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含能材料  2015 

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

DOI: 10.11943/j.issn.1006-9941.2015.11.022

Keywords: 1,3,5,7-四硝基-1,3,5,7-四氮杂环辛烷 3,7-二硝基-1,3,5,7-四氮杂双环[3.3.1]壬烷(DPT) 硝酸铵 硝化 密度泛函理论(DFT) 反应机理

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Abstract:

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NH4+ 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NH4+ 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NH4+ 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NH4+ 对HMX产率的提高起主导作用。采用密度泛函理论(DFT)对NH4+ 在DPT硝解反应过程中的作用机理进行了理论解释,得出HNO3/NH4+ 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

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