Synthesis Of Ferrocene Methyl Triazole (imidazole) Ionic Metal Complex And Its Catalysis During Combustion

Ferrocene burning rate(BR)catalyst has been widely used in solid propellants,due to their good catalytic ability,combustibility,dispersion,thermal stability and good compatibility.Now,commercialized ferrocene-based burning rate catalysts,such ascatocene,tert-butylferrocene,n-butyferrocene,bis(ethylferrocenyl)methane and n-octylferrocene,have excellent combustion catalytic effects,they still have the following problems in their applications:(1)seriously reducing the stability of the propellants in air;(2)accelerating the aging of the exposed surface of the propellants due to the migration of the no functional group derivatives;(3)strong migratory tendency leading to their use in low concentration.In order to solve these problemes,60 novel ionic coordination compounds were designed and synthesized to retard migration andvolatilization of ommercialized ferrocene-based BR catalysts,to enhance the energy level of the propellants and to improve the performance of the propellants.The research contents of this thesis are as follows:(1)Employing some transition metal ions as the central cation and ferrocenylmethyl imidazole or ferrocenylmethyl-1,2,4-triazole as ligands,picrate,trinitroresorcinolate or 1,1,3,3-tetracyanopropenide as anions,60 novel coordination compounds with molecular structure,were designed and synthesized([M(L)4(H2O)2]m(Y)n:M= Cr3+,Mn2+,Fe2+,Co2+,Ni2+,Cu2+,Zn2+,Cd2+,Bi3+,Pb2+.L=FcMTz,FcMIz.Y= PA,TNR,TCP.m=1,2.n=2,3).The synthesis process is simple and easy to be purified and separated.Environment-friendly and cheap water and alcohol were used in the synthetic process.The new compounds were characterized by single-crystal X-ray diffraction,FT-IR,UV-Vis,and EA.(2)Thermal stability of the synthesized coordination compound was evaluated by TG technology.The result showed that all the compounds have good thermal stability.The thermal stability of the complexes with 1,1,3,3-tetracyanopropenide as anions is better than those of other complexes,and the central transition metals have no significant effect on the thermal stability of the complexes.(3)The redox properties of compounds 1-60 were measured bycyclicvoltammetry(CV).The results showed that most oxidation-reduction potential value of these compounds are higher than these neutral ferrocene burning rate catalysts NBF and TBF.These compounds showed that these compounds are irreversible redox systems,indicating that they are difficult to be oxidized and stable in air.(4)Compounds 1-60 catalytic activities in the thermal degradation catalytic performances were determined by DSC method.It was found that when 5 wt.%compounds 1-60 was added to ammonium perchlorate(AP),each compound can narrow the temperature span of AP,the released heat of AP increased to the highest value-2270 J·g-1.The mixture of 5 wt.%compounds with RDX can advance the decomposition temperature peak from 237.0 ? to 217.2 ?,release heat is increased from-830.6 J·g-1 to-1783.1 J·g-1.A few compounds have catalytic effect on the thermal decomposition of HMX.(5)The thermal decomposition of compound 1 and its mixtures with AP,RDX or HMX in 1:4 was studied by TG-IR-GC-MS and DSC techniques.The results showed that the decomposition process of compound 1 could be proposed as follows:the first loss is the crystallized and coordination water,then is the ligand FcMTz,followed by the anion picrate,the final residue is the metal oxides Mn2O3 and Fe2O3 by analyzing the gaseous products and their releasing order.Compound 1 had a certain catalytic effect on AP,RDX,and HMX.It can reduce the activation energy of AP from 140.615 kJ·mol-1 to 89.33 kJ·mol-1,the activation energy of RDX decreases from 170.515 kJ·mol-1 to 150.23 kJ·mol-1,and the activation energy of HMX decreases from 541.682 kJ·mol-1 to 346.772 kJ·mol-1.To sum up,sixty ferrocene-containing high-nitrogen ion complexes have good thermal stability and strong antioxidant capacity.It is not easy to be oxidized at room temperature.At the same time,they have good combustion catalytic effects on the main components of the solid propellants and expected to be new ferrocene-based burning rate catalyst candidates.