呋咱并哒嗪基稠环化合物结构与性能的理论研究(英文)  

Theoretical Investigation on Structure and Performance of Furazano-[3,4-d]-pyridazine-based Fused-ring Compounds

作　　者：王可[1] 刘宁[1] 武宗凯 付小龙[1] 李焕[1] 舒远杰[1] 李军强[1] 庞维强[1] WANG Ke;LIU Ning;WU Zong-kai;FU Xiao-long;LI Huan;SHU Yuan-jie;LI Jun-qiang;PANG Wei-qiang(Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

机构地区：[1]西安近代化学研究所,陕西西安710065

出　　处：《火炸药学报》2018年第3期236-242,共7页Chinese Journal of Explosives & Propellants

基　　金：National Natural Science(No.51373159); Funds for International Cooperation and Exchange(No.51511130036)

摘　　要：基于密度泛函理论,在B3LYP/6-311g(d,p)水平下,设计了3组新型呋咱并哒嗪基稠环化合物,对其结构和性能进行研究,并使用Kamlet-Jacobs计算其爆轰性能。结果表明,A组和B组化合物具有较好的共面性并且二面角变化范围为±5°,但C组化合物由于更多官能团间的排电子效应使得其共面性被严重损害;另外,与RDX和HMX相比,所有设计化合物均具有较高的密度(1.896～2.153g/cm^3)、爆速(8.55～9.98km/s)和爆压(33.70～48.90GPa);随所含硝基官能团数目的增加,对应化合物的密度、爆轰性能(N3取代化合物爆轰性能变化趋势相反),比冲和撞击感度逐渐增加,但其生成焓、键离解能、带宽和电火花感度逐渐减小(N_3.取代化合物的生成焓和电火花感度变化趋势相反);另外,这些官能团降低分子稳定性的顺序为:-ONO_2>-C(NO_2)_3>-CF(NO_2)_2>-NO_2>-N_3;NO_2取代(A1,B1和C1)和CF(NO_2)_2取代(A3)4种稠环化合物有潜力成为高能密度材料。Three series of novel furazano-[3,4- d ]-pyridazine-based fused-ring compounds were designed, and their structures and performance were studied by density functional theory （DFT） at B3LYP/6-311g（d, p） level. Detonation performance was estimated by Kamlet-Jacobs equations. The results show that the compounds of A and B series exhibit good coplanarity and their dihedral angles vary within ±5°, but the coplanarity of C series was particularly damaged because of electron-withdrawing effect of more functional groups. Otherwise, all designed nitro-containing compounds possess high densities （1.896-2.153 g/cm 3）, detonation velocities （8.55-9.98 km/s） and detonation pressures （33.70-48.90 GPa） compared with RDX and HMX. As the number of nitro-containing groups increases, the densities, detonation performance and specific impulse （ I sp ） and impact sensitivities gradually increase （the trend of detonation performance is contrary for N 3-substituted compounds）, but the heats of formation （HOFs）, bond dissociation energies （BDEs）, band gaps （ ΔE ）, and electric spark sensitivities （ E ES ） gradually decrease （the trend of HOFs and E ES is contrary for N 3-substituted compounds）. Otherwise, these functional groups decrease molecular stabilities in the order of -ONO 2〉-C（NO 2） 3〉-CF（NO 2） 2〉-NO 2〉-N 3. Four kinds of NO 2-replaced（A1, B1 and C1） and CF（NO 2） 2-substituted （A3） fused-ring compounds have the potential to become high-energy density materials （HEDMs）.

关 键 词：呋咱并哒嗪 密度泛函理论 爆轰性能 共面性 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O641[理学—物理化学]