Abstract: The thermal hazard of organic peroxides should be assessed to predict and avoid runaway decomposition.In this paper，the Setaram C80 was used to investigate thermal decomposition of several organic peroxides such as cumene hydroperoxide(CHP)，tert-butyl hydroperoxide(TBHP)，dicumyl peroxide(DCP)，di-tert-butyl peroxide(DTBP)，benzoyl peroxide(BPO)，tert-butyl peroxybenzoate(TBPB)，methyl ethyl ketone peroxide(MEKP)，2,5-dimethyl-2,5-di(tert-butylperoxy)hexane(DHBP)and 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane(TMCH).Decomposition heat of the organic peroxides was calculated from isothermal scanning curves.The nth-order or autocatalytic reaction kinetics model was established for these organic peroxides，and self accelerating decomposition temperature(SADT)was derived by using Semenov model.The results showed that decomposition of the organic peroxides mostly followed nth-order model with approximate reaction order of 1，however，some of them preferred to autocatalytic model.The SADT of the organic peroxides calculated was in good agreement with values from literatures，demonstrating reaction kinetics fitting and SADT calculating in this paper are of scientific.

Key words: organic peroxide, self accelerating decomposition temperature, thermal hazard, reaction kinetics, autocatalytic

摘要： 为了预防及控制有机过氧化物的分解爆炸事故，需要对其热危害进行必要的评估。利用塞塔姆C80微量热仪对不同种类的9种有机过氧化物进行热扫描测试，并分别利用n级反应模型及自催化反应模型对扫描曲线进行拟合，准确得到了这些物质的分解热及分解机理。根据反应动力学数据，采用Semenov爆炸模型及联合国H.3-等温储存试验原理，得到了9种有机过氧化物的临界温度及自加速分解温度（SADT）。结果表明，大部分有机过氧化物分解遵循n级反应模型，反应级数在1左右，少部分有机过氧化物分解时有一定的自催化效应。所得的SADT数据与文献值符合较好，证明本文动力学模拟及SADT计算方法的科学性。

关键词: 有机过氧化物, 自加速分解温度, 热危害, 反应机理, 自催化