耐热炸药NBTTP的合成反应优化及热分解性能  

Synthesis and Thermal Properties of Heat⁃resistant Explosive NBTTP

作　　者：张倩[1,2] 刘宁 马玲[1] 段秉蕙 卢先明[1,2] 王伯周 ZHANG Qian;LIU Ning;MA Ling;DUAN Bing-hui;LU Xian-ming;WANG Bo-zhou(Xi′an Morden Chemistry Research Institute,Xi′an 710065,China;State Key Laboratory of Fluorine and Nitrogen Chemical,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：《含能材料》2021年第8期705-712,I0005,共9页Chinese Journal of Energetic Materials

基　　金：国家自然科学基金资助(21703168)。

摘　　要：为研究耐热炸药2,4,8,10‐四硝基‐苯基吡啶基‐1,3a,6,6a‐四氮杂戊搭烯(NBTTP)的合成工艺及热性能,以苯并三氮唑和2‐氯‐3‐硝基吡啶为原料,通过取代、环化和硝化三步反应合成出了耐热炸药NBTTP。采用红外光谱(FTIR)、核磁共振(NMR)对产物进行了结构表征,并对环化反应进行了工艺条件优化;采用差示扫描量热仪和热失重分析仪对NBTTP的热分解及热失重历程、热分解动力学及相关热爆炸参数进行了研究。结果表明:当亚磷酸三乙酯与1‐(3‐硝基‐2‐吡啶)‐1H‐苯并三唑(BTP)的投料比为3∶1时,环化反应收率最高(83.44%);NBTTP仅存在一个剧烈的放热阶段,该放热阶段的起始分解温度为388.79℃,分解峰温在406.23℃;NBTTP的热分解反应动力学方程为dα/dt=(6.36×10^(14)/β)(1-α)exp[-2.34×10^(5)/(RT)],热分解反应的活化熵、活化焓及活化自由能分别为23.60 J·mol^(-1)·K^(-1)、228.97 kJ·mol^(-1)和213.46 kJ·mol^(-1);自加速分解温度TSADT为655.11 K。2,4,8,10‐Tetranitro‐benzopyrido‐1,3a,6,6a‐tetraazapentalene(NBTTP)was synthesized from 1H‐benzotriazole and 2‐chloro‐3‐nitropyridine via displacement,cyclization and nitration.The structure of NBTTP was characterized by FTIR and NMR.In addition,the reaction condition of cyclization was optimized.Its thermalbehavior was analyzed by TG‐DTG,while its thermal decomposition behavior,kinetic parameters and thermodynamic parameters were obtained by DSC.The results shows that the highest yield was up to 83.44%,when the molar ratio of triethylphosphite and the BTP was 3∶1.NBTTP presents a main single exothermal event with initial at around 388.79℃and maximum at around 406.23℃.Its non‐isothermal kinetics equations of thermal decomposition may be described as dα/dt=(6.36×10^(14)/β)(1-α)exp[-2.34×10^(5)/(RT)].The entropy(ΔH^(≠)),enthalpy(ΔH^(≠)),free energy(ΔG^(≠))and self‐accelerating decomposition temperature(TSADT)were 23.60 J·mol^(-1)·K^(-1),228.97 kJ·mol^(-1),213.46 kJ·mol^(-1)and 655.11 K,respectively.

关 键 词：耐热炸药 2 4 8 10‐四硝基‐苯基吡啶基‐1 3a 6 6a‐四氮杂戊搭烯(NBTTP) 合成 热分解动力学 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术]