Dipartimento di Ingegneria Chimica, Facoltà di Ingegneria, Università di Napoli Federico II, Ple V Tecchio 80, 80125 Napoli, Italy.
J Hazard Mater. 2011 Mar 15;187(1-3):157-63. doi: 10.1016/j.jhazmat.2011.01.023. Epub 2011 Jan 13.
Dicumylperoxide (DCP) is one of the most used peroxides in the polymer industry. It has been reported that its thermal decomposition can result in runaway phenomena and thermal explosions with significant economic losses and injuries to people. In the present paper thermal behaviour of dicumylperoxide in cumene was investigated over the temperature range of 393-433 K under aerated and de-aerated conditions. The results indicated that when oxygen was present, the decomposition rate did not follow a simple pseudo-first order kinetic as previously reported in literature. A satisfactory fit of the experimental data was, in this case, achieved by means of kinetic expression derived under the assumption of an autocatalytic scheme of reaction. The reaction rate was, on the contrary, correctly described by a pseudo-first order kinetic in absence of oxygen. Under both aerated and de-aerated conditions, chemical analysis showed that the decomposition mainly resulted in the formation of acetophenone and dimethylphenylcarbinol with minor occurrence of 2,3-dimethyl-2,3-diphenylbutane. The formation of methane and ethane was also invariably observed while the appearance of cumylhydroperoxide as a reaction intermediate was detected under only aerated conditions. Therefore, two reaction schemes were proposed to explain system behaviour in the presence of oxygen and after its purging.
过氧化二枯基（DCP）是聚合物工业中最常用的过氧化物之一。据报道，其热分解会导致失控现象和热爆炸，造成重大经济损失和人员伤亡。本文研究了过氧化二枯基在枯烯中的热行为，在有氧和无氧条件下，温度范围为 393-433 K。结果表明，当存在氧气时，分解速率不像文献中先前报道的那样遵循简单的拟一级动力学。在这种情况下，通过假设反应的自动催化方案推导出的动力学表达式，可以很好地拟合实验数据。相反，在没有氧气的情况下，反应速率可以通过拟一级动力学正确描述。在有氧和无氧条件下，化学分析表明，分解主要生成苯乙酮和二甲基苯基甲醇，同时少量生成 2,3-二甲基-2,3-二苯基丁烷。甲烷和乙烷的形成也始终存在，而只有在有氧条件下才检测到过氧枯基作为反应中间体的出现。因此，提出了两个反应方案来解释有氧存在和氧气清除后的系统行为。
