5,5′-二硝胺基-3,3′-亚甲基-联-1,2,4-三唑的合成、分子构型及热性能  

Synthesis,thermal performance and quantum chemistry of 5,5′-Dinitrimino-3,3′-methylene-1H-1,2,4-bistriazole

作　　者：郭涛[1] 黄晓川[1] 王子俊[1] 刘敏[1] 秦明娜[1] 邱少君[1] Guo Tao Huang Xiaochuan Wang Zijun Liu Min Qin Mingna Qiu Shaojun(Xi＇an Modern Chemistry Research Institute,Xi＇an 710065)

机构地区：[1]西安近代化学研究所,西安710065

出　　处：《化工新型材料》2016年第12期200-203,206,共5页New Chemical Materials

摘　　要：以氨基胍碳酸氢盐(AG·HCO3)与丙二酸为原料,经合环反应得到5,5′-二胺基-3,3′-亚甲基-联-1,2,4-三唑(DAMT),再通过HNO3-NH4NO3体系硝化得到目标产物5,5′-二硝胺基-3,3′-亚甲基-联-1,2,4-三唑(DNAMT),总产率为92.1%。采用量子化学方法计算确定具有硝基亚胺结构的DNAMT分子构型更加稳定。通过热重和差示扫描量热法等方法研究DNAMT的热行为,升温速率10K/min时,DNAMT的初始热分解温度为248.7℃,峰温为260.9℃,放热量为1849.4J/g。计算得到DNAMT的热分解反应活化能E为225.3kJ/mol,指前因子A为1.585×1022s-1。热力学方程计算得到DNAMT的初始分解温度Te0以及自加速分解温度TSADT均为225.8℃,热爆炸临界温度Tb为235.4℃;DNAMT热分解反应的热力学参数ΔH≠、ΔS≠、ΔG≠分别为222.3kJ/mol、174.3J/(K·mol)和132.7kJ/mol。A high-energy methylen-bridged-bistriazole,DNAMT, was synthesized through cyelization and nitration reaction from AG. HCOa and malonic acid,and the total yield was 92.1%. The structure of DNAMT was confirmed to be a nitroimine. Typical TG and DSC curves indicated the thermal hehavior of DNAMT included only one obvious exothermic decomposition stage. The melting enthalpy （ΔHm）, the extrapolated onset temperature and the peak temperature were 1849.4J/g,248.7℃ and 260.9℃ respectively. The apparent activation energy （Ea） and pre-exponential factor （A） were 225.3kJ/mol and 1. 585 × 10^22. 2 s^- 1. The enthalpy of activation （ΔH^≠）, entropy of activation （ΔS^≠）, free energy of activa tion （ΔG^≠）,self-accelerating decomposition temperature （TsAI）T） and critical temperature of thermal explosion （Tb） were determined as 222.3J/（K·mol）,174.3kJ/mol,132.7kJ/mol,225.8℃ and 235.4℃ ,respectively.

关 键 词：含能材料 5 5′-二胺基-3 3′-亚甲基-联-1 2 4-三唑 5 5′-二硝胺基-3 3′-亚甲基-联-1 2 4-三唑 量子化学 分子构型 热分解反应动力学 

分 类 号：TQ560.1[化学工程—炸药化工]