, Carmen M.; Álvarez, Élida; Cañizo, Adriana I.

doi:10.1021/jo991459i

Cited by 37 publications

(30 citation statements)

References 8 publications

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“…The kinetic data obtained in this work, and other results previously described by various authors for different cyclic peroxides (Cafferata et al, 1984;Cafferata et al, 1990;Cafferata et al, 1991;Eyler et al, 1994;Eyler et al, 2000;Barreto and Cañizo, 2004;Sheng et al, 2004;Cañizo, 2006;Iglesias et al, 2009), allowed to associate the rate constants with the unimolecular rupture process of one peroxidic bond as the rate-determining step of the decomposition route (Scheme 2).…”

Section: Kinetic Studiessupporting

confidence: 68%

Effect of ionic liquid on the thermal decomposition of cyclic organic peroxides

Barreto

Rodríguez

Morales

et al. 2019

Arabian Journal of Chemistry

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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.

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Section: Kinetic Studiessupporting

confidence: 68%

Effect of ionic liquid on the thermal decomposition of cyclic organic peroxides

Barreto

Rodríguez

Morales

et al. 2019

Arabian Journal of Chemistry

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“…However, the use of cyclic multifunctional initiators has not been reported in solution polymerizations carried out in ILs as solvents. As it was previously reported, the thermal decomposition of this kind of multifunctional initiators is strongly dependent of the solvent used . Moreover, when monomers such as MMA and styrene were employed as the reaction media, there was clear evidence of a strong dependence of the monomer nature on the initiators decomposition.…”

Section: Introductionsupporting

confidence: 55%

Solution Polymerization of Methyl Methacrylate in an Ionic Liquid Employing Cyclic Multifunctional Initiators

Rodríguez

Acuña

Enríquez-Medrano

et al. 2017

Macromolecular Symposia

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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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“…The multi‐functional cyclic peroxides can be obtained through the reaction of hydrogen peroxide with ketone compounds at low temperatures (−10, −15°C), using an inorganic acid, such as sulfuric acid, as a catalyst. Regarding the thermal decomposition kinetics of some cyclic organic peroxides, it has been extensively reported . For instance, the thermolysis of pinacolone diperoxide [PDP, 3,6‐ditertbutyl‐3,6‐dimethyl‐1,2,4,5‐tetraoxacyclohexane, [Figure (a)], acetone cyclic triperoxide [ACTP, 3,3,6,6,9,9‐hexamethyl‐1,2,4,5,7,8‐hexaoxacyclononane, [Figure (b); R= CH 3 )] and diethyl ketone triperoxide [DEKTP, 3,3,6,6,9,9‐hexaethyl‐1,2,4,5,7,8‐hexaoxacyclononane [Figure (b); R = CH 2 CH 3 )] has been reported in different organic solvents (or mixtures of them), including acetone, toluene, ethylbenzene, chlorobenzene, acetonitrile, ethanol, among others.…”

Section: Introductionmentioning

confidence: 99%

Thermal decomposition of diethyl ketone triperoxide in methyl methacrylate: Theoretical and experimental study of the initial solvation state and its influence on the polymerization process

Rodríguez¹,

Enríquez-Medrano²,

Grande

et al. 2015

J of Applied Polymer Sci

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The decomposition rate constant (kd) of diethyl ketone triperoxide (DEKTP, 3,3,6,6,9,9‐hexaethyl‐1,2,4,5,7,8‐hexaoxacyclononane) in methyl methacrylate (MMA) was determined by the kinetic study of its thermal decomposition at temperatures from 110 to 140°C. The calculated kd for DEKTP in MMA was 2.4 times lower (at 130°C) compared with that previously determined and reported in styrene (St). Density functional theory (DFT) calculations demonstrated that the decomposition of DEKTP molecule in MMA required higher interaction energy than in St, thus explaining its lower kd value. Bulk polymerization kinetics of MMA using DEKTP as the initiator revealed the presence of an induction period, in contrast with St polymerization, providing clear evidence of the solvation state influence at early polymerization stages. This work provides mechanistic insights into the interactions among the multi‐functional cyclic peroxide DEKTP and vinyl monomers; St and MMA, and their influence on the polymerization kinetics. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 42905.

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Thermal Decomposition Reaction of Acetone Triperoxide in Toluene Solution

Cited by 37 publications

References 8 publications

Effect of ionic liquid on the thermal decomposition of cyclic organic peroxides

Effect of ionic liquid on the thermal decomposition of cyclic organic peroxides

Solution Polymerization of Methyl Methacrylate in an Ionic Liquid Employing Cyclic Multifunctional Initiators

Thermal decomposition of diethyl ketone triperoxide in methyl methacrylate: Theoretical and experimental study of the initial solvation state and its influence on the polymerization process

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