Synthesis,Characterization and Migration of Ionic Polyferrocenyl Compounds of 5‐Ferrocenyl‐1H‐tetrazole and Their Effects During Combustion

Eighteen ionic polyferrocenyl compounds with 5‐ferrocenyl‐1H‐tetrazolate as anion and mono‐ and dinuclear ferrocenyl‐alkylammonium as cations were synthesized and characterized by ¹H NMR, ¹³C NMR, FT‐IR, and UV/Vis spectroscopy, and elemental analysis. Molecular structures of three compounds were further confirmed by single‐crystal X‐ray diffraction. Their thermal stability was evaluated by TG and DSC and found that they are of high thermal stability. The cyclic voltammetry analysis suggested that each of the compounds exhibits only an irreversible redox wave of the ferrocene units in the molecule. Both migration and volatility test results showed that, on comparison with those of Catocene, all tested compounds exhibit much more excellent anti‐migration ability and most of the tested compounds have lower volatility. Their effects on the thermal disintegration of ammonium perchlorate (AP), 1,3,5‐trinitro‐1,3,5‐triazacyclohexane (RDX), and 1,2,5,7‐tetranitro‐1,3,5,7‐tetraazacyclooctane (HMX) were measured by DSC. The results revealed that most of the compounds exhibit significant catalytic effects on the thermal degradation of AP and RDX. Particularly, most of the compounds containing one ferrocene unit in their cations show higher activity than that of Catocene. These compounds can be used as alternatives to Catocene in the composite solid propellants.     

Mono‐ and Dinuclear Ferrocenyl Ionic Compounds with Polycyano Anions. Characterization,Migration, and Catalytic Effects on Thermal Decomposition of Energetic Compounds

Neutral ferrocene‐based burning rate (BR) catalysts show strong migration trends and volatility during long‐time storage and curing of the composite solid propellants. To reduce these disadvantages thirty‐two ferrocenyl quaternary ammonium compounds, paired with polycyano anions, were synthesized and characterized by ¹H NMR, ¹³C NMR, and UV/Vis spectroscopy, as well as elemental analysis. Additionally, crystal structures of eight compounds were confirmed by single‐crystal X‐ray diffraction. TG and DSC analyses indicated that the compounds containing 1,1,2,3,3‐pentacyanopropenide anions show high thermal stability. Cyclic voltammetry studies suggested that they are quasi‐reversible or irreversible redox systems. Anti‐migration tests verified that the tested compounds show very low migration tendency and some of them exhibit no migration after 30 days aging at 70 °C. Their catalytic efficiency in the thermal decomposition of ammonium perchlorate (AP), 1,3,5‐trinitro‐1,3,5‐triazacyclohexane (RDX), and 1,2,5,7‐tetranitro‐1,3,5,7‐tetraazacyclooctane (HMX) were examined by DSC analyses. The results revealed that most of the compounds exhibit distinct effects on the thermal degradation of AP and RDX. Two compounds have good catalytic ability in the thermal decomposition of HMX, representing rare examples of the reported ferrocenyl ionic compounds, which display catalytic property during combustion of HMX.     

Dinuclear (Ferrocenylmethyl)imidazolium Ionic Compounds with Polycyano Anions. Characterization,Migration, and Effects during Combustion

Alkyl‐substituted ferrocene‐based burning rate catalysts exhibit high migration and volatility during curing process and prolonged storage of the composite solid propellants. To deal with the drawbacks twenty‐one dinuclear (ferrocenylmethyl)imidazolium compounds paired with polycyano anions, were synthesized and characterized by ¹H NMR, ¹³C NMR, UV/Vis, elementary analysis, and both 2 and 11 were further characterized by single‐crystal X‐ray diffraction. The migration test revealed that the compounds have excellent anti‐migration ability. The cyclic‐voltammetry results suggested that they are quasi‐reversible or irreversible redox systems. The TG/DSC analyses showed that the compounds are highly thermal stable. Their effects on the thermal decomposition of ammonium perchlorate (AP) and 1,3,5‐trinitro‐1,3,5‐triazacyclohexane (RDX) were additionally examined. The results showed that the new compounds have strong effects on the thermal decomposition of both AP and RDX during combustion. Both 13 and 21 are more excellent than catocene for increasing the released heats of AP and can be used as alternatives of catocene in the composite solid propellants.     

Ferrocenyl Ionic Compounds Containing [Fe(CN)6]3– Anions: Synthesis,Characterization, and Catalytic Effects during Combustion

Twenty‐eight novel ferrocenyl ionic compounds, composed of mononuclear 1‐ferrocenylmethylalkyldimethylammoniums, 1‐ferrocenylmethyl‐3‐alkylimidazoliums, or their dinuclear analogs and [Fe(CN)₆]^3– anion, were designed and synthesized to tackle significant volatility and migration tendency of ferrocene‐based burning rate catalysts (BRCs) used currently in the composite solid propellants. The new compounds were characterized by UV/Vis, FT‐IR, and elementary analysis. The crystal structures of compounds 2· 5H₂O and 3· CH₂Cl₂ · 4H₂O verified the successful preparation of the desired ionic compounds. The TG tests at 70 °C for 24 h revealed that the new compounds exhibit lower volatility than catocene. The cyclic‐voltammetry results suggested that new compounds are quasi‐reversible or irreversible redox systems. TheTG/DSC analyses exhibited that the compounds are of highly thermal stability. Their catalytic effects on the thermal degradation of ammonium perchlorate (AP), 1,3,5‐trinitro‐1,3,5‐triazacyclohexane (RDX), and 1,3,5,7‐tetranitro‐1,3,5,7‐tetrazacyclooctane (HMX) were investigated. The results showed that most of the compounds exert great effects on the thermal degradation of AP and RDX during combustion. 11 and 2 are comparable to catocene in the thermal decomposition of AP and RDX, respectively, and can therefore be used as alternatives of catocene in a composite solid propellant. Some new compounds are unexpectedly active in promoting the thermal disintegration of HMX.     

“One‐Step” Synthesis of Ionic Ferrocenyl Compounds of Ferrocenylmethyldimethylamine. Characterization,Migration, and Catalytic Properties During Combustion

Alkylferrocene‐based burning rate catalysts exhibit high migration tendency and volatility during prolonged storage and fabrication process of the solid propellants. To retard the migration problems, eight ionic compounds composed of ferrocenylmethyldimethylammonium cation paired with a common energetic anion, were synthesized by “one‐step” procedure. The compounds were characterized by FT‐IR, NMR, and UV/Vis spectroscopy as well as elementary analysis. Their crystal structures were confirmed by single‐crystal X‐ray diffraction. The TG and DSC analyses indicated that they exhibit high thermal stability. Cyclic voltammetry studies suggested that most of them show reversible or quasi‐reversible redox waves. The anti‐migration results revealed that 1 – 4 are low‐migratory compounds, but 5 exhibits high migration trends. The TG curves at 70 °C for 24 h showed that all of them have low volatility. They have from high to low impact sensitivity depending on the anions of the compounds. They all exhibit significant effect on the thermal decomposition of ammonium perchlorate (AP) and some of them accelerate the thermal degradation of 1,3,5‐trinitro‐1,3,5‐triazacyclohexane (RDX). Among them 4 is the best one. Unexpectedly, compound 5 , with 1H‐tetrazolate as anion, can decompose into its original reactants at the temperature just higher than its melting point and could show smart‐material functionality in solid propellants.     

Synthesis and catalytic performance of ferrocene‐based compounds as burning rate catalysts

To overcome migration problems of ferrocene‐based burning rate catalysts and to enhance burning rate of ammonium perchlorate (AP)‐based propellants, eleven ferrocene‐based compounds ( 1 – 11 ) were synthesized by the condensation reaction of ferrocenecarbonyl chloride with corresponding amines and alcohols. The synthesis of 1 – 11 was confirmed using ¹H NMR, Fourier transform infrared and UV–visible spectroscopy. Their electrochemical properties were analyzed using cyclic voltammetry. The compounds showed redox behavior due to the presence of ferrocene. Their catalytic behavior in the thermal decomposition of AP was investigated using thermogravimetry (TG) and differential TG (DTG). In the presence of 5 wt% 1 – 11 , the thermal decomposition temperature of AP was significantly decreased. TG and DTG analyses showed that 1 – 11 had a good catalytic effect in the thermal decomposition of AP. Anti‐migration studies showed that migration of 1 – 11 was slower than that of 2,2‐bis(ethylferrocenyl)propane (catocene) and ferrocene. The effect of the presence of polar elements like oxygen and nitrogen on anti‐migration behavior of small ferrocene‐based compounds was also investigated. Oxygen‐containing compounds showed better anti‐migration behavior than nitrogen‐containing compounds.     

Synthesis and Characterization of a Dinuclear Nitrogen‐Rich Ferrocenyl Ligand and Its Ionic Coordination Compounds and Their Catalytic Effects During Combustion

Alkylferrocene‐based burning‐rate catalysts (BRCs) exhibit distinct migration tendency and high volatility and thus result in inferior performance of composite solid propellants during their combustion processes. To deal with these drawbacks, a novel dinuclear nitrogen‐rich ferrocene derivative, 4‐amino‐3,5‐bis(4‐ferrocenyl‐1,2,3‐triazolyl‐1‐methyl)‐1,2,4‐triazole (BFcTAZ) and its twenty seven ionic coordination compounds, [M₂(BFcTAZ)₂(H₂O)₄]_mX_n·xH₂O (M = Cr³⁺, Mn²⁺, Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺ and Pb²; X = polycyano anions), were synthesized and characterized by FT‐IR, UV/Vis, and elementary analysis. Crystal structure of BFcTAZ was further confirmed by single‐crystal X‐ray diffraction and a general molecular structure of the new complexes was proposed. Their high thermal stability was verified by TG technique. Cyclic voltammetry studies suggested that the new compounds are diverse redox systems. Their effects on the thermal degradation of some common oxidizers were measured by DSC technique. The results indicated that most of the new complexes exert great effects on the thermal decomposition of AP, RDX, and 1,1‐diamino‐2,2‐dinitroethylene (FOX‐7) and some of them are more active than catocene. The Cu²⁺ complexes are among the excellent ones. However, only six compounds have appreciable catalytic activity in the thermal degradation of HMX.     

Tris(2‐aminoethyl)amine‐based ferrocene‐terminated dendrimers as burning rate catalysts for ammonium perchlorate‐based propellant decomposition

Ferrocene‐based derivatives show potential application as burning rate catalysts (BRCs) for solid composite propellants. However, migration problems of simple ferrocene‐based derivatives limit their application as BRCs in solid composite propellants. To overcome the migration problems of ferrocene‐based BRCs and to enhance the burning rate of ammonium perchlorate (AP)‐based propellants, zero‐ to second‐generation tris(2‐aminoethyl)amine‐based ferrocene‐terminated dendrimers (G0, G1 and G2) were synthesized. The structures of G0, G1 and G2 were confirmed using ¹H NMR, Fourier transform infrared and UV–visible spectroscopies. The electrochemical behavior of G0, G1 and G2 was investigated using cyclic voltammetry. It was found that G0, G1 and G2 showed redox behavior due to the presence of ferrocene and this redox behavior was diffusion controlled over the investigated scan range. The burning rate catalytic effect of G0, G1 and G2 on thermal decomposition of AP was investigated using thermogravimetry and differential thermogravimetry. G0, G1 and G2 showed good catalytic effect on the thermal decomposition of AP. Anti‐migration studies showed that migration of G0, G1 and G2 was much slower than that of 2,2‐bis(ethylferrocenyl)propane (catocene) and ferrocene.     

Synthesis,Crystal Structure,and Properties of Energetic Copper(II) Complex based on 3,5‐Dinitrobenzoic Acid and 1,5‐Diaminotetrazole

Energetic copper(II) complexes based on 3,5‐dinitrobenzoic acid (HDNBA) and 1,5‐diaminotetrazole (DAT), Cu(DNBA)₂(H₂O)₂ ( 1 ) and Cu(DAT)₂(DNBA)₂ ( 2 ) were synthesized and characterized by elemental analysis, IR spectroscopy, single‐crystal and powder X‐ray diffraction. In both complexes, Cu^II was coordinated to a plane tetragon, by four oxygen atoms from two DNBA^– ions and two coordinated H₂O molecules for 1 , and by two oxygen atoms and two nitrogen atoms from different DNBA^– ions and DAT ligands for 2 . Differential scanning calorimetry (DSC) and thermogravimetry (TG) analyses were employed to measure the thermal decomposition processes and non‐isothermal kinetics parameters of the complexes. The thermal decomposition onset temperatures of 1 and 2 are 321 and 177 °C. The apparent activation energies of the first exothermic decomposition peaks of 1 and 2 are 247.2 and 185.2 kJ · mol^–1. Both 1 (35 J, > 360 N) and 2 (12.5 J, > 360 N) are less sensitive than RDX. The catalytic effects on the decomposition of ammonium perchlorate (AP) of 1 and 2 were studied by DSC. All results supported the potential applications of the energetic complexes as additives of solid rocket propellants.     

Ionic Ferrocenyl Coordination Compounds Derived from Imidazole and 1,2,4‐Triazole Ligands and Their Catalytic Effects During Combustion

Alkylferrocene‐based burning‐rate catalysts (BRCs) show conspicuous migration tendency and volatility during prolonged storage and fabrication process of a composite solid propellant. To enhance anti‐migration ability of the BRCs, forty novel ionic coordination compounds, [M(L)₄(H₂O)₂]_mX_n (M = Mn²⁺, Co²⁺, Cu²⁺, Ni²⁺, Zn²⁺, Fe²⁺, Pb²⁺, Cr³⁺, Bi³⁺, or Cd²⁺; L = ferrocenylmethyl imidazole or ferrocenylmethyl‐1,2,4‐triazole; X = picrate or trinitroresorcinolate), were synthesized and characterized by FT‐IR, UV/Vis, and elementary analysis. Additionally, the crystal structures of six compounds were confirmed by single‐crystal X‐ray diffraction. The TG analyses revealed that the new compounds show high thermal stability. Cyclic voltammetry studies suggested that theyare irreversible redox systems. Their catalytic activities in the thermal degradation of ammonium perchlorate (AP), 1,3,5‐trinitro‐1,3,5‐triazacyclo‐hexane (RDX) and 1,2,5,7‐tetranitro‐1,3,5,7‐tetraazacyclooctane (HMX) were examined by DSC technique. The results indicated that all the new compounds exert great effects on the thermal decomposition of AP and RDX, among them some compounds are more active than catocene. Compound 26 has good catalytic ability in the thermal decomposition of HMX, representing a rare example of the reported ferrocene‐based BRCs which show catalytic activity during combustion of HMX.     

Thermal Decomposition Behavior and Non-isothermal Decomposition Reaction of Copper（ll） Salt of 4-Hydroxy-3,5-dinitropyridine Oxide and Its Application in Solid Rocket Propellant

The thermal decomposition behavior and kinetic parameters of the exothermic decomposition reactions of the title compound in a temperature‐programmed mode have been investigated by means of DSC, TG‐DTG and lower rate Thermolysis/FTIR. The possible reaction mechanism was proposed. The critical temperature of thermal explosion was calculated. The influence of the title compound on the combustion characteristic of composite modified double base propellant containing RDX has been explored with the strand burner. The results show that the kinetic model function in differential form, apparent activation energy E_a and pre‐exponential factor A of the major exothermic decomposition reaction are 1‐a,207.98 kJ*mol^?1 and 10^15.64 s^?1, respectively. The critical temperature of thermal explosion of the compound is 312.87 C. The kinetic equation of the major exothermic decomposition process of the title compound at 0.1 MPa could be expressed as: dα/dT=10^16.42 (1–α)e‐2.502×10⁴/T As an auxiliary catalyst, the title compound can help the main catalyst lead salt of 4‐hydroxy‐3,5dinitropyridine oxide to enhance the burning rate and reduce the pressure exponent of RDX‐CMDB propellant.     

Synthesis of Ferrocene-based Esters as Burning Rate Catalysts and their Anti-migration Study

Ferrocene-based (Fc-based) burning rate catalysts (BRCs) play an essential role in the solid rocket propellants. However, the migration problem during curing and storage limits their applications. To retard the migration problems of Fc-based BRCs and to increase the burning rate (BR) of AP-based propellants, Fc-based esters compounds (Es-Fcs) were synthesized. The synthesized Es-Fcs were characterized by X-ray diffraction, proton nuclear magnetic resonance (¹H NMR),¹³C NMR and Fourier transform infrared (FT-IR) spectroscopy. The electrochemical behaviors of Es-Fcs were investigated by cyclic voltammetry (CV). The BR catalytic activity of Es-Fcs on thermal decomposition of AP were examined by thermogravimetry (TG). Thermal analysis results showed that these Es-Fcs had good BR catalytic effects on thermal decomposition of AP. It was found that the anti-migration performance of Es-Fcs were better than catocene and Fc.     

CuO nanoparticles supported on three‐dimensional nitrogen‐doped graphene as a promising catalyst for thermal decomposition of ammonium perchlorate

In the present work, CuO nanoparticles grown on three‐dimensional nitrogen‐doped graphene‐based frameworks (CuO@3D‐(N)GFs) were synthesized using a two‐step method. After the synthesis of three‐dimensional nitrogen‐doped graphene, CuO nanoparticles were deposited on it, by adding cupric acetate followed by thermal treatment. Different analysis methods were used to characterize the products. The as‐prepared nanocomposite was used as a promising catalyst for thermal decomposition of ammonium perchlorate (AP) as one of the most common oxidizer in composite propellants. Differential scanning calorimetry (DSC) and thermogravimetry analysis (TGA) techniques were used to investigate the thermal decomposition of ammonium perchlorate. According to the DSC/TGA, high temperature decomposition of AP decreased to 111 °C in the presence of 4% CuO@3D‐(N)GFs and the total heat release (ΔH) from decomposition of AP increased to 1893 J g^?1 which is much more than 590 J g^?1 for pure AP.     

Combination of 1,2,4‐Oxadiazole and 1,2,5‐Oxadiazole Moieties for the Generation of High‐Performance Energetic Materials

Salts generated from linked 1,2,4‐oxadiazole/1,2,5‐oxadiazole precursors exhibit good to excellent thermal stability, density, and, in some cases, energetic performance. The design of these compounds was based on the assumption that by the combination of varying oxadiazole rings, it would be possible to profit from the positive aspects of each of the components. All of the new compounds were fully characterized by elemental analysis, IR spectroscopy, ¹H, ¹³C, and (in some cases) ¹⁵N NMR spectroscopy, and thermal analysis (DSC). The structures of 2 – 3 and 5 ‐ 1 ?5 H₂O were confirmed by single‐crystal X‐ray analysis. Theoretical performance calculations were carried out by using Gaussian 03 (Revision D.01). Compound 2 ‐ 3 , with its good density (1.85 g cm^?3), acceptable sensitivity (14 J, 160 N), and superior detonation pressure (37.4 GPa) and velocity (9046 m s^?1), exhibits performance properties superior to those of 1,3,5‐trinitroperhydro‐1,3,5‐triazine (RDX).     

Nitration Products of 5‐Amino‐1H‐tetrazole and Methyl‐5‐amino‐1H‐tetrazoles – Structures and Properties of Promising Energetic Materials

The nitration of 5‐amino‐1H‐tetrazole ( 1 ), 5‐amino‐1‐methyl‐1H‐tetrazole ( 3 ), and 5‐amino‐2‐methyl‐2H‐tetrazole ( 4 ) with HNO₃ (100%) was undertaken, and the corresponding products 5‐(nitrimino)‐1H‐tetrazole ( 2 ), 1‐methyl‐5‐(nitrimino)‐1H‐tetrazole ( 5 ), and 2‐methyl‐5‐(nitramino)‐2H‐tetrazole ( 6 ) were characterized comprehensively using vibrational (IR and Raman) spectroscopy, multinuclear (¹H, ¹³C, ¹⁴N, and ¹⁵N) NMR spectroscopy, mass spectrometry, and elemental analysis. The molecular structures in the crystalline state were determined by single‐crystal X‐ray diffraction. The thermodynamic properties and thermal behavior were investigated by using differential scanning calorimetry (DSC), and the heats of formation were determined by bomb calorimetric measurements. Compounds 2, 5 , and 6 were all found to be endothermic compounds. The thermal decompositions were investigated by gas‐phase IR spectroscopy as well as DSC experiments. The heats of explosion, the detonation pressures, and velocities were calculated with the software EXPLO5, whereby the calculated values are similar to those of common explosives such as TNT and RDX. In addition, the sensitivities were tested by BAM methods (drophammer and friction) and correlated to the calculated electrostatic potentials. The explosion performance of 5 was investigated by Koenen steel sleeve test, whereby a higher explosion power compared to RDX was reached. Finally, the long‐term stabilities at higher temperatures were tested by thermal safety calorimetry (FlexyTSC). X‐Ray crystallography of monoclinic 2 and 6 , and orthorhombic 5 was performed.     

Thermal decomposition of RDX/AP by TG–DSC–MS–FTIR

The method of TG–DSC–MS–FTIR simultaneous analysis has been used to study the thermal decomposition mechanism of the RDX/AP (1/2) mixture. TG–DSC showed that there were two mass loss processes for thermal decomposition of RDX/AP. The first one was mainly ascribed to the thermal decomposition of RDX. Addition of AP to RDX causes decomposition to take place abruptly, after melting, resulting in a very sharp and strong peak at lower temperature. The apparent activation energies, calculated by model-free Friedman method, of this process were negative. The second mass loss process of RDX/AP was confirmed to be the thermal decomposition of AP, catalyzed by RDX. This process can be divided into three stages, which were an nth-order autocatalytic and two one-dimensional diffusion stages, respectively. There was a competition among the formation reactions of N₂O, HNCO, and HCl for the first stage and between NO₂ and N₂O for the later two stages. The production of N₂O dominated in the second stage, while NO₂ did in the third stage.     

Fully C/N‐Polynitro‐Functionalized 2,2′‐Biimidazole Derivatives as Nitrogen‐ and Oxygen‐Rich Energetic Salts

Through the use of a fully C/N‐functionalized imidazole‐based anion, it was possible to prepare nitrogen‐ and oxygen‐rich energetic salts. When N,N‐dinitramino imidazole was paired with nitrogen‐rich bases, versatile ionic derivatives were prepared and fully characterized by IR, and ¹H, and ¹³C NMR spectroscopy and elemental analysis. Both experimental and theoretical evaluations show promising properties for these energetic compounds, such as high density, positive heats of formation, good oxygen balance, and acceptable stabilities. The energetic salts exhibit promising energetic performance comparable to the benchmark explosive RDX (1,3,5‐trinitrotriazacyclohexane).     

没食子酸铋锆的制备、表征及其燃烧催化作用

以没食子酸、硝酸铋和硝酸氧锆为原料, 首次合成出了双金属有机盐——没食子酸铋锆, 采用有机元素分析、X射线荧光(XRF)光谱和傅里叶变换红外(FTIR)光谱对其进行了表征. 在程序升温条件下, 利用热重(TG)分析、差示扫描量热法(DSC)、固相原位反应池/FTIR 联用技术, 研究了没食子酸铋锆的热行为和热分解机理,描述了没食子酸铋锆的热分解过程, 分析得出其最终分解产物为Bi₂O₃、ZrO₂和C. 利用螺压工艺制备了含没食子酸铋锆的推进剂样品, 研究了没食子酸铋锆对双基(DB)推进剂燃烧性能的影响, 分析了其燃烧催化作用. 结果表明, 没食子酸铋锆对双基推进剂的燃烧具有良好的催化作用, 是一种高效的燃烧催化剂; 没食子酸铋锆热分解的最终产物是催化燃烧的主要物质, 锆和碳则起辅助催化的作用.     

Synthesis of ferrocene‐modified poly(glycidyl methacrylate) and its burning rate catalytic property

A series of ferrocene‐modified poly(glycidyl methacrylate) (PGMA‐Fc) compounds were synthesized and applied as burning rate catalysts in simulative solid propellant to overcome migration problems. ¹H NMR and Fourier transform infrared spectroscopies and gel permeation chromatography were used to characterize the synthesized polymers. Their electrochemical behavior was evaluated using cyclic voltammetry. Their catalytic performance for the decomposition of ammonium perchlorate (AP) was investigated using thermogravimetric analysis. Anti‐migration studies were conducted in migration tubes under 50°C. The results show that PGMA‐Fc has a good catalytic effect on lowering the thermal decomposition temperature of AP. Anti‐migration studies show that PGMA‐Fc has better anti‐migration performance than ferrocene and catocene.     

Progress on the synthesis and catalytic and anti‐migration properties of ferrocene‐based burning rate catalysts

Burning rate catalysts are of great importance in solid composite propellants for their unique property of accelerating combustion speed. Among various kinds of burning rate catalysts, ferrocene and its derivatives exhibit excellent catalytic effects and have become the most widely used burning rate catalysts. However, these simple ferrocenyl compounds trend to migrate in solid composite propellants during storage, which causes great damage to the propellants, equipment and environment and can even affect personal safety. The exploration of novel anti‐migratory ferrocene‐based compounds has become an advanced research hotspot in the field of burning rate catalysis. This review focuses on recent progress on the synthesis and catalytic properties of ferrocene‐based polymers and ferrocene derivatives as burning rate catalysts. Two main aspects of anti‐migratory exploration, i.e. synthesis of ferrocene‐based polymers and modification of the side groups of ferrocene, are summarized. Ferrocene‐based polymers can be obtained via condensation polymerization, addition polymerization, ring‐opening polymerization, polymer reactions, etc. Ferrocenyl compounds with active groups and ferrocene‐based metal coordination compounds were developed instead of the methods of lengthening the carbon chain of side groups and improving molecular polarity. Also, possible mechanisms of burning rate catalytic activity and migration are discussed and analyzed. Finally, the key points of the development of ferrocene‐based burning rate catalysts and solid composite propellants are proposed. Copyright © 2016 John Wiley & Sons, Ltd.