1,1′-二羟基-3,3′-二硝基5-,5′-联-1,2,4-三唑含能离子盐合成、晶体结构及性能

摘要

以1,1′-二羟基-3,3′-二硝基-5,5′-联-1,2,4-三唑(DNOBT)为原料,分别与3-氨基-1,2,4-三唑、草酰肼、二肼基四嗪反应合成了DNOBT的3-氨基-1,2,4-三唑盐(DNOBT-3-AT)、草酰肼盐(DNOBT-ODH)、二肼基四嗪盐(DNOBT-DHT)三种含能离子盐,用红外光谱、核磁及元素分析对其结构进行了表征;培养了DNOBT-3-AT的单晶,X射线衍射分析表明其晶体为单斜晶系,空间群为P2(1)/c;利用Gaussian 09程序和Kamlet-Jacobs方程计算了DNOBT-3-AT、DNOBT-ODH、DNOBT-DHT的物化与爆轰性能,采用差示扫描量热(DSC)研究了这三种化合物的热性能,结果表明,DNOBT-3-AT、DNOBT-ODH、DNOBT-DHT爆速分别为7736.4,7729.56,7974.64 m·s-1,爆压分别为26.8,26.74,28.56 GPa;第一个热分解峰温度分别为276.54,257.02,154.15℃,相较于DNOBT-ODH和DNOBT-DHT,DNOBT-3-AT具有更好的热稳定性.%Using 3, 3′-dinitro-5, 5′-bis-1, 2, 4-triazole-1, 1′-diolate ( DNOBT ) as starting material, three energetic ionic salts (DNOBT-3-AT,DNOBT-ODH,DNOBT-DHT)were synthesized by reaction with 3-amino-1,2,4-triazole,oxalyl dihydrazide,3,6-dihydrazine-1,2,4,5-tetrazine, respectively, and their structures were characterized by FT-IR, NMR and elementary analysis.The single crystal of DNOBT-3-AT was cultivated,and its crystal structure was determined by X-ray crystallography.It is found that DNOBT-3-AT crystallizes in monoclinic system, space group P2(1)/c.Their physico-chemistry and detonation properties were calculated by Gaussian 09 program and Kamlet-Jacobs formula.Meanwhile, the thermal behaviors of the three compounds were studied with differential scanning calorimetry ( DSC).Results show that the detonation velocities are 7736.4, 7729.56, 7974.64 m· s-1 , and the detonation pressures are 26.8, 26.74, 28.56 GPa, respectively.The first exothermic decomposition peak temperatures of DNOBT-3-AT, DNOBT-ODH and DNOBT-DHT are 276.54, 257.02, 154.15 ℃, respectively, which shows that DNOBT-3-AT has better thermal stability than DNOBT-ODH and DNOBT-DHT.