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Thermal decomposition characteristics of diethyl azodicarboxylate dissolved in three ionic liquids as solvents
Journal of Molecular Liquids ( IF 5.3 ) Pub Date : 2020-01-24 , DOI: 10.1016/j.molliq.2020.112564
Qian Yu , Shang-Hao Liu , Zi-Ru Guo , Chen-Rui Cao , Lai-Wang Bin , Chi-Min Shu

Azo-peroxyester, a multifunctional elemental energetic material, has low efficiency when indirectly acting on the target product in a reaction. If azo-peroxyester is dissolved in an appropriate solvent, the yield is greatly improved. With the aim of perfecting the safety of diethyl azodicarboxylate (DEAD) in industrial process applications, this study evaluated the inherent safety of DEAD when dissolved in different reagents by using differential scanning calorimetry and a thermal activity monitor III. The thermokinetic parameters, exothermic onset temperature (To), time to maximum rate under isothermal conditions (TMRiso), and apparent activation energy (Ea), were determined in order to reveal factors influencing the reaction mechanism. Comparing with pure DEAD, T0 was lower when DEAD was dissolved in three ionic liquids: 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium tetrafluoroborate, and 1-butyl-3-methylimidazolium bis(trifluoromethyl)sulfonyl)imide. Additionally, Ea and TMRiso were considerably higher, indicating there was an improvement in both efficiency and thermal safety of DEAD for the reaction process. These results support the applications of DEAD in industrial process safety, and set a foundation for future laboratory investigation.



中文翻译:

溶于三种离子液体的偶氮二羧酸二乙酯的热分解特性

偶氮过氧酯是一种多功能元素高能材料,在反应中间接作用于目标产物时效率较低。如果将偶氮过氧酯溶解在适当的溶剂中,则产率会大大提高。为了完善工业过程应用中偶氮二羧酸二乙酯(DEAD)的安全性,本研究使用差示扫描量热法和热活性监测仪III评估了溶解在不同试剂中的DEAD的固有安全性。热动力学参数,放热起始温度(T o),等温条件下达到最大速率的时间(TMR iso)和表观活化能(E a进行测定,以揭示影响反应机理的因素。与纯DEAD相比,当DEAD溶于以下三种离子液体中时,T 0较低:1-丁基-3-甲基咪唑六氟磷酸盐,1-丁基-3-甲基咪唑四氟硼酸盐和1-丁基-3-甲基咪唑双(三氟甲基)磺酰基酰亚胺。另外,E aTMR iso相当高,表明DEAD在反应过程中的效率和热安全性都有改善。这些结果支持DEAD在工业过程安全中的应用,并为将来的实验室研究奠定了基础。

更新日期:2020-01-24
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