摘要
为了研究离域型阳离子五唑盐的结构和性质,以盐酸胍为原料,通过缩合、硝化和复分解等反应,首次合成得到了3种离域型阳离子五唑盐2,5,8-三甲基-2,3,5,6,8,9-六氢-2,3a,5,6a,8,9a-六氮杂非那烯鎓五唑盐(4)、2,5,8-三叔丁基-2,3,5,6,8,9-六氢-2,3a,5,6a,8,9a-六氮杂非那烯鎓五唑盐(5)和2,5,8-三硝基-2,3,5,6,8,9-六氢-2,3a,5,6a,8,9a-六氮杂非那烯鎓五唑盐(8)。采用了X-射线单晶衍射(XRD)、傅里叶变换红外光谱(FT-IR),核磁共振谱(NMR)和元素分析等进行了分析表征;利用热重法(TG)和差示扫描量热法(DSC)测定了热分解过程;经密度泛函理论研究了化合物6和8的爆轰性能。结果表明:阳离子具有良好的共轭体系,与五唑阴离子相互垂直,不存在π-π、氢键及配位等稳定性因素;化合物4、5和8的初始分解温度分别为91.8℃、101.33℃和105.2℃;化合物6和8的爆速分别为8572 m·s^(-1)和8604 m·s^(-1),爆压分别为31.99 GPa和30.84 GPa。
In order to study the structure and properties of pentazolates with a delocalized cation,2,5,8-trimethyl-2,3,5,6,8,9-hexahydro-2,3a,5,6a,8,9a-hexaazaphenalene pentazolate(4),2,5,8-tris(tert-butyl)-2,3,5,6,8,9-hexahydro-2,3a,5,6a,8,9a-hexaazaphenalene pentazolate(5),and 2,5,8-trinitro-2,3,5,6,8,9-hexahydro-2,3a,5,6a,8,9a-hexaazaphenalene pentazolate(8)were synthesized via condensation,nitration and metathesis starting from guanidine hydrochloride.X-ray single crystal diffraction(XRD),fourier transform infrared spectroscopy(FT-IR),nuclear magnetic resonance spectroscopy(NMR),and elemental analysis were used for analysis and characterization;The thermal decomposition process was measured by thermogravimetry(TG)and differential scanning calorimetry(DSC).The detonation properties of compounds 6 and 8 were calculated using density functional theory.Results show that the cations have a good conjugated system,which are perpendicular to pentazolate anions;There are no stability factors such as π-π,hydrogen bond,and coordination.The initial decomposition temperatures of compounds 4,5,and 8 are 91.8℃,101.33℃,and 105.2℃,respectively.The detonation velocities of compounds 6 and 8 are 8572 m·s^(-1) and 8604 m·s^(-1),respectively,and the detonation pressures are 31.99 GPa and 30.84 GPa.
作者
王鑫雨
王雨晴
黄明
张莉
陈政国
杨海君
WANG Xinyu;WANG Yuqing;HUANG Ming;ZHANG Li;CHEN Zhenguo;YANG Haijun(School of Materials and Chemistry,Southwest University of Science and Technology,Mianyang 621010,China;Institute of Chemical Materials,China Academy of Engineering Physics,Mianyang 621999,China)
出处
《合成化学》
2025年第9期616-621,共6页
Chinese Journal of Synthetic Chemistry
基金
国家自然科学基金资助项目(22075260)
四川省自然科学基金面上项目(2022NSFSC0288)。
关键词
含能材料
合成
离域型阳离子
五唑盐
晶体结构
energetic material
synthesis
delocalized cation
pentazolate
crystal structure
