十二氢十二硼酸双(二烷基-5-氨基四唑)盐的合成、表征及热性能

Synthesis, Characterization and Thermal Behavior of Bis(dialkyl-5-aminotetrazolium) Dodecadodecaborates

尝试将十二氢十二硼阴离子(B_(12)H_(12)^(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、^(13)C NMR、^(11)B 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.

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.