Study On Synthesis,burning Rate Catalytic And Anti-migration Properties Of Ferrocene-based Homo And Hetero Cyclic Compounds And Acrylic Polymer

Composite solid propellants(CSPs)are energetic materials and usually consist of metallic fuel aluminum(Al),a combustible binder hydroxyl-terminated polybutadiene(HTPB),an inorganic oxidizer ammonium perchlorate(AP)and a trace amount of other components such as curing agent,stabilizer and burning rate catalysts(BRCs).The inclusion of BRCs from the metallocene family(e.g.,ferrocene and catocene)has been a promising avenue for increasing propellant BR efficiently.Ferrocene-based BRCs are one of the most widely used BRCs because of their good microscopic homogeneities in distribution and good compatibility with the organic binder.However,the use of ferrocene-based BRCs have some drawbacks that they sublime easily and migrate to the surface of the propellants during curing or long term storage.Migration makes the propellant burn unevenly and reduces its anti-aging ability due to formation of highly sensitive boundary layers.To overcome the migration problem much attention has been paid to the preparation of novel anti-migration ferrocene-based BRCs.In this thesis,different ferrocene-based BRCs were designed and successfully synthesized.It was found that the presence of oxygen and nitrogen in the ferrocenebased BRCs made them polar,which resulted in the dipole-dipole interactions between ferrocene-based BRCs and AP.The formation of hydrogen bonding and dipole-dipole interactions in the synthesized BRCs resulted in good anti-migration properties of ferrocene-based BRCs.These ferrocene-based BRCs were also found to have an accelerating catalytic effect on the thermal decomposition temperatures of AP.1)Ferrocene-based homo cyclic amide compounds(AM-Fcs)were synthesized as BRCs.The structures of these synthesized AM-Fcs were characterized by X-ray photoelectron spectroscopy(XPS),Ultraviolet-visible(UV-Vis),proton nuclear magnetic resonance(1H NMR),carbon nuclear magnetic resonance(13C NMR)and Fourier transform infrared(FT-IR)spectroscopy.The electrochemistry property of AMFcs were examined by cyclic voltammetry(CV)and the results indicated that the AMFcs showed good electrochemical performances.The BR catalytic effect of AM-Fcs on the thermal decomposition of AP was investigated by thermogravimetry(TG)and differential thermogravimetry(DTG).According to TG results,the AM-Fcs exhibited high catalytic effects on the thermal degradation of AP.Anti-migration studies confirmed that the migration of AM-Fcs were much slower than commonly used ferrocene-based burning rate catalyst,2,2-bis(ethyl ferrocenyl)propane(catocene).2)Ferrocene-based hetero cyclic ester compounds(Es-Fcs)containing polar elements(oxygen and nitrogen)were synthesized by the coupling reaction of ferrocene carboxylic acid with corresponding alcohols.The successful synthesis of Es-Fcs were confirmed by X-ray diffraction(XRD),XPS,1H NMR,13C NMR and FT-IR.The electrochemical properties of Es-Fcs were analyzed by CV.The BR catalytic activity of Es-Fcs on thermal decomposition of AP was investigated by TG and BR catalytic mechanism on thermal decomposition of AP were also proposed.The Es-Fcs showed good catalytic effects on the thermal degradation of AP according to TG experiments.Anti-migration property of Es-Fcs were better than catocene and ferrocene.3)Ferrocene-based hetero cyclic furan and triazole compounds(FT-Fcs)were prepared by the coupling reaction of ferrocene carboxylic acid to corresponding furan and triazole monomers.The prepared FT-Fcs were characterized by XPS,1H NMR,13C NMR and FT-IR.The CV test was used to study the electrochemical properties of FTFcs.The TG measurements were used to investigate the BR catalytic activity of FT-Fcs on thermal decomposition of AP.Anti-migration behavior of FT-Fcs were investigated.The presence of electronegative elements result in the dipole-dipole interactions and the presence of N-H groups resulted in the hydrogen bonding of these compounds with AP and also with binding agent,which resulted in better anti-migration properties in comparison with catocene and ferrocene.4)Ferrocene-based homo cyclic phenol compounds(PD-Fcs)were successfully synthesized by the coupling reaction of ferrocene carboxylic acid to corresponding monomers and their structures were investigated by XPS,1H NMR and FT-IR.In order to investigate the electrochemical characteristics of PD-Fcs,CV experiment were performed.The catalytic effect of PD-Fcs on the thermal degradation of AP were measured by TG and was effective in accelerating the decomposition process.Antimigration behavior of PD-Fcs were investigated and was better than that of catocene and ferrocene.5)Ferrocene-based hetero cyclic thiazole and succinimide compounds(HT-Fcs)and poly(2-hydroxyethyl ferrocene carboxylate-co-N-acryloxysuccinimide)(p(Fc-HEAco-NSA))were successfully prepared and characterized by XRD,XPS,1H NMR and FT-IR.The CV results of the prepared compounds suggested that their electrochemical behaviors in solution are quasi-reversible or irreversible.To study the catalytic effect of HT-Fcs and p(Fc-HEA-co-NSA)on thermal decomposition of AP,TG test were performed.It was found that the HT-Fcs and p(Fc-HEA-co-NSA)exhibited good catalytic effects on the thermal decomposition of AP.The anti-migration tests verified that migration tendency of HT-Fcs and p(Fc-HEA-co-NSA)can be extremely retarded in comparison with that of catocene and ferrocene.