Synthesis,Characterization And Thermal Behavior Of ANQ Derivatives

1-Amino-2-nitroguandine(ANQ)and its four derivatives were researched in this th esis.These compounds are 1-(2,4-dinitrophenylamino)-2-nitroguanidine(DNPANQ),1-(2,4,6-trinitrophenylamino)-2-nitroguanidine(TNPANQ),1-amino-2-nitroguanidine-3,5-dinitrosa licylic salt(ANQ·DNS·3H2O),1-carbamide-2-nitroguanidine(CANQ·H2O),respectively,which were characterized by Elemental analysis,Infrared Spectroscopy and Nuclear Ma gnetic Resonance.Moreover,the single crystals of ANQ,TNPANQ,ANQ·DNS·3H2O and CANQ·H2O were obtained by slow evaporation method and determined by X-Ray Diffraction(XRD),and the results were listed as below:ANQ:CH5N5O2,Monoclinic,P2(1)/c;TNPANQ:C7H12N8O8,Monoclinic,P2(1)/c;.ANQ DNS·3H20:C8H9N7O12,Triclinic,P-1;CANQ·H2O:C2H8N6O4,Monoclinic,C2/c.The thermal behavior of ANQ,DNPANQ,TNPANQ,ANQ·DNS·3H20,CANQ·H20 were studied under non-isothermal condition by DSC-TG/DTG method.The Kissinger method,Ozawa method and integral method were employed to calculated the thermal decomposition kinetics parameters and kinetics equations.The thermal decomposition kinetics equations of DNPANQ,ANQ DNS·3H20 and CANQ·H20 are d?/dT=1022.59/?4?3/4exp(-205935×105/RT),d?/dT=1010.55/?3(1-?)[-ln(1-?)2/3exp(-1.03533×105/RT)d?/dT=1023.07/?[4(1-?)3/2[-ln(1-?)]3/4]exp(-2.2943×105/RT),respectively.The entropy of activation,enthalpy of activation and Gibbs free energy of activation for five compounds were obtained.The self-accelerating decomposition temperature and the critical temperature of thermal explosion were also calculated.The values of TSADT and Tb rise with the increase of nitrogen content in molecule ANQ(58.81%)>CANQ H20(46.66%)>DNPANQ(34.38%)>TNPANQ(33.94%)>ANQ·DNS·3H20(27.79%)?The specific heat capacities of five compounds were determined with continuous Cp mode of Micro-DSCIII,and the results were listed as below:ANQ:Cp(J·g-1·K-1)=0.3632+2.8810x10-3 T DNPANQ:Cp(J·g-1·K-1)=-5.482+4.274x10-2 T-6.904×10-5 T2 TNPANQ:Cp(J g-1·K-1)=-6.1644+4.2646×10-2 T-6.061×10-5 T2 ANQ·DNS·3H20:Cp(J·g-1·K+1)=0.3420+2.8358×10-3T CANQ· H20:CP(J·g-1·K-1)=-18.426+0.1305T-2.1931×10-4T2The enthalpy changes,entropy changes,Gibbs free energy changes of five compounds were obtained,relative to the standard temperature 298.15K.The adiabatic time-to-explosion of compounds were 43.92,8.45,6.51,14.17,26.56 s,respectively,which were in accordance with the change trend of TSADT and Tb.The impact sensitivity of ANQ,DNPANQ,TNPANQ and CANQ·H2O were 6.76,4.51?3.38?11.27 J,respectively.Based on these thermodynamic parameters(TSADT,adiabatic explosive time,Is)of five compounds,the conclusion can be obtained as follows:the more the nitrogen content is,the better thermal safety is.