4,4',5,5'-四硝基-2,2'-联咪唑及其含能离子盐的合成及热性能

以乙酸铵和乙二醛为原料,经环化、硝化等反应合成了4,4',5,5'-四硝基-2,2'-联咪唑(TNBI),然后TNBI与有机胺反应,获得了TNBI的二氨基呋咱盐(DAFTNBI)、草酰肼盐(ODTNBI)、二肼基四嗪盐(HTTNBI)、缩二胍盐(DBGTNBI)、脒基脲盐(DGUTNBI)、4-氨基-1,2,4-三唑盐(DATTNBI)、尿素盐(DUTNBI)等七种有机胺含能离子盐,采用红外光谱、核磁、元素分析等手段表征了化合物的结构;培养了TNBI·H2O单晶,结构分析表明,TNBI·H_2O为单斜晶系,空间群为P2(1)/n,晶体学参数为:a=0.5051(17)nm,b=0.8528(3)nm,c=1.5270(5)nm,β=96.948(6)°,V=0.6529(4)nm~3,Z=4,Dc=1.781 g·cm~(-3);利用差示扫描量热(DSC)、热重(TG)等热分析方法研究了七种含能离子盐的热性能,结果表明,含能离子盐的热分解峰温分别为199.23,204.52,230.13,266.96,240.63,187.98,260.19℃,热稳定性较好。

Synthesis and Thermal Properties of 4,4',5,5'-Tetranitro-2,2'-biimidazole and Its Energetic Ion Salts

4,4',5,5'-Tetranitro-2,2'-biimidazole(TNBI) was synthesized using ammonium acetate and glyoxal as starting materials by the reactions of cyclic condensation and nitration.A series of 4,4',5,5'-tetranitro-2,2'-biimidazolate energetic ion salts were prepared with the cations as 3,4-diaminofurazan(DAFTNBI),oxalyl dihydrazide(ODTNBI),3,6-dihydrazino-1,2,4,5-tetrazine (HTTNBI),biguanide(DBGTNBI),gunanyl urea(DGUTNBI),4-amino-1,2,4-triazole(DATTNBI),urea(DUTNBI).The structures of all compounds were confirmed by IR,1H NMR,13C NMR and elemental analysis.The single crystal of TNBI · H2O was obtained in the water system.The crystal of TNBI·H2O belongs to monoclinic system,space group P2 (1)/n,cell parameters:a=0.5051(17) nm,b=0.8528(3) nm,c=1.5270(5) nm,β=96.948(6)°,V=0.6529(4) nm3,Z=4,Dc=1.781 g·cm-3.The thermal properties of seven energetic ion salts were studied by differential scanning calorimetry(DSC) and thermogravimetric (TG).Results show that the thermal decomposition peaks of these energetic ionic salt are at 199.23,204.52,230.13,266.96,240.63,187.98℃ and 260.19℃,respectively,which indicates that their thermal stability is good.