有机溶剂对过氧化环己酮热危险性的减敏效果评价

Inhibitive effect on the thermal hazard of cyclohexanone peroxide by the organic solvents

在纯过氧化环己酮(CYHPO)储运中常添加减敏剂,以降低其热危险性。为了对比评价减敏性能,采用绝热加速量热仪测试了纯CYHPO及加入等质量邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二辛酯(DOP)、正己酸(HAA)和环己醇(CCH)后的热危险参数,并计算了上述5种样品的反应动力学常数和绝热校正数据,建立了包括初始放热温度T0和绝热反应加速度SARC的减敏效果判据,对4种减敏剂的热危险性减敏效果进行了评价。结果表明,DOP对CYHPO热危险性的减敏效果最好。

In this paper,we have made a study of the thermal hazard characteristics of the pure CYHPO and its mixtures with dibutyl phthalate（DBP）,dioctyl phthalate（DOP）,hexanoic acid（HAA） and cyclohexanol（CCH） by using an adiabatic accelerating rate calorimeter（ARC）. We have also found that the above said four organic solvents are popularly used as inhibitors to reduce the thermal instability. We have also obtained the major thermal decomposition reaction parameters,which are crucial to the thermal hazard evaluation,such as the initial exothermic temperature,the final exothermic temperature and the maximum selfheating rate. In addition,we have also observed and tracked the variation of temperature and self-heating rising rate with the prolonging of the time. What is more,we have worked out the reaction order n,the activating energy Eaand the pre-exponential factor A of the above mentioned samples by using the rate constant method. All the above mentioned testing results demonstrate that the addition of the above four inhibitors can not only change the thermal decomposition process,but also affect the chemical reaction mechanism by the fact that adding DBP into CYHPO gives rise to third-order reaction,whereas adding HAA or CCH changes reaction order from second order to the first order. In order to consider the worst condition,the initial test result must be modified to the fully adiabatic condition with the help of thermal inertia factor Φ,which indicates that the final exothermic temperature,adiabatic temperature rise,initial self-heating rate and temperature at maximum self-heating rate all become much higher at the totally adiabatic condition compared to the testing condition,which means that the effect of high temperature damage caused by thermal explosion of testing samples would be magnified at purely adiabatic conditions. However,since neither of the original tested data nor the adiabatic modified results is enough to describe the hazard level,it is necessary to establish a criterion which can quantify the effect of the four inhibitors. Based on the adiabatic compatibility of the evaluation method,the criterion here we have proposed consists of the initial exothermic temperature T0 and the average reaction acceleration SARC,the latter of which can be represented by the thermal decomposition reaction characteristics.Thus,it can be concluded from the results that the initial exothermic temperature of these test samples should be 60. 4 ℃,79. 9℃,69. 6 ℃,59. 59 ℃ and 54. 88 ℃,respectively,whereas the mean accelerations should be 0. 085 2 ℃ / min2,0. 351 4 ℃ /min2,0. 022 5 ℃ /min2,0. 048 1 ℃ /min2 and 0. 012 7 ℃ /min2,in which DOP proves to have the best effect of the four above mentioned testing inhibitors for CYHPO.