【摘要】 本文对过氧化3,5,5-三甲基己酰（1）在30,40,50℃苯中的分解动力学、笼效应、分解主要产物及用galvinoxyl（3）捕获的产物进行了测定。结果表明,当起始浓度在0.04到0.43mol.L^-1范围内时,1在苯中的分解符合一级加二分之三级动力学;笼效应为0.6;也基本上符合作者以前提出的过氧化月桂酰（2）在苯中的分解机理。与2相比,1在同样温度下的自发分解有较大的速率、较大的笼效应以及较少的诱导分解,这应归因于1分子内的枝化,尤其是β-甲基的存在,引起的分解反应物与过渡态之间的较大熵增。更多还原

【Abstract】 The kinetics of decomposition of 3, 5, 5-trimethylhexanoyl peroxide (1) in benzene has been studied at 30, 40 and 50℃ and the cage effect of decomposition has been determined by scavenging method. The relative amounts of the main products of decomposition of 1 at 50℃ with change of initial concentration have been determined. The results showed that the decomposition of 1 followed first plus three halves order kinetics as reported for lauroyl peroxide (2), but had a larger cage effect of 0.6. The mechanism of decomposition of 1 is practically the same as what we have proposed for 2. The faster rate and larger cage effect but less induced decomposition of 1 than that of 2 are attributed to the branching of the molecule of 1, especially to the presence of β-methyl group, which causes a larger entropy increase in the transition state.更多还原