基于乌洛托品笼状结构阳离子的五唑盐合成  

Synthesis of Pentazolate Salts Based on Methenamine Cage-like Cations

作　　者：江天宇 刘天林 王康才[1] 夏宏蕾 张文全[1] JIANG Tian-yu;LIU Tian-lin;WANG Kang-cai;XIA Hong-lei;ZHANG Wen-quan(Institute of Chemical Materials,CAEP,Mianyang 621999,China)

机构地区：[1]中国工程物理研究院化工材料研究所,四川绵阳621999

出　　处：《含能材料》2024年第6期631-640,I0003,共11页Chinese Journal of Energetic Materials

基　　金：国家自然科学基金(22022512)。

摘　　要：基于两种乌洛托品笼状阳离子结构,合成了两种新的五唑盐——乌洛托品五唑盐(C_(6)H_(13)N_(9),1)和甲基化乌洛托品五唑盐(C_(7)H_(15)N_(9),2)。通过X-射线单晶衍射、红外光谱(IR)、质谱(MS)和核磁共振(NMR)对合成的五唑盐进行了结构表征,并采用热重分析(TG)和差示扫描量热分析(DSC)测试其热分解行为。使用原子化法计算了化合物1和2的生成焓,使用EXPLO5预测了爆轰性能,并采用BAM方法测试其撞击感度和摩擦感度。测试结果显示,化合物1属于单斜晶系(P21/c),晶胞参数为a=13.6795(2)Å,b=11.6892(1)Å,c=12.5941(2)Å,V=1937.53(5)Å^(3),α=γ=90°,β=105.822(1)°,Z=8,Dc=1.448 g·cm^(-3),化合物2属于单斜晶系(P21/m),晶胞参数为a=6.9025(5)Å,b=7.6042(5)Å,c=10.6808(9)Å,V=538.50(7)Å^(3),α=γ=90°,β=106.148(8)°,Z=2,Dc=1.389 g·cm^(-3)。化合物1和2的热分解温度分别为90.0℃和82.8℃,理论爆速爆压分别为8291 m·s^(-1),20.33 GPa和7862 m·s^(-1),17.41 GPa。测得化合物1和2的撞击感度和摩擦感度分别为5 J,288 N和3 J,86 N。Based on two urotropine cage-like cationic structures,two new pentazolate salts,urotropine pentazolate salt(C_(6)H_(13)N_(9),1)and methylated urotropine pentazolate salt(C_(7)H_(15)N_(9),2),were synthesized.The synthesized pentazolate salts were structurally characterized by X-ray single crystal diffraction,infrared spectroscopy(IR),mass spectrometry(MS)and nuclear magnetic resonance(NMR),and were analyzed by thermogravimetric analysis(TG)and differential scanning calorimetry(DSC)to evaluate their thermal decomposition behaviors.The formation enthalpy of compound 1 and 2 was calculated using the atomization method,the detonation performance was predicted using EXPLO5,and the impact sensitivity and friction sensitivity were tested using the BAM method.The results show that compound 1 belongs to the monoclinic crystal system(P21/c),and the crystal cell parameters are a=13.6795(2)Å,b=11.6892(1)Å,c=12.5941(2)Å,V=1937.53(5)Å^(3),α=γ=90°,β=105.822(1)°,Z=8,Dc=1.448 g·cm^(-3);compound 2 belongs to the monoclinic crystal system(P21/m),and the crystal cell parameters are a=6.9025(5)Å,b=7.6042(5)Å,c=10.6808(9)Å,V=538.50(7)Å^(3),α=γ=90°,β=106.148(8)°,Z=2,Dc=1.389 g·cm^(-3).The thermal decomposition temperature of compound 1 is 90.0℃,and 82.8℃for compound 2.The detonation velocity and pressure of compound 1 and 2 are 8291 m·s^(-1) and 20.33 GPa,7862 m·s^(-1) and 17.41 GPa,respectively.While the measured impact sensitivity and friction sensitivity of compound 1 and 2 are 5 J and 288 N,3 J and 86 N,respectively.

关 键 词：五唑 乌洛托品 笼状阳离子 非金属盐 合成 

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]