摘要
为改善钝感炸药3‑硝基‑1,2,4‑三唑‑5‑酮(NTO)的酸性,将NTO分别与3,5‑二氨基‑1,2,4‑三唑(3,5‑DATr)、咪唑(IMZ)反应,制备得到了NTO·(3,5‑DATr)含能离子盐(Ⅰ)和NTO/IMZ含能共晶(Ⅱ)。通过溶剂挥发法培养得到了单晶,利用X‑射线单晶衍射仪确定了其晶体结构。晶体Ⅰ属于单斜晶系,空间群为P21/c,Mr=229.19,晶胞参数a=3.5687(7)Å,b=17.245(3)Å,c=14.655(3)Å,β=93.79(3),V=899.9(3)Å^(3),Z=4,D_(c)=1.692 g·cm^(-3);晶体Ⅱ属于正交晶系,空间群为Pbcn,Mr=207.17,晶胞参数a=16.9398(16)Å,b=5.6802(5)Å,c=17.9111(19)Å,V=1723.4(3)Å^(3),Z=4,D_(c)=1.597 g·cm^(-3)。采用差示扫描量热法(DSC)和热失重法(TG)研究了其热分解行为,结果表明二者均具有良好的热稳定性。运用Gaussian 09程序对化合物结构进行优化并计算其生成焓,用EXPLO 5软件对二者的爆速和爆压进行了评估(Ⅰ:D=7662.3 m·s^(-1),p=21.0 GPa;Ⅱ:D=6490.2 m·s^(-1),p=14.6 GPa)。采用BAM方法测试了其机械感度,结果表明,二者均对撞击和摩擦钝感(IS>40 J,FS>360 N)。利用pH计测试了化合物标样的pH值,在0.01 mol·L^(-1)的标准溶液中NTO,Ⅰ和Ⅱ的pH值分别为2.92(22.8℃),4.10(22.7℃),4.98(22.8℃),表明盐和共晶的形成在一定程度上改善了NTO的酸性。
In order to decrease the acidity of insensitive explosive 3‑nitro‑1,2,4‑triazol‑5‑one(NTO),NTO·(3,5‑DATr)energetic ionic salt(Ⅰ)and NTO/IMZ energetic co‑crystal(Ⅱ)were prepared by the reactions of NTO with 3,5‑diamino‑1,2,4‑triazole(3,5‑DATr)and imidazole(IMZ).The single crystals were obtained by solvent volatilization,and the crystal structures were measured by single crystal X‑ray diffraction.CrystalⅠbelongs to monoclinic crystal system,space group P21/c,with Mr=229.19,a=3.5687(7)Å,b=17.245(3)Å,c=14.655(3)Å,β=93.79(3)°,V=899.9(3)Å^(3),Z=4,D_(c)=1.692 g·cm^(-3);CrystalⅡbelongs to orthorhombic crystal system,space group Pbcn,with Mr=207.17,a=16.9398(16)Å,b=5.6802(5)Å,c=17.9111(19)Å,V=1723.4(3)Å^(3),Z=8,D_(c)=1.597 g·cm^(-3).Differential scanning calorimetry(DSC)and thermal weight loss method(TG)were used to test their thermal decomposition properties,and the results show that bothⅠandⅡhave good thermal stability.The Gaussian 09 program was used to optimize the molecular structures and calculate their enthalpy of formation.Software EXPLO 5 was used to calculate the detonation velocity and pressure ofⅠ(D=7662.3 m·s^(-1),p=21.0 GPa)andⅡ(D=6490.2 m·s^(-1),p=14.6 GPa).The mechanical sensitivity was tested by the BAM method.Results show that both of them are insensitive towards impact and friction(IS>40 J,FS>360 N).The pH value of standard samples were measured by pH meter.The pH values of NTO,Ⅰ,andⅡin 0.01 mol·L^(-1) standard solution are 2.92(22.8℃),4.10(22.7℃),and 4.98(22.8℃),respectively,indicating that the formation of salt and co‑crystal significantly decrease the acidity of NTO.
作者
毕玉帆
陆祖嘉
董文帅
曹文丽
张建国
BI Yu-fan;LU Zu-jia;DONG Wen-shuai;CAO Wen-li;ZHANG Jian-guo(State Key Laboratory of Explosion Science and Technology,Beijing Institute of Technology,Beijing 100081,China)
出处
《含能材料》
EI
CAS
CSCD
北大核心
2022年第2期111-120,共10页
Chinese Journal of Energetic Materials
基金
国家自然科学基金资助(U1830134)。
