5-硝基-3-三硝甲基-1H-1,2,4-三唑和5,5'-双(三硝甲基)-3,3'-偶氮-1H-1,2,4-三唑的合成与理论研究  

Synthesis and Theoretical Studies of 5-N itro-3-trinitromethyl-1H-1,2,4-triazole and5,5'-Bis( trinitromethyl)-3,3'-azo-1H-1,2,4-triazole

作　　者：肖啸[1] 姚二岗[1,2] 刘庆[1] 丁可伟[1] 苏海鹏[1] 李陶琦[1] 张敏[1] 葛忠学[1] 

机构地区：[1]西安近代化学研究所,陕西西安710065 [2]燃烧与爆炸技术重点实验室,陕西西安710065

出　　处：《含能材料》2016年第1期45-52,共8页Chinese Journal of Energetic Materials

基　　金：国防"973"计划(No.613740102)

摘　　要：以氨基胍碳酸氢盐与丙二酸为原料,经缩合-环化反应、重氮化-取代反应、氧化偶联反应和硝化反应分别合成出5-硝基-3-三硝甲基-1H-1,2,4-三唑(TNNT)和5,5'-双(三硝甲基)-3,3'-偶氮-1H-1,2,4-三唑(BTNAT)。用红外光谱、核磁共振、元素分析表征了它们的结构。进行了B3LYP/6-31G(d,p)基组水平下它们的全结构优化和自然键轨道(NBO)分析。用DSC测定了它们的分解温度。结果表明,10℃·min^(-1)升温速率,氮气气氛条件下,TNNT和BTNAT的分解温度分别为135℃和146℃。5 -N itro-3 -tri nitromethyl-1 H-1 , 2,4-triazole （ TN NT ） and 5,5 ＇-bis （ trin itromethyl ） -3,3 ＇-azo-1 H-1 , 2,4-triazole （ BTNAT ） were synthesized via condensation-cyclization, diazotization-substitution, oxidation-coupling and nitration reaction using aminoguanidinium hydrogen carbonate and malonic acid as raw materials, respectively. Their structures were characterized by IR spec- trometry, NMR and elemental analyses. Their whole structure optimization and natural bond orbital （NBO） analysis were carried out at the B3LYP/6-31G （d, p） basis set level. Their decomposition temperature was measured by DSC. Results show that the decomposition temperature of TNNT and BTNAT under the conditions of 10 ℃ ~ min-I and N2 atmosphere is 135 ℃ and 146 ℃, respectively.

关 键 词：5-硝基-3-三硝甲基-1 H-1 2 4-三唑(TNNT) 5 5’-双(三硝甲基)-3 3’-偶氮-1 2 4-三唑(BTNAT) 硝化 密度泛函理论 

分 类 号：TQ560.1[化学工程—炸药化工]