摘要/Abstract

尝试将十二氢十二硼阴离子（B₁₂H₁₂^2-）与含烷基的氨基四唑阳离子结合，得到了一系列新型的硼氢氨基四唑盐含能材料.首先以1-或2-位单烷基化的5-氨基四唑（5-ATZ）为原料，分别与碘甲烷、碘乙烷进行双烷基化反应，合成双烷基的5-氨基四唑的碘盐，其中烷基包括甲基、乙基、正丁基、正己基，而烷基的位置包括1，3-或1，4-位；再与自主合成的十二氢十二硼酸钾在水溶液中经复分解反应，合成了十一种新型十二氢十二硼酸双（二烷基-5-氨基四唑）盐，收率均在70%以上，且在提纯、干燥等条件下化学性质稳定.通过FT-IR、¹H NMR、¹³C NMR、¹¹B NMR、质谱及元素分析对十一种产物的结构进行了准确表征.采用热重分析（TG）和差示扫描量热（DSC）研究了十一种目标化合物的热性能，结果表明，这十一种目标化合物的热稳定性较高，热分解温度都在200℃以上，1，4-二甲基、1-甲基-4-乙基、1，3-二甲基、1-甲基-3-乙基、1-乙基-3-甲基的5种盐的快速热分解发生在结晶熔化之前；其他6种盐的快速热分解发生在结晶熔化之后.这一系列高能化合物在新型含能材料研究中具有重要价值.
关键词: 十二氢十二硼酸盐, 氨基四唑, 二烷基-5-氨基四唑, 含能材料, 合成, 热性能
We tried combining dodecahydrodecaborane anion (B₁₂H₁₂^2-) with aminotetrazole cation into a series of new borohydrino-tetrazolium salt as a kind of energetic materials. Firstly, by using 1-or 2-5-aminotetrazole (5-ATZ) as the raw material, dialkylated 5-aminotetrazolium iodide was synthesized via dialkylation reaction with methyl iodide and ethyl iodide. And then, the dialkylated 5-aminotetrazolium iodides was used to react with potassium dodecylhydrodecaborate in an aqueous solution by metathesis. Finally, eleven novel bis(dialkyl-5-aminotetrazolium) dodecahydrododecaborates were synthesized. All of them were in yield of above 70%, and their chemical properties were stable under the conditions of purification and drying. These compounds have been characterized by FT-IR, ¹H NMR, ¹³C NMR, ¹¹B NMR, mass spectrometry, and elemental analysis. In inspecting their thermal properties using differential scanning calorimetry (DSC) and thermogravimetric analysis (TG) technologies, the results showed that eleven kinds of bis(dialkyl-5-aminotetrazolium) dodecahydrododecaborates have higher thermal stability and the thermal decomposition temperatures of them are mostly above 200℃. In molecular structures, their thermal stability decrease with the increase of the 4-position alkyl when the 1-position alkyl maintains the same. The rapid thermal decomposition of the five compounds, 1,4-dimethyl, 1-methyl-4-ethyl, 1,3-dimethyl, 1-methyl-3-ethyl, and 1-ethyl-3-methyl, occurred before the melting, and the rapid thermal decomposition of the other 6 compounds occurred after the crystals melting. These high-energetic compounds are of great importance in developing new high-performance propellants.
Key words: dodecadodecaborate, tetrazolium, dialkyl-5-aminotetrazole, energetic material, synthesis, thermal property


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