BuAENA合成工艺物料的热危险性研究

Thermal hazard of materials in the BuAENA synthesis process

为研究丁基叠氮乙基硝胺(BuAENA)叠氮化反应过程中物料的热危险性,以反应过程中所涉及的原料、6种反应中间物料和产物为研究对象,对其热稳定性展开研究。采用差示扫描量热法(DSC)获得了物料的热分解曲线,筛选出最不稳定的物料。采用绝热加速量热法(ARC)研究了最不稳定物料在绝热条件下的热分解历程,建立了绝热动力学模型,并获得T_(D24)等热安全性参数。结果表明,刚加入NaN_(3)时刻的反应液物料(1#样品)最不稳定,在绝热条件下的分解绝热温升为404.34℃,分解热为867.13 J/g,按照失控反应严重度评估准则判定其发生失控分解的后果是严重的;1#样品的绝热分解活化能E_(a)=150.55 kJ/mol,指前因子lnk_(0)=29.44 s^(-1),反应级数n=0.16,基于动力学模型得到绝热条件下24 h达到最大反应速率的温度T_(D24)=132.14℃。因此,在BuAENA叠氮化反应过程中,反应温度应控制在132.14℃以下,以确保反应的安全性。

The thermal stability of raw materials,six reactants and product involved in the azide reaction process of N⁃butyl azideethylitramine(BuAENA)were studied to assess the thermal hazard.The thermal decomposition curves was obtained by differential scanning calorimetry(DSC)to screen out the most unstable material,and the corresponding thermal decomposition process under the adiabatic condition was characterized by accelerating rate calorimetry(ARC).The adiabatic kinetic model was established,and the thermal safety parameters such as T_(D24) were predicted.The results show that the reactant just after adding NaN_(3)(1#sample)is the most unstable,and its adiabatic temperature rise and decomposition heat under the adiabatic condition are 404.34℃and 867.13 J/g,respectively,suggesting a great potential of runway reaction based on the severity evaluation criterion.The thermal decomposition activation energy E_(a),pre⁃exponential factor lnk_(0) and reaction order n of 1#sample under the adiabatic condition are 150.55 kJ/mol,29.44 s^(-1) and 0.16,respectively.Based on the kinetic model,the maximum reaction rate is achieved after 24 h under the adiabatic condition and the corresponding temperature to T_(D24) is 132.14℃.Therefore,the temperature in the process of azide reaction should be controlled below 132.14℃to ensure the safety.