An oxygen- and nitrogen-rich pentazolium ion salt based on a stepwise metathesis reaction and its synthesis method
The preparation of oxygen-rich and nitrogen-rich pentazolium ion salts by stepwise metathesis reaction solves the problem of insufficient energy release of all-nitrogen pentazolium ion compounds, and realizes the preparation of efficient and high-energy explosive materials.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- NANJING UNIV OF SCI & TECH
- Filing Date
- 2024-11-25
- Publication Date
- 2026-05-26
AI Technical Summary
Existing all-nitrogen pentazolium ion compounds lack oxygen, making it difficult for them to undergo vigorous redox reactions, resulting in insufficient energy release levels.
By combining oxygen-rich ions with all-nitrogen pentazolium ions through a stepwise metathesis reaction, an oxygen-rich and nitrogen-rich pentazolium ion salt is constructed. An intermediate product is prepared by reacting 4,5-diamino-3-aminomethyl-1,2,4-triazole hydrochloride and dinitramide silver salt in a specific solvent. The intermediate product is then further reacted with pentazolium silver salt to obtain the target product.
The preparation of oxygen- and nitrogen-enriched pentazolium ion salts with high yield and high purity was achieved. The products have high energy release performance, high density, and fast detonation velocity, making them suitable for high-energy explosives.
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Figure CN122079908A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of energetic materials and relates to an oxygen- and nitrogen-rich pentazolium ion salt based on a stepwise metathesis reaction and its synthesis method. Background Technology
[0002] Energetic materials, as the primary energy source for defense weapons, directly determine the strength of weapon systems based on their performance. Therefore, the research and development of energetic materials plays a crucial role in national defense science and technology and national economic construction. With the advancement of military technology, the requirements for explosive performance are becoming increasingly stringent. Nitrogen-rich heterocyclic energetic compounds, due to their inherent high positive enthalpy of formation and energy-rich N-N, CN, and NO bonds, are widely recognized as ideal high-energy-density materials. However, the lack of oxygen in pernitrogen pentazolium ions makes them difficult to undergo vigorous redox reactions, significantly reducing their energy release levels. By utilizing stepwise metathesis reactions to combine oxidizing oxygen-rich ions with pernitrogen pentazolium ions to construct oxygen-rich and nitrogen-rich pentazolium ion salts, the energy release levels of pernitrogen pentazolium energetic compounds can be significantly improved; however, such compounds have not yet been reported. Summary of the Invention
[0003] The purpose of this invention is to provide an oxygen-enriched and nitrogen-enriched pentazolium ion salt and its preparation method, which features simple raw material handling, short reaction time, high yield, and high product purity.
[0004] In a first aspect, the present invention provides an oxygen-enriched and nitrogen-enriched pentazolium ion salt (TDP), the chemical formula of which is C3H 10 N 14 O4 has the following structure:
[0005]
[0006] In a second aspect, the present invention provides a method for synthesizing the oxygen-enriched and nitrogen-enriched pentazolium ion salt described in the first aspect, comprising:
[0007] (1) The step of reacting 4,5-diamino-3-aminomethyl-1,2,4-triazole hydrochloride with silver dinitramide in a reaction solvent to prepare an intermediate product;
[0008] (2) The intermediate product obtained in step (1) and silver pentazolium salt continue to react to prepare the target product.
[0009]
[0010] Preferably, the reaction is carried out at room temperature in the dark.
[0011] Preferably, the reaction solvent is a mixed solution of deionized water and methanol in a volume ratio of 1:1.
[0012] Preferably, in step (1), the reaction time is 0.5-4 hours, preferably 1 hour.
[0013] Preferably, in step (1), after the reaction is complete, the product is filtered and washed to obtain the intermediate product.
[0014] Preferably, in step (2), the reaction time is 0.5-4 hours, and more preferably 1 hour.
[0015] Preferably, in step (2), after the reaction is complete, the target product crystals are obtained by filtration and rotary evaporation under reduced pressure.
[0016] Thirdly, the present invention provides a single crystal prepared from the oxygen- and nitrogen-enriched pentazolium ion salt described in the first aspect, which is obtained by dissolving solid powder in methanol solvent and allowing it to evaporate naturally.
[0017] Preferably, the crystal is a monoclinic crystal, space group P21 / c, with the following unit cell parameters. α=γ=90°, β=90.470°,
[0018] Fourthly, the present invention provides the use of the oxygen-rich and nitrogen-rich pentazolium ion salt described in the first aspect as an explosive. Compared with the prior art, the present invention has the following advantages:
[0019] (1) Unlike the design approach of energetic organic ionic salts, this method utilizes distributed metathesis to effectively combine high-energy ionic components with oxidizing and reducing properties, constructing oxygen- and nitrogen-rich high-energy molecules. Using TATT as a high-nitrogen coating framework, oxidizing dinitramide ions and reducing pernitrogen pentazolium ions are arranged alternately and symmetrically within the framework, enabling rapid, efficient, and complete redox reactions upon detonation to instantly release energy, significantly improving the energy release level of the compound. The reaction process is simple, with a high overall yield (greater than 90%).
[0020] (2) The oxygen- and nitrogen-rich pentazolium ion TDP of this invention has a room temperature crystal density as high as 1.65 g / cm³. 3 It has a detonation velocity of 8615 m / s and a thermal decomposition temperature of 109℃, exhibiting excellent overall performance and promising application prospects. Attached Figure Description
[0021] Figure 1 This is the TDP NMR spectrum (H1N).
[0022] Figure 2 This is the carbon NMR spectrum of TDP.
[0023] Figure 3 This is a single-crystal diagram of TDP.
[0024] Figure 4This is the TG-DSC curve of TDP. Detailed Implementation
[0025] The present invention will be further described below with reference to the embodiments.
[0026] Example 1:
[0027] At room temperature and in the dark, 0.186 g (1 mmol) of 4,5-diamino-3-aminomethyl-1,2,4-triazole dihydrochloride was added to 20 mL of water, followed by 0.215 g (1 mmol) of silver dinitramide. After reacting for 0.5 hours, the precipitate was filtered and washed with deionized water. The filtrate was collected, and 0.179 g (1 mmol) of silver pentaazole was added under light-protected conditions. After reacting for 0.5 hours, the precipitate was filtered, and the filtrate was rotary evaporated under reduced pressure to obtain 0.28 g of white powder solid TDP, with a yield of approximately 91.8%. Its 1H and 1C spectra are shown below. Figure 1 and Figure 2 As shown, the data is as follows:
[0028] 1 H NMR (300MHz, DMSO-d6): δ = 6.46 (s), 8.47 (s), 9.07 (s) ppm; 13 C NMR (125MHz, DMSO-d6): δ = 32.3, 146.7, 151.8ppm; Elemental analysis for C4H 11 N 13 O4(305.22): C15.74, H 3.63, N 59.66%; found: C 15.70, H 3.59, N 60.01%.
[0029] Example 2
[0030] The process is the same as in Example 1, except that the reaction time for each of the two steps is extended to 1 hour, yielding 0.27 g of white powder solid TDP with a yield of approximately 88.5%.
[0031] Example 3
[0032] The process is the same as in Example 1, except that the reaction solvent is changed from 20 mL of water to 20 mL of a mixed solution (methanol:deionized water = 1:1), yielding 0.29 g of white powder solid TDP, with a yield of approximately 95.1%.
[0033] Example 4
[0034] The process is the same as in Example 1, except that the reaction solvent is changed from 20 mL of water to 20 mL of methanol, yielding 0.25 g of white powder solid TDP, with a yield of approximately 82.0%.
[0035] Example 5
[0036] The process is the same as in Example 1, except that the reaction solvent is changed from 20 mL of water to 20 mL of methanol, and the reaction time for both steps is extended to 1 hour, yielding 0.24 g of white powder solid TDP with a yield of approximately 78.7%.
[0037] Example 6
[0038] The process is the same as in Example 1, except that the reaction solvent is changed from 20 mL of water to 20 mL of a mixed solution (methanol:deionized water = 1:1), and the reaction time for both steps is extended to 1 hour, yielding 0.298 g of white powder solid TDP with a yield of approximately 97.0%.
[0039] Example 7
[0040] The process is the same as in Example 1, except that the reaction solvent is changed from 20 mL of water to 20 mL of a mixed solution (methanol:deionized water = 1:1), and the reaction time for both steps is extended to 2 hours, yielding 0.28 g of white powder solid TDP with a yield of approximately 91.8%.
[0041] The obtained white powder solid TDP was dissolved in methanol and allowed to evaporate naturally to obtain single crystals, the structure of which is as follows: Figure 3 As shown, the crystal data is presented in Table 1 below. The TG-DSC curve of the crystal is shown below. Figure 4 As shown.
[0042] Table 1
[0043]
[0044]
[0045] The resulting crystals have a density as high as 1.65 g / cm³. 3 It has a detonation velocity of 8615 m / s and a thermal decomposition temperature of 109℃, an impact sensitivity of 10 J, and a friction sensitivity of 108 N.
Claims
1. An oxygen- and nitrogen-rich pentazolium ion salt, characterized in that, Its chemical formula is C3H 10 N 14 O4 has the following structure:
2. A method for synthesizing an oxygen- and nitrogen-enriched pentazolium ion salt, characterized in that, include: (1) The step of reacting 4,5-diamino-3-aminomethyl-1,2,4-triazole hydrochloride with silver dinitramide in a reaction solvent to prepare an intermediate product; (2) The intermediate product obtained in step (1) and silver pentazolium salt continue to react to prepare the target product.
3. The method as described in claim 2, characterized in that, The reaction was carried out at room temperature in the dark.
4. The method as described in claim 2, characterized in that, The reaction solvent is a mixed solution of deionized water and methanol in a volume ratio of 1:
1.
5. The method as described in claim 2, characterized in that, In step (1), the reaction time is 0.5-4 hours, preferably 1 hour.
6. The method as described in claim 2, characterized in that, In step (2), the reaction time is 0.5-4 hours, preferably 1 hour.
7. The method as described in claim 2, characterized in that, In step (2), after the reaction is complete, the target product crystals are obtained by filtration and rotary evaporation under reduced pressure.
8. A single crystal of an oxygen- and nitrogen-rich pentazolium ion salt, characterized in that, It is obtained by dissolving the solid powder of the oxygen-rich and nitrogen-rich pentazolium ion salt as described in claim 1 in methanol solvent and allowing it to evaporate naturally.
9. The single crystal as described in claim 8, characterized in that, The crystal is a monoclinic crystal, space group P21 / c, with unit cell parameters [missing information]. α=γ=90°, β=90.470°, 10. Use of an oxygen-enriched nitrogen-enriched pentazolium ion salt as described in claim 1, or an oxygen-enriched nitrogen-enriched pentazolium ion salt single crystal as described in claim 8 or 9, as an explosive.