CN114315489A - Synthesis method of heat-resistant energy-containing material azide 5-aminotetrazole zinc energy-containing complex - Google Patents
Synthesis method of heat-resistant energy-containing material azide 5-aminotetrazole zinc energy-containing complex Download PDFInfo
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Abstract
The invention provides a synthesis method of a heat-resistant energy-containing material azide 5-amino tetrazole zinc energy-containing complex, which comprises the following steps: adding dimethyl sulfoxide and water, adding 5-aminotetrazole and zinc nitrate hexahydrate under stirring, stirring until the mixture is completely dissolved, heating for reaction, recovering to room temperature after the reaction is finished, filtering, and drying to obtain the azide 5-aminotetrazole zinc energetic complex. The synthetic method is simple, the yield can reach 87% at least, and is higher than the yield of 28% in the prior art. The two main raw materials of the invention, namely the 5-aminotetrazole and the zinc nitrate hexahydrate are low-cost and easily-obtained commercial reagents. The method can prepare an organic metal complex which contains a non-lead component, has low addition amount and high energy and is used as a novel green burning rate catalyst.
Description
Technical Field
The invention belongs to the field of propellants, relates to a burning rate catalyst, and particularly relates to a synthesis method of a heat-resistant energy-containing material azide 5-amino tetrazole zinc energy-containing complex.
Background
The solid propellant is an energetic composite material, and particularly is a solid mixture consisting of solid fuel, solid oxide and additives (burning rate catalyst and the like). Throughout the development process of the propellant, the development of the solid propellant will be developed towards the direction of high energy, cleanness and safety in the future. The burning rate catalyst is one of the important components for regulating and improving the burning performance of the solid propellant undoubtedly, and is a very key functional material in the formulation of the solid propellant. Therefore, the search for new high-energy, clean and safe burning rate catalysts for improving the energy characteristics, combustion characteristics and the like of the propellant is still one of the hot areas of research of scientists.
The low signature signal characteristic of solid propellants is of increasing interest as modern warfare and local defense place higher demands on tactical missile technology. The low-characteristic signal propellant requires that the characteristic signals of smoke, flame and the like of a fuel gas plume are low, so that the missile is not easy to detect, identify and intercept, namely the missile is free from smoke and flame. 5-Aminotetrazole (5-Aminotetrazole, 5-AT for short) is taken as a typical tetrazole type high-nitrogen compound, the character of the tetrazole type high-nitrogen compound is white granular or flaky crystal, the tetrazole type high-nitrogen compound is firstly synthesized by Thiele in 1892 years, and 5-AT is a five-membered nitrogen heterocyclic compound with a molecular formula of CH3N5The nitrogen content is high (82.4% by mass), the standard molar enthalpy of formation is high (208.7kJ/mol) due to the high number of N-N bonds, C-N bonds and greater ring tensions in the molecule, the oxygen balance is-65.83%, and the melting point is 202.4 ℃. Is a nitrogen-rich energetic material with excellent performance. In addition, the catalyst also has high positive enthalpy of formation and good thermodynamic stability, most of decomposition products are nitrogen which is environment-friendly, and the metal salt of the catalyst is favorable for reducing characteristic signals when being used as a burning rate catalyst and added into a propellant. Therefore, the 5-aminotetrazole metal salt is more researched to be used for the pyrotechnic gas generating agent, and also can be used as a new optional component to be applied to the biradical propulsionAgent-related reports.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a synthesis method of a heat-resistant energy-containing material azide 5-aminotetrazole zinc energy-containing complex, and solve the technical problems of difficult raw material acquisition and low yield of the preparation method in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for synthesizing azide 5-amino tetrazole zinc energetic complex comprises the following steps: adding dimethyl sulfoxide and water, adding 5-aminotetrazole and zinc nitrate hexahydrate under stirring, stirring until the mixture is completely dissolved, heating for reaction, recovering to room temperature after the reaction is finished, filtering, and drying to obtain the azide 5-aminotetrazole zinc energetic complex.
The invention also has the following technical characteristics:
the molar ratio of the 5-aminotetrazole to the zinc nitrate hexahydrate is 1: 1.
80mL of dimethyl sulfoxide and 20mL of water are added for every 1mmol of 5-aminotetrazole and zinc nitrate hexahydrate.
The temperature rise reaction is carried out for 12-24 hours when the temperature rises to 110 ℃.
Compared with the prior art, the invention has the following technical effects:
the synthetic method is simple, the yield can reach 87% at least, and is only 28% compared with the yield in the prior art.
(II) the two main raw materials of the invention, namely 5-aminotetrazole and zinc nitrate hexahydrate are cheap and easily available commercial reagents.
The method can prepare an organic metal complex which contains a non-lead component, is low in addition amount and high in energy and serves as a novel green burning rate catalyst.
(IV) the azide 5-amino tetrazole zinc complex has high nitrogen content which is 57%. The azide 5-amino tetrazole zinc complex has good thermal stability and heat resistance, and the decomposition temperature is 350 ℃.
(V) the azide 5-amino tetrazole zinc complex has a catalytic effect on thermal decomposition of CL-20, FOX-7 and an absorbent (NC + NG) as a burning rate catalyst, wherein the decomposition temperature of the CL-20 and the FOX-7 can be advanced, the heat release rate of the absorbent is obviously accelerated, and the characteristics of a good energy-containing catalyst are shown.
Drawings
FIG. 1 is a crystal structure diagram of azide 5-amino tetrazole zinc complex.
FIG. 2 is a surface morphology diagram of azide 5-amino tetrazole zinc complex.
FIG. 3 is a DSC catalysis effect diagram of azide 5-amino tetrazole zinc complex on CL-20.
FIG. 4 is a DSC catalysis effect diagram of azide 5-amino tetrazole zinc complex on FOX-7.
FIG. 5 is a chart showing the DSC catalytic effect of the azide 5-aminotetrazole zinc complex on the absorbent (NC + NG).
The present invention will be explained in further detail with reference to examples.
Detailed Description
The conception of the invention is as follows:
the future development of missile weapons requires that solid propellants not only have very high energy, but also have the characteristics of low characteristic signals, bluntness, environmental protection and the like. In recent years, 5-aminotetrazole (5-ATZ) is a new energetic material, is a high nitrogen compound, has higher density, enthalpy of formation and gas formation amount, has lower sensitivity than RDX (hexogen) and HMX (octogen), and can achieve the effect of less smoke or no smoke because most of gas products are nitrogen. The substance has great application prospect in the field of propellants, and has become a novel environment-friendly green high-energy compound with great potential, which is called green energetic materials (GEMs for short). It is worth noting that the nitrogen content of the 5-aminotetrazole is up to 82.3 percent, and the formation enthalpy is 208.7kJ-1And has proper mechanical sensitivity and thermal sensitivity. In addition, it has physicochemical properties such as positive enthalpy of formation, good thermal stability, and low risk of explosion, and the likeThe catalyst is often used in combination with a metal as a burn rate catalyst.
Metal-Organic frameworks (MOFs), also known as Metal-Organic compounds (MOCs), are a new class of materials with periodic and supramolecular network structures that are self-assembled from Metal central ions and Organic ligands. The MOFs material is different from general organic and inorganic materials, integrates the characteristics between organic polymers and inorganic metal ions, and synthesizes functional materials by controlling reaction conditions (such as selection of reactants, concentration of reactants, pH, reaction time and the like). The MOFs material is different from common organic and inorganic materials, integrates the characteristics between organic polymers and inorganic metal ions, and synthesizes functional materials by controlling reaction conditions. It is worth mentioning that in recent years, scientists have attracted considerable attention to coordinate 5-aminotetrazole compounds with metal ions to form metal organic frameworks, and the metal organic frameworks are used as catalysts containing burn rate, and the metal coordination compounds of 5-aminotetrazole (ATz) are being studied more frequently. The application of tetrazolium salt in the smokeless composite modified double-base propellant containing hexogen is explored by Dengmen and the like, and researches show that the metal salt of tetrazolium has a good catalytic effect and can reduce the pressure index in a pressure range of 6-10 MPa.
Therefore, the 5-aminotetrazole and the metal salt zinc nitrate are subjected to coordination reaction to obtain the high-energy and insensitive 5-aminotetrazole zinc energetic complex simultaneously containing four energy groups (three 5-aminotetrazole groups and one azide group), wherein the nitrogen content of the complex is 57%.
The azide 5-amino tetrazole zinc energetic complex has the following structure:
the present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention fall within the protection scope of the present invention.
Example 1:
the embodiment provides a method for synthesizing an azide 5-amino tetrazole zinc energetic complex, which comprises the following steps: in a 10mL three-neck flask, 8mL of dimethyl sulfoxide and 2mL of water are added, 36.3mg (0.1mmol) of 5-aminotetrazole and 19.0mg (0.1mmol) of zinc nitrate hexahydrate are added under stirring, the mixture is stirred until the mixture is completely dissolved, and the temperature is raised to 110 ℃ for reaction for 12 hours. After the reaction was completed, the reaction was returned to room temperature, filtered and dried to obtain a white solid with a yield of 96%.
Example 2:
the embodiment provides a method for synthesizing an azide 5-amino tetrazole zinc energetic complex, which comprises the following steps: adding 80mL of dimethyl sulfoxide and 20mL of water into a 250mL three-neck flask, adding 363mg (1mmol) of 5-aminotetrazole and 190mg (1mmol) of zinc nitrate hexahydrate while stirring, stirring until the materials are completely dissolved, heating to 110 ℃, and reacting for 24 hours. After the reaction was completed, the reaction was returned to room temperature, filtered and dried to obtain a white solid product with a yield of 87%.
And (3) structural identification:
infrared Spectrum (KBr, cm)-1): 3263(-NH stretching vibration), 1667, 1517(-C ═ N stretching vibration), 2176(N ═ N-N stretching vibration)-Telescopic vibration);
raman Spectroscopy (cm)-1): azide group peak position 1330.67; 240.681, respectively;
elemental analysis: c3H6N16O2Zn
Calculated value (%): c8.13, H1.82, N56.92;
found (%): c8.15, H1.88, N57.00.
The crystal structure diagram of the product is shown in FIG. 1, and the SEM surface morphology diagram of the product.
The above data confirm that the white solid product obtained by the reaction of the synthesis methods of the above examples 1 and 2 is the target product azido 5-aminotetrazole zinc complex.
And (3) testing thermal performance:
the decomposition temperature of the nitrine 5-amino tetrazole zinc complex is 350 ℃.
Example 3:
the embodiment provides the application of the nitrine 5-amino tetrazole zinc energetic complex as a burning rate catalyst. The azide 5-amino tetrazole zinc energetic complex is obtained by adopting the synthesis method of the azide 5-amino tetrazole zinc energetic complex in the embodiment 1.
And (3) testing thermal performance:
the 5-amino tetrazole zinc complex is respectively mixed with CL-20, FOX-7 and an absorbent (NC + NG), and the addition amount of the complex as a burning rate catalyst is 5% (mass fraction). The test data are shown in fig. 3, 4 and 5, respectively. As can be seen from figures 3 to 5, the azide 5-amino tetrazole zinc complex has a catalytic effect on thermal decomposition of CL-20, FOX-7 and an absorbent (NC + NG) as a burning rate catalyst, wherein the decomposition temperature of the CL-20 and the FOX-7 can be advanced, the heat release rate of the absorbent is obviously accelerated, and the characteristics of a good energy-containing catalyst are shown.
Note:
the DSC is carried out in a nitrogen environment at a heating rate of 10 ℃/min.
CL-20, hexanitrohexaazaisowurtzitane.
FOX-7, diaminodinitroethylene.
NC, namely nitrocotton.
NG, namely nitroglycerin.
Claims (4)
1. A method for synthesizing azide 5-amino tetrazole zinc energetic complex is characterized by comprising the following steps: adding dimethyl sulfoxide and water, adding 5-aminotetrazole and zinc nitrate hexahydrate under stirring, stirring until the mixture is completely dissolved, heating for reaction, recovering to room temperature after the reaction is finished, filtering, and drying to obtain the azide 5-aminotetrazole zinc energetic complex.
2. The method for synthesizing the azide 5-aminotetrazole zinc energetic complex as defined in claim 1, wherein the molar ratio of the 5-aminotetrazole to the zinc nitrate hexahydrate is 1: 1.
3. The method for synthesizing azide 5-aminotetrazole zinc energetic complex as defined in claim 1, wherein 80mL of dimethyl sulfoxide and 20mL of water are added for every 1mmol of 5-aminotetrazole and zinc nitrate hexahydrate.
4. The method for synthesizing the azide 5-aminotetrazole zinc energetic complex as defined in claim 1, wherein the temperature rise reaction is carried out at a temperature of 110 ℃ for 12-24 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108424339A (en) * | 2018-03-23 | 2018-08-21 | 西北工业大学 | A kind of preparation method of high nitrogen two dimension conjugated structure doping vario-property nitrolite crystal |
| CN112919997A (en) * | 2021-02-05 | 2021-06-08 | 西安近代化学研究所 | graphene-Schiff base energetic MOFs and preparation method thereof |
| CN112939708A (en) * | 2021-02-08 | 2021-06-11 | 陕西师范大学 | Imidazole and pyrazole combustion rate catalyst containing ferrocenyl methyl-1, 2, 3-triazolyl group and preparation method thereof |
| CN113501831A (en) * | 2021-07-15 | 2021-10-15 | 西安近代化学研究所 | 5-aminotetrazole zinc complex, and synthesis method and application thereof |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108424339A (en) * | 2018-03-23 | 2018-08-21 | 西北工业大学 | A kind of preparation method of high nitrogen two dimension conjugated structure doping vario-property nitrolite crystal |
| CN112919997A (en) * | 2021-02-05 | 2021-06-08 | 西安近代化学研究所 | graphene-Schiff base energetic MOFs and preparation method thereof |
| CN112939708A (en) * | 2021-02-08 | 2021-06-11 | 陕西师范大学 | Imidazole and pyrazole combustion rate catalyst containing ferrocenyl methyl-1, 2, 3-triazolyl group and preparation method thereof |
| CN113501831A (en) * | 2021-07-15 | 2021-10-15 | 西安近代化学研究所 | 5-aminotetrazole zinc complex, and synthesis method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| 《兵器工业科学技术辞典》编辑委员会: "《兵器工业科学技术辞典 火药与炸药》", 31 December 1991, 国防工业出版社 * |
| BO-JUN TAN: "Facile synthesis and superior properties of a nitrogen-rich energetic Zn-MOF with a 2D azide-bridged bilayer structure", 《DALTON TRANSACTIONS》 * |
| 曹承阳: "五氨基四氮唑类推进剂的热解、燃烧特性及应用研究", 《中国博士学位论文全文数据库工程科技Ⅱ辑》 * |
| 武碧栋: "含能叠氮配合物[M(DAT)2(n3)2](DAT=1,5-二氨基四唑)的制备、结构表征和性能研究", 《第五届全国强动载效应及防护学术会议暨复杂介质/结构的动态力学行为创新研究群体学术研讨会论文集》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115784824A (en) * | 2022-10-30 | 2023-03-14 | 南京理工大学 | Nano SiO 2 Preparation method of coated penta-amino tetrazole |
| CN115784824B (en) * | 2022-10-30 | 2024-04-30 | 南京理工大学 | Nano SiO2Preparation method of coated pentaaminotetrazole |
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