5,5′-肼基双四唑二羟胺盐的合成与性能  

Synthesis and Properties of 5,5′-(Hydrazine-1,2-diyl)bis(1H-tetrazole)dihydroxylammonium

作　　者：刘亚静[1] 刘浩然 葛瑞荣 赵宝东 刘卫孝[1] 高福磊[1] 张萌 LIU Ya-jing;LIU Hao-ran;GE Rui-rong;ZHAO Bao-dong;LIU Wei-xiao;GAO Fu-lei;ZHANG Meng(Xi'an Modern Chemistry Research Institute,Xi'an 710065,China;China International Engineering Consulting Corporation,Beijing 100000,China;Mechanical and Electrical Technology Company,Hefei Anhui 231135,China;Bureau of Military Representative of the PLA in Xi'an,Xi'an 710065,China)

机构地区：[1]西安近代化学研究所,陕西西安710065 [2]中国国际工程咨询有限公司,北京100000 [3]安徽红星机电科技有限公司,安徽合肥231135 [4]陆装驻西安地区航空军事代表室,陕西西安710065

出　　处：《火炸药学报》2022年第5期651-657,共7页Chinese Journal of Explosives & Propellants

基　　金：国家自然科学基金(No.22005238,No.21875185)。

摘　　要：以5-氨基四唑为原料,经氧化、还原及中和反应合成了5,5'-肼基双四唑二羟胺盐(HBT-HA),并利用红外光谱、核磁共振、元素分析对产物进行了表征。利用差示扫描量热法(DSC)、热失重法(TG)对HBT-HA进行了热分解研究,并结合Kissinger法和Ozawa法及相关方程计算了HBT-HA的热动力学参数、热爆炸临界温度;基于实测密度(ρ=1.519g/cm^(3))和预估生成焓(ΔH f=1877.3kJ/mol),利用Explo5(V6.04)软件预估了HBT-HA的爆速、爆压和爆热,采用BAM撞击感度测试仪测试了HBT-HA的感度;优化了HBT-HA的合成工艺,并测试了HBT-HA与双基推进剂的相容性。结果表明,中和反应较佳反应条件为:以水为反应溶剂,反应温度为10~15℃,n(HBT)∶n(NH_(2)OH)=1∶5时反应1h;HBT-HA的热分解峰温为241.7℃,活化能、指前因子、热爆炸临界温度分别为271.18kJ/mol、63.90s^(-1)、513.15K;预估的爆速、爆压和爆热分别为9118m/s、33.1GPa和10.65MJ/kg,HBT-HA的撞击感度大于60.0J;相容性测试结果表明,HBT-HA可提高双基推进剂的热稳定性。Taking 5-aminotetrazole(5-AT)as raw material,5,5'-(hydrazine-1,2-diyl)bis(1H-tetrazole)dihydroxylammonium(HBT-HA)was synthesized via oxidation,reduction and neutralization reaction.The structure of HBT-HA was characterized by IR,NMR and elemental analysis.Thermal decomposition properties of HBT-HA were studied by differential scanning calorimetry(DSC)and thermogravimetry(TG).Its thermal decomposition kinetic parameters and thermodynamic parameters were calculated by Kissinger and Ozawa methods.Based on the experimental density(ρ=1.519g/cm^(3))and calculated enthalpy of formation(ΔH f=1877.3kJ/mol),the detonation velocity,detonation pressure and detonation heat of HBT-HA were calculated by Explo5(V6.04).The impact sensitivity of HBT-HA was measured by the BAM drop hammer apparatus.In addition,its synthesis process was optimized,and the compatibility of double-base propellant and HBT-HA was tested.The results show that the optimized reaction conditions of neutralization are as follows:water as reaction solvent,the molar ratio of HBT and NH_(2)OH is 1∶5,the reaction temperature is 10—15℃,and reaction time is 1h.The decomposition peak temperature of HBT-HA is 241.7℃.The activation energy of HBT-HA is 271.18kJ/mol,the pre-exponential factor is 63.90s^(-1) and the critical temperature of thermal explosion is 513.15K.The detonation velocity,detonation pressure and detonation heat are 9118m/s,33.1GPa and 10.65MJ/kg,respectively,the impact sensitivity is more than 60.0J,and the compatibility test indicates that the thermostability of double-base propellant can be improved by HBT-HA.

关 键 词：有机化学 含能材料 富氮含能离子盐 5 5′-肼基双四唑 中和反应 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O62[理学—有机化学]