3-gem-dinitro-1, 2, 4-isofurazan energetic salt and synthesis method thereof

Abstract

The invention discloses a 3-gem-dinitro-1, 2, 4-isofurazan energetic salt and a synthesis method thereof, the structural formula of the energetic salt is shown in the specification, and the energetic salt is prepared through a double decomposition reaction among 3-gem-dinitro-1, 2, 4-isofurazan potassium salt, silver nitrate, guanidine hydrochloride, aminoguanidine hydrochloride and triaminoguanidine hydrochloride. The preparation method is simple and efficient; the synthesized 3-gem-dinitro-1, 2, 4-isofurazan guanidine salt, the synthesized 3-gem-dinitro-1, 2, 4-isofurazan aminoguanidine salt and the synthesized 3-gem-dinitro-1, 2, 4-isofurazan triaminoguanidine salt compound are all insensitive energetic materials (ISgt; 39J, FSgt; 360N), which is a nitrogen-rich energetic compound with excellent safety performance.

Description

Technical Field

[0001] The invention belongs to the technical field of energetic materials and relates to a 3-gemin-dinitro-1,2,4-isofurazan energetic salt and a synthesis method thereof. Background Art

[0002] High-energy-density materials (HEDMs) used in mixed explosives, propellants, propellants, and pyrotechnics are key materials for achieving "long-range strike" and "high-efficiency damage" in weaponry, and play a vital role in weaponry research and development. Nitrogen-rich compounds have become a research hotspot for the synthesis of a new generation of high-energy-density energetic materials due to their high formation enthalpy, large gas production, and low detonation product pollution. Energetic salts with high lattice energy have high density and good stability, making their preparation a highly efficient method for creating new energetic compounds. Isofurazan is an important matrix for energetic compounds, but existing isofuroxan energetic salts have high sensitivities (IS < 10 J, FS < 150 N), making them unsuitable for application. Summary of the Invention

[0003] In view of the deficiencies in the prior art, the object of the present invention is to provide a 3-gemin-dinitro-1,2,4-isofurazan energetic salt and a synthesis method thereof, so as to solve the problem that the isofurazan energetic salt compounds synthesized in the prior art have high sensitivity.

[0004] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0005] A 3-gemin-dinitro-1,2,4-isofurazan energetic salt, whose structural formula is shown in (I):

[0006]

[0007] The synthesis method of the energetic salt of 3-geminal dinitro-1,2,4-isofuroxan is as follows: 3-geminal dinitro-1,2,4-isofuroxan potassium salt is dispersed in deionized water, an aqueous silver nitrate solution is slowly added dropwise in a dark environment, and the mixture is stirred at room temperature for 0.5 hours. After the reaction is completed, a white precipitate is precipitated, and the 3-geminal dinitro-1,2,4-isofuroxan silver salt compound is obtained by filtering and washing.

[0008] The 3-gamma-dinitro-1,2,4-isofurazan silver salt compound is then dispersed in deionized water, and the guanidine hydrochloride aqueous solution, aminoguanidine hydrochloride aqueous solution, or triaminoguanidine hydrochloride aqueous solution is stirred and dropped into the 3-gamma-dinitro-1,2,4-isofurazan silver salt turbid solution, stirred for 1 hour in the dark, filtered and the filtrate is collected, and the solvent water is removed by rotary evaporation to obtain 3-gamma-dinitro-1,2,4-isofurazan guanidine salt, 3-gamma-dinitro-1,2,4-isofurazan aminoguanidine salt, or 3-gamma-dinitro-1,2,4-isofurazan triaminoguanidine salt compound.

[0009] The present invention also includes the following technical features:

[0010] Specifically, the molar ratio of the potassium salt of 3-gemin-dinitro-1,2,4-isofuroxan, silver nitrate, and guanidine hydrochloride is 1:1.5:0.8.

[0011] Specifically, the molar ratio of the potassium salt of 3-gem-dinitro-1,2,4-isofuroxan, silver nitrate, and aminoguanidine hydrochloride is 1:1.5:0.8.

[0012] Specifically, the molar ratio of the potassium salt of 3-gemin-dinitro-1,2,4-isofuroxan, silver nitrate, and triaminoguanidine hydrochloride is 1:1.5:0.8.

[0013] Compared with the prior art, the present invention has the following technical effects:

[0014] The preparation method of the 3-geminal dinitro-1,2,4-isofurazanguanidine salt, 3-geminal dinitro-1,2,4-isofurazan aminoguanidine salt and 3-geminal dinitro-1,2,4-isofurazan triaminoguanidine salt compound of the present invention is simple and efficient. Nitrogen-rich cations have a rich hydrogen bond network and a high positive formation enthalpy, which makes the internal hydrogen bond types of nitrogen-rich energetic salts more and thus have low sensitivity. The 3-geminal dinitro-1,2,4-isofurazanguanidine salt, 3-geminal dinitro-1,2,4-isofurazan aminoguanidine salt and 3-geminal dinitro-1,2,4-isofurazan triaminoguanidine salt compounds synthesized by the present invention are all insensitive energetic materials (IS>39J, FS>360N), and are nitrogen-rich energetic compounds with excellent safety performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 This is the single crystal molecular structure diagram of 3-gemin-dinitro-1,2,4-isofurazanidine salt.

[0016] Figure 2 This is the single crystal molecular structure diagram of 3-gemin-dinitro-1,2,4-isofuroxanaminoguanidine salt.

[0017] Figure 3 This is the single crystal molecular structure diagram of 3-gemin-dinitro-1,2,4-isofuroxan triaminoguanidine salt. DETAILED DESCRIPTION

[0018] The present invention provides a 3-geminal dinitro-1,2,4-isofurazan energetic salt and a synthesis method thereof, which provide a cation with a high nitrogen content for the 3-geminal dinitro-1,2,4-isofurazan parent anion to obtain a 1,2,4-isofurazan nitrogen-rich energetic compound, and also provide three insensitive energetic salts.

[0019] The synthetic route of the present invention is as follows:

[0020]

[0021] The compounds of the present invention, 3-gemin-dinitro-1,2,4-isofuroxanguanidine salt, 3-gemin-dinitro-1,2,4-isofuroxan aminoguanidine salt and 3-gemin-dinitro-1,2,4-isofuroxan triaminoguanidine salt, are all prepared by a double decomposition reaction between 3-gemin-dinitro-1,2,4-isofuroxan potassium salt and silver nitrate, guanidine hydrochloride, aminoguanidine hydrochloride and triaminoguanidine hydrochloride.

[0022] The preparation method of the 3-gemin-dinitro-1,2,4-isofurazanguanidine salt, 3-gemin-dinitro-1,2,4-isofurazanaminoguanidine salt and 3-gemin-dinitro-1,2,4-isofurazantriaminoguanidine salt compounds of the present invention comprises the following steps:

[0023] 3-dinitro-1,2,4-isofurazan potassium salt is dispersed in deionized water, and a silver nitrate aqueous solution is slowly added dropwise under light-shielding conditions, and the reaction is stirred at room temperature for 0.5 h. After the reaction is completed, a white precipitate is precipitated, and a 3-dinitro-1,2,4-isofurazan silver salt compound is obtained by filtering, washing, and other steps. The 3-dinitro-1,2,4-isofurazan silver salt compound is then dispersed in deionized water, and a guanidine hydrochloride aqueous solution, an aminoguanidine hydrochloride aqueous solution, or a triaminoguanidine hydrochloride aqueous solution is added dropwise to the 3-dinitro-1,2,4-isofurazan silver salt turbid solution with stirring, and the mixture is stirred for 1 h in the dark. The filtrate is filtered and collected, and the solvent water is removed by rotary evaporation to obtain 3-dinitro-1,2,4-isofurazan guanidine salt, 3-dinitro-1,2,4-isofurazan aminoguanidine salt, and 3-dinitro-1,2,4-isofurazan triaminoguanidine salt compounds, respectively.

[0024] Among them, the molar ratio of 3-dinitro-1,2,4-isofuroxan potassium salt, silver nitrate, and guanidine hydrochloride is 1:1.5:0.8. The molar ratio of 3-dinitro-1,2,4-isofuroxan potassium salt, silver nitrate, and aminoguanidine hydrochloride is 1:1.5:0.8. The molar ratio of 3-dinitro-1,2,4-isofuroxan potassium salt, silver nitrate, and triaminoguanidine hydrochloride is 1:1.5:0.8.

[0025] Specific embodiments of the present invention are given below. It should be noted that the present invention is not limited to the following specific embodiments, and all equivalent modifications made on the basis of the technical solution of this application fall within the protection scope of the present invention.

[0026] Example 1:

[0027] This embodiment provides a 3-geminal dinitro-1,2,4-isofurazan energetic salt and a synthesis method thereof, the synthesis route is:

[0028]

[0029] At room temperature, 0.78 g of AgNO3 was added to a 250 mL single-necked flask, and 5 mL of deionized water was added dropwise. After the AgNO3 was completely dissolved, the single-necked flask was covered with a black antistatic bag (to avoid light). Subsequently, 70 mL of an aqueous solution of 0.85 g of DO-K was added to the single-necked flask, stirred for 15 minutes, filtered, and washed with deionized water. The filter cake was collected in a 25 mL beaker, and 5 mL of deionized water was added to the beaker. While stirring, 0.28 g of a saturated aqueous solution of guanidine hydrochloride was added, stirred for 15 minutes, and the filtrate was collected by filtration. It was rotary evaporated and dried to obtain light yellow-green block crystals.

[0030] Example 2:

[0031] This embodiment provides a 3-geminal dinitro-1,2,4-isofurazan energetic salt and a synthesis method thereof, the synthesis route is:

[0032]

[0033] At room temperature, 1.3 g of AgNO3 was added to a 250 mL single-necked flask, and 10 mL of deionized water was added dropwise. After the AgNO3 was completely dissolved, the single-necked flask was covered with a black antistatic bag (to avoid light). Subsequently, a 100 mL aqueous solution of 1.2 g of DO-K was added to the single-necked flask, stirred for 15 minutes, filtered, washed with deionized water, and the filter cake was collected in a 25 mL beaker. 5 mL of deionized water was added to the beaker, and 0.3 g of a saturated aqueous solution of aminoguanidine hydrochloride was added with stirring. The mixture was stirred for 15 minutes, the filtrate was collected by filtration, rotary evaporated, and dried to obtain colorless block crystals.

[0034] Example 3:

[0035] This embodiment provides a 3-geminal dinitro-1,2,4-isofurazan energetic salt and a synthesis method thereof, the synthesis route is:

[0036]

[0037] At room temperature, 0.2 g of AgNO3 was added to a 100 mL single-necked flask, and 2 mL of deionized water was added dropwise. After the AgNO3 was completely dissolved, the single-necked flask was covered with a black antistatic bag (to avoid light). Subsequently, 50 mL of an aqueous solution of 0.212 g of DO-K was added to the single-necked flask, stirred for 15 minutes, filtered, and washed with deionized water. The filter cake was collected in a 25 mL beaker, and 5 mL of deionized water was added to the beaker. A saturated aqueous solution of 80 mg of triaminoguanidine hydrochloride was added with stirring, stirred for 15 minutes, and the filtrate was collected by filtration, rotary evaporated, and dried to obtain light yellow needle-shaped crystals.

[0038] The structure of the 3-gemin-dinitro-1,2,4-isofurazanidine salt prepared in Example 1 is as follows:

[0039] Crystal structure characterization: The single crystal molecular structure of 3-gemin-dinitro-1,2,4-isofurazanidine salt compound is as follows Figure 1 Its crystal data and structure refinement parameters are shown in Table 1.

[0040] Elemental analysis: C4H7N7O5 (%): Found: C, 20.34; H, 3.01; N, 41.99; Calculated: C, 20.61; H, 3.03; N, 42.06.

[0041] 1 H NMR (500MHz, DMSO-d6): δ: 9.61 (s, 1H, CH), 7.09 (br.s, 6H, NH2). 13 C NMR (DMSO-d6), δ: 122.6 (s, C (NO2) 2); 162.2, 167.2 (CH), 158.7 (C-NH2).

[0042] IR,ν / cm -1 :3449,3358,3277,3211,3129,2771,2225,1655,1544,1518,1460,1376,1342,1271,1254,1188,1146,1107,1087,961,897,819,749.

[0043] Structural identification data confirmed that the substance obtained by the above preparation method is 3-gemin-dinitro-1,2,4-isofurazanidine salt.

[0044] The structure of the 3-gemin-dinitro-1,2,4-isofurazanaminoguanidine salt prepared in Example 2 is identified as follows:

[0045] Crystal structure characterization: The single crystal molecular structure of 3-gemin-dinitro-1,2,4-isofurazanaminoguanidine salt is as follows Figure 2 Its crystal data and structure refinement parameters are shown in Table 2.

[0046] Elemental analysis: C4H8N8O5 (%): Found: C, 20.34; H, 3.01; N, 41.99; Calculated: C, 19.36; H, 3.25; N, 45.15.

[0047] 1 H-NMR (500MHz, DMSO, δ): 9.60 (s, 1H), 8.59 (s, 1H), 7.22 (br, 2H), 6.84 (br, 2H), 4.69 (s, 2H).

[0048] 13C NMR (MHz, DMSO, δ): 122.6 (s, C (NO2) 2); 162.2, 167.2 (CH), 160.1.

[0049] IR,ν / cm -1 :3414,3357,3277,3211,3128,2772,2225,1658,1545,1518,1460,1376,1342,1272,1187,1146,1106,1087,961,897,819,749,611.

[0050] Structural identification data confirmed that the substance obtained by the above preparation method is 3-gemin-dinitro-1,2,4-isofuroxanaminoguanidine salt.

[0051] The structure of the 3-gemin-dinitro-1,2,4-isofurazan triaminoguanidine salt prepared in Example 3 is identified as follows:

[0052] Crystal structure characterization: The single crystal molecular structure of 3-dinitro-1,2,4-isofurazan triaminoguanidine salt is as follows: Figure 3 Its crystal data and structure refinement parameters are shown in Table 3.

[0053] Elemental analysis: C4H 10 N 10 O5 (%): Found: C, 17.30; H, 3.55; N, 50.35; Calculated: C, 17.27; H, 3.62; N, 50.35.

[0054] 1 H NMR (500MHz, DMSO-d6): δ: 9.6 (s, 1H, CH), 8.59 (s, 3H, NH), 4.48 (s, 6H, NH2).

[0055] 13 C NMR (DMSO-d6), δ: 122.3 (s, C (NO2) 2); 158.99 (C (NH) 3), 162.2, 166.7 (CH).

[0056] IR,ν / cm -1 :3319,3210,3127,3104,1685,1615,1553,1521,1498,1472,1427,1376,1365,1329,1270,1255,1185,1150,1127,1103,1086,948,898,883,816,752,713,638,609.

[0057] Structural identification data confirmed that the substance obtained by the above preparation method is 3-gemin-dinitro-1,2,4-isofuroxan triaminoguanidine salt.

[0058] Properties of 3-gemin-dinitro-1,2,4-isofurazan energetic salt:

[0059] (1) Physical and chemical properties of 3-gemin-dinitro-1,2,4-isofurazanidine salt

[0060] Appearance: light yellow transparent block crystals Solubility: slightly soluble in dimethyl sulfoxide and water, insoluble in ethyl acetate, acetone, etc.

[0061] Decomposition point peak: 156℃

[0062] Friction feel (FS): 360N

[0063] Impact (IS): 40J

[0064] Table 1 Crystal data and structure refinement parameters of 3-gemin-dinitro-1,2,4-isofurazanidine salt

[0065]

[0066] (2) Physical and chemical properties of 3-dinitro-1,2,4-isofurazanaminoguanidine salt

[0067] Appearance: light yellow transparent block crystals Solubility: slightly soluble in dimethyl sulfoxide and water, insoluble in ethyl acetate, acetone, etc.

[0068] Decomposition point peak: 155℃

[0069] Friction feel (FS): 360N

[0070] Impact (IS): 40J

[0071] Table 2 Crystallographic data and structure refinement parameters of 3-dinitro-1,2,4-isofurazanaminoguanidine salt

[0072]

[0073] (3) Physical and chemical properties of 3-dinitro-1,2,4-isofurazan triaminoguanidine salt

[0074] Appearance: light yellow transparent block crystals Solubility: slightly soluble in dimethyl sulfoxide and water, insoluble in ethyl acetate, acetone, etc.

[0075] Decomposition point peak: 172℃

[0076] Friction feel (FS): 360N

[0077] Impact (IS): 39J

[0078] Table 3 Crystal data and structure refinement parameters of 3-dinitro-1,2,4-isofurazan triaminoguanidine salt

[0079]

[0080] (4) Detonation properties of 3-gemin-dinitro-1,2,4-isofurazan energetic salt:

[0081] Table 4 Comprehensive properties of energetic salts of 3-gemin-dinitro-1,2,4-isofurazan

[0082]

[0083]

[0084] Application of energetic salts of 3-gemin-dinitromethyl-l,2,4-oxadiazole:

[0085] The 3-gemin-dinitromethyl-1,2,4-oxadiazole energetic salt of the present invention can be widely used in the technical fields of explosives, propellants and pyrotechnics.

Claims

1. A 3-gemin-dinitro-1,2,4-isofurazan energetic salt, characterized in that: Its structural formula is shown in (I):

2. The method for synthesizing the energetic salt of 3-gemin-dinitro-1,2,4-isofurazan according to claim 1, wherein 3-gemin-dinitro-1,2,4-isofuroxan potassium salt was dispersed in deionized water, and silver nitrate aqueous solution was slowly added dropwise under light-shielding conditions, and the mixture was stirred at room temperature for 0.5 h. After the reaction was completed, a white precipitate was precipitated, which was filtered and washed to obtain a 3-gemin-dinitro-1,2,4-isofuroxan silver salt compound; The 3-gamma-dinitro-1,2,4-isofurazan silver salt compound is then dispersed in deionized water, and the guanidine hydrochloride aqueous solution, aminoguanidine hydrochloride aqueous solution, or triaminoguanidine hydrochloride aqueous solution is stirred and dropped into the 3-gamma-dinitro-1,2,4-isofurazan silver salt turbid solution, stirred for 1 hour in the dark, filtered and the filtrate is collected, and the solvent water is removed by rotary evaporation to obtain 3-gamma-dinitro-1,2,4-isofurazan guanidine salt, 3-gamma-dinitro-1,2,4-isofurazan aminoguanidine salt, or 3-gamma-dinitro-1,2,4-isofurazan triaminoguanidine salt compound.

3. The method for synthesizing the energetic salt of 3-geminal dinitro-1,2,4-isofurazan as claimed in claim 2, wherein: The molar ratio of the 3-gemin-dinitro-1,2,4-isofuroxan potassium salt, silver nitrate and guanidine hydrochloride is 1:1.5:0.

8.

4. The method for synthesizing the energetic salt of 3-gemin-dinitro-1,2,4-isofurazan according to claim 2, wherein The molar ratio of the 3-gemin-dinitro-1,2,4-isofuroxan potassium salt, silver nitrate and aminoguanidine hydrochloride is 1:1.5:0.

8.

5. The method for synthesizing the energetic salt of 3-gemin-dinitro-1,2,4-isofurazan according to claim 2, wherein: The molar ratio of the 3-gemin-dinitro-1,2,4-isofuroxan potassium salt, silver nitrate and triaminoguanidine hydrochloride is 1:1.5:0.8.

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