二叔丁基过氧化物的热失控动力学研究

Study on Thermal Runaway Dynamics of Di-tert-butyl Peroxide

为研究二叔丁基过氧化物(DTBP)热失控危险性,利用C600微量量热仪对DTBP热分解动力学进行试验研究,测定DTBP在不同升温速率下的起始放热温度和分解热,分别用非等转化率法和等转化率法得到DTBP热分解反应的动力学参数。用非等转化率法确定反应的最佳反应级数为1,相应的活化能分别为137.75、132.60、128.61和122.93 kJ/mol,指前因子分别为8.82×1012、6.69×1012、2.06×1012和3.89×10111/s。用等转化率法确定的活化能范围为102～138 kJ/mol,并拟合出活化能与转化率的关系曲线。结合计算出的动力学参数,通过对DTBP分解机理的分析,可以推断其具有热失控危险性。

In order to investigate the thermal runaway risk of di-tert-butyl peroxide （DTBP）, a C600 heat flux calorimeter was used to evaluate the thermal decomposition behavior of DTBP at different heating rates. The exothermic onset temperature values and decomposition heat values were determined, respectively. The thermokinetic parameters were calculated by the non-isoconversional and isoconversional methods. The optimal n （reaction order） ,value obtained by the non-isoconyersional method was 1; the Ea （ activation energy） values were 137.75, 132.60, 128.61 and 122.93 kJ/mol; and the corresponding A values were 8.82×10^12、6.69×10^12、2.06×10^12 and 3.89×10^11 1/s The Ea values obtained by the isoconversional method were 102 - 138 kJ/mol. The relationship involving the Ea value and conversion degree was fitted. According to the calculated dynamic parameters and the further analysis of decomposition mechanism, it shows that the DTBP has a thermal runaway risk.