| In this paper,the mono substituted product 1-amino-1-?2,4-dinitroanilino?-2,2-dinitroethy lene potassium salt K?DNCB-FOX-7?was obtained by the reaction of 1,1-diamino-2,2-dinitroethylene?FOX-7?with 2,4-dinitrochlorobenzene?DNCB?,the mono substituted prod uct 1-amino-1-picrylamino-2,2-dinitroethylene?PICL-FOX-7?and its potassium salts 1-ami no-1-picrylamino-2,2-dinitroethylene potassium salt?K?PICL-FOX-7??were obtained by t he reaction of FOX-7 and 2,4,6-trinitrochlorobenzene?PICL?.It was found that the reac tion products of FOX-7 and DNCB and PICL were all mono substituted products rath er than disubstituted products by the influence of weakened polarity of carbon-carbon double bond and increased space hindrance through a large number of experiments an d analysis.The products of ethanedial-1,2-bis-?2-?1-amino-2,2-dinitroethenyl??hydrazone?EDNH?and 3-dinitroethylene-5-hydroxyl-1,2,4-triazine?DNTA?were obtained through t he reaction of AHDNE,a derivative of FOX-7,with glyoxal under acidic and basic c onditions,respectively.In addition,AHDNE could react with acetylacetone in aqueous solution to get cyclic compound 1-?1-amino-2,2-dinitroethenyl?-3,5-dimethyl-5-hydroxyl-4H-pyrazol?APDNE?.Moreover,the single crystals of K?DNCB-FOX-7?,K?PICL-FOX-7?,PICL-FOX-7 and APDNE were characterized by X-Ray Diffraction:K?DNCB-FOX-7?: C8H5KN6O8,Orthorhombic,Pbca;K?PICL-FOX-7?: C8H4KN7O10,Monoclinic,P21/n;PICL-FOX-7: C8H5N7O10,Monoclinic,P21/n;APDNE: C7H11N5O5,Triclinic,P-1;In this paper,the DSC-TG/DTG method was used to analyze the thermal decomposition process of K?DNCB-FOX-7?,K?PICL-FOX-7?,PICL-FOX-7,APDNE,EDNH and DNTA under different heating rates.Its peak temperature were 240.74,233.59,164.55,169.96,236.43,278.23 oC,and enthalpy of decomposition were 1709,1305,969.3,1161,1050,2282J·g-1,respectively.The apparent activation energy and prefinger factors of six compounds were obtained by Kissinger,Ozawa and integral methods,and the thermal decomposition kinetics equations of these compounds were also obtained.The self acceleration decomposition temperature of K?DNCB-FOX-7?,K?PICL-FOX-7?,PICL-FOX-7,APDNE,EDNH and DNTA were 225.69,214,90.955,152.42,193.92,242.46 oC,respectively.The relationship equation of specific heat capacity and temperature of six compounds were obtained by using the Micro-DSCIII calorimeter:K?DNCB-FOX-7?:Cp(J·g-1·K-1)=0.38+2.5794×10-3 TK?PICL-FOX-7?:Cp(J·g-1·K-1)=0.43+2.1156×10-3 TPICL-FOX-7:Cp=-1.73+1.08×10-1 T-1.52×10-4T2APDNE:Cp(J·g-1·K-1)=-6.0482+4.5399×10-2 T-7.0957×10-5 T2EDNH:Cp(J·g-1·K-1)=79.6412-0.784 T+2.594×10-3 T2-2.8441×10-6 T3DNTA:Cp(J·g-1·K-1)=44.6471-0.445 T+1.4995×10-3 T2-1.6734×10-6 T3The standard molar ratio of six products were 404.46,421.12,608.86,289.1,383.6,169.28J·mol-1·K-1,respectively.The adiabatic detonation time of K?DNCB-FOX-7?,K?PICL-FOX-7?,PICL-FOX-7,APDNE,EDNH and DNTA were 19.8,14.3,6.9,20.1,95,120 s,respectively.And for the same series of compounds,there is a certain correlation between adiabatic detonation time and critical temperature of thermal explosion.The impact sensitivity of K?DNCB-FOX-7?,K?PICL-FOX-7?,PICL-FOX-7,APDNE,EDNH,DNTA were 20.8,10.4,8.8,14,25,35 J,respectively.And the interaction of the electronic functional groups and steric hindrance effect have a great influence on the impact sensitivity of the compounds from the result. |
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