3-硝基胍-1,2,4-三唑[4,3-b]-s-四嗪及其脒基脲盐的合成与性能研究  

Synthesis and Performances of 3-Nitroguanidino-1,2,4-triazolo[4,3-b]-s-tetrazine and Its Guanylurea Salts

作　　者：贾思媛[1] 张海昊[1] 毕福强[1,2] 王伯周 张家荣[1] JIA Si-yuan;ZHANG Hai-hao;BI Fu-qiang;WANG Bo-zhou;ZHANG Jia-rong(Xi′an Modern Chemistry Research Institute,Xi′an 710065,China;State key Laboratory of Fluorine&Nitrogen Chemicals,Xi′an 710065,China)

机构地区：[1]西安近代化学研究所,陕西西安710065 [2]氟氮化工资源高效开发与利用国家重点实验室,陕西西安710065

出　　处：《火炸药学报》2019年第5期455-459,I0002,共6页Chinese Journal of Explosives & Propellants

基　　金：国家自然科学基金(No.201503162)

摘　　要：以3,6-双(3,5-二甲基吡唑)-1,2,4,5-四嗪为原料,通过取代、环化、酸化反应合成出3-硝基胍-1,2,4-三唑[4,3-b]-s-四嗪(NGTT),自主设计合成了新型含能离子盐3-硝基胍-1,2,4-三唑[4,3-b]-s-四嗪的脒基脲盐(NGTT-M),并采用红外光谱、核磁共振、元素分析等进行了结构表征;优化了关键中间体3-(3,5-二甲基吡唑-1-基)-1,2,4-三唑[4,3-b]-s-四嗪(DMPTT)的合成条件,收率达到82%;采用DSC对比研究了NGTT和NGTT-M的热稳定性,并采用量子化学方法研究了NGTT及其阴离子的几何构型,计算了NGTT和NGTT-M的爆速、爆压及单元比冲等能量性能。结果表明,NGTT和NGTT-M的分解温度分别为250、221.1℃;密度分别为1.77、1.77 g/cm 3;生成焓分别为567.3、500.7 kJ/mol;爆速分别为7 366.8、7 391.9 m/s;爆压分别为23.4、23.0 GPa;燃温分别为2 475.2、1 834.8 K;特征速度分别为1 404.2、1 269.2 m/s;单元比冲分别为2 210.5、2 016.7 N·s/kg,表明NGTT-M具有氮含量高、热稳定性良好、产气量大、燃温低的特点。Using 3,6-bis(3,5-dimethylpyrazol-1-yl)-1,2,4-tetrazine as the starting material,3-nitroguanidino-1,2,4-triazolo[4,3-b]-s-tetrazine(NGTT)was synthesized through substitution,cyclization and acidification reactions.A novel energetic N-gualnylurea salt of 3-nitroguanidino-1,2,4-triazolo[4,3-b]-s-tetrazine(NGTT-M)was synthesized for the first time,and their structures were characterized by NMR,IR and elemental analysis.The cyclization reaction conditions for the key intermediate 3-(3,5-dimethylpyrazol-1-yl)-1,2,4-triazole[4,3-b]-s-tetrazine(DMPTT)were optimized with a yield up to 82%.The thermal stabilities of NGTT and NGTT-M were studied by DSC method,and the geometric structures of NGTT and its anion were studied by quantum chemistry methed.The detonation velocity,detonation pressure and specific impulse as monopropellant of NGTT and NGTT-M were calculated.The results show that the decomposition points of NGTT and NGTT-M are 250℃and 221.1℃with the densities of 1.77 and 1.77 g/cm 3,the heat of formation of 567.3 and 500.7 kJ/mol,the detonation velocities of 7 366.8 and 7 391.9 m/s,the detonation pressure of 23.4 and 23.0 GPa,combustion temperature of 2 475.2 and 1 834.8K,characteristic velocities of 1 404.2 and 1 269.2 m/s,and specific impulses of 2 210.5 and 2 016.7 N·s/kg,showing that NGTT-M possesses high nitrogen content and good thermal stability,large gas production and low combustion temperature.

关 键 词：有机化学 富氮含能化合物 3-硝基胍-1 2 4-三唑[4 3-b]-s-四嗪 NGTT 含能离子盐 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] TQ560[化学工程—炸药化工]