4H,8H-双呋咱并[3,4-b:3′,4′-e]吡嗪(DFP)有机双胺盐的合成及性能研究

Synthesis and Properties of Organic Diamino Salts of 4H,8H-Difurazano[3,4-b:3′,4′-e]pyrazine(DFP)

为改善4H,8H-双呋咱并[3,4-b:3′,4′-e]吡嗪(DFP)结构存在的酸性问题,以DFP和有机胺为原料,合成了DFP的氨基胍盐(DAGDFP)、氨基脲盐(DSDFP)、1,3-二氨基胍盐(DBAGDFP)、脒基脲盐(DGUDFP)、胍盐(DGDFP)、缩二胍盐(DBGDFP)、三氨基胍盐(DTAGDFP)等7种有机双胺盐化合物;通过核磁共振谱、红外光谱和元素分析对其结构进行了表征;采用DSC和TG法分析了目标化合物的热性能;采用BAM标准方法测试了机械感度;通过Kamlet-Jacobs方程和最小自由能法分别计算了DFP双胺盐的爆轰参数和单元推进剂的燃烧性能。结果表明,DFP双胺盐热稳定性良好,撞击感度均大于40J,摩擦感度均大于360N,为钝感含能离子盐;DSDFP热分解温度为273.4℃,理论爆速为7891m/s,爆压为27.07GPa,比冲为2352N·s/kg,特征速度为1462.9m/s,爆轰性能优于TNT,比冲和特征速度较偶氮四唑胍盐(GZT)大幅提高,有望应用于气体发生剂和固体推进剂等。

To solve the acidity of 4H,8H-difurazano[3,4-b:3′,4′-e]pyrazine(DFP),seven organic diamino salts of DFP were synthesized with the cations as aminoguanidine(DAGDFP),semicarbazide(DSDFP),1,3-diaminoguanidine(DBAGDFP),guanyl urea(DGUDFP),guanidine(DGDFP),biguanide(DBGDFP)and triaminoguanidine(DTAGDFP)using DFP and organic amines as starting materials.The structures of target compounds were confirmed by 1H NMR,13C NMR,IR,and elemental analysis.The thermal behaviors of these compounds were studied by DSC and TG methods,and the mechanical sensitivities were tested according to the standard BAM method.The detonation parameters and the monopropellant performances were calculated by Kamlet-Jacobs equations and the minimum free energy method,respectively.The results show that the target compounds exhibit good thermal stability,and are insensitive energetic ionic salts with impact sensitivity higher than 40J and friction sensitivity greater than 360N.DSDFP displays better detonation performance than TNT and higher specific impulse than guanidinium azotetrazolate(GZT)with decomposition peak temperature of 273.4℃,detonation velocity of 7891m/s,detonation pressure of 30.11GPa,specific impulse of 2352N·s/kg and characteristic velocity of 1462.9m/s.It is expected to be applied in gas generator and solid propellant.