Azido azole-1,3,4-triazine fused energetic materials: A bioinspired strategy for tuning thermal stability and sensitivity of metal-free primary explosives via hierarchical hydrogen-bond self-assembly

作者：Lei Yang, Wei Du, Jing Feng, Jinshan Li, Qing Ma · 发表于：Chemical Engineering Journal · 年份：2023 · DOI：10.1016/j.cej.2023.141689 · 被引用次数：28 · 研究领域：Energetic Materials and Combustion、Synthesis and Characterization of Heterocyclic Compounds、Thermal and Kinetic Analysis

Primary explosives are useful but they usually pose low thermal stability and underlying safety threat to manufacturers and users. It is highly desirable yet challenging to develop next-generation primary explosives with lead-free, environmentally friendly, high-dense, thermostable and safe organic energetic materials for replacement. Here, inspired by biosystem’s architecture, we report a simple and efficient hierarchical hydrogen-bond self-assembly strategy to synthesize high-performance primary explosives with enhanced thermal stability (T onset > 200 °C) and decreased sensitivity (40 J). Owing to the above-efficient strategy, 7-azide-3-(1H-tetrazol-5-yl)-[1,2,4]triazolo[5,1-c] [1,2,4]triazin-4-amine-2- oxide ( EM-4 ) and 7-azide-4-amino-3-nitro-[1,2,4]triazolo[5,1-c][1,2,4]triazine ( EM-6) feature high densities of 1.825 and 1.816 g cm −3 , much superior to their analogues 7-azide-3-(1H-tetrazol-5-yl)-[1,2,4]triazolo[5,1-c][1,2,4]triazin-4-amine ( EM-3 ) and 8-azide-4-amino-3,7-dinitropyrazolo-[5,1-c][1,2,4]triazine ( EM-9 ), comparable to that of 6-azido-8-nitrotetrazolo[1,5- b ]-pyridazine-7-amine ( ANTP ). Meanwhile, EM-3 (T d = 225 °C), EM-4 (T d = 290 °C) and EM-6 (T d = 210 °C) exhibit better thermal stability and lower sensitivities (IS = 40 J) than those representative metal-free primary explosives (T d = 114–193 °C, IS = 0.25–17 J). The as-synthesized materials all feature superior performance to those of commercially scale-up and industrial applicable primary ex...