1,4-二硝胺基-3,6-二硝基吡唑[4,3-c]并吡唑-氨基脲盐的合成、晶体结构及性能

Synthesis, Crystal Structure and Properties of 1,4-Dinitramino-3,6-dinitropyrazolo[4,3-c]pyrazole′s Aminourea Salt

以1,4-二氨基-3,6-二硝基吡唑[4,3-c]并吡唑(DADNP)为原料,经硝化、中和、复分解等反应合成了1,4-二硝胺基-3,6-二硝基吡唑[4,3-c]并吡唑-氨基脲盐(DAUDNANP),采用红外光谱、1HNMR、13CNMR及元素分析等方法表征了目标物结构;获得了1,4-二硝胺基-3,6-二硝基吡唑[4,3-c]并吡唑(DNANP·C2H5OH)和DAUDNANP的单晶并进行了晶体结构解析;利用DSC方法对DAUDNANP的热稳定性进行了研究;采用Gaussian09程序中的CBS-4M方法和Kamlet-Jacobs方程预估了DAUDNANP的爆轰性能。结果表明,化合物DNANP·C2H5OH晶体为三斜晶系,空间群为P-1,晶体学参数为:a=0.9746(3)nm,b=0.9952(3)nm,c=1.0883(3)nm,α=112.344(4)°,β=109.918(5)°,γ=94.820(5)°,V=0.8899(4)nm3,Z=2,μ=0.140mm-1,F(000)=424;化合物DAUDNANP晶体为三斜晶系,空间群为P-1,晶体学参数为:a=0.48613(11)nm,b=0.9153(2)nm,c=1.0186(2)nm,α=94.446(3)°,β=103.120(3)°,γ=97.230(3)°,V=0.43524(17)nm^3,Z=1,μ=0.164mm^-1,F(000)=240;DAUDNANP的两个热分解峰温度分别为158.1和176.4℃,晶体密度为1.79g/cm3,爆速为8516m/s,爆压为32.6GPa,生成热为409.7kJ/mol,爆热为5750kJ/kg。DAUDNANP是一种性能较好的新型高能量密度材料。

1,4-Dinitramino-3,6-dinitropyrazolo[4,3-c]pyrazole ′ s aminourea salt (DAUDADNP) was synthesized by the reactions of nitrification, neutralization, and metathesis using 1,4-diamino-3,6-dinitropyrazolo[4,3-c]pyrazole (DADNP) as starting material.The structure of target compound was characterized by means of IR spectra, NMR ( 1H and 13 C) and elemental analysis.The single crystals of 1,4-dinitramino-3,6-dinitropyrazolo[4,3-c]pyrazole (DNANP·C 2H 5OH) and DAUDADNP were obtained, and their crystal structures were analyzed.The thermal stability of DAUDADNP was tested by DSC method.The detonation properties of DAUDADNP were estimated by CBS-4M methed and Kamlet-Jacobs equation in Gaussian 09 program.The results show that the crystal of DNANP·C 2H 5OH belongs to the triclinic system, space group P -1, cell parameters:a =0.974 6(3) nm, b =0.995 2(3) nm, c =1.088 3(3) nm,α= 112.344(4)°,β=109.918(5)°,γ=94.820(5)°, V =0.889 9(4) nm 3, Z =2,μ=0.140 mm -1 , F (0 0 0)=424.The crystal of DAUDNANP belongs to the triclinic system,space group P -1, cell parameters:a =0.486 13(11) nm, b =0.915 3(2) nm, c =1.018 6(2) nm,α=94.446(3)°,β=103.120(3)°,γ=97.230(3)°, V =0.435 24(17) nm^3, Z =1,μ=0.164 mm -1, F (0 0 0)=240.The two thermal decomposition peak temperatures of DAUDADNP were 158.1℃ and 176.4℃, respectively.The formation heat of DAUDADNP was 409.7 kJ/mol and the crystal density was 1.79 g/cm 3, the detonation velocity was 8 516 m/s, the detonation pressure was 32.6 GPa, and the heat of detonation was 5 750 kJ/kg, showing that DAUDNANP is a new high energy density material with preferable properties .