高能低感含氨基单质炸药的理论设计与合成研究

Considering the dangerous sensitivity problem of high explosives, it is is urgently required to synthesize novel explosive compounds with both low sensitivity and high energetic density to improve the safety of explosives while maintaining their high energetic characteristics. In this work, several methods have been developed to improve the density and safety of the disigned explosive compounds, such as combining the insensitive property of explosives with amino group and the high energy of nitramine explosives, introducing amino groups into the current explosives with high energetic density, designing multi-nitrogen heterocycles with conjugated system containing N-N and C-N high energy bonds and so on. With the formation intermolecular and intramolecular hydrogen-bond of N-OoooH-N type, the density and safety of the disigned explosive compounds could be improved greatly, so as to solve the contradiction between high energy and low sensitivity. Based on the research of regular relationship between molecular as well as crystal structure and explosive property as well as security performance, several explosive compounds were selected through theoretical calculation and simulation. Expolsive samples could be obtained with different synthetic reactions such as condensation, N-nitration, N-oxidation, C-nitration, VNS amination and so on. After analyzing and comparing the mechanical sensitivity, thermal decomposition property and explosion velocity among the obtained samples, target explosives with premium quality were selected and finally, the theory to design explosive molecules as well as the synthetic method were completed and optimized.

针对高能炸药危险感度高的不足，为提高炸药的安全性，同时保持其高能特性，需要合成高能低感单质炸药。采用将含氨基炸药的钝感性与含硝胺炸药的高能性相结合、向现有高能单质炸药分子中引入氨基、设计含有N-N 和C-N 高能键的多氮杂环共轭化合物等技术途径，通过形成N-OoooH-N型分子或离子间氢键，提高所设计合成的单质炸药的密度和安全性，寻求解决单质炸药的高能量与低感度之间的矛盾。对炸药分子进行理论计算和模拟，在求得分子和晶体结构与爆炸和安全性能之间的规律性联系基础上，筛选出多个高能低感含氨基单质炸药，对其进行合成路线设计和合成实验方法研究。通过缩合反应、硝化反应和胺化反应、氧化反应等合成手段，获得几种高能低感单质炸药的样品。在对炸药样品进行机械感度、热分解特性、密度和爆速等主要安全和爆炸性能的测定及分析比较后，优选出性能优良的高能低感单质炸药目标化合物，并优化其合成方法，完善炸药分子设计理论。

针对高能炸药危险感度高的不足，为提高炸药的安全性，同时保持其高能特性，需要合成高能低感单质炸药。采用将含氨基炸药的钝感性与含硝胺炸药的高能性相结合、向现有高能单质炸药分子中引入氨基、高能键的多氮杂环共轭化合物等技术途径，解决单质炸药的高能量与低感度之间的矛盾。对炸药分子进行理论计算和模拟，获得分子结构与爆炸和安全性能之间的规律性基础上，筛选出多个高能低感含氨基单质炸药，对其进行合成路线设计和合成实验方法研究，获得了几种高能低感单质炸药化合物，完善了炸药分子设计理论。.项目分析了单质炸药分子中引入氨基对提高稳定性的作用，设计研究了六硝基八氢化二咪唑[4,5-b:4',5'-e]吡嗪-2,6-(1H,3H)-N,N'-二亚硝胺及其中间体分子结构、性能与安全的构效关系，对2,6-双(二硝基亚甲基)-1,3,4,5,7,8-六硝基十二氢二咪唑[4,5-b:4',5'-e]吡嗪的分子结构、性能与安全的构效关系、分子构象的影响规律进行了理论研究。研究了苯并杂环系列衍生物分子结构中的并环、共轭、氢键以及基团效应对与性能的影响规律，设计研究了系列双环黑索今衍生物和硝基胍类化合物的分子结构与性能的构效规律。.项目实验合成了4,8-二硝基八氢化二咪唑[4,5-b:4',5'-e]吡嗪-2,6-(1H,3H)-N,N'-二亚硝胺、2,6-二氨基-3,7-二硝亚胺基-2,4,6,8-四氮杂双环［3,3,0］辛烷；结合FOX-7分子中含有氨基的特征，合成了1,1-二苦氨基-2,2-二硝基乙烯。合成和表征了1,1'-二羟基-5,5'-联四唑铵盐、羟胺盐和5-氨基四唑盐三种非金属离子盐，以及钴盐、铜盐和铅盐三种金属离子盐，研究了其热分解动力学和钝感特性。实验研究了硝仿及其衍生物的合成及工艺优化，以及杂多酸催化钝感硝胺炸药TEX的合成工艺的改进；研究了离子液体催化醛胺缩合反应制备氮杂环化合物，以及苯并咪唑及其衍生物的合成及反应机理。