Xue Qi, Bi Fu-Qiang, Zhang Jun-Lin, Wang Zi-Jun, Zhai Lian-Jie, Huo Huan, Wang Bo-Zhou, Zhang Sheng-Yong
State Key Laboratory of Fluorine & Nitrogen Chemicals, Xi'an Modern Chemistry Research Institute, Xi'an, China.
Department of Chemistry, Technische Universität München, Garching bei München, Germany.
Front Chem. 2020 Feb 20;7:942. doi: 10.3389/fchem.2019.00942. eCollection 2019.
Design and synthesis of new compounds with both high detonation performances and good safety properties have always been a formidable task in the field of energetic materials. By introducing -ONO and -NHNO moieties into 1,2,4-oxadiazole- and 1,2,5-oxadiazole-based backbones, a new family of energetic materials, including ammonium 3-nitramino-4-(5-hydroxymethyl-1,2,4-oxadiazol-3-yl)-furazan (4), 3,3'-bis[5-nitroxymethyl-1,2,4-oxadiazol-3-yl]-4,4'-azofuroxan (6), [3-(4-nitroamino-1,2,5-oxadiazol-3-yl)-1,2,4-oxadiazol-5-yl]-methylene nitrate (8), and its energetic ionic salts (10-12), were synthesized and fully characterized. The energetic and physical properties of the materials were investigated through theoretical calculations and experimental determination. The results show that the oxadiazole-based compounds exhibit high enthalpy of formations, good detonation performances, and extraordinary insensitivities. In particular, the hydrazinium salt (11) shows the best energetic properties (11: = 1.821 g cm; = 35.1 GPa, = 8,822 m s, IS = 40 J, FS > 360N). The ESP and Hirshfeld surface analysis indicated that a large number of hydrogen bonds as well as π-π stacking interactions within molecules might be the key reason for their low sensitivities and high energy-density levels.
设计并合成同时具备高爆轰性能和良好安全性能的新型化合物，一直是含能材料领域一项艰巨的任务。通过将-ONO和-NHNO基团引入基于1,2,4-恶二唑和1,2,5-恶二唑的主链中，合成了一系列新型含能材料，包括3-硝氨基-4-(5-羟甲基-1,2,4-恶二唑-3-基)呋咱铵(4)、3,3'-双[5-硝氧甲基-1,2,4-恶二唑-3-基]-4,4'-偶氮呋咱(6)、[3-(4-硝氨基-1,2,5-恶二唑-3-基)-1,2,4-恶二唑-5-基]亚甲基硝酸盐(8)及其含能离子盐(10 - 12)，并对其进行了全面表征。通过理论计算和实验测定研究了这些材料的能量和物理性质。结果表明，基于恶二唑的化合物表现出高生成焓、良好的爆轰性能和非凡的钝感性能。特别是，肼盐(11)表现出最佳的能量性能(11: = 1.821 g cm; = 35.1 GPa, = 8,822 m s, IS = 40 J, FS > 360N)。静电势(ESP)和 Hirshfeld表面分析表明，分子内大量的氢键以及π-π堆积相互作用可能是其低感度和高能量密度水平的关键原因。
