Synthesis,Structure And Performance Studies Of Triazole Nitogen-rich Derivatives

Nitogen-Rich compound is a new kind of energetic material,and it can be used as raw material which is widely used in airbag and raft.The development of new type of gas generating agent is hotspot in the field of energetic material.The triazole derivatives including triazole molecular and salts compounds have been chosen to study for their high nitrogen content and stability.The synthesis method,thermal analysis,impact and friction sensitivity,combustion and explosion characters of the researched compounds have been discussed as follows:?1?The synthesis method for 4,5-Dicyano-2H-1,2,3-triazole?DCT?has been obtained through analyzing the influence factors and byproducts of reaction.The reaction useddiaminomaleodinitrile as the starting materials,with average yield of95.2%.It also gained an average yield 89.7%when scaled up to 10 mol scale.?2?4,5-di?5-tetrazolyl?-1,2,3-triazole?BTTZ?was synthesized with a new method,and the reaction time was reduced greatly by using catalyst.BTTZ has been obtained through analyzing the influence factors and byproducts of reaction.It also gained an average yield78.68%when scaled up to 10 mol scale.?3?2-methyl-4,5-dicyano-2H-1,2,3-triazole?MDCT?was synthesized for the first time.MDCT has been obtained using DCT as the starting materials and the influence factors were analyzed.Its structure was characterized by elemental analysis,infrared spectrum and nuclear magnetic resonance spectrum.The cultivation of a single crystal of2-methyl-4-acylamino-5-cyano-2H-1,2,3-triazole was reported.?4?The DCTNa·H₂O,DCTAg,5ATC,DATC and MDATI were synthesized according to the literature method,and three triazole salts?5ATDCT,DATDCT,MDATDCT?were synthesized for the first time.The structure was characterized by elemental analysis,infrared spectrum and nuclear magnetic resonance spectrum.?5?The density founction theory?DFT?was employed to research the quantitative calculation of tetrazole compounds.Geometric optimization were calculated using B3-LYP functional with 6-31+G**basis set,all the optimized structures were characterized to be true local energy minima on the potential energy surface without imaginary frequencies.A method of density prediction to the designed energetic salts was supplied,on which the lattice energies of the salts were calculated.The enthalpy of isodesmic reaction was obtained by combining the MP2/6-311++G**energy difference for the reaction,the scaled zero-point energies,and other thermal factors.The enthalpies of formation for the designed salts were back-calculated through Born-Haber energy cycles.?6?The thermal stabilities,sensitivities to friction and impact and constant volume energies of combustion for DCT,BTTZ,MDCT,5ATDCT,DATDCT and MDATDCT were measured.The heats of formation and detonation performance parameters?pressure and volecity?were calculated based on experimental datas.BTTZ was used as the gas generating agents,and the main performance parameters of gas generant were tested such as impact sensitivity,TG-DTA thermal analysis and P-t curve were also studied.