ACTIVATION OF THE DECOMPOSITION OF TERT-BUTYL PEROXYPIVALATE WITH TRIALKYLALUMINUM COMPOUNDS

The decomposition of tert-butyl peroxypivalate (TBPPI) in the presence of trialkylaluminium activators was examined in an optical cell using in-situ Raman spectroscopy. The measurements were carried out in the temperature range between 90 and 165 degrees C at pressures between 1 and 1800 bar. The trialkylaluminium compounds used were triethyl, trih exyl, trioctyl and tridodecylaluminium which were employed in quantita tive ratios of up to 1 mol trialkylaluminium per mol peroxide. From th e graphs showing the peroxide concentration as a function of time, the rate constant, the energy of activation and the half-life time of the decomposition reaction were determined. A comparison of these data wi th the parameters of the decomposition of pure TBPPI in solution clear ly illustrated the acceleration of the decomposition reaction as a res ult of the influence of the organoaluminium compound. By means of the NMR spectra of the individual components and their mixture it was poss ible to show that the activated decomposition takes place via trialkyl aluminium/peroxide complexes.