耐热化合物5,5'-双(4-硝基-1,2,5-噁二唑-3-基)偶氮-1,3,4-噻二唑(BNOAT)合成优化、结构表征及基础应用性能研究OA
Optimal Synthesis,Structural Characterization and Performances Studies of Heat-resistant Compound 5,5'-Bis(2-nitro-1,2,5-oxadiazol-3-yl)azo-1,3,4-thiadiazole(BNOAT)
为了研究含S元素含能化合物的性能,以丙二腈为原料,经合环、水解、缩合环化、氨基氧化等步骤,合成了5,5'-双(4-硝基-1,2,5-噁二唑-3-基)偶氮-1,3,4-噻二唑(BNOAT),对其中氨基氧化关键步骤进行合成条件优化,获得反应的最优条件,提出了缩合环化反应机理并首次获得了缩合环化产物3-氨基-4-(5-氨基-1,3,4-噻二唑-2-基)呋咱(AATF)的单晶;采用傅里叶红外光谱、核磁共振及元素分析对中间体和目标化合物进行了结构鉴定;采用差示扫描量热-热重仪对3-硝基-4-(5-硝基-1,3,4-噻二唑-2-基)呋咱(NNTF)和BNOAT的热行为进行分析,对二者和常见含能组分HMX、RDX、CL-20以及DNTF的相容性进行了研究;通过EXPLO5(v.6.04)预测了其爆轰性能并采用BAM标准方法完成了感度测定.结果表明,AATF单晶样品结合一个乙腈分子,属于单斜晶系,P21/n空间群,晶胞参数为 a=10.2786(3)Å,b=8.986 3(2)Å,c=10.2899(3)Å,β=95.129(1)°;NNTF 的热分解温度为 169.9℃,理论爆速为7438m/s,爆压为24.3 GPa,撞击感度为7J,摩擦感度为180N;BNOAT的热分解温度为269.9 ℃,理论爆速为7 900m/s,爆压为28.2GPa,撞击感度为9J,摩擦感度＞360N;BNOAT是一种潜在的耐热低感含能材料;NNTF和HMX、RDX、CL-2 0相容性好,与DNTF混合后,较NNTF的第一热分解温度169.9℃提前了 10℃;BNOAT和HMX、RDX、DNTF相容性好,BNOAT和CL-20混合后,较CL-20的热分解峰温提前了 7.5℃.
In order to study the properties of sulfur-containing energetic compounds,5,5'-bis(2-nitro-1,2,5-oxadiazol-3-yl)azo-1,3,4-thiadiazole(BNOAT)was synthesized through four steps of cyclization,hydrolysis,condensation-cyclization,and amino oxidation by using malononitrile as the starting material.The key step of amino oxidation was optimized and the optimal reaction conditions were obtained.A reaction mechanism for the condensation-cyclization process was proposed,and single crystal of 3-amino-4-(2-amino-1,3,4-thiadiazole)furazan(AATF)was obtained.The structures of intermediates and target compounds were characterized by FT-IR,NMR,and elemental analysis.The thermal behaviors and of 3-nitro-4-(5-nitro-1,3,4-thiadiazole-2-yl)furazan(NNTF)and BNOAT were analyzed using DSC-TG.Their compatibility with common energetic com-ponents(HMX,RDX,CL-20,and DNTF)was investigated by DSC.The detonation performances were predicted by EXPLO5(v.6.04),and the sensitivities to impact and friction were tested by BAM method.The single-crystal results show that the sin-gle crystal of AATF·CH3CN belongs to the monoclinic crystal system,space group P21/n.The unit cell parameters are a=10.2786(3)Å,b=8.9863(2)Å,c=10.2899(3)Å,and β=95.129(1)°.NNTF possesses the thermal decomposition temperature of 169.9 ℃,theoretical detonation velocity of 7438 m/s,detonation pressure of 24.3 GPa,impact sensitivity of 7J,and friction sensitivity of 180 N.BNOAT exhibits thermal decomposition temperature of 269.9 ℃,theoretical detonation velocity of 7900m/s,detonation pressure of 28.2GPa,impact sensitivity of 9J,and friction sensitivity above 360N,which indicates that BNOAT is a promising heat-resistant low-sensitivity energetic compound.NNTF exhibits good compatibility with HMX,RDX,and CL-20,its initial thermal decomposition temperature(169.9 ℃)is reduced by 10 ℃ when mixed with DNTF.BNOAT demonstrates good compatibility with HMX,RDX,and DNTF,its thermal decomposition peak temperature is reduced by 7.5 ℃ when mixed with CL-20.
张家荣;曾刚毅;马玲;杨凯迪;罗义芬;王伯周
西安近代化学研究所,陕西西安 710065||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西安近代化学研究所,陕西西安 710065||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西安近代化学研究所,陕西西安 710065||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西安近代化学研究所,陕西西安 710065||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西安近代化学研究所,陕西西安 710065||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西安近代化学研究所,陕西西安 710065||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
军事科技
物理化学耐热炸药1,3,4-噻二唑含S含能化合物BNOATAATFNNTF
physical chemistryheat-resistant explosive1,3,4-thiazolesulfur-containing energetic compoundBNOATAATFNNTF
《火炸药学报》 2026 (2)
143-152,10
国家自然科学基金(No.22275146)
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