螯合型均四嗪骨架含能MOFs的构筑及性能研究

High explosives with high heat-resistant properties have wide applications in some weapon systems designed for special purposes, deep-well perforator, and some others. Synthesis of novel heat-resistant explosives has been one of the research hot-topics in the field of energetic materials. However, traditional CHNO-based heat-resistant explosives are now facing several problems including limited categories, low energy, and complicated synthetic methods, etc. In order to offset those drawbacks, this project aims to use nitrogen-rich s-tetrazine derivatives as multidentate ligands for the construction of chelated coordination energetic MOFs. Through constructing the rigid structural framework by chelated coordination, hydrogen bond net, and π-π interaction, the thermal stabilities of energetic MOFs will be significantly enhanced. In addition to the adjustable structures, the energetic performance and thermal stability of energetic MOFs will be also rationally tuned. Structure-property relationships between crystal structure, energy, sensitivity and thermal stability will be studied systematically. Through this project, a series of chelated E-MOFs with aesthetic structures, high energy-density and high thermal stabilities will be obtained, thereby providing a theoretical basis and data foundation for the development of novel chelated coordination heat-resistant explosives.

耐热炸药在某些具有特殊用途的武器装备、石油深井射孔等领域具有广泛的应用。设计开发新型耐热炸药是含能材料领域的研究热点之一。针对传统CHNO类高耐热炸药种类有限、能量偏低和合成方法繁琐等问题，本项目拟采用高氮均四嗪衍生物作为多齿含能配体，通过在含能配体骨架上嵌入螯合配位点方式增强含能MOFs材料晶体结构中的刚性限制，从而提高材料热稳定性来构建新型耐热炸药；利用含能MOFs材料结构的可调变性来调控材料的能量水平和热稳定性，探索含能MOFs材料结构上配体同金属离子之间的配位模式、氢键网格、π-π作用等对材料性能的影响规律，获得材料结构、能量和热稳定性之间的内在关系。通过本项目研究，将获得系列具有结构新颖、高能量和高热稳定性的新型含能MOFs材料，为下一步设计开发具有应用潜力的螯合配位型高耐热炸药提供理论基础和实验依据。

针对传统CHNO类高耐热炸药种类有限、能量偏低和合成方法繁琐等问题，本项目采用高氮含能化合物作为配体，通过在含能配体骨架上嵌入螯合配位位点的方式增强目标含能MOFs骨架结构上的刚性限制作用，从而提高材料热稳定性，构筑了系列具有高耐热性能的含能MOFs。本项目研究内容主要为：1) 含能MOFs的设计与合成；2) 含能MOFs结构鉴定与性能研究；3)探索含能MOFs结构与热稳定性之间的构效关系。本项目共设计合成了18种含能MOFs，其中热分解温度高于280oC的有11种，热分解温度最高为349oC。本项目通过对含能MOFs结构的调变，实现了对其热稳定性的调控，探索了含能MOFs配体同金属离子之间的配位方式对热稳定性性能的影响规律。此外，本项目还研究了EMOF-1对固体推进剂燃烧性能的影响。EMOF-1的添加能够有效地提高固体推进剂在3-9MPa压力范围内的燃烧速率。EMOF-1在固体推进剂燃烧催化剂方面表现出巨大的应用潜力。本项目研究获得了系列具有结构新颖和高热稳定性的新型含能MOFs，能够为下一步设计开发具有应用潜力的螯合配位型高耐热炸药提供理论基础和实验依据。