2,6,8,12-四硝基-2,4,6,8,10,12-六氮杂异伍兹烷的合成及量子化学研究  

Synthesis and Quantum Chemical Study on 2,6,8,12-Tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane

作　　者：李玉川[1,2] 祁才[2] 孙成辉[1] 庞思平[1] 赵信岐[1] 

机构地区：[1]北京理工大学材料科学与工程学院,北京100081 [2]北京理工大学生命科学与技术学院,北京100081

出　　处：《含能材料》2010年第2期121-127,共7页Chinese Journal of Energetic Materials

基　　金：国家自然科学基金(No.20772011);国家自然科学基金与中国工程物理研究院联合基金(No.10576002)资助项目

摘　　要：以2,6,8,12-四乙酰基-2,4,6,8,10,12-六氮杂异伍兹烷(TAIW)为原料,经过三氟乙酸酐保护、硝化、脱保护等反应,制得了2,6,8,12-四硝基-2,4,6,8,10,12-六氮杂异伍兹烷(TNH2IW);用SnCl2分步还原六硝基六氮杂异伍兹烷(HNIW,CL-20)也可制得TNH2IW。在DFT-B3LYP/6-31G*水平下求得了TNH2IW的分子几何、电荷分布和热力学性质,计算了TNH2IW的热容、熵等热力学参数,给出了这些参数和温度之间的函数关系。在不破坏笼形结构和硝基的原则下通过构建等键反应求得TNH2IW的生成热为461kJ·mol-1。计算表明TNH2IW的爆速为9.13km.s-1,爆压为38.9GPa,爆轰性能高于TNT和RDX,与HMX相当。2,6,8,12-Tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane（TNH2IW）was synthesized from 2,6,8,12-tetraacetyl-2,4,6,8,10,12-hexaazaisowurtzitane（TAIW）by protection,nitration and deprotection.TNH2IW could also been obtained by reduction of hexanitrohexaazaisowurtzitane（HNIW,CL-20）with SnCl2.The molecular geometries,electric structures,and thermodynamic properties of TNH2IW were calculated using the density functional theory（DFT）method at the B3LYP/6-31G level.The thermodynamic parameters including heat capacities and entropies were calculated,and also the polynomial functions between thermodynamic parameters and temperature were determined.The accurate heat of formation 461 kJ·mol-1 of TNH2IW in gas phase was obtained via designed isodesmic reaction in which the cage and the nitro group have been kept.The data obtained from the present study show a satisfactory detonation performance,with detonation velocity of 9.13 km·s-1 and detonation pressure of 38.9 GPa,both of which are higher than those of TNT and RDX,not worse than those of HMX counterparts.

关 键 词：有机化学 四硝基六氮杂异伍兹烷(TNH2IW) 合成 密度泛函理论(DFT) 爆轰性能 

分 类 号：TQ560.1[化学工程—炸药化工]