THE THERMAL DECOMPOSITION OF CUMENE HYDROPEROXIDE IN RELATION TO CERTAIN ASPECTS OF EMULSION COPOLYMERIZATION

Abstract

Cumene hydroperoxide decomposes near 100 °C. in reactive solvents but only slightly in stable solvents. The decomposition is not a simple first order reaction. The results may be interpreted as the sum of a first and a three-halves order reaction. Approximate over-all energies of activation of the decomposition determined from the data obtained for the decomposition in cumene (31 kcal. per mole), methanol (31 kcal. per mole), styrene (20 kcal. per mole), and the energy of activation for the initial unimolecular step in benzene–styrene mixtures (30.4 kcal. per mole) agree with the values reported for similar peroxides and hydroperoxides in similar solvents. The energy of activation for the radical-induced decomposition is 6.5 kcal. per mole. The data suggest that the first step of the decomposition is the unimolecular reaction involving scission of the O–O bond. If the resultant C6H5C(CH3)2O∙ radical is not reactive towards the solvent, it tends to lose either a phenyl or a methyl radical and form acetone or acetophenone respectively. The former reaction predominates. The decomposition rapidly becomes autocatalytic, particularly in cumene at higher temperatures, presumably because of the radical-induced decomposition of the hydroperoxide. The identified products of decomposition in cumene can be explained by the various reactions of the radicals formed in the mixture. The polymerization shortstop 2,5-ditertiarybutylhydroquinone reacts rapidly below 0 °C. with an equimolar weight of cumene hydroperoxide, and the resulting products retard further thermal decomposition at 90 °C. quite strongly. The shortstop 2,4-dinitrochlorobenzene does not react with cumene hydroperoxide and would seem to act merely as a powerful retarder for the decomposition at the higher temperature. The effect of other related compounds on the decomposition of cumene hydroperoxide in styrene was less marked and agrees with the relatively less effectiveness of these compounds as stoppers in emulsion copolymerization.