铵离子对3,7-二硝基-1,3,5,7-四氮杂双环[3.3.1]壬烷(DPT)硝解反应影响（英）

基于3,7-二硝基-1,3,5,7-四氮杂双环3.3.1]壬烷(DPT)在HNO₃-NH₄NO₃及HNO₃中两种硝解机理,分别通过实验和理论计算方法对NH+4 在DPT硝解反应中的作用进行了研究。将三种不同的铵盐 (NH₄)₂HPO₄,(NH₄)₂SO₄和CH₃COONH₄添加到硝解体系中,考察了NH+4 对HMX产率的影响。结果表明,与NH₄NO₃的作用相似,以上三种铵盐可提高HMX产率,提高率分别为41.5%、37.4%和20.7%。在不同的HNO₃-铵盐体系中,当NH+4 与DPT的摩尔比接近10时,HMX的产率均达到最大值,分别为56.3%、52.2%和35.5%。对比了HNO₃-铵盐和HNO₃-硝酸盐体系中DPT硝解反应的结果,发现NH+4 对HMX产率的提高起主导作用。采用密度泛函理论(DFT)对NH+4 在DPT硝解反应过程中的作用机理进行了理论解释,得出HNO₃/NH+4 体系中DPT硝解反应的活化能为133.95 kJ·mol^-1,低于HNO₃体系中的376.73 kJ·mol^-1。

Influence of Ammonium Ion on Nitrolysis of 3,7-Dinitro-1,3,5,7-tetraazabicyclo[3,3,1]nonane (DPT)

Based on the two mechanisms of 3, 7-dinitro-1, 3, 5, 7-tetraazabicyclo3,3,1] nonane (DPT) nitrolysis via HNO₃-NH₄NO₃ or HNO₃, the effects of NH₄⁺ in nitrolysis of DPT were studied by experiment and theoretical calculation. The effect of NH₄⁺ on the yield of HMX was studied with adding the ammonium salts including (NH₄)₂HPO₄, (NH₄)₂SO₄ and CH₃COONH₄ to nitrate solution system. Results show that the above-mentioned ammonium salts can improve the yield of HMX to 41.5%, 37.4% and 20.7%, respectively. Their function is similar to NH₄NO₃. In different nitric acid-ammonium salt systems, when the molar ratio of NH₄⁺ and DPT is close to 10, the yield of HMX reaches a maximum value of 56.3%, 52.2% and 35.5%, respectively. Results of the nitrolysis of DPT in nitric acid-ammonium salt systems and nitric acid-nitrate system are compared, finding that NH₄⁺ plays a dominant role in improving the yield of HMX. The reaction mechanism of NH₄⁺ in the nitrolysis process of DPT is theoretically explained by the density functional theory (DFT), deriving that the activation energy of DPT nitrolysis in HNO₃/NH₄⁺ is 133.95 kJ·mol^-1, lower than 376.73 kJ·mol^-1 in HNO₃.