四氮唑-紫精类配体构筑的高能钝感金属-有机框架化合物研究

Development of primary explosives plays a key role in modernization of defense technology, initiators and pyrotechnics. Energetic metal-organic framework (MOFs) is expected to be an important research for new primary explosive with features of green, high energy and insensitive. How to reduce sensitivity for external stimulation becomes a key problem for practical applications, when try to increase energy of complex for promoting the ability of detonation. With the development of porous MOFs functional applications, the method of thermal stability MOFs body wrapping energetic guest molecules is expected to solve the problem. The project will focus on the development of a novel strategy using MOFs compounds to reduce the sensitivity, which constructed by tetrazole-viologen derivatives, and research the contribution of energy and effect of sensitivity about some factors, such as the ligand, metal ions and guest molecules, and then build an effective MOFs body by optimizing syntheses of the ligands. On the other hand, the project will study the effect of structure type, weak intermolecular interactions for sensitivity by use of first-principle calculations, and summarize relationship between the structure and the structure of energetic properties. Finally, the study will form an efficient synthetic strategy based on energetic MOFs compounds to develop new primary explosive, in order to promote the process of modernization of initiators and pyrotechnics.

起爆药的发展是火工品和国防科技现代化的关键，金属-有机框架（MOFs）含能化合物因其优异的爆轰性能已成为绿色、高能钝感新型起爆药的重要研究方向。提高MOFs含能化合物的稳定性和能量从而提升爆轰应用的同时，如何降低对外界刺激的感度是其实现实用化应用的关键；而随着微孔MOFs功能化应用的发展，利用具有稳定孔道结构的MOFs主体包裹含能客体分子有望解决这一问题。本项目致力于合成四氮唑-紫精类配体以构筑稳定MOFs主体，包裹和限制含能客体分子；研究不同配体、金属离子和客体分子对MOFs含能化合物的能量贡献和感度影响，建立具有优异含能性质的MOFs主体框架结构模型；同时利用第一性原理计算，探讨结构类型、弱分子间相互作用等因素对感度的影响，明晰结构与含能性质之间的关系，发展可作为新型起爆药的MOFs含能化合物高效合成策略，获得系列具有应用前景的新型起爆药，从而推动火工品和国防科技的现代化发展进程。

本项目立足于“绿色”、高能钝感的新型起爆药，通过MOFs含能化合物的设计，研究其构筑的有效策略。利用设计合成的四氮唑-紫精类配体，通过晶体工程手段，设计合成MOFs主体，同时含能客体分子有效填充，获得MOFs含能化合物；目前，已通过有机合成策略，完成了数十种配体的合成制备，并进行了含能MOFs的设计合成，通过含能材料性能测试及相关分析手段（理论计算等），验证了系列含能材料的表现，例如，获得两个化合物爆炸热量是商用叠氮化Pb(N3)2的2-4倍，并且具有较好的稳定性，热稳定性大于200 ℃、撞击感度大于1 J、摩擦感度大于5 N、静电火花感度大于4 mJ，爆炸产物对环境污染少，是一种高性能起爆药。本研究课题共发表论文13篇，申请专利3项；相关工作分析了与高性能相关的可能因素，为合成高能钝感新型起爆药提供理论指导和成熟的合成策略。