N_2O_5/HNO_3硝解乌洛托品制备RDX的机理  

The Mechanism for the Preparation of RDX from the Nitrolysis of Hexamethylenetetramine with N_2O_5/HNO_3

作　　者：王志鑫[1] 杨红伟[1] 伍波[1] 吕春绪[1] 程广斌[1] 

机构地区：[1]南京理工大学化工学院,江苏南京210094

出　　处：《火炸药学报》2015年第6期45-50,共6页Chinese Journal of Explosives & Propellants

基　　金：国家自然科学基金资助(21376121)

摘　　要：利用13 C NMR谱监测了乌洛托品(HA)在N2O5/HNO3和N2O5/HNO3/CH2Cl2硝化体系中硝解反应的历程,根据实验13 C NMR谱和计算13 C NMR谱的解析结果,并结合HA硝解反应过程中可能存在中间体和副产物的13 CNMR理论计算结果,提出了硝解历程中可能存在的中间体与副产物的结构,推测了HA在N2O5/HNO3体系中的硝解历程为:HA首先与两分子HNO3结合生成乌洛托品二硝酸盐(HADN);HADN再经环三亚甲基硝胺母体逐步降解为黑索今(RDX)。The reaction mechanism for the nitrolysis of hexamethylenetetramine(HA)in the nitrating system of N2O5/HNO3 and N2O5/HNO3/CH2Cl2 was monitored by using 13 C NMR spectroscopy.Based on the analytical result of the 13 C NMR spectrum,and combined the result of calculated 13 C NMR of the possible intermediates and by-products in the nitrolysis reaction process of HA,the structures of the possible intermediates and by-products in the nitrolysis reaction process of HA were presented.A possible mechanism for the nitrolysis of HA in the nitrating system of N2O5/HNO3 was speculated.In the first step,hexamethylenetetramine dinitrate(HADN)was formed via one molecular HA and two molecular HNO3.And then,HADN gradually degrades to RDX via cyclotrimethylen enitramine matrix.

关 键 词：有机化学 乌洛托品 HA N2O5/HNO3 RDX 硝解机理 13CNMR 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] TQ203[化学工程—有机化工]