过氧化苯甲酸叔丁酯合成反应热危险性分析

Thermal hazard analysis for synthesis of tert-butyl peroxybenzoate

为尽量减小过氧化苯甲酸叔丁酯(TBPB)2步合成反应的热危险性,采用反应量热仪(RC1e)研究反应物用量对反应过程的摩尔反应热(ΔHm)、绝热温升(ΔTad)以及最高合成反应温度(MTSR)的影响;气相色谱表征TBPB的产率以及叔丁基过氧化氢(TBHP)的转化率,并分析其与ΔH_m、ΔT_(ad)以及MTSR之间的关系;差示扫描量热仪(DSC)测试反应产物的热分解特性,判断其发生热分解的可能性与严重度。结果表明:TBPB第2步合成反应的ΔH_m、ΔT_(ad)、MTSR都比第1步反应大。苯甲酰氯的增加会同时提高反应的ΔH_m、ΔT_(ad)以及MTSR。由苯甲酰氯过量引起的产率下降,伴随着反应热危险性的升高。苯甲酰氯的增加,会降低第2步反应产物发生热分解的可能性与严重度。

For the sake of minimizing the thermal hazard of two step synthesis reaction of TBPB,an RC1 e was used to study the effect of reactant amount on the reaction heat（ΔH_m）,adiabatic temperature rise（ΔT_（ad））,and MTSR of the reaction.Gas chromatography was used to detect the yield of TBPB and the conversion rate of tert-butyl hydroperoxide（TBHP）.The relationships between them and ΔH_m,ΔT_（ad）,and MTSR were analyzed.DSC was used to study the thermal decomposition characteristics of the products of the synthesis reaction of TBPB.Moreover,the possibility and severity of thermal decomposition were estimated for the products.Results show that ΔH_m,ΔT_（ad）,and MTSR of the second step in the synthesis reaction are higher than those in the first step,that increasing in benzoyl chloride can enhance ΔH_m,ΔT_（ad）,and MTSR,that excess of benzoyl chloride can reduce the yield and increase the thermal hazard of the reaction,and that an increase in benzoyl chloride,can reduce the possibility and severity of thermal decomposition of the products in the second step.