Polynitro-triphenylenediamine energetic compound and preparation method thereof
By preparing polynitrotriphenyldiamine-based energy-containing compounds, the problem of insufficient thermal stability and reliability of existing materials in extreme environments is solved, and a novel high-thermal stability energy-containing materials are provided, suitable for aerospace and unconventional oil and gas mining.
Patent Information
- Application Number
- CN202410132907.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-01-31
- Publication Date
- 2025-08-01
AI Technical Summary
The existing polynitrobiophenyl energy-containing materials are difficult to maintain high thermal stability and reliable explosiveness in extreme environments, and cannot meet the harsh needs of modern military, deep well blasting and aerospace.
The preparation method of polynitrotriphenyldiamine-based energy-containing compounds is used to synthesize polynitrotriphenyldiamine-based energy-containing compounds with high thermal stability and high melting point through specific chemical reactions, including the use of concentrated sulfuric acid, potassium nitrate, nitrobenzene derivatives and fumigated nitric acid and other raw materials, and the compounds (3), (5) or (7) are prepared through a series of stirring and heating steps.
It provides a class of energy-containing materials with novel structures, with high thermal stability and melting point, suitable for industrial production, low cost and reliable detonation, and is suitable for aerospace and unconventional oil and gas mining.
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Figure CN120398698A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the field of chemical engineering, and specifically relates to polynitroterphenylenediamine-based energetic compounds and a preparation method thereof. Background Art
[0002] With the rapid development of modern military technology, deep well blasting and aerospace industry, more demanding usage environments and various extreme conditions in space have put forward higher requirements for the heat resistance performance and energy level of energetic materials. Heat-resistant energetic materials refer to a class of energetic materials that have a relatively high melting point (thermal decomposition point) and a relatively low vapor pressure, can still maintain appropriate sensitivity and a relatively high energy after being subjected to a high-temperature environment for a long time, and can reliably initiate detonation. Polynitrobenzene-based energetic compounds usually have relatively good thermal stability, relatively high thermal decomposition temperature and relatively high melting point, so they are usually a class of good heat-resistant explosives and have important applications in aerospace and unconventional oil and gas exploitation. Summary of the Invention
[0003] The purpose of the present invention is to provide polynitroterphenylenediamine-based energetic compounds. At the same time, providing a preparation method thereof is another purpose of the present invention. To achieve the above purposes, the present invention adopts the following technical solutions:
[0004] Polynitroterphenylenediamine-based energetic compounds, the energetic compounds having the structure of the following formula:
[0005]
[0006] wherein R is a halogen or C-NO2.
[0007] Further, the energetic compounds have the structure of the following formula (3) or formula (5) or formula (7):
[0008]
[0009]
[0010] Further, the synthesis route of energetic compound (3) is:
[0011]
[0012] Further, the preparation method of energetic compound (3) includes the steps:
[0013] S1. Under magnetic stirring at 0 - 5 °C, concentrated sulfuric acid and KNO3 are successively added to the reaction flask. After adding KNO3, stirring is continued for 10 - 15 minutes. Then, 2,3,4 - trifluoronitrobenzene is slowly added dropwise into the mixture through a dropping funnel. After the addition of 2,3,4 - trifluoronitrobenzene is complete, the system is slowly heated to 80 - 85 °C and monitored by TLC until the reaction is complete. The mixture is poured into ice water and filtered to obtain a light yellow precipitate, yielding compound (1);
[0014] S2. Under magnetic stirring at room temperature, compound (1) and aniline are successively added to the reaction flask. Then the mixture is slowly heated to 95 - 100 °C and stirred for 24 - 30 hours. Then the mixture is cooled and the precipitate is filtered to obtain compound (2);
[0015] S3. Under magnetic stirring, compound (2) is slowly added to cold fuming HNO3. After the addition is complete, the system is allowed to rise to room temperature naturally and stirring is continued for 36 - 40 hours. Then the reaction mixture is poured into ice water, and a large amount of yellow solid is produced. After filtration, the collected solid is added to concentrated HNO3 under magnetic stirring and stirred for 4 - 5 hours, and then the insoluble substances are filtered off. Then, the filtrate is slowly poured into ice water again, and a large amount of precipitate is produced. After filtration and drying, the energetic compound (3) is obtained.
[0016] Furthermore, the synthetic route of the energetic compound (5) is as follows:
[0017]
[0018] Furthermore, the preparation method of the energetic compound (5) includes the steps:
[0019] S1. Under magnetic stirring at 0 - 5 °C, concentrated sulfuric acid and KNO3 are successively added to the reaction flask. After adding KNO3, stirring is continued for 10 - 15 minutes. Then, 2,3,4 - trichloronitrobenzene is slowly added dropwise into the mixture through a dropping funnel. After the addition of 2,3,4 - trichloronitrobenzene is complete, the system is slowly heated to 80 - 85 °C and monitored by TLC until the reaction is complete. The mixture is poured into ice water and filtered to obtain a light yellow precipitate, yielding compound (8);
[0020] S2. Under magnetic stirring at room temperature, compound (8) and aniline are successively added to the reaction flask. Then the mixture is slowly heated to 95 - 100 °C and stirred for 24 - 30 hours. Then the mixture is cooled and the precipitate is filtered to obtain compound (4);
[0021] S3. Under magnetic stirring, compound (4) was slowly added to cold fuming HNO3. After addition, the system was allowed to warm to room temperature naturally and stirring was continued for 41 - 45 hours. Then, the reaction mixture was poured into ice water, and a large amount of yellow solid was produced. After filtration, the collected solid was added to concentrated HNO3 under magnetic stirring and stirred for 4 - 5 hours, and then the insoluble substances were filtered off. Then, the filtrate was slowly poured into ice water again, and a large amount of precipitate was produced. After filtration and drying, the energetic compound (5) was obtained.
[0022] Furthermore, the synthetic route of the energetic compound (7) is as follows:
[0023]
[0024] Furthermore, the preparation method of the energetic compound (7) includes the steps:
[0025] S1. Under magnetic stirring at room temperature, 1,5 - difluoro - 2,4 - dinitrobenzene and aniline were successively added to a reaction flask. Then, the mixture was slowly heated to 95 - 100 °C and stirred for 24 - 30 hours. Then, the mixture was cooled, and the precipitate was filtered to obtain compound (6);
[0026] S2. Under magnetic stirring, compound (6) was slowly added to cold fuming HNO3. After addition, the system was allowed to warm to room temperature naturally and stirring was continued for 41 - 45 hours. Then, the reaction mixture was poured into ice water, and a large amount of yellow solid was produced. After filtration, the collected solid was added to concentrated HNO3 under magnetic stirring and stirred for 4 - 5 hours, and then the insoluble substances were filtered off. Then, the filtrate was slowly poured into ice water again, and a large amount of precipitate was produced. After filtration, the solid was recrystallized with ethyl acetate - methanol to obtain compound (7).
[0027] The beneficial effects of the present invention are as follows:
[0028] The polynitro - terphenylenediamine - type energetic compounds provided by the present invention are a class of energetic materials with novel structures and reliable initiation performance. They have relatively high thermal stability, relatively high thermal decomposition temperature, and relatively high melting point. Their production process is simple, cost - saving, and suitable for industrial production and promotion. Description of the Drawings
[0029] Figure 1 It is the carbon spectrum of compound (1) (CDCl3);
[0030] Figure 2 It is the carbon spectrum of compound (1) (CDCl3);
[0031] Figure 3 The hydrogen spectrum of compound (2) (DMSO);
[0032] Figure 4Carbon spectrum of compound (2) (DMSO);
[0033] Figure 5 Fluorine spectrum of compound (2) (DMSO);
[0034] Figure 6 Hydrogen spectrum of compound (3) (DMSO);
[0035] Figure 7 Carbon spectrum of compound (3) (DMSO);
[0036] Figure 8 Fluorine spectrum of compound (3) (DMSO);
[0037] Figure 9 Hydrogen spectrum of compound (5) (DMSO);
[0038] Figure 10 Carbon spectrum of compound (5) (DMSO);
[0039] Figure 11 Hydrogen spectrum of compound (7). Detailed implementation mode
[0040] The present invention provides several energetic compounds of polynitroterphenylenediamine type, and the energetic compounds of polynitroterphenylenediamine type have the following general formula:
[0041]
[0042] Wherein R is halogen or C-NO2.
[0043] Specifically, the energetic compound has the structural formula of formula (3) or formula (5) or formula (7) as follows:
[0044]
[0045]
[0046] Example 1
[0047] The synthesis route of energetic compound (3) is as follows:
[0048]
[0049] The preparation method of energetic compound (3) includes:
[0050] 1. Synthesis of compound (1):
[0051] Under magnetic stirring at 0°C, concentrated sulfuric acid (250 mL) and KNO3 (40.4 g, 400.0 mmol) were added sequentially to a 500 mL reaction flask. After the addition of potassium nitrate, stirring was continued for 10 minutes, and then 2,3,4-trifluoronitrobenzene (53.10 g, 300.0 mmol) was slowly added dropwise to the mixture through a dropping funnel. After the addition of 2,3,4-trifluoronitrobenzene, the system was slowly heated to 85°C until the reaction was complete (monitored by TLC). The mixture was poured into ice water and filtered to obtain a light yellow precipitate to obtain compound (1). In this example, the mass of compound (1) obtained was 60.89 g, and the yield was 91.0%.
[0052] The NMR data of compound (1) are as follows Figures 1-2 As shown, 1 H NMR (600MHz, CDCl3) δ = 8.81 (m, 1H); 13 C NMR (125MHz, CDCl3); δ=117.87,132.79,141.19,142.22,148.65,150.42; 19 F NMR (564MHz, CDCl3); δ = -124.20, -146.21.ESI-HRMS: m / z anion calcd for C6F3N2O4, [M] - :221.0792,found:221.0718;
[0053] 2. Synthesis of compound (2):
[0054] Under magnetic stirring at room temperature, compound 1 (9.20 g, 40 mmol) and aniline (50 mL) were added sequentially to a 100 mL reaction flask, and the mixture was slowly heated to 100° C. and stirred for 24 hours. The mixture was then cooled and the precipitate was filtered to obtain compound (2). In this example, compound (2) was obtained as a red powder with a mass of 12.07 g and a yield of 85.00%.
[0055] The NMR data of compound (2) are as follows Figures 3-5 As shown, 1 H NMR (600M, D6-DMSO): δ = 6.99-7.02 (m, 2H), 7.07-7.09 (d, J = 8.4Hz, 4H), 7.24-7.27 (m, 4H), 8.71 (s, 1H), 9.29 (s, 2H); 13CNMR(125MHz, D6-DMSO), δ=100.00, 120.40, 122.45, 124.12, 129.06, 130.02, 133.72, 140.98, 143.12, 144.55; 19 F NMR(564MHz, D6-DMSO); δ= -120.09.
[0056] 3. Synthesis of Compound (3):
[0057] Under magnetic stirring, Compound (2) (7.36 g, 20 mmol) was slowly added to cold fuming HNO3 (90%-95%, 50 mL). After addition, the system was allowed to warm to room temperature naturally and stirred for an additional 36 hours. Then, the reaction mixture was poured into 300 mL of ice water, and a large amount of yellow solid was formed. The solid was filtered. Under magnetic stirring, the collected solid was added to concentrated HNO3 (65%, 50 mL) and stirred for 4 hours, and then the insoluble matter was filtered off. Then, the filtrate was slowly poured into 300 mL of ice water again, and a large amount of precipitate was formed. After filtration and drying, Compound (3) was obtained. In this example, the obtained Compound (3) was a yellow powder with a mass of 9.61 g and a yield of 75.31%.
[0058] The NMR data of Compound (3) are as Figures 6-8 shown as follows: 1 H NMR(D6-DMSO): δ=8.71(s, 1H), 8.81(s, 4H); 13 C NMR(D6-DMSO): δ=120.98, 125.59, 130.48, 136.30, 138.61, 140.71, 143.77, 145.52; 19 F NMR(564MHz, D6-DMSO); δ= -129.12.
[0059] Example 2
[0060] The synthetic route of energetic compound (5) is as follows:
[0061]
[0062] The preparation method of energetic compound (5) includes the steps:
[0063] 1. Synthesis of compound (8): Under magnetic stirring at 0 °C, concentrated sulfuric acid and KNO3 were successively added to the reaction flask. After adding KNO3, stirring was continued for 10 minutes, and then 2,3,4-trichloronitrobenzene was slowly dropped into the mixture through a dropping funnel. After the addition of 2,3,4-trichloronitrobenzene was completed, the system was slowly heated to 85 °C and monitored by TLC until the reaction was completed. The mixture was poured into ice water and filtered to obtain a light yellow precipitate, thus obtaining compound (8);
[0064] 2. Synthesis of compound (4): Under magnetic stirring at room temperature, compound (8) and aniline were successively added to the reaction flask, and then the mixture was slowly heated to 100 °C and stirred for 24 hours. Then the mixture was cooled, and the precipitate was filtered to obtain compound (4);
[0065] Synthesis of compound (5): Under magnetic stirring, compound (4) (7.70 g, 20 mmol) was slowly added to cold fuming HNO3 (90%-95%, 50 mL). After the addition, the system was allowed to rise to room temperature naturally and stirred for another 41 hours. Then the reaction mixture was poured into 300 mL of ice water, and a large amount of yellow solid was produced and filtered. Under magnetic stirring, the collected solid was added to concentrated HNO3 (65%, 50 mL) and stirred for 4 hours, and then the insoluble substances were filtered off. Then, the filtrate was slowly poured into 300 mL of ice water again, and a large amount of precipitate was produced. After filtration and drying, compound (5) was obtained. In this example, the obtained compound (5) was a yellow powder with a mass of 11.17 g and a yield of 85.30%.
[0066] The NMR data of compound (5) is as Figures 9-10 shown as: 1 1H NMR (D6-DMSO): δ = 8.74 (s, 1H),
[0067] 8.81 (s, 4H); 13 13C NMR (D6-DMSO): δ = 121.66, 123.96, 125.65, 131.53, 139.27.
[0068] Example 3
[0069] The synthetic route of energetic compound (7) is as follows:
[0070]
[0071] The preparation method of energetic compound (7) includes the steps:
[0072] 1. Synthesis of compound (6): Under magnetic stirring at room temperature, 1,5-difluoro-2,4-dinitrobenzene and aniline were successively added to a reaction flask, and then the mixture was slowly heated to 100 °C and stirred for 24 hours. Then, the mixture was cooled, and the precipitate was filtered to obtain compound (6).
[0073] 2. Under magnetic stirring, compound (6) (7.00 g, 20 mmol) was slowly added to cold fuming HNO3 (90%-95%, 50 mL). After addition, the system was allowed to rise to room temperature naturally and stirred for an additional 41 hours. Then, the reaction mixture was poured into 300 mL of ice water, and a large amount of yellow solid was produced. The solid was filtered. Under magnetic stirring, the collected solid was added to concentrated HNO3 (65%, 50 mL) and stirred for 4 hours, and then the insoluble substances were filtered off. Then, the filtrate was slowly poured into 300 mL of ice water again, and a large amount of precipitate was produced. After filtration, the solid was recrystallized from ethyl acetate - methanol to obtain compound (7). In this example, the obtained compound (7) was a pale yellow powder with a mass of 8.13 g and a yield of 61.13%.
[0074] The NMR data of compound (7) is as Figure 11 shown as: 1 H NMR (D6-DMSO): δ = 8.70 (s, 1H), 8.78 (s, 4H).
[0075] The performance test data of each compound is as shown in Table 1 below
[0076] Appendix Table 1:
[0077] Table 1 Physicochemical properties of 3, 5, and 7, in comparison to other energetic compounds
[0078]
[0079] The above are only the preferred embodiments of the present invention and are not used to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.
Claims
1. Polynitro-terphenylenediamine energetic compounds, characterized in that the energetic compounds have the structure of the following formula: wherein R is a halogen or C-NO₂.
2. The polynitroterphenylenediamine-based energetic compound according to claim 1, wherein The energetic compounds have the structure of formula (3) or formula (5) or formula (7) as follows:
3. The preparation method of the polynitro-terphenylenediamine-based energetic compound as described in claim 2, wherein The synthetic route of energetic compound (3) is:
4. The preparation method of the polynitro-terphenylenediamine-based energetic compound as described in claim 3, characterized in that, The preparation method of energetic compound (3) includes the steps: S1. Under magnetic stirring at 0 - 5 °C, concentrated sulfuric acid and KNO₃ are successively added to the reaction flask. After adding KNO₃, continue stirring for 10 - 15 minutes, and then slowly drip 2,3,4-trifluoronitrobenzene into the mixture through a dropping funnel. After the addition of 2,3,4-trifluoronitrobenzene is complete, slowly heat the system to 80 - 85 °C and monitor until the reaction is complete using TLC. Pour the mixture into ice water and filter to obtain a light yellow precipitate, obtaining compound (1); S2. Under magnetic stirring at room temperature, compound (1) and aniline are successively added to the reaction flask, and then the mixture is slowly heated to 95 - 100 °C and stirred for 24 - 30 hours, and then the mixture is cooled and the precipitate is filtered to obtain compound (2); S3. Under magnetic stirring, slowly add compound (2) to cold fuming HNO₃. After the addition is complete, let the system rise to room temperature naturally and continue stirring for 36 - 40 hours. Then pour the reaction mixture into ice water, and a large amount of yellow solid is produced. Filter, add the collected solid to concentrated HNO₃ under magnetic stirring and stir for 4 - 5 hours, then filter off the insoluble substances. Then, slowly pour the filtrate into ice water again, and a large amount of precipitate is produced. After filtering and drying, energetic compound (3) is obtained.
5. The preparation method of the polynitro-terphenylenediamine energetic compound as described in claim 2, characterized in that The synthetic route of energetic compound (5) is:
6. The preparation method of the polynitro-terphenylenediamine energetic compound as described in claim 5, characterized in that, The preparation method of energetic compound (5) includes the steps: S1. Under magnetic stirring at 0 - 5 °C, concentrated sulfuric acid and KNO₃ are successively added to the reaction flask. After adding KNO₃, continue stirring for 10 - 15 minutes, and then slowly drip 2,3,4-trichloronitrobenzene into the mixture through a dropping funnel. After the addition of 2,3,4-trichloronitrobenzene is complete, slowly heat the system to 80 - 85 °C and monitor until the reaction is complete using TLC. Pour the mixture into ice water and filter to obtain a light yellow precipitate, obtaining compound (8); S2. Under magnetic stirring at room temperature, compound (8) and aniline are successively added to the reaction flask, and then the mixture is slowly heated to 95 - 100 °C and stirred for 24 - 30 hours, and then the mixture is cooled and the precipitate is filtered to obtain compound (4); S3. Under magnetic stirring, slowly add compound (4) to cold fuming HNO₃. After the addition is complete, let the system rise to room temperature naturally and continue stirring for 41 - 45 hours. Then pour the reaction mixture into ice water, and a large amount of yellow solid is produced. Filter, add the collected solid to concentrated HNO₃ under magnetic stirring and stir for 4 - 5 hours, then filter off the insoluble substances. Then, slowly pour the filtrate into ice water again, and a large amount of precipitate is produced. After filtering and drying, energetic compound (5) is obtained.
7. The preparation method of the polynitro-terphenylenediamine energetic compound according to claim 2, characterized in that, The synthetic route of the energetic compound (7) is as follows:
8. The preparation method of the polynitro terphenylenediamine energetic compound as described in claim 2, characterized in that, The preparation method of the energetic compound (7) includes the steps: S1. Under magnetic stirring at room temperature, 1,5-difluoro-2,4-dinitrobenzene and aniline are successively added into a reaction flask, and then the mixture is slowly heated to 95 - 100 °C and stirred for 24 - 30 hours. Then the mixture is cooled, and the precipitate is filtered to obtain compound (6); S2. Under magnetic stirring, compound (6) is slowly added into cold fuming HNO3. After addition, the system is allowed to rise to room temperature naturally and stirred for another 41 - 45 hours. Then the reaction mixture is poured into ice water, and a large amount of yellow solid is produced. After filtration, the collected solid is added to concentrated HNO3 under magnetic stirring and stirred for 4 - 5 hours, and then the insoluble substances are filtered off. Then, the filtrate is slowly poured into ice water again, and a large amount of precipitate is produced. After filtration, the solid is recrystallized with ethyl acetate - methanol to obtain compound (7).