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.     

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.     

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 Based on 5‐Ferrocenyl‐1H‐tetrazole. Synthesis,Characterization, Migration,and Catalytic Effects During Combustion

Ferrocenyl ionic compounds, consisting of the 5‐ferrocenyltetrazolate anion and a guanidinium or a 1‐alkyl‐3‐methylimidazolium cation, were synthesized and characterized by ¹H NMR, ¹³C NMR, and UV/Vis spectroscopy, as well as elementary analysis. The molecular structures of four compounds were additionally confirmed by single‐crystal X‐ray diffraction. Results of the TG and DSC analyses showed that some compounds display high thermal stability. Cyclic voltammetry investigations suggested that the compounds exhibit redox waves for the ferrocenyl groups and are considered as irreversible redox systems. Migration studies revealed that migration trends of the compounds are much lower than that of 2, 2‐bis(ethylferrocenyl)propane (Catocene), extensively used in composite solid propellants. Their catalytic performances for 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 evaluated by DSC and/or TG techniques. Most of the compounds exhibit high catalytic efficiency in the thermal degradation of AP and RDX. Those of the guanidine‐containing compounds 1 – 3 are better, implying that nitrogen‐rich moieties are beneficial to enhancing released heats of some energetic materials. These guanidine salts could be used as ferrocene‐based burning rate catalyst candidates in 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.     

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.     

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.     

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.     

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.     

“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 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.     

Synthesis and combustion catalytic activity of ferrocene-based energetic compounds

Ammonium perchlorate (AP) is a common oxidizer in composite solid rocket propellants due to its excellent burning characteristics, good processability, and storability. Owing to their outstanding catalytic effects, ferrocene, and its derivatives have become the most widely used burning rate catalysts (BRCs). The addition of ferrocene and its derivatives to AP rendered performance optimization. In this study, azole-based ferrocenyl compounds were successfully synthesized. The compounds were characterized by single-crystal X-ray diffraction, UV-vis spectroscopy, and other techniques. The thermal degradation of AP catalyzed by these compounds was evaluated by differential scanning calorimetry and thermogravimetric analysis. Results revealed that the decomposition peak temperature of AP dramatically decreases and that the released heat of AP significantly increases with the new compounds as additives. Hence, the six azole-based ferrocenyl BR catalysts are favorable for the combustion catalytic activity.     

双核茂铁四氮唑的合成及对高氯酸铵热分解的催化作用

首先以二茂铁为原料合成丙基桥联的双聚二茂铁(DFP), 经甲酰化得到丙基桥联的双聚二茂铁甲醛(DFP-CHO, 1), 再与NH₂OH·5HCl进行缩合反应得到双核二茂铁肟(2), 然后脱水得到丙基桥联双聚二茂铁甲腈(3), 最后在(n-C₄H₉)₃SnCl 的催化作用下与NaN₃进行[2+3]环加成反应, 生成目标产物丙基桥联双聚二茂铁四唑(4); 通过¹H NMR, FTIR和ESI-MS对目标产物的结构进行了表征. 利用差示扫描量热分析(DSC)和热重(TG)分析研究了这2个双聚二茂铁氮杂衍生物的燃速催化性能, 结果表明, 通过添加质量分数为5%的丙基桥联双聚二茂铁氮杂化合物3和4均使高氯酸铵(AP)的热分解温度降至100℃左右.     

Effect of iron-containing catalysts on thermal decomposition of cured GAP-AP propellants

The effects of various burning rate catalysts on thermal decomposition of cured glycidyl azide polymer (GAP)-ammonium perchlorate (AP) propellants have been studied by means of thermal analysis and a modified vacuum stability test (MVST). Four types of iron-containing catalysts examined in this paper are catocene, ferrocenecarboxaldehyde (FCA), ferrocene, and ferric oxide. Results of differential thermal analysis (DTA) and thermogravimetric analysis (TG) revealed that the catalysts play an important role in the decomposition of both AP and GAP. The peak decomposition temperature (T _m) of DTA curves and onset decomposition temperature (T _o) of TG patterns considerably shifted to a lower temperature as the concentration of catalysts increased in the propellants. The endothermic temperature of AP, however, is unaffected by the presence of burning rate catalysts in all cases. The activation energy of decomposition of the propellants in range of 80 to 120°C is determined, based on the MVST results.     

鬼臼毒素及其衍生物热分解反应的动力学研究

The thermal behavior and thermal decomposition kinetic parameters of podophyllotoxin （1） and 4 derivatives, picropodophyllin （2）, deoxypodophyllotoxin （3）, fl-apopicropodophyllin （4）, podophyllotoxone （5） in a temperature-programmed mode have been investigated by means of DSC and TG-DTG. The kinetic model functions in differential and integral forms of the thermal decomposition reactions mentioned above for first stage were established. The kinetic parameters of the apparent activation energy Ea and per-exponential factor A were obtained from analy- sis of the TG-DTG curves by integral and differential methods. The most probable kinetic model function of the decomposition reaction in differential form was （1- a）^2 for compounds 1-3,2/3·a^-1/2 for compound 4 and 1/2（1-a）·[-In（1-a）]^-1 for compound 5. The values of Ea indicated that the reactivity of compounds 1-5was increased in the order： 5〈4〈2〈1〈3. The values of the entropy of activation △S^≠, enthalpy of activation △H^≠ and free energy of activation △G^≠ of the reactions were estimated. The values of △G^≠ indicated that the thermal stability of compounds 1-3 with the samef（a） was increased in the order： 2〈3〈1.     

Thermal studies of chitin–chitosan derivatives

New poly(azo) amino-chitosan compounds were obtained from the azo coupling reaction of N-benzyl chitosan and diazonium salts. The thermal behavior of these compounds was studied by thermogravimetric analysis (TG), differential thermogravimetric analysis (DTG), TG coupled with a Fourier-transform infrared, and differential scanning calorimetry (DSC). TG/DTG curves of chitin–chitosan polymer showed two thermal events attributed to water loss and decomposition of the polysaccharide after cross-linking reactions. Thermal analysis of the poly(azo) amino-chitosan compounds showed that the decomposition temperatures decreased when compared to the starting chitin–chitosan and N-benzyl chitosan. DSC results showed an agreement with the TG/DTG analyses. Thermal behavior of poly(azo) amino-chitosans suggest that these compounds could be considered as potential thermal sensors.     

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 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.     

The Non‐Isothermal Decomposition Kinetics of NaNTO·H2O and the Relationship between its Structure and Properties

NaNTO·H₂O was prepared by mixing 3‐nitro‐1,2,4‐triazol‐5‐one (NTO) aqueous solution and sodium hydroxide aqueous solution. Its thermal decomposition and kinetics were studied under non‐isothermal conditions by DSC and TG/DTG methods. The kinetic parameters were obtained from analysis of the DSC and TG/DTG curves by the Kissinger method, the Ozawa method, the differential method and the integral method. The most probable mechanism function for the thermal decomposition of the first stage was suggested by comparing the kinetic parameters. The critical temperature of thermal explosion (T_b) was 240.93 °C. The theoretical investigation on the structure unit of the title compound was carried out by DFT‐B3LYP/CEP‐31G methods; atomic net charges and the population analysis were discussed.     

Synergistic Catalytic Effect of a Series of Energetic Coordination Compounds based on Tetrazole‐1‐acetic Acid on Thermal Decomposition of HMX

A series of energetic coordination compounds [Co(tza)₂}_n ( 1 ), [Bi(tza)₃]_n ( 2 ), {[Cu₄(tza)₆(OH)₂] · 4H₂O}_n ( 3 ), [Mn(tza)₂]_n ( 4 ), {[Bi(tza)(C₂O₄)(H₂O)] · H₂O}_n ( 5 ) and [Fe₃O(tza)₆(H₂O)₃]NO₃ ( 6 ) based on tetrazole‐1‐acetic acid (Htza) were synthesized though environmentally friendly methods. The coordination compounds were characterized by elemental analyses, IR spectroscopy, single‐crystal and powder X‐ray diffraction (PXRD), thermogravimetric analyses (TG), and differential scanning calorimetry (DSC). Their catalytic performances and the synergetic catalytic effects between 1 and 2 , 3 and 4 , 5 and 6 on the thermal decomposition of octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine (HMX) were all investigated by DSC. The results revealed that compounds 1 – 6 are thermally stable energetic compounds and they all exhibit high catalytic action for HMX thermal decomposition. The catalytic effects of the compounds on HMX thermal decomposition are closely related to the oxides, which come from the decomposition of the compounds, but have no positive relationships with the heat releases of the compounds themselves. Moreover, the synergetic catalytic effects between 1 and 2 , 3 and 4 , 5 and 6 were observed. Their mixtures at different mass ratio have different synergetic catalytic effects, and the sequence of the biggest synergetic index (SI) in each system is copper‐manganese system (compounds 3 and 4 ) > iron‐bismuth system (compounds 5 and 6 ) > cobalt‐bismuth system (compounds 1 and 2 ), indicating that the synergistic catalytic effects are mainly related to the combination and the proportion of the compounds.