双阳离子型咪唑含能盐的合成及性能

Synthesis and Properties of Bis-cationic Imidazolium Energetic Salts

以2?甲基咪唑为原料,二溴甲烷为桥联试剂,经过亚甲基桥联、季铵化、硝化反应得到了双阳离子含能化合物3,3′?亚甲基双(2?甲基?1?硝酰氧乙基咪唑)二硝酸盐,然后通过复分解反应得到一系列分别以苦味酸负离子、二硝酰胺负离子、3,5?二硝基?1,2,4?三氮唑负离子和5?硝基四唑负离子为阴离子的双阳离子型含能盐。所合成的含能盐经紫外可见光谱(UV?Vis)、红外光谱(IR)、质谱(MS)、核磁共振(NMR)、元素分析和热重分析(TGA)等分析表征。采用Kamlet?Jacobs方程估算了所合成双阳离子含能盐的爆速和爆压等爆轰参数。结果表明,双阳离子含能盐具有良好的热稳定性,其分解温度均高于169℃,第一阶段的热分解峰值温度均接近200℃。除了5?硝基四唑双阳离子盐,其余双阳离子含能盐均较对应单阳离子咪唑含能盐具有更高的热分解温度;同时所有双阳离子含能盐较对应单阳离子含能盐具有更高的熔点;部分双阳离子咪唑含能盐较对应单阳离子含能盐具有更高的密度。3,3′?亚甲基双(2?甲基?1?硝酰氧乙基咪唑)二(3,5?二硝基?1,2,4?三唑)盐和3,3′?亚甲基双(2?甲基?1?硝酰氧乙基咪唑)二(5?硝基四唑)盐的爆速和爆压介于2,4,6?三硝基甲苯(TNT)和黑索今(RDX)之间,表现出较好的爆轰性能。

Using 2-methylimidazole as raw material and dibromo methane as a bridging reagent,a bis-cationic energetic com-pound,3,3′-methylene-bis(2-methyl-1-nitroxyethylimidazolium)dinitrate(3)was synthesized via.methylene-bridging,quaternization,and nitration reactions.Then a series of bis-cationic energetic salts were obtained via the metathesis reactions of compound 3 with negative ions of picrate,dinitramide,3,5-dinitro-1,2,4-triazolate,and 5-nitrotetrazolate as anions.All the synthesized energetic salts were analyzed and characterized by ultraviolet visible spectrum(UV-Vis),infrared spectrum(IR),mass spectrum(MS),nuclear magnetic resonance(NMR),elemental analysis,and thermogravimetric analysis(TGA).The detonation peformance of the synthesized bis-cationic energetic salts,such as detonation velocity and detonation pressure,were estimated by Kamlet-Jacobs equation.Results show that the bis-cationic energetic salts have a good thermal stability,their decomposition temperatures are above 169 oC and their thermal decomposition peak temperatures are close to 200℃for the first decomposition stage.The bis-cationic energetic salts apart from 5-nitrotetrazolate bis-cationic energetic salt have a better thermal stability than the corresponding mono-cationic im-idazolium energetic salts.At the same time,all the bis-cationic energetic salts have a higher melting point than the corresponding mono-cationic energetic salts.Some bis-cationic imidazolium energetic salts have a higher density than the corresponding mono-cationic energetic salts.The detonation velocities and detonation pressures of 3,3′-methylene-bis(2-methyl-1-nitroxyethylimidazolium)-d(i 3,5-dinitro-1,2,4-triazolate)and 3,3′-methylene-bis(2-methyl-1-nitroxyethylimidazolium)-d(i 5-nitrotetrazolate)are between those of 2,4,6-trinitrotoluene(TNT)and 1,3,5-trinitroperhydro-1,3,5-triazine(RDX),showing better detonation performances.