摘要
1-亚硝基-3,5,7-三硝基-1,3,5,7-四氮杂环辛烷(MNX)是3,7-二硝基-1,3,5,7-四氮杂双环[3.3.1]壬烷(DPT)硝解制备奥克托今(HMX)的中间体。为了研究DPT与发烟硝酸反应生成MNX的机理,在反应中加入甲醛。研究了DPT与红烟硝酸(HNO_3/N_2O_4)反应制备MNX新工艺。考察了硝酸、N_2O_4、NH_4NO_3的加入量和反应温度对反应的影响。通过正交实验确定了最佳的反应条件。用GJB772A-97方法和WJ/T9038.3-2004方法测试了MNX的感度。结果表明,甲醛可以促进DPT与发烟硝酸反应生成MNX,提出了DPT在硝酸中经过氧化还原过程的亚硝解反应机理。在-25℃时,其最优反应条件是N_2O_4与DPT的摩尔比为1∶1,NH_4NO_3与DPT的摩尔比为2.5∶1,MNX的收率为83.5%。MNX撞击感度和静电火花感度低于RDX和HMX,摩擦感度介于黑索今(RDX)和HMX之间。
1-Nitroso-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane（ MNX） is an intermediate in the production of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane（ HMX） from 3,7-dinitro-1,3,5,7-tetraazabicyclo[3.3.1]nonane（ DPT） by nitrolysis. To study the mechanism of HMX formation from DPT and fuming nitric acid,formaldehyde was added into the reaction. A new process of preparing MNX by reaction of DPT in red fuming nitric acid（ HNO3/N2O4） was investigated. The influence of reaction temperature,loading amounts of nitric acid,N2O4 and NH4NO3 on the reaction was investigated. The optimum reaction conditions were determined by an orthogonal experiment. The sensitivities of MNX were measured by GJB772 A-97 method and WJ/T9038.3-2004 method. Results show that formaldehyde can promote the reaction of DPT and fuming nitric acid to form MNX and the nitrosolysis reaction mechanism in the redox of DPT in nitric acid is proposed.The yield of MNX is 83.5% under the optimized reaction conditions of molar ratio of N2O4 to DPT as 1 ∶1 and molar ratio of NH4NO3 to DPT as 2.5 ∶1 at-25 ℃. Its impact sensitivity and electrostatic sensitivity of MNX are lower than those of RDX and HMX,while the fricon tisensitivity is between RDX and HMX.
作者
张宇
徐子帅
顾光辉
张路遥
罗军
ZHANG Yu;XU Zi-shuai;GU Guang-hui;ZHANG Lu-yao;LUO Jun(School of Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094 , China;Gansu Yin Guang Chemical Industry Group Co.Ltd., Baiyin 730900 , China)
出处
《含能材料》
EI
CAS
CSCD
北大核心
2018年第5期398-403,共6页
Chinese Journal of Energetic Materials
基金
江苏省"青蓝工程"资助
