含四唑多环自组装含能化合物的合成、晶体结构及性能  

Synthesis,Crystal Structures and Properties of Tetrazole Based Polycyclic Self-assembled Energetic Compounds

作　　者：杨雅麟 秦逸枫 夏江璐 杜慧英 李馨宇 伍波 马丛明 YANG Ya-lin;QIN Yi-feng;XIA Jiang-lu;DU Hui-ying;LI Xin-yu;WU Bo;MA Cong-ming(State Key Laboratory of Environment‑friendly Energy Materials,Southwest University of Science and Technology,Mianyang 621010,China;School of life science and engineering,Southwest University of Science and Technology,Mianyang 621010,China;College of Safety Science and Engineering,Nanjing Tech University,Nanjing 211800,China)

机构地区：[1]西南科技大学环境友好能源材料国家重点实验室,四川绵阳621010 [2]西南科技大学生命科学与工程学院,四川绵阳621010 [3]南京工业大学安全科学与工程学院,江苏南京211800

出　　处：《含能材料》2024年第6期591-600,共10页Chinese Journal of Energetic Materials

基　　金：四川省自然科学基金(2024NSFSC2029)。

摘　　要：多环富氮含能化合物因其在构建低机械感度、良好热稳定性和高密度新型含能分子方面的独特优势,而备受国内外研究人员关注。研究将四唑环接入稠环中构建新型多环富氮骨架,利用其作为高能有机燃料和氢键供体,进一步与富有氢键受体的氧化性结构单元HClO_(4)通过非共价键自组装,合成了3种不含结晶水的新型多环自组装含能化合物——7-氨基-6-(2H-四唑-5-基)-吡唑并[1,5‑a]嘧啶高氯酸盐(1),7-氨基-6-(2H-四唑-5-基)-[1,2,4]三唑并[1,5‑a]嘧啶高氯酸盐(2)和2,7-二氨基-6-(2H-四唑-5-基)-[1,2,4]三唑并[1,5‑a]嘧啶高氯酸盐(3)。采用核磁共振谱(H NMR)、X-射线单晶衍射(XRD)分析对其结构进行表征,利用差示扫描量热仪-热重联用(DSC-TG)和BAM法测试其热稳定性和机械感度,并运用Gaussian 09程序和EXPLO5 V6.05.02预测其爆轰性能。结果表明,3种化合物均有较高的晶体密度(密度ρ:1.75~1.86 g·cm^(-3))、良好的热稳定性(热分解起始温度Td:184~260℃)和爆轰性能(爆速v:7343~7570 m·s^(-1);爆压p:21.1~22.8 GPa),优于传统炸药三硝基甲苯(TNT)。其中化合物1(撞击感度IS>40 J,摩擦感度FS=216 N)和化合物3(IS=25 J,FS=240 N)展现出低的机械感度。Polycyclic energetic compounds with high nitrogen content have attracted much attention owing to their distinctive ad-vantages in constructing novel energetic molecules with low mechanical sensitivity,good thermal stability and high density.The construction of polycyclic skeletons involves the incorporation of tetrazole into fused heterocycle,serving as high-energy organic fuel and hydrogen bond donors.Three self-assembled non-hydrated energetic compounds,namely 7-amino-6-(2H-tetrazol-5-yl)-pyrazolo[1,5-a]pyrimidine(1),7-diamino-6-(2H-tetrazol-5-yl)-[1,2,4]triazolo[1,5-a]pyrimidine perchlorate(2),and 2,7-diamino-6-(2H-tetrazol-5-yl)-[1,2,4]triazolo[1,5-a]pyrimidine perchlorate(3),were synthesized through noncovalent self-assembly of polycyclic skeleton with the oxidizing structural unit HClO_(4) rich in hydrogen bond acceptors.The structural characterization employed nuclear magnetic resonance(NMR)spectroscopy and single crystal X-ray diffraction,while thermal behaviors and mechanical sensitivities were determined by differential scanning calorimetry-thermogravimetry and BAM methods.Detonation performances were predicted utilizing the Gaussian 09 program and EXPLO5 V6.05.02.The results show that three compounds exhibit high crystal densities(ρ:1.75-1.86 g·cm^(-3)),good thermal stabilities(decomposition temperature(onset):184-260℃),and good detonation performances(detonation velocity:7343-7570 m·s^(-1);detonation pressure:21.1-22.8 GPa),surpassing those of traditional explosives trinitrotoluene(TNT).Both compound 1(impact sensitivity(IS)>40 J,friction sensitivity(FS)=216 N)and compound 3(IS=25 J,FS=240 N)exhibit low mechanical sensitivity.

关 键 词：自组装含能化合物 多环结构 四唑 高氯酸根 热稳定性 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O64[理学—物理化学]