| The heterocyclic compound especially a triazole ring is considered to be a skeleton compound,due to the rich derivatization of two symmetric“C”sites,and high energy chemical bonds such as-NN-,-N=N-,-CN-and-C=N-,having a high buildup by itself.A bicyclic or polycyclic compound having a triazole ring as a skeleton,contains more nitrogen than its monocyclic derivative.And the distribution of nitrogen elements with a lone pair of electrons making the structure more stable in energetic materials,is more uniform.It has received extensive attention in the field of energetic materials.Due to its multi-modal coordination mode,stable framework structure and good physicochemical properties,Coordination Polymers(CP)are called a new class of materials with great potential in energetic materials.In this paper,3-amino-1H-1,2,4-triazole-5carboxylic acid was used as a raw material to synthesize methyl 5-amino-1H-1,2,4-triazole-3-carboxylate(HABTNA),that the bicyclic nitrogen-rich product with asymmetric configuration through three steps of“esterification reaction,Hydrolysis of hydrazine hydrate and using MNNG to generate a ring”.At the same time,we constructed a 3D-structured compound[Cs(ABTNA)H2O](3D EMOF 1)with HABTNA as a ligand.The structures of ligands HABTNA and 3D EMOF 1 were characterized by 13C NMR,MS,IR,elemental analysis and single crystal X-ray diffraction.The thermal decomposition properties of the two were investigated by differential scanning calorimetry.The decomposition temperature of EMOF 1 was 225°C,which was much higher than that of HABTNA.The combustion heat of the two was measured by using an oxygen bomber,and the detonation performance was predicted according to Hess's law,EXPLO 5 program and Kamlet-Jacobs empirical formula.The predicted detonation velocity of EMOF 1 is6780 m·s-1,which is greater than HABTNA.Both have an impact sensitivity of 60 J and a friction sensitivity of 360 N,which is an insensitive energetic compound.Through systematic pyrotechnic performance experiments and designing a chlorine-free orange light pyrotechnic formulation,EMOF 1 was proved to be the first orange colorant with high purity and high light intensity.Using 5-amino-1H-1,2,4-triazole-5carboxylic acid as raw material,a one-step method was used to construct compound 5,5'-(diazene-1,2-diyl)bis(4H-1,2,4-triazole-3-carboxylic acid)(H2DTCA),which have the azo-linked structure.The coordination polymer NRCP 1 with flame color effect was constructed by using H2DTCA as a ligand.Similarly,13C NMR,MS,IR,elemental analysis and single crystal X-ray diffraction were used to characterize the ligand and NRCP 1.The combustion heat was measured by an oxygen bomber to be-2786.8 k J·mol-1,the decomposition temperature was measured by TGA/DSC to be 426°C,the impact sensitivity was 60 J,and the friction sensitivity was 360 N.The optimum amount of addition was determined by a confined bomb experiment,and the flame color experiment showed that it had a good flame color effect.A class of cationic coordination polymers(ECCP 1)having a helical configuration was constructed by using 3-amino-1H-1,2,4-triazole-5-carbohydrazide(ATCA)as a ligand.Similarly,13C NMR,MS,IR,elemental analysis and single crystal X-ray diffraction were used to characterize the ECCP 1.The crystal density of ECCP 1 is2.534 g·cm-1,which is much larger than the theoretical density of the compound by physical mixing.The identification of physicochemical properties showed that ECCP 1has good hygroscopicity,physical stability and thermal stability.The impact sensitivity is 5 J and the friction sensitivity is 72 N,which is a kind of insensitive energetic compound.Lead plate test proves that the compound has excellent detonation performance.It must be mentioned that this ECMOF is an energetic material with great potential for application of the safety detonator as an ultrafast photosensitive initiating material for laser direct initiation,whose initiation delay time is as low as 73 ms using only 200 m J initiation energy. |
PDF Full Text Request