新型四唑-5-甲酰肼高氯酸镍高氮含能配合物的合成与性能

Synthesis and properties of novel high nitrogen energetic complex of nickel perchlorate with tetrazole⁃5⁃formylhydrazine

寻找绿色低毒的无铅起爆药一直是含能材料的重要研究方向,本研究以1H-四唑-5-甲酸乙酯为原料通过肼解反应、配位反应合成了新型四唑类配体1H-四唑-5-甲酰肼(TZCA)及其高氯酸镍配合物Ni(TZCA)2(ClO4)2(ECCs-1),通过X-射线单晶衍射、红外光谱、核磁、元素分析、热重及同步热分析仪对其进行了结构表征和热分解性能测试;采用氧弹量热法测试了ECCs-1的燃烧热并采用盖斯定律和K-J方程预测了其爆轰性能;采用BAM方法测试了ECCs-1的感度;烤燃实验和铅板测试表征其起爆性能。结果表明,TZCA密度为1.83 g·cm^(-3),单斜晶系,C2/c空间群,堆积方式为V型交错堆积,ECCs-1粉末密度为1.90 g·cm^(-3),撞击感度为17 J,摩擦感度为72 N,热分解温度为336℃,其热分解反应活化能为183.3 kJ·mol^(-1),热爆炸临界温度为309.8℃,活化熵为46.745 J·K-1·mol^(-1),活化焓为178.563 kJ·mol^(-1)。热烤实验和铅板测试结果表明,ECCs-1具有良好的起爆性能。

To search green,low‑toxicity lead‑free primary explosive,a new tetrazole derivative ligand 1H‑5‑acylhydrazide tetrazole(TZCA)and its complex Ni(TZCA)2(ClO4)2(ECCs‑1)were synthesized by hydrazinolysis and coordination reactions using ethyl 1H‑tetrazole‑5‑carboxylate as the raw material.The molecular structure and thermal decomposition properties of the title complex were tested by X‑ray single crystal diffraction,IR diffraction,NMR,elemental analysis,thermogravimetric and simultaneous thermal analyzers.The heat of combustion of ECCs‑1 was tested by oxygen bomb calorimetry and its energy parameters were predicted based on Hess law and K‑J equation.Sensitivities of ECCs‑1 were tested by BAM test methods.The results show that the density of TZCA is 1.83 g·cm^(-3),monoclinic crystal system,C2/c space group,the stacking mode is V‑staggered stacking.The density of ECCs‑1 powder is 1.90 g·cm^(-3),impact sensitivity is 17 J,friction sensitivity is 72 N,thermal decomposition temperature is 336℃,activation energy of the thermal decomposition reaction is 183.3 kJ·mol-1,thermal explosion critical tem‑perature is 309.8℃,activation entropy is 46.745 J·K^(-1)·mol^(-1),and the activation enthalpy is 178.563 kJ·mol^(-1).The hot baking and lead plate tests both show that ECCs‑1 has a good detonation performance.