CN113896748B - Binuclear ferrocenyl energetic compound and synthesis method and application thereof - Google Patents
Binuclear ferrocenyl energetic compound and synthesis method and application thereof Download PDFInfo
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- CN113896748B CN113896748B CN202111305647.1A CN202111305647A CN113896748B CN 113896748 B CN113896748 B CN 113896748B CN 202111305647 A CN202111305647 A CN 202111305647A CN 113896748 B CN113896748 B CN 113896748B
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Abstract
The invention belongs to the technical field of energetic compounds, and particularly relates to a binuclear ferrocenyl energetic compound and a synthesis method and application thereof. The structural general formula (I) of the compound is as follows:the novel binuclear ferrocenyl energetic compound with high combustion catalytic activity, good thermal stability and oxidation resistance is synthesized by selecting ferroceneformaldehyde and amino nitrogen-containing heterocycle as raw materials, has active catalytic group binuclear ferrocene and nitrogen-rich energetic groups, solves the problem of migration volatility of the ferrocenyl compound as a combustion rate catalyst, and can also improve the combustion rate catalytic activity of the AP-based solid rocket propellant.
Description
Technical Field
The invention belongs to the technical field of energetic compounds, and particularly relates to a binuclear ferrocenyl energetic compound and a synthesis method and application thereof.
Background
Ferrocene and its derivatives as combustion rate catalyst in Ammonium Perchlorate (AP) -based solid rocket propellant have effects of increasing combustion rate and reducing propellant pressure index, and decompose high-activity Fe in combustion process2O3Having excellent catalytic properties, a number of twoFerrocenium derivatives are used as burn rate catalysts in solid propellants. The commercial ferrocene burning-rate catalyst can generate the phenomena of migration, volatilization, oxidation, crystallization and the like in the processing and storage processes, so that the burning-rate catalyst is unevenly distributed in a solid propellant, the propellant is unstable in combustion, and the service life of the propellant is seriously influenced.
Disclosure of Invention
The invention aims to provide a binuclear ferrocenyl energetic compound, a synthesis method thereof and application thereof in a combustion catalyst. The binuclear ferrocenyl energetic compound has a certain catalytic action on AP. The nitrogen-rich heterocyclic compound contains a large amount of N-N, N ═ N and C-N bonds with high enthalpy of formation, has the characteristics of high energy, good heat resistance, high density and the like, and most of combustion products are environment-friendly N2And CO2Etc. is a green high-energy compound. The two ferrocenyl rings and the nitrogen-containing heterocyclic ring are combined to form the binuclear ferrocenyl energetic compound, the compound not only has an active catalytic group binuclear ferrocene, but also has a nitrogen-rich energetic group, so that the problem of migration volatility of the ferrocenyl compound as a burning rate catalyst is solved, and the combustion rate catalytic activity of the AP-based solid rocket propellant can be improved.
The realization process of the invention is as follows:
a binuclear ferrocenyl energetic compound, which has a structural general formula (I) as follows:
wherein R is selected from any one of the following:
the synthesis method of the binuclear ferrocenyl energetic compound specifically comprises the following steps: taking ferrocenecarboxaldehyde and amino nitrogen heterocycle as raw materials, adding a base catalyst triethylamine, and performing reflux reaction to obtain a ferrocenyl energetic Schiff base compound; the mixture was not separated and NaBH was added under ice-bath conditions4And (3) carrying out reduction reaction, adjusting the pH value to 5-6 after the reaction is completed, and separating and purifying by column chromatography to obtain the target product binuclear ferrocenyl energetic compound, wherein the amino nitrogen heterocycle is selected from 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole, 5-amino-2-methyltetrazole or 5-amino-1-methyltetrazole.
Wherein the molar ratio of the ferrocenecarboxaldehyde to the amino nitrogen heterocycle is 2: 1.
When the amino nitrogen heterocyclic ring is used, an alcohol solvent is required to be added for dissolving.
The application of the binuclear ferrocenyl energetic compound in a rocket combustion catalyst.
The synthetic route of the binuclear ferrocenyl energetic compound is as follows:
the invention has the following positive effects:
the invention synthesizes a novel binuclear ferrocenyl energetic compound with high catalytic activity, good thermal stability and oxidation resistance. A series of binuclear ferrocenyl energetic compounds are synthesized by taking ferrocenecarboxaldehyde and a nitrogen-containing heterocycle as raw materials. The two ferrocene units and the energy-containing unit are combined, the molecular weight and the polarity are increased to improve the anti-migration performance, and the introduction of the nitrogen-containing heterocycle can improve the energy level of the propellant, so that the use requirement of the solid propellant is met, and the catalytic activity of the ferrocene compound as a combustion rate catalyst is improved.
Drawings
FIG. 1 is a crystal structure diagram of Compound a;
FIG. 2 is a crystal structure diagram of Compound b;
FIG. 3 is a crystal structure diagram of Compound c;
FIG. 4 is a crystal structure diagram of Compound d;
FIG. 5 is a TG plot for compounds a-d;
FIG. 6 is a CV plot for compounds a-d;
FIG. 7 is a DPV profile of compounds a-d;
FIG. 8 is a DSC graph of compounds a-d catalyzing amine perchlorates.
Detailed Description
The present invention will be further described with reference to the following examples.
The compound a, the compound b, the compound c and the compound d obtained in the embodiments 1-4 are novel dinuclear ferrocenyl energetic compounds with high catalytic activity, good thermal stability and oxidation resistance, the compound not only has active catalytic group dinuclear ferrocene, but also has nitrogen-rich energetic groups, the problem of migration volatility of the ferrocenyl compound as a burning rate catalyst is solved, and the combustion rate catalytic activity of the AP-based solid rocket propellant can be improved.
EXAMPLE 1 Synthesis of Compound a
Adding 3-amino-1, 2, 4-triazole (5mmol) into 25mL methanol, adding ferrocene formaldehyde (10mmol), dripping 5 drops of triethylamine (base catalyst), refluxing, monitoring reaction process by TLC (thin layer chromatography), reacting for 6h, cooling to room temperature, and adding excessive NaBH several times in ice bath4And monitoring the reaction process by TLC, after the reaction is completed, adding 30mL of distilled water, adjusting the pH value to 5-6 by glacial acetic acid, stirring at normal temperature for 12h, and separating and purifying by adopting a column chromatography (a stationary phase is silica gel, a mobile phase is petroleum ether and ethyl acetate, wherein the volume ratio of the petroleum ether to the ethyl acetate is 1:1) to obtain a yellow solid compound a. FIG. 1 is a crystal structure diagram of Compound a.
EXAMPLE 2 Synthesis of Compound b
Adding 4-amino-1, 2, 4-triazole (5mmol) into 25mL methanol, adding ferrocene carboxaldehyde (10mmol), dripping 5 drops of triethylamine, refluxing, monitoring the reaction process by TLC, reacting for 6h, cooling to room temperature, and adding excessive NaBH a little for many times in ice bath4And monitoring the reaction process by TLC, after the reaction is completed, adding 30mL of distilled water, adjusting the pH value to 5-6 by glacial acetic acid, stirring at normal temperature for 12h, and separating and purifying by adopting a column chromatography (a stationary phase is silica gel, a mobile phase is petroleum ether and ethyl acetate, wherein the volume ratio of the petroleum ether to the ethyl acetate is 1:1) to obtain a yellow solid compound b. FIG. 2 is a crystal structure diagram of Compound b.
EXAMPLE 3 Synthesis of Compound c
Adding 5-amino-2-methyltetrazole (5mmol) into 25mL methanol, adding ferrocenecarboxaldehyde (10mmol), dripping 5 drops of triethylamine, refluxing, monitoring the reaction process by TLC, reacting for 6h, cooling to room temperature, and adding excessive NaBH a little by many times in ice bath4And monitoring the reaction process by TLC, after the reaction is completed, adding 30mL of distilled water, adjusting the pH value to 5-6 by glacial acetic acid, stirring at normal temperature for 12h, and separating and purifying by adopting a column chromatography (a stationary phase is silica gel, a mobile phase is petroleum ether and ethyl acetate, wherein the volume ratio of the petroleum ether to the ethyl acetate is 1:1) to obtain a yellow solid compound c. FIG. 3 is a crystal structure diagram of Compound c.
EXAMPLE 4 Synthesis of Compound d
Adding 5-amino-1-methyltetrazole (5mmol) into 25mL of methanol, adding ferrocene formaldehyde (10mmol), dripping 5 drops of triethylamine, refluxing, monitoring the reaction process by TLC, reacting for 6h, cooling to room temperature, and adding excessive NaBH a little for many times under ice bath4TLC monitoringAnd (3) measuring the reaction process, after the reaction is completed, adding 30mL of distilled water, adjusting the pH value to 5-6 with glacial acetic acid, stirring at normal temperature for 12h, and separating and purifying by adopting a column chromatography (a stationary phase is silica gel, a mobile phase is petroleum ether and ethyl acetate, wherein the volume ratio of the petroleum ether to the ethyl acetate is 1:1) to obtain a yellow solid compound d. FIG. 4 is a crystal structure diagram of Compound d.
EXAMPLE 5 testing of the thermal stability of the Compounds
The thermal stability of the binuclear ferrocenyl energetic compound is researched by a thermogravimetric analyzer (TG), the test temperature range is 30-600 ℃ at the heating rate of 10 ℃/min under the nitrogen atmosphere, and the total sample dosage is about 1 mg. The rapid weight loss process of the compound a occurs at 260-418 ℃, the weight loss is about 52.36 percent, and the rapid weight loss process is caused by the decomposition of C-N bond fracture triazole connected with nitrogen heterocycles in the compound and the collapse of two ferrocene frameworks; the rapid weight loss process of the compound b occurs at 309 ℃ of 240 ℃ and 43 percent, and is caused by the decomposition of C-N bond fracture triazole connected with nitrogen heterocycle in the compound and the collapse of two ferrocene skeletons; the rapid weight loss process of the compound C occurs at 349 ℃ of 240-; the rapid weight loss process of the compound d occurs at 263-348 ℃, the weight loss is about 45 percent, and the rapid weight loss process is caused by the breakage of C-N bonds connected with nitrogen heterocycles in the compound, the decomposition of tetrazole and the collapse of two ferrocene frameworks. The test result shows that the energy-containing compound of the binuclear ferrocene has better thermal stability. See fig. 5.
EXAMPLE 6 testing of the Compound for Redox
The electrochemical properties of the binuclear ferrocenyl energetic compound are researched by Cyclic Voltammetry (CV) and Differential Pulse Voltammetry (DPV), the redox characteristics of the binuclear ferrocenyl energetic compound are investigated, a three-electrode system is adopted, a glassy carbon electrode is used as a working electrode, a platinum wire electrode is used as a counter electrode, and Ag/Ag is used as a silver/silver (Ag/Ag) electrode+The electrode is a reference electrode and is prepared0.1mol/mL of the compounds a to d, a 0.1mol/mL solution of tetrabutylammonium tetrafluoroborate in acetonitrile as a supporting electrolyte, a scanning rate of 100mv/s, and a scanning voltage of-0.5 to 0.4.
It can be seen from the CV and DPV plots that compounds a-d have a similar set of redox peaks, Δ E, at 48-233mvPThe five compounds are not easy to be oxidized and do not have complete redox reversibility because the ferrocenyl is taken as an electron donor, the triazole and tetrazole groups are taken as electron acceptors, the density of electron cloud on the ferrocene is reduced because the triazole and tetrazole groups have strong electron-withdrawing capability, the ferrocene is not easy to be oxidized and changed, and the oxidation potential and the reduction potential of the compounds are higher than those of neutral compounds NBF, TBF and CATocene, which indicates that the compounds have stronger oxidation resistance. Because the two ferrocene groups of the compounds a-d are relatively symmetrical, only one pair of reversible redox peaks of ferrocene can be seen in a CV curve chart, but the two ferrocene groups of the compound d can be seen through DPV that are not simultaneously oxidized and reduced and two ferrocene electrons are transferred because the symmetry ratio of the compound d is poor; the symmetry of the compounds a, b and c is stronger, the two ferrocene tend to be equivalent, and the two ferrocene are simultaneously oxidized and reduced in electrochemical test. See fig. 6 and 7.
EXAMPLE 7 test of catalytic Performance of Compound Combustion catalyst
A Differential Scanning Calorimeter (DSC) is used for researching the catalytic performance of the binuclear ferrocenyl energetic compound on the perchloric acid amine, the compound and AP are mixed according to the mass ratio of 1:3, the heating rate is 10 ℃/min, the test temperature range is 30-600 ℃ under the nitrogen atmosphere, and the total sample dosage is about 1.7 mg. The thermal decomposition process of pure AP is divided into two parts, namely a low-temperature exothermic peak (337 ℃) and a high-temperature exothermic peak (442 ℃), and a small endothermic peak exists from the low-temperature exothermic peak to the high-temperature exothermic peak, because the heat absorbed by the AP thermal decomposition forming gas at the stage is larger than the heat released by the AP thermal decomposition forming gas.
When the compounds a-d are respectively added into AP, crystal system transformation endothermic peaks do not obviously move, which shows that the crystal system transformation temperature of the AP is hardly influenced by the addition of the compounds a-d, but the decomposition exothermic temperature is advanced to some extent, the compound a advances the low-temperature exothermic peak temperature and the high-temperature exothermic peak temperature of pure AP by 161 ℃ and 125 ℃, and the exothermic quantities are 428.5J/g and 2155.4J/g respectively; the compound b advances the pure AP low-temperature exothermic peak temperature and the pure AP high-temperature exothermic peak temperature by 159 ℃ and 128 ℃ respectively, the exothermic quantities are 543.5J/g and 1903.02J/g respectively, the exothermic quantity is obviously increased, the decomposition exothermic temperature range is reduced, and the exothermic is more concentrated; the compound c advances the low-temperature exothermic peak temperature and the high-temperature exothermic peak temperature of pure AP by 156 ℃ and 123 ℃ respectively, the exothermic quantities are 237J/g and 2282.6J/g respectively, and the exothermic quantities are increased; the compound d advances the low-temperature exothermic peak temperature and the high-temperature exothermic peak temperature of pure AP by 134 ℃ and 124 ℃ respectively, the exothermic quantities are 381.9J/g and 1942.95J/g respectively, and the decomposed exothermic peak has sharp peak shape and rapid decomposition. Experimental results show that the binuclear ferrocene energetic compound has good combustion catalytic activity on AP. See fig. 8.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and is not intended to limit the invention to the particular forms disclosed. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (5)
2. the method for synthesizing a dinuclear ferrocenyl energetic compound according to claim 1, wherein: with ferrocenyl methylAldehyde and amino nitrogen heterocycle are taken as raw materials, an alkali catalyst triethylamine is added, and a ferrocenyl energetic Schiff base compound is obtained through reflux reaction; the mixture was not separated and NaBH was added under ice-bath conditions4And (3) carrying out reduction reaction, adjusting the pH value to 5-6 after the reaction is completed, and separating and purifying by column chromatography to obtain the target product binuclear ferrocenyl energetic compound, wherein the amino nitrogen heterocycle is selected from 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole, 5-amino-2-methyltetrazole or 5-amino-1-methyltetrazole.
3. The method of synthesis according to claim 2, wherein: the mol ratio of the ferrocenecarboxaldehyde to the amino nitrogen heterocycle is 2: 1.
4. The method of synthesis according to claim 2, wherein: when the amino nitrogen heterocyclic ring is used, an alcohol solvent is required to be added for dissolving.
5. The use of the dinuclear ferrocenyl energetic compound of claim 1 in rocket combustion catalysts.
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