Antioxidants and stabilizers. XL. Contributors to the thermal decomposition of tert‐butyl hydroxyperoxide

Abstract

The rate of decomposition of tert‐butyl hydroperoxide in benzene solution within the temperature range of 132 to 170°C has been investigated. At concentrations of tert‐butyl hydroperoxide lower than 0.03 mole/1. the reaction occurs via a monomolecular mechanism (activation energy Eb = 36.7 ± 3 kcal/mole). At higher concentrations the initial rate of decomposition is that of a second‐order reaction with respect to hydroperoxide (activation energy Ea = 16 ± 4 kcal/mole). The reaction mechanism has been discussed, and the activation energy of the reaction of tert‐butoxyl radicals with tert‐butyl hydroperoxide has been estimated.

Kinetic analysis of polydicyclopentadiene oxidation

“…-tert-butyl hydroperoxide where E 1 ¼ 155 kJ mol À1 for unimolecular decomposition [62] decreases to 60e80 kJ mol À1 [63] in presence of cobalt (II) or cobalt (III) salts.…”

Antioxidants and stabilizers. XLI. reaction of tert‐butyl hydroperoxide with 2,2′‐methylenebis(4‐methyl‐6‐tert‐butylphenol)

“…= 0.82), and tetramer (V, = 80.5 c; *We have found that colored compounds were able to oxidize KI at conditions of iodometrical determination of hydroperoxide, however, the fault was within the limit of The peak,V, = 132 c,corresponding to benzene is worth mentioning. As has been described [13], the benzene used did not contain any impurities detectable by GLC even if the sensitivity was increased 200 times on five phases of different type. This peak always appeared after a large charge of benzene was injected into the chromatographc column.…”

“…The portion of tert-butyl alcohol formed by decomposition of TBH in the presence of methylenebisphenol is considerably smaller than in the case of the decomposition of TBH alone under the same conditions [13]. Table I gives the concentrations of the low-molecular weight reaction products after 1500 min of reaction.…”

“…k2 has been defined in [13], k3 (1. mole-'min-') is the rate constant of the reaction of TBH with methylenebisphenol. The loss of methylenebisphenol can be derived from eq.…”

“…The reaction of tert-butyl hydroperoxide and 2,2'-methylenebis(4-methyl-6tert-butylphenol) was investigated by using the same technique as for the decomposition of tert-butyl hydroperoxide alone in sealed evacuated ampoules [13]. The indidivual ampoules were heated at a given temperature, and the content was distributed for the individual analyses.…”