基于哒嗪并唑类共轭骨架的低感高能单质炸药合成及性质研究

Explosives are the basic energy materials of modern weapon systems, which is of importance to national defense and economic security. The low detonation performance of insensitive explosives and the low security of the high explosives limit the improvement of weapons’ operational capability as well as the surviving ability of weapons and soldiers. However, the high detonation performance and the high security of explosives have always been a difficult contradiction to be reconciled. Pyridazine-azole fused rings have high heats of formation, high densities and high stabilities due to its high nitrogen contents and conjugated structure. So pyridazine-azole fused rings are very suitable to be parent ring of low-sensitivity and high-energy explosives. In this project, a series of single explosives based on pyridazine-azole fused rings will be designed and synthesized. Intramolecular hydrogen bond conjugation systems will be constructed by introducing energetic groups reasonably to the new low-sensitivity and high-energy explosive molecules. On the basis of identification of composition, structure and purity, the physical and chemical properties of the new explosives will be studied. The detonation performance, safety and thermal stability of the new explosive molecules will be studied deeply by combining field measurements and theoretical calculations. And the intrinsic relationship between structure, energy and security will be obtained so as to provide theoretical basis for the subsequent researches and applications of the explosives.

炸药是现代武器系统的基础能源物质，对于国防建设和国民经济保障具有重要意义。低感炸药的爆轰性不足、高能炸药的安全性不高是限制现代武器装备综合作战能力和战场生存能力进一步提高的主要限制因素之一。然而炸药的高爆轰性能和高安全性一直以来就是一对难以协调的矛盾体。哒嗪并唑类共轭骨架拥有高氮含量和共轭结构，因而具有高生成焓、高密度和高稳定性的特点，十分适合作为低感高能炸药分子的母体环。构筑基于哒嗪并唑类骨架的炸药分子有具有重要的研究意义。本项目拟基于哒嗪并唑类共轭稠环骨架，通过含能基团的合理引入构筑分子内氢键共轭体系，设计并合成一系列新型低感高能的单质炸药分子。在完成组成、结构和纯度鉴定的基础上，开展其理化性质研究；通过实测与理论计算相结合的方法，对新型炸药分子的爆轰性能、安全性和热稳定性等进行深入研究，获得其结构-能量-安全性之间的内在关系，为哒嗪并唑类共轭稠环单质炸药的后续应用研究奠定基础。

围绕项目研究目标与研究内容，采用溴化氰关环、叠氮化钠关环等关环策略，构筑了包括四唑并哒嗪稠环、三唑并哒嗪稠环等2类哒嗪并唑类共轭骨架，然后基于这些具有高稳定性、高密度的哒嗪并唑类共轭稠环骨架，引入硝基、硝胺基、硝酸酯基、氮氧化、叠氮基等为制爆单元，引入氨基为稳定化单元，同时通过官能团的合理排布构造分子内和分子间氢键、形成π-π堆积，设计并合成了20余个新型哒嗪并唑类稠环炸药分子，按用途分为低感高能炸药、耐热炸药、传爆药、高能炸药等。采用核磁、高分辨率质谱、单晶X射线衍射、傅里叶变换红外、元素分析等现代表征手段对它们的结构进行了充分表征与鉴定，按照相关方法测试或计算获得了这些单质炸药分子密度、生成焓、热稳定性、撞击感度、摩擦感度、爆速、爆压等物化性质与爆轰性能等参数，并利用理论计算与实验结合的方法深入分析了结构与性能之间的内在关系，揭示了此类化合物能量与感度的适配性关系。本项目的研究大大加深了对哒嗪并唑类共轭稠环单质炸药的设计、合成、稳定性、安全性和能量特性的理解，系列炸药分子的开发与构效关系研究，可以为后续新型先进炸药分子的创制提供理论和实验支持，最终为我国炸药配方研制提供候选材料。同时，本项目也取得了丰富的成果，公开发表基金标注论文4篇，均为第三标注；另有待申请中国发明专利1项、待发表论文1篇（第三标注，已投稿）。