CN108821983B - Heat-resistant compound taking benzene ring as matrix and preparation method and application thereof - Google Patents
Heat-resistant compound taking benzene ring as matrix and preparation method and application thereof Download PDFInfo
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- CN108821983B CN108821983B CN201810807332.9A CN201810807332A CN108821983B CN 108821983 B CN108821983 B CN 108821983B CN 201810807332 A CN201810807332 A CN 201810807332A CN 108821983 B CN108821983 B CN 108821983B
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- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/52—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
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Abstract
The invention belongs to the technical field of compound preparation, and discloses a heat-resistant compound taking a benzene ring as a matrix, and a preparation method and application thereof. The heat-resistant compound is 2-fluoro-1, 3-diamino-4, 6-dinitrobenzene, and the preparation method comprises the following steps: under the magnetic stirring at room temperature, mixing ammonia water or ammonia alcohol solution with solid 2,3, 4-trifluoro-1, 5-dinitrobenzene, stirring, filtering, washing and drying after the reaction is finished to obtain the heat-resistant compound 2-fluoro-1, 3-diamino-4, 6-dinitrobenzene shown in the formula I. Compared with TATB, the 2-fluoro-1, 3-diamino-4, 6-dinitrobenzene has better detonation performance and sensitivity similar to that of TATB, and the synthetic method is very simple, high in yield and easy for industrial production; the compound is insoluble in water and environment-friendly, so that the potential industrial value of the compound is higher, and the compound has great significance for the research of novel heat-resistant explosives.
Description
Technical Field
The invention belongs to the technical field of compound preparation, and particularly relates to a heat-resistant compound taking a benzene ring as a matrix, and a preparation method and application thereof.
Background
Precision percussion, high efficiency destructive power and high viability are goals pursued by modern weapons, and to achieve these goals, High Energy Density Materials (HEDM) as weapons energy carriers must meet the requirements of high energy, high density, low vulnerability, environmental suitability, and high thermal stability. In recent years, with the development of cosmonautic industry and the exploitation of underground resources such as petroleum and natural gas, explosive with high pressure (or low pressure) and high temperature resistance, called heat-resistant explosive for short, is more and more urgently needed. The heat-resistant explosive refers to an explosive which can maintain proper mechanical sensitivity and reliably detonate after being subjected to a high-temperature environment for a long time, and the explosive has the detonation performance of common explosives and generally needs to have a higher melting point and a higher thermal decomposition temperature (over 250 ℃). The heat-resistant explosive is firstly researched to meet the requirements of military affairs, aerospace and the like (such as space vehicles needing to withstand high-temperature environments, separation of different levels of spaceships and the like), and nowadays, the heat-resistant explosive is mainly used for blasting equipment of oil-gas well perforating bullets and is divided into heat-resistant single-substance explosives and heat-resistant mixed explosives. Meanwhile, the thermal explosive is classified into a high temperature explosive (energetic compound having a thermal decomposition temperature of 250 ℃ or more and 300 ℃ or less) and an ultra high temperature explosive (energetic compound having a thermal decomposition temperature of more than 300 ℃) according to the difference in the temperature to be endured. The heat-resistant elementary explosive can be used for filling heat-resistant detonators and heat-resistant detonating cords, and more importantly, can be used as a basic component of heat-resistant mixed explosives, such as perforating charge in petroleum technology and the like which are widely applied; on the other hand, the development of some new heat-resistant single-substance explosives is aimed at meeting special requirements of space navigation, and due to the development of rockets, missiles and space shuttles in speed, particularly the emergence of space weapons, the requirement of thermal stability is provided for the explosives. The spacecraft is influenced by aerodynamic effect, space and moon vacuum environment in the flying process, so that the spacecraft needs to be heated for disinfection and sterilization before entering space and returning to the earth, but the conventional explosive (such as cyclonite) is not stable enough under high temperature or low pressure for a long time, is easy to evaporate even under aerodynamic effect, and cannot meet the requirements. Therefore, in recent years, some countries have paid attention to research on how to improve the thermal stability of the currently developed explosives such as hexogen and octogen, and have also been developing some new heat-resistant explosives resistant to ultra-high temperature to meet special needs in terms of space navigation and the like.
Disclosure of Invention
The invention aims to provide a heat-resistant compound which takes a benzene ring as a matrix, namely 2-fluoro-1, 3-diamino-4, 6-dinitrobenzene (ZXC-10), and the heat-resistant compound has very good heat stability.
The invention also aims to provide the preparation method of the heat-resistant compound, which has the advantages of safe raw materials, simple required equipment, simple and feasible preparation method and higher yield.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a heat-resistant compound taking a benzene ring as a matrix, which has a structural formula shown as a formula I:
the invention also provides a preparation method of the heat-resistant compound, which comprises the following steps:
under the magnetic stirring at room temperature, mixing ammonia water or ammonia alcohol solution with solid 2,3, 4-trifluoro-1, 5-dinitrobenzene, stirring, filtering, washing and drying after the reaction is finished to obtain the heat-resistant compound 2-fluoro-1, 3-diamino-4, 6-dinitrobenzene shown in the formula I.
The method comprises the following steps: under magnetic stirring, adding ammonia water or an ammonia alcohol solution with a certain concentration into solid 2,3, 4-trifluoro-1, 5-dinitrobenzene, filtering and washing after complete reaction to obtain a product 2-fluoro-1, 3-diamino-4, 6-dinitrobenzene, wherein the reaction temperature is 0-100 ℃;
the second method comprises the following steps: under magnetic stirring, adding solid 2,3, 4-trifluoro-1, 5-dinitrobenzene into ammonia water or ammonia alcohol solution with certain concentration, filtering and washing after complete reaction to obtain the product 2-fluoro-1, 3-diamino-4, 6-dinitrobenzene, wherein the reaction temperature is 0-100 ℃.
Further, the molar ratio of ammonia to 2,3, 4-trifluoro-1, 5-dinitrobenzene in the ammonia water or the ammonia alcohol solution is not less than 4.
Further, the concentration of ammonia gas in the ammonia water or the ammonia alcohol solution is 10-100%.
Further, the concentration of ammonia in the ammonia water is 40%.
The invention also provides application of the heat-resistant compound in preparation of a heat-resistant explosive.
Compared with the existing heat-resistant explosive with excellent performance, the invention has the beneficial effects that:
1. the target compound 2-fluoro-1, 3-diamino-4, 6-dinitrobenzene obtained by the invention has excellent performance (shown in table 1), and can be widely applied to special fields such as deep oil wells or space exploration; compared with common heat-resistant explosives such as TATB (1,3, 5-triamino-2, 4, 6-trinitrotoluene), the explosive has better detonation performance, is insoluble in water, is environment-friendly, has higher potential industrial value, and has great significance for the research of novel heat-resistant explosives.
2. The preparation method of the target compound 2-fluoro-1, 3-diamino-4, 6-dinitrobenzene has the advantages of safe raw materials, simple required equipment, simple and feasible preparation method compared with TATB, high yield, high purity, easy purification and easy recrystallization.
3. Compared with TATB, the compound of the invention is easier for industrialized production.
Drawings
FIG. 1 shows the crystal shape of 2-fluoro-1, 3-diamino-4, 6-dinitrobenzene which is a heat-resistant compound according to the present invention.
Detailed Description
The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. The test methods in the following examples are conventional methods unless otherwise specified.
Thin Layer Chromatography (Thin Layer Chromatography, TLC), also known as Thin Layer Chromatography, belongs to solid-liquid adsorption Chromatography. The invention utilizes TLC technology to detect the residual amount of the 2,3, 4-trifluoro-1, 5-dinitrobenzene in the reaction kettle, judges whether the reaction is finished or not, and if the residual amount is 0, the reaction is finished.
In the invention, 2-fluoro-1, 3-diamino-4, 6-dinitrobenzene is marked as ZXC-10; 1,3, 5-triamino-2, 4, 6-trinitrotoluene is noted as TATB.
Example 1
The preparation process of heat resisting compound 2-fluoro-1, 3-diamino-4, 6-dinitrobenzene with benzene ring as the mother body includes the following steps:
accurately weighing 5.0 g of 2,3, 4-trifluoro-1, 5-dinitrobenzene, putting the weighed material into a 100 ml eggplant-shaped bottle, adding 50 ml of 40% concentrated ammonia water under room temperature magnetic stirring, continuing stirring at room temperature until the reaction is complete (TLC detection, the time is about 21 hours), filtering, washing to obtain a bright yellow solid (2-fluoro-1, 3-diamino-4, 6-dinitrobenzene), wherein the yield is 93.01%; nuclear magnetic resonance of the sameThe hydrogen spectrum is1H NMR(600MHz,DMSO-d6,TMS,ppm),＝8.63(s,1H),7.55(s,4H)；13C NMR(125MHz,DMSO-d6,TMS,ppm),＝138.30,136.10,123.23,122.39；ElementalAnalysis for C6H5FN4O4(216.13):calcd.C,33.75；H,2.16；F:8.65；N,25.89；found:C,33.34；H,2.33；F:8.79；N,25.92；O,29.61。
Example 2
The preparation process of heat resisting compound 2-fluoro-1, 3-diamino-4, 6-dinitrobenzene with benzene ring as the mother body includes the following steps:
accurately weighing 5.0 g of 2,3, 4-trifluoro-1, 5-dinitrobenzene, putting the weighed material into a 100 ml eggplant-shaped bottle, adding 10 ml of 40% concentrated ammonia water under room temperature magnetic stirring, continuing stirring at room temperature until the reaction is complete (TLC detection, the time is about 47 hours), filtering and washing to obtain a bright yellow solid (2-fluoro-1, 3-diamino-4, 6-dinitrobenzene), wherein the yield is 90.65%.
Example 3
The preparation process of heat resisting compound 2-fluoro-1, 3-diamino-4, 6-dinitrobenzene with benzene ring as the mother body includes the following steps:
accurately weighing 5.0 g of 2,3, 4-trifluoro-1, 5-dinitrobenzene, adding the mixture into a 100 ml eggplant-shaped bottle filled with 50 ml of 40% concentrated ammonia water under magnetic stirring at room temperature, continuing stirring at room temperature until the reaction is complete (TLC detection, the time is about 21 hours), filtering and washing to obtain a bright yellow solid (2-fluoro-1, 3-diamino-4, 6-dinitrobenzene), wherein the yield is 92.76%.
Example 4
The preparation process of heat resisting compound 2-fluoro-1, 3-diamino-4, 6-dinitrobenzene with benzene ring as the mother body includes the following steps:
accurately weighing 5.0 g of 2,3, 4-trifluoro-1, 5-dinitrobenzene, putting the weighed material into a 100 ml eggplant-shaped bottle, adding 20 ml of ethylene glycol under room temperature magnetic stirring, introducing ammonia gas until the reaction is finished (TLC detection, the time is about 11 hours), filtering and washing to obtain a bright yellow solid (2-fluoro-1, 3-diamino-4, 6-dinitrobenzene), wherein the yield is 84.23%.
Example 5
The preparation process of heat resisting compound 2-fluoro-1, 3-diamino-4, 6-dinitrobenzene with benzene ring as the mother body includes the following steps:
accurately weighing 100.0 g of 2,3, 4-trifluoro-1, 5-dinitrobenzene, adding the mixture into a 500 ml eggplant-shaped bottle filled with 300 ml of 40% concentrated ammonia water under room temperature magnetic stirring, continuously stirring the mixture at room temperature until the mixture is completely reacted (TLC detection lasts about 21 hours), filtering and washing the mixture to obtain a bright yellow solid (2-fluoro-1, 3-diamino-4, 6-dinitrobenzene), wherein the yield is 93.76%.
Example 6 comparison of Performance parameters
Reference is made to the method described in example 1 for determining the enthalpy of formation of 2-fluoro-1, 3-diamino-4, 6-dinitrobenzene (ZXC-10) and 1,3, 5-triamino-2, 4, 6-trinitrotoluene (TATB), for generating heat, detonation, for measuring the Density of 2-fluoro-1, 3-diamino-4, 6-dinitrobenzene (ZXC) and trinitrotoluene (TATB) using a densitometer (3H-2000 Betsard company), the results are detailed in table 1.
TABLE 1 Performance parameters of ZXC-10 and TATB
The results show that: the density of ZXC-10 is 0.09 larger than that of TATB, the enthalpy of formation of ZXC-10 is increased by 17.64 percent than that of TATB, the heat of formation of ZXC-10 is increased by 14.12 percent than that of TATB, the detonation velocity of ZXC-10 is increased by 2.41 percent than that of TATB, and the detonation pressure of ZXC-10 is increased by 8.00 percent than that of TATB.
The above-mentioned embodiments are merely preferred embodiments of the present invention, which are merely illustrative and not restrictive, and it should be understood that other embodiments may be easily made by those skilled in the art by replacing or changing the technical contents disclosed in the specification, and therefore, all changes and modifications that are made on the principle of the present invention should be included in the scope of the claims of the present invention.
Claims (6)
1. A heat-resistant compound using a benzene ring as a matrix is characterized in that the structural formula is shown as formula I:
2. the method for preparing the heat-resistant compound according to claim 1, wherein the heat-resistant compound 2-fluoro-1, 3-diamino-4, 6-dinitrobenzene is obtained by mixing ammonia water or an ammonia alcohol solution with solid 2,3, 4-trifluoro-1, 5-dinitrobenzene under magnetic stirring at room temperature, stirring, filtering, washing and drying after the reaction is finished.
3. The method for producing a heat-resistant compound according to claim 2, wherein the molar ratio of ammonia to 2,3, 4-trifluoro-1, 5-dinitrobenzene in the aqueous ammonia or the ammonia alcohol solution is 4 or more.
4. The method for producing a heat-resistant compound according to claim 2, wherein the concentration of ammonia gas in the aqueous ammonia or the ammonia alcohol solution is 10 to 100% by mass.
5. The method according to claim 2, wherein the concentration of ammonia gas in the ammonia water is 40% by mass.
6. Use of the heat resistant compound of claim 1 in the preparation of a heat resistant explosive.
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| CN109810006B (en) * | 2019-02-21 | 2021-11-23 | 信阳师范学院 | Fusion-cast explosive 3,4, 5-trifluoro-2, 6-dinitroaniline and preparation method and application thereof |
| CN112266181B (en) * | 2020-11-17 | 2022-08-02 | 衡阳凌云特种材料有限公司 | Heat-proof/insulation composite material and preparation method and application thereof |
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