Design,Synthesis Of Ferrocenyl Pyrazole(Imidazole) Derivatives And Study Of Burning-rate Catalysis Performance

Ferrocenyl derivative is a unique kind of decomposition catalyst of hydroxyl-terminated polybutadiene(HTPB).According to the reports,ferrocenyl derivatives with significant effect on the thermal decomposition of ammonium perchlorate(AP)have several characteristics on their molecular structure:(1)The substituent group with long carbon chains is better than the short;(2)The dinuclear ferrocenyl derivatives are better than the single;(3)Compound with hydroxyl,amine,epoxy group and other polar groups is better than that with non-polar groups;(4)Compound with nitrogen heterocyclic is better than catenulate;(5)The liquid is better than the solid.Thus,we designed and synthesized a series of ferrocenyl derivatives with nitrogen heterocyclic,and then polar group containing fluorine was led in,expecting to get ferrocenyl derivatives with overall excellent burning-rate catalysis performance.1.Eight novel dinuclear ferrocenyl pyrazole derivatives(5-12)had been synthesized and structurally characterized by IR,MS,'H NMR,19F NMR,13C NMR,HRMS and X-ray crystal diffraction.Electrochemical properties of these species were studied by cycle voltammetry(CV)and differential pulse voltammetry(DPV).The ferrocenyl units of each compound displayed two steps of electrochemically reversible one-electron transfer processes.Because of excellent burning-rate catalysis effect of ferrocenyl derivatives on AP,it's of great importance to the decomposition of HTPB.Thus,we studied the thermal behavior and catalytic performance for thermal decomposition of AP by TG and DSC.The results indicated that synthetic products all have efficient catalytic effect on the thermal decomposition of AP.What's more,along with the increasing polarity,the burning-rate catalysis performance slightly weakened,when electron withdrawing group of fluorine was brought in.2.Five novel singel ferrocenyl pyrazole derivatives(19-23)had been synthesized and structurally characterized by IR,MS,1H NMR,19F NMR,13C NMR,HRMS and X-ray crystal diffraction.Electrochemical properties of these species were studied by CV and DPV.Thermal behavior and catalytic performance for thermal decomposition of AP were studied by TG and DSC.The results indicated that synthetic products all have efficient catalytic effect on the thermal decomposition of AP.What's more,along with the increasing polarity,the burning-rate catalysis performance slightly weakened,when electron withdrawing group of fluorine was brought in.3.Six novel ferrocenyl imidazole derivatives(26-31)had been synthesized,and then they were reacted with iodomethane(32-37),finally exchanged anion with ammonium hexafluorophosphate to get six corresponding ferrocene-based imidazolium salts(38-43).These compound were structurally characterized by 1R,MS,'H NMR,19F NMR,13C NMR,HRMS and X-ray crystal diffraction.Electrochemical properties of these species were studied by CV and DPV.Thermal behavior and catalytic performance for thermal decomposition of AP were studied by TG and DSC.The results indicated that synthetic products all have efficient catalytic effect on the thermal decomposition of AP.