The Synthesis And Properties Of Energetic Derivatives Of Nitroguanidine

In this paper,N-methyl-N'-nitroso-nitroguanidine?MNNG?was synthesized using n itroguanidine as raw materials,and then six kinds of nitroguanidine energetic derivativ es were synthesized using MNNG,namely 3-?aminonitroguanidino?-6-?3,5-dimethylpyraz ole?-1,2,4,5-tetrazine?ANPTz?,3,6-bis?aminonitroguanidino?-1,2,4,5-tetrazine?BANTz?,2,2'-?carbonylamino?-1-binitroguanidine?CABNG?,2,2'-?malonylamino?-1-binitroguanidi ne?MABNG?,1-?formylamino?-2-nitroguanidine?FANG?,and 1-?acetylamino?-2-nitrog uanidine?AANG?.The structure of six compounds were characterized by EA,FT-IR,¹H NMR and ¹³C NMR.The crystal structures of ANPTz,CABNG and FANG were determined by X-ray single crystal diffractometer,and the crystal structure analysis res ults were listed as below:ANPTz,Formula:C₈H₁₁N₁₁O₂;Crystal system and Space group:Monoclinic,P-1;?=1.521 g·cm^-3;Cell parameters:a=7.867?4??,b=8.873?5??,c=9.501?5??;CABNG·2H₂O,Formula:C₆H₂₄N₂₀O₄;Crystal system and Space group:Monoclin ic,P2₁/c;?=1.572 g·cm^-3;Cell parameters:a=19.903?7??,b=14.678?5??,c=8.939?3??;FANG,Formula:C₂H₅N₅O₃;Crystal system and Space group:Monoclinic P2₁/c;?=1.675 g·cm^-3;Cell parameters:a=4.279?3??,b=16.116?11??,c=8.236?6??;The thermal decomposition behaviors of six compounds were investigated by differential scanning calorimetry?DSC?and thermogravimetry?TG?,the thermal decomposition peak temperatures of the compounds were 211.03?200.32?207.16?202.17?200.96 and 196.81?,respectively.The kinetic parameters and optimal mechanism equations were obtained by Ozawa method,Kissinger method and integration method.The specific heat capacities of ANPTz,BANTz,CABNG,MABNG,FANG and AANG were determined by Micro-DSC?microcalorimrter and the specific heat capacities of six compounds at 298.15 K were obtained(1.2177,1.2767,1.3890,1.2903,1.2065 and 1.2566 J·g^-1·K^-1,respectively).Then variation of three thermodynamic functions of enthalpy,enthalpy and Gibbs free energy of six compounds in the temperature range of 283 to 353 K were calculated and obtained.The constant volume combustion heat of the four compounds CABNG,MABNG,FANG,and AANG were determined by oxygen bomb calorimeter?IKA C5000?and their standard molar enthalpy of formation were-405.18?-475.63?-168.95 and-239.84 k J?mol^-1,respectively.Moreover,the thermal safety of the above compounds were evaluated by self-acceleration decomposition temperature(T_SADT),thermal ignition temperature(T_be),thermal explosion critical temperature(T_bp),adiabatic to explosion time(t _TIAD),and their impact sensitivities?I_s?were measured.Through calculated the detonation velocity and detonation pressure to evaluate their detonation properties.The detonation velocity and detonation values of the three crystalline compounds are:603.61,7839.67,8302.28 m·s^-1 and 23.67,25.67,30.01 GPa.