多氮杂环偕二硝甲基含能化合物的合成与性能研究

The studies of gem-dinitro N-heterocyclic compounds has gained an increasing attentions around the world in the recent years, the existence of gem-dinitro group trends to give higher densities and oxygen balances comparing to nitro, amino, and azido groups by incorporating with N-heterocyclic building blocks. However, due to the strong electron withdrawing effect of the gem-dinitro group, most reported gem-dinitro N-heterocyclic compounds which have single ring system exhibit poor thermal stability and high sensitivity. To address this problem, gem-dinitro compounds which multi N-heterocyclic rings were designed, the high positive heat of formation of the N-heterocyclic rings building block is benefit to improve the thermal stability and sensitivity while maintain their energy level by incorporating with gem-dinitro groups. A series of new energetic compounds were designed and synthesized, their structures were fully characterized by nuclear magnetic resonance spectroscopy (NMR), infrared spectroscopy, elemental analyzer and X-ray single crystal diffraction. Their thermal stability, vacuum stability, impact and friction sensitivities were measured, the detonation parameters and their detonation products were calculated.

相对于硝基，氨基和叠氮基等基团，偕二硝甲基具有更高的密度和氧平衡，偕二硝甲基等多硝基官能团化的氮杂环材料成为了近年来含能材料领域研究的热点。偕二硝甲基的强吸电子效应使单杂环结构在外界作用下容易开环，因而大多数氮杂环已报道的单杂环偕二硝甲基化合物具有热稳定性差，感度高等不足。本研究利用多氮杂环骨架的高生成焓和良好的热稳定性来弥补偕二硝甲基基化合物存在的生成焓低，热稳定性差等方面的不足，并通过阴阳离子间协同作用降低目标化合物的机械感度，有效平衡目标化合物的能量水平和稳定性。在此基础上合成了一系列含能离子盐，利用核磁，红外，元素分析以及X-射线单晶衍射仪并对其结构进行了分析表征，对其热稳定，真空安定性，摩擦和撞击感度进行了测试，最后通过计算获得其爆炸产物及爆轰参数。

含能材料作为武器系统必不可少的威力和动力能量来源，广泛用于各种战略和战术武器系统，在国防和国民经济中有着重要作用。高能高安全含能化合物的创制是近来含能材料领域的研究热点。本项目利用多氮杂环骨架的高生成焓和良好的热稳定性及偕二硝甲基的高密度和氧平衡的协同作用来实现含能化合物综合性能的提升，设计制备了一系列新型偕二硝甲基含能离子化合物，总结偕二硝甲基的数量和取代位置及多氮杂环骨架对密度、生成热、爆速、爆压、安定性等的影响规律和构效关系，实现对偕二硝甲基含能离子盐性能的有效调控。