Zhang Zhi-Bin, Xu Cai-Xia, Yin Xin, Zhang Jian-Guo
State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081, PR China.
Dalton Trans. 2016 Dec 21;45(47):19045-19052. doi: 10.1039/c6dt03960j. Epub 2016 Nov 18.
The development of new environmentally friendly energetic compounds with reasonable detonation performance and safety is a long-term target in energetic materials research. A new energetic eco-friendly salt of hydrazine 5,5'-bitetrazole-1,1'-diolate (HA·BTO) is developed based on the reaction of 1H,1'H-5,5'-bitetrazole-1,1'-diolate (BTO) with hydrazine hydrochloride (HA·HCl), and fully characterized. The monocrystal of the title salt is obtained and the structure is determined by powder X-ray diffraction and single crystal X-ray diffraction. Results show that the salt belongs to the triclinic space group P1[combining macron] with a relatively high density of 1.912 g cm under 298 K. The properties of the salt are discussed in detail. The thermal decomposition behaviors of the salt are tested, indicating that the salt has good thermal stability with a decomposition temperature above 200 °C. The enthalpy of formation for the salt is dependent on the combustion heat date measured by oxygen bomb calorimetry with a result of 425.6 kJ mol, which is the same level as TKX-50, and four times higher than that of RDX. The detonation pressure (P) and detonation velocity (D) of the salt are calculated as 8931 m s and 36.1 GPa, which are higher than those of RDX. In addition, the impact and friction sensitivities are tested through a relevant standard method with a result of 28 J and 120 N, which are better than those of TKX-50. We can draw the conclusion that the salt could provide a promising future in use as a kind of insensitive explosive alternative. The discovery also contributes significantly to the expansion and application of the chemistry of 1H,1'H-5,5'-bitetrazole-1,1'-diolate, as well as N-heterocyclic compounds.
开发具有合理爆轰性能和安全性的新型环保含能化合物是含能材料研究的长期目标。基于1H,1'H-5,5'-联四唑-1,1'-二醇盐（BTO）与盐酸肼（HA·HCl）的反应，开发了一种新型的环保型肼盐5,5'-联四唑-1,1'-二醇盐（HA·BTO），并对其进行了全面表征。获得了该标题盐的单晶，并通过粉末X射线衍射和单晶X射线衍射确定了其结构。结果表明，该盐属于三斜晶系空间群P1[结合宏]，在298 K下具有相对较高的密度1.912 g/cm³。详细讨论了该盐的性质。测试了该盐的热分解行为，表明该盐具有良好的热稳定性，分解温度高于200°C。该盐的生成焓取决于用氧弹量热法测得的燃烧热数据，结果为425.6 kJ/mol，与TKX-50处于同一水平，是RDX的四倍。计算出该盐的爆轰压力（P）和爆轰速度（D）分别为8931 m/s和36.1 GPa，高于RDX。此外，通过相关标准方法测试了其冲击和摩擦感度，结果分别为28 J和120 N，优于TKX-50。我们可以得出结论，该盐作为一种钝感炸药替代品具有广阔的应用前景。这一发现也为1H,1'H-5,5'-联四唑-1,1'-二醇盐以及N-杂环化合物的化学扩展和应用做出了重要贡献。
