A 1,2,3-triazole ion salt, preparation method and use thereof

Abstract

The present invention discloses a 1,2,3-triazole ion salt, a preparation method thereof, and uses thereof. The present invention provides a triazole compound ion salt represented by Formula III-S-1 or III-S-2. The 1,2,3-triazole ion salt provided by the present invention has one or more advantages including high nitrogen content, high detonation velocity, high energy, high impact sensitivity, and high safety. It can be used in high-energy explosives, gas generators, and solid propellants. The preparation method of the 1,2,3-triazole ion salt provided by the present invention has a short route and high yield. #imgabs0#

Description

Technical Field

[0001] The present invention relates to a 1,2,3-triazole ion salt, a preparation method and application thereof. Background Art

[0002] Nitrogen-rich energetic compounds have high formation enthalpies and decompose into environmentally friendly nitrogen gas with low characteristic signals, making them a research hotspot in the field of high-energy-density materials. Azoles, such as pyrazole, imidazole, triazole, and tetrazole, are considered the core skeletal structures of nitrogen-rich materials and have been widely used in the design and synthesis of novel nitrogen-rich energetic compounds. Some azoles exhibit excellent detonation properties. The introduction of highly electron-withdrawing energetic groups such as -NO2 and -N3 onto the azole ring renders the NH of the azole ring highly acidic, allowing the preparation of corresponding nitrogen-rich energetic ion salts. These energetic compounds exhibit extremely low vapor pressures, high thermal stability, and low sensitivity. Among them, 1,2,3-triazole, a five-membered nitrogen heterocycle composed of three consecutive nitrogen atoms, exhibits excellent stability and a high formation enthalpy, making it an ideal energetic heterocyclic skeletal structure.

[0003] At present, some 1,2,3-triazole energetic compounds have been reported in China, some of which have good detonation properties and have certain application potential in the field of explosives. For example, Zhang et al. reported 4-R-5-nitro-1,2,3-triazole and its derivatives (R = NO2, NNO2 and N3), and the corresponding energetic ion salt density is the largest 1.86g cm -3 , the maximum explosion speed can reach 9505m s -1 , with comparable performance to HMX (J. Mater. Chem. A, 2015, 3, 14768-14778). However, the synthesis route of 1,2,3-triazole energetic ion salts is very long, as shown below, requiring 11 steps to obtain the target product precursor, thus greatly limiting its application.

[0004] Summary of the Invention

[0005] The technical problem to be solved by the present invention is to overcome the low impact sensitivity and low safety issues of triazole energetic compounds in existing literature, thereby providing a 1,2,3-triazole ion salt, a preparation method thereof, and its use. The 1,2,3-triazole ion salt provided by the present invention has one or more advantages of high detonation velocity, high energy, high impact sensitivity, and high safety, and can be used in high-energy explosives, gas generators, and solid propellants. The preparation method of the 1,2,3-triazole ion salt provided by the present invention has a short route and high yield.

[0006] The present invention solves the above technical problems through the following technical solutions.

[0007] The present invention provides a triazole compound ion salt as shown in formula III-S-1 or III-S-2,

[0008]

[0009] The cation (R) in the triazole compound ion salt is K + NH4 + 、

[0010] The triazole compound ion salt as shown in formula III-S-1 or III-S-2 can be any of the following compounds:

[0011]

[0012] The present invention provides a method for preparing the triazole compound ion salt as shown in formula III-S-1 or III-S-2, which is method 1, 2 or 3;

[0013] When the cation in the triazole compound ion salt is 1, it is method 1:

[0014] The method 1 comprises the following steps: in an aqueous solution, performing a metathesis reaction on compound 5 and compound 5-1 to obtain compound III-S-1;

[0015]

[0016] Where R is K + NH4 + 、

[0017] X1 is a halogen;

[0018] When the number of cations in the triazole compound ion salt is 2, it is method 2:

[0019] The method 2 comprises the following steps: reacting a triazole compound as shown in formula III with compound 5-2 to obtain compound III-S-2;

[0020]

[0021] Where R is K + NH4 + 、

[0022] X2 is OH - 、CO3 2-、HCO3 - 、SO3 2- 、S 2- or PO4 3- ;

[0023] When the cation in the triazole compound ion salt is 1 K + When it is method 3:

[0024] The method 3 comprises the following steps:

[0025] Step 1: Compound 3 reacts with a nitrating agent to obtain a product;

[0026] Step 2: In an alcohol solvent, the product obtained in step 1 is reacted with a potassium salt to obtain compound III-S-1;

[0027]

[0028] The nitrating agent is a mixture of fuming nitric acid and anhydride or a mixture of fuming nitric acid and concentrated sulfuric acid, and the anhydride is one or more of trifluoroacetic anhydride, acetic anhydride and nitric anhydride.

[0029] In the method 1, in the metathesis reaction, the R can be NH4 + 、

[0030] In the method 1, in the metathesis reaction, X1 can be chlorine or iodine, for example, chlorine.

[0031] In the method 1, in the double decomposition reaction, the compound 5-1 can be ammonium chloride, hydrazine hydrochloride, hydroxylamine hydrochloride, guanidine hydrochloride or aminoguanidine hydrochloride.

[0032] In the method 1, in the metathesis reaction, the molar ratio of the compound 5-1 to the compound 5 can be (0.8-1.2):1, for example, 1:1.

[0033] In the method 1, in the double decomposition reaction, the mass volume ratio of the compound 5 to the aqueous solution can be a conventional mass volume ratio for such reactions in the art, as long as it does not affect the reaction.

[0034] In the method 1, the temperature of the metathesis reaction can be room temperature.

[0035] In the method 1, the metathesis reaction time can be 1 to 5 hours, for example 3 hours.

[0036] In the method 1, the metathesis reaction may further include post-processing, and the post-processing includes filtration and concentration.

[0037] The method 1 may further comprise the following steps: in an aqueous solution, compound 4 is subjected to a double decomposition reaction with a silver salt to obtain compound 5;

[0038]

[0039] In the method 1, in the double decomposition reaction, the silver salt can be silver nitrate or silver sulfate, such as silver nitrate.

[0040] In the method 1, in the double decomposition reaction, the molar ratio of the silver salt to the compound 4 can be (0.8-1.2):1, for example, 1:1.

[0041] In the method 1, in the double decomposition reaction, the mass volume ratio of the compound 4 to the aqueous solution can be a conventional mass volume ratio for such reactions in the art, as long as it does not affect the reaction.

[0042] In the method 1, the temperature of the metathesis reaction can be room temperature.

[0043] In the method 1, the double decomposition reaction time can be 0.5 to 1.5 hours, for example, 1 hour.

[0044] In the method 1, the metathesis reaction may further include post-treatment, and the post-treatment includes filtration.

[0045] In the method 2, the R can be NH4 + 、

[0046] In the method 2, X2 can be OH - 、CO3 2- or HCO3 - .

[0047] In the method 2, the compound 5-2 can be aqueous ammonia, aqueous hydroxylamine solution, hydrazine hydrate, guanidine carbonate or aminoguanidine bicarbonate.

[0048] In the method 2, the molar ratio of the compound 5-2 to the triazole compound represented by formula III can be (1-2):1, for example, 1:1 or 2:1.

[0049] In the method 2, the reaction can be carried out in an atmosphere of pH ≥ 7. The reaction is preferably carried out in an atmosphere of pH = 7 or pH > 7.

[0050] In the method 2, the reaction temperature can be room temperature.

[0051] In the method 2, the reaction time can be 0.5 to 6 hours, preferably 1 to 5 hours, such as 1 hour, 3 hours or 5 hours.

[0052] In the method 2, the reaction may further include post-treatment, and the post-treatment includes concentration.

[0053] The method 2 may further comprise the following steps: compound 4 is subjected to a protonation reaction with an acid to obtain a triazole compound as shown in formula III;

[0054]

[0055] In the method 2, the acid may be hydrochloric acid or sulfuric acid.

[0056] In the method 2, the protonation reaction can be carried out in an atmosphere of pH ≤ 5.

[0057] In the method 2, the protonation reaction may further include post-treatment, wherein the post-treatment includes extraction. The extraction solvent may be an ester solvent and / or an ether solvent, such as ethyl acetate and / or diethyl ether.

[0058] The method 1 and the method 2 may further comprise the following steps independently:

[0059] Step a: Compound 3 reacts with a nitrating agent to obtain a product;

[0060] Step b: reacting the product obtained in step a with a potassium salt in an alcohol solvent to obtain compound 4;

[0061]

[0062] The nitrating agent is a mixture of fuming nitric acid and anhydride or a mixture of fuming nitric acid and concentrated sulfuric acid, and the anhydride is one or more of trifluoroacetic anhydride, acetic anhydride and nitric anhydride.

[0063] The conditions of steps a and b in the reaction are the same as those of steps 1 and 2 in method 3.

[0064] Said method 1 and method 2 may independently further comprise the following steps: in a solvent, in the presence of an oxidizing agent, compound 2 undergoes a substitution reaction with hydrochloric acid to obtain compound 3;

[0065]

[0066] In the method 1 and the method 2, in the substitution reaction, the hydrochloric acid preferably has a concentration of 37% hydrochloric acid.

[0067] In the methods 1 and 2, in the substitution reaction, the oxidant may be one or more of sodium nitrite, isopropyl nitrite, isoamyl nitrite, and nitrosyl fluoroborate, such as sodium nitrite.

[0068] In the method 1 and the method 2, in the substitution reaction, the solvent may be one or more of water, methanol, ethanol and isopropanol, such as water.

[0069] In the method 1 and the method 2, in the substitution reaction, the molar ratio of the hydrochloric acid to the compound 2 can be (4-6):1, for example, 5:1.

[0070] In the method 1 and the method 2, in the substitution reaction, the molar ratio of the oxidizing agent to the compound 2 can be (0.8-1.6):1, for example, 1.2:1.

[0071] In the method 1 and the method 2, in the substitution reaction, the mass volume ratio of the compound 2 to the solvent can be 0.06 to 0.09 g / mL, for example, 0.073 g / mL.

[0072] In the methods 1 and 2, in the substitution reaction, the mass volume ratio of the oxidant to the solvent may be 0.02 to 0.05 g / mL, for example, 0.035 g / mL.

[0073] In the methods 1 and 2, in the substitution reaction, the temperature for adding the oxidant can be around 0°C, for example, -5 to 5°C.

[0074] In the method 1 and the method 2, the temperature of the substitution reaction can be 0°C to room temperature.

[0075] In the method 1 and the method 2, the substitution reaction time can be 5 to 8 hours, preferably 6 to 7 hours, for example 6 hours or 7 hours.

[0076] In the above methods 1 and 2, the substitution reaction may further include post-treatment, wherein the post-treatment includes extraction. The extraction solvent may be an ester solvent and / or an ether solvent, such as ethyl acetate and / or diethyl ether.

[0077] Said method 1 and method 2 may independently further comprise the following steps: in a solvent, 5-cyano-4-nitro-1,2,3-triazole is subjected to an addition reaction with hydroxylamine to obtain compound 2;

[0078]

[0079] In the method 1 and the method 2, in the addition reaction, the hydroxylamine can be a hydroxylamine aqueous solution, preferably a 50% hydroxylamine aqueous solution.

[0080] In the method 1 and the method 2, in the addition reaction, the solvent may be one or more of water, an alcohol solvent and tetrahydrofuran, such as water.

[0081] In the method 1 and the method 2, in the addition reaction, the molar ratio of the hydroxylamine to the 5-cyano-4-nitro-1,2,3-triazole can be (0.8-1.2):1, for example, 1:1.

[0082] In the method 1 and the method 2, in the addition reaction, the mass volume ratio of the 5-cyano-4-nitro-1,2,3-triazole to the solvent can be 0.4 to 0.5 g / mL, for example 0.45 g / mL.

[0083] In the method 1 and the method 2, the temperature of the addition reaction may be 70-100°C, for example 100°C.

[0084] In the method 1 and the method 2, the addition reaction time may be 0.5 to 18 hours, preferably 1 to 12 hours, for example 1 hour, 6 hours or 12 hours.

[0085] In the method 1 and the method 2, the addition reaction may further include post-treatment, and the post-treatment includes filtration.

[0086] In the method 3, in the step 1, the nitrating agent can be a mixture of fuming nitric acid and trifluoroacetic anhydride or a mixture of fuming nitric acid and concentrated sulfuric acid, preferably a mixture of fuming nitric acid and concentrated sulfuric acid.

[0087] In the method 3, in the step 1, the volume ratio of the fuming nitric acid to the acid anhydride or concentrated sulfuric acid in the nitrating reagent can be 1:1.

[0088] In the method 3, in the step 1, the preparation temperature of the nitrating reagent can be -20 to 10°C, preferably -15 to 5°C, for example -15°C, -5°C or 5°C.

[0089] In the method 3, in the step 1, the mass volume ratio of the compound 3 to the nitrating agent can be 0.05 to 0.15 g / mL, for example 0.1 g / mL.

[0090] In the method 3, in the step 1, the reaction temperature can be from -20°C to room temperature, for example, from -15°C to room temperature, from -5°C to room temperature, or from 5°C to room temperature.

[0091] In the method 3, in the step 1, the reaction time can be 4 to 20 hours, preferably 6 to 12 hours, for example 6 hours, 9 hours or 12 hours.

[0092] In method 3, in step 1, the reaction may further include post-treatment, wherein the post-treatment includes quenching and extraction. The quenching solvent may be ice water. The extraction solvent may be an organic chlorine-containing solvent and / or an ether solvent, preferably chloroform and / or diethyl ether.

[0093] In the method 3, in the step 2, the potassium salt can be potassium iodide, potassium hydroxide, potassium carbonate or potassium bicarbonate, such as potassium iodide.

[0094] In the method 3, in the step 2, the alcohol solvent may be methanol.

[0095] In the method 3, the mass volume ratio of the compound 3 to the alcohol solvent can be 0.02 to 0.04 g / mL, for example, 0.03 g / mL.

[0096] In the method 3, the molar ratio of the potassium salt to the compound 3 can be (2-4):1.

[0097] In the method 3, in the step 2, the reaction temperature can be room temperature.

[0098] In the method 3, in the step 2, the reaction time can be 10 to 20 hours.

[0099] In the method 3, in the step 2, the reaction may further include post-treatment, which includes filtration, washing and recrystallization. The washing solvent may be an alcohol solvent, such as methanol.

[0100] The present invention provides a compound as shown in Formula 2 or Formula 3,

[0101]

[0102] The present invention provides a high-energy explosive or solid propellant, which comprises the triazole compound ion salt shown in formula III-S-1 or III-S-2.

[0103] In the present invention, the room temperature is 15 to 35°C.

[0104] In the present invention, 50% in the 50% hydroxylamine aqueous solution is a mass fraction.

[0105] Without violating the common sense in the art, the above-mentioned preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention.

[0106] The reagents and raw materials used in the present invention are commercially available.

[0107] The positive progress of the present invention is that the 1,2,3-triazole ion salt provided by the present invention has one or more advantages of high nitrogen content, high detonation velocity, high energy, high impact sensitivity and high safety, and can be applied to high-energy explosives, gas generators and solid propellants. In addition, the present invention uses readily available 5-cyano-4-nitro-1,2,3-triazole as a starting material and can obtain the product through only four reaction steps. BRIEF DESCRIPTION OF THE DRAWINGS

[0108] Figure 1 The single crystal structure of 5-dinitromethyl-4-nitro-1,2,3-triazole potassium salt (4) is shown.

[0109] Figure 2 The single crystal structure of 5-dinitromethyl-4-nitro-1,2,3-triazole diammonium salt (13) is shown. DETAILED DESCRIPTION

[0110] The present invention is further illustrated by way of examples below, but the present invention is not limited to the scope of the examples. Experimental methods in the following examples where specific conditions are not specified were performed according to conventional methods and conditions, or selected according to the product specifications.

[0111] Example 1

[0112] Preparation of Intermediate 2:

[0113] In a single-necked eggplant flask, 2.4 g (17.26 mmol) of 5-cyano-4-nitro-1,2,3-triazole was added and dissolved in 4.3 mL of water. 1.05 mL (17.26 mmol) of 50% hydroxylamine aqueous solution was added dropwise. The temperature was raised to reflux and the reaction was carried out for 1 h. The yellow product, intermediate 2, was obtained by filtration with a yield of 62.0%. 1 H NMR (d6-DMSO): 10.98 (s, 1H, OH), 8.48 (s, 2H, NH2)ppm; 13 C NMR (d6-DMSO): 151.02, 146.64, 133.95ppm; IR (KBrpellet): 3654, 3626, 3486, 3177, 2349, 2285, 1661, 1558, 1511, 1396, 1339, 1272, 1208, 1141, 1098, 999, 956, 844, 786, 764, 729, 698, 501, 415.

[0114] Example 2

[0115] Preparation of Intermediate 2:

[0116] In a single-necked eggplant flask, 2.4 g (17.26 mmol) of 5-cyano-4-nitro-1,2,3-triazole was added and dissolved in 4.3 mL of water. 1.05 mL (17.26 mmol) of a 50% aqueous hydroxylamine solution was added dropwise. The mixture was heated to reflux and reacted for 6 h. Filtering afforded a yellow product, Intermediate 2, in a 64.0% yield. Characterization data were the same as in Example 1.

[0117] Example 3

[0118] Preparation of intermediate 2:

[0119] In a single-necked eggplant flask, 2.4 g (17.26 mmol) of 5-cyano-4-nitro-1,2,3-triazole was added and dissolved in 4.3 mL of water. 1.05 mL (17.26 mmol) of a 50% aqueous hydroxylamine solution was added dropwise. The mixture was heated to reflux and reacted for 12 h. Filtering afforded a yellow product, Intermediate 2, in a 65.0% yield. Characterization data were the same as in Example 1.

[0120] Example 4

[0121] Preparation of intermediate 3:

[0122] At room temperature, in a three-necked flask, intermediate 2 (3.01 g, 17.49 mmol) was added to a mixture of 25 mL of water and 7.8 mL of 37% hydrochloric acid. After the intermediate 2 was dissolved, an aqueous sodium nitrite solution (1.46 g, 21.10 mmol, 8.5 mL) was added dropwise at about 0°C. The mixture was then reacted at 0-5°C for 1 h, and the temperature was raised to room temperature and the reaction was continued for 6 h. After the reaction was completed, the reaction solution was extracted with ether (70 mL × 6) and washed with saturated brine. The organic phase was dried, filtered, and concentrated to obtain compound 3 with a yield of 85.0%. 1 H NMR(d6-DMSO): 13.19(s, 1H, OH)ppm; 13 EN MR(d6-DMSO): 149.78, 133.66, 123.68ppm; IR(KBrpellet): 3261, 2960, 2859, 2282, 1998, 1 620, 1557, 1519, 1436, 1382, 1354, 1236, 1214, 1161, 1003, 943, 834, 769, 756, 694, 651, 492.

[0123] Example 5

[0124] Preparation of intermediate 3:

[0125] At room temperature, intermediate 2 (3.01 g, 17.49 mmol) was added to a mixture of 25 mL of water and 7.8 mL of 37% hydrochloric acid in a three-necked flask. After dissolution of intermediate 2, an aqueous sodium nitrite solution (1.46 g, 21.10 mmol, 8.5 mL) was added dropwise at approximately 0°C. The mixture was then reacted at 0-5°C for 6 h. The temperature was then raised to room temperature and the reaction continued for 1 h. After completion of the reaction, the reaction solution was extracted with ethyl acetate (70 mL x 6) and washed with saturated brine. The organic phase was dried, filtered, and concentrated to obtain compound 3 in an 87.0% yield. Characterization data were the same as in Example 4.

[0126] Example 6

[0127] Preparation of intermediate 3:

[0128] At room temperature, intermediate 2 (3.01 g, 17.49 mmol) was added to a mixture of 25 mL of water and 7.8 mL of 37% hydrochloric acid in a three-necked flask. After dissolution of intermediate 2, an aqueous sodium nitrite solution (1.46 g, 21.10 mmol, 8.5 mL) was added dropwise at approximately 0°C. The mixture was then allowed to react at 0-5°C for 3 h. The temperature was then raised to room temperature and the reaction continued for 3 h. After completion of the reaction, the reaction solution was extracted with ethyl acetate (70 mL x 6) and washed with saturated brine. The organic phase was dried, filtered, and concentrated to obtain compound 3 in an 80.0% yield. Characterization data were the same as in Example 4.

[0129] Example 7

[0130] Preparation of 5-dinitromethyl-4-nitro-1,2,3-triazole potassium salt (4):

[0131] Add 10mL of trifluoroacetic anhydride to a three-necked flask and stir, and then lower the system temperature to -15°C. Add 10mL of fuming HNO3 dropwise while stirring, and then add intermediate 3 (2g) in batches. React at about -15°C for 3h, then warm to room temperature and continue to react for 6h. After the reaction is completed, quench with ice water and extract with chloroform (60mL×6). The organic phase is washed with saturated brine (60mL). The organic phase is dried, filtered, and concentrated to obtain a light yellow liquid. Dissolve the above liquid with 28mL of methanol, add a methanol solution of potassium iodide (3.63g, 40mL) dropwise, stir overnight, filter, wash with methanol, and recrystallize to obtain product 4 with a yield of 69.1%. The single crystal structure is shown in the figure below. Figure 1 shown. 13CNMR (d6-DMSO): 149.28, 131.57, 123.25ppm; IR (KBr pellet): 3855, 3822, 3753, 3651, 2736, 2348, 2234, 1560, 1461, 1387, 1322, 1228, 1201, 1129, 1061, 1012, 984, 837, 813, 762, 750, 741, 678, 604.

[0132] Example 8

[0133] Preparation of 5-dinitromethyl-4-nitro-1,2,3-triazole potassium salt (4):

[0134] 10 mL of trifluoroacetic anhydride was added to a three-necked flask with stirring. The system temperature was lowered to approximately 5°C. 10 mL of fuming HNO3 was added dropwise with stirring. Then, intermediate 3 (2 g) was added portionwise. The reaction was allowed to react at approximately 5°C for 30 min, then warmed to room temperature and continued for 12 h. After completion of the reaction, the mixture was quenched with ice water and extracted with chloroform (60 mL x 6). The organic phase was washed with saturated brine, dried, filtered, and concentrated to obtain a pale yellow liquid. The above liquid was dissolved in 28 mL of methanol, and a methanol solution of potassium iodide (3.63 g, 40 mL) was added dropwise. After stirring overnight, the mixture was filtered, washed with methanol, and recrystallized to obtain product 4 in a yield of 65.5%. Characterization data are the same as in Example 7.

[0135] Example 9

[0136] Preparation of 5-dinitromethyl-4-nitro-1,2,3-triazole potassium salt (4):

[0137] 10 mL of concentrated sulfuric acid was added to a three-necked flask, the system temperature was lowered to about -5°C, and 10 mL of fuming HNO3 was added dropwise with stirring. Then, intermediate 3 (2 g) was added in batches. The reaction was allowed to proceed at about -5°C for 6 h, then warmed to room temperature and continued for 30 min. After completion of the reaction, the mixture was quenched with ice water and extracted with ether (60 mL x 6). The organic phase was washed with saturated brine, dried, filtered, and concentrated to obtain a pale yellow liquid. The above liquid was dissolved in 28 mL of methanol, and a methanol solution of potassium iodide (3.63 g, 40 mL) was added dropwise. After stirring overnight, the mixture was filtered, washed with methanol, and recrystallized to obtain product 4 in a yield of 72.3%. Characterization data are the same as in Example 7.

[0138] Example 10

[0139] Preparation of 5-dinitromethyl-4-nitro-1,2,3-triazole diammonium salt (13):

[0140] Its structural formula is as follows:

[0141]

[0142] At room temperature, 5-dinitromethyl-4-nitro-1,2,3-triazole potassium salt (512 mg, 2 mmol) was added to a single-necked flask and dissolved in 5 mL of water. The mixture was acidified with dilute hydrochloric acid to a pH ≤ 5, and then extracted with ethyl acetate (50 mL x 3). The combined organic phases were filtered, dried, and concentrated until a small amount of solvent remained. 25% aqueous ammonia was then added dropwise until the pH was > 7. The mixture was stirred at room temperature for 1 h and concentrated to obtain a yellow solid, the target product 13, with a yield of 89.9%. The single crystal structure is shown in the figure below. Figure 2 shown. 1 H NMR (500MHz, DMSO-d6, ppm): 7.32 (s, 8H, NH4 + ); 13 C NMR (500MHz, DMSO-d6, ppm): 148.70, 134.99, 127.02; IR (KBr pellet): 3202, 1682, 1567, 1393, 1323, 1203, 1122, 1014, 837, 816, 760, 745, 676cm -1 ; Elemental analysis (%)calcd for C3H8N8O6 (252.15): C, 14.29; H, 3.20; N, 44.44. Found: C, 13.93; H, 3.19; N, 43.71.

[0143] Example 11

[0144] 5-Dinitromethyl-4-nitro-1,2,3-triazole dihydrazine salt (14)

[0145] Its structural formula is as follows:

[0146]

[0147] At room temperature, 4-dinitromethyl-5-nitro-1,2,3-triazole potassium salt (572 mg, 2.23 mmol) was added to a single-necked flask and dissolved in 5 mL of water. The mixture was acidified with dilute sulfuric acid to a pH ≤ 5, and then extracted with ether (50 mL x 4). The combined organic phases were filtered, dried, and concentrated until a small amount of solvent remained. Hydrazine hydrate solution was then added dropwise until the pH reached 7. The mixture was stirred at room temperature for 5 h and concentrated to obtain a yellow solid, the desired product 14, in a yield of 95.6%.

[0148] 1 H NMR(d6-DMSO): 7.09(s, 5H)ppm; 13C NMR (d6-DMSO): 150.40, 135.02, 126.88ppm; IR (KBrpellet): 3243, 3035, 2578, 2240, 1560, 1467, 139 0, 1323, 1227, 1204, 1130, 1082, 1014, 986, 964, 838, 815, 778, 762, 750, 741, 679, 605, 450; Elemental analysis forC3H 10 N 10 O6(M W 282.21), calcd: C, 12.77; H, 3.57; N, 49.64. Found: C, 12.63; H, 3.63; N, 49.34.

[0149] Example 12

[0150] 5-Dinitromethyl-4-nitro-1,2,3-triazole bishydroxylamine salt (15)

[0151]

[0152] At room temperature, 4-dinitromethyl-5-nitro-1,2,3-triazole potassium salt (512 mg, 2 mmol) was added to a single-necked flask and dissolved in 5 mL of water. The mixture was acidified with dilute sulfuric acid to a pH ≤ 5, and then extracted with ether (50 mL x 4). The combined organic phases were filtered, dried, and concentrated until a small amount of solvent remained. A 50% aqueous hydroxylamine solution was then added dropwise until the pH reached 7. The mixture was stirred at room temperature for 5 h and concentrated to yield the desired product 15 as a yellow solid in a 94.2% yield.

[0153] 1 H NMR (d6-DMSO): 9.90 (s, 8H, NH3OH)ppm; 13 C NMR (d6-DMSO): 156.60, 149.10, 134.12, 128.61ppm. Elemental analysis for C3H8N8O8(M W 284.15), calcd: C, 12.68; H, 2.84; N, 39.44. Found: C, 12.65; H, 2.86; N, 39.43.

[0154] Example 13

[0155] 5-Dinitromethyl-4-nitro-1,2,3-triazole biguanide salt (16)

[0156] Its structural formula is as follows:

[0157]

[0158] At room temperature, 5-dinitromethyl-4-nitro-1,2,3-triazole potassium salt (423 mg, 1.65 mmol) was added to a single-necked flask and dissolved in 20 mL of water. The mixture was acidified with hydrochloric acid to a pH ≤ 5 and extracted with ethyl acetate (50 mL x 4). The combined organic phases were filtered, dried, and concentrated until a small amount of solvent remained. An equimolar amount of guanidine carbonate solution was then added dropwise. The mixture was stirred at room temperature for 3 h and concentrated to yield the desired product 16 as a yellow solid in a 50.1% yield.

[0159] 1 H NMR (d6-DMSO): 7.02 (s, 6H, NH2)ppm; 13 C NMR (d6-DMSO): 158.04, 150.37, 134.91, 126.70ppm, IR (KBr pellet): 3203, 2348, 2277, 1659, 1561, 1455, 1389, 1341, 1204, 1125, 1021, 840, 813, 748, 675, 520; Elemental analysis for C5H 12 N 12 O6(M W 336.23), calcd: C, 17.86; H, 3.60; N, 49.99. Found: C, 18.04; H, 3.89; N, 49.36.

[0160] Example 14

[0161] 5-Dinitromethyl-4-nitro-1,2,3-triazole bisaminoguanidine salt (17)

[0162] Its structural formula is as follows:

[0163]

[0164] At room temperature, 5-dinitromethyl-4-nitro-1,2,3-triazole potassium salt (432 mg, 1.69 mmol) was added to a single-necked flask and dissolved in 20 mL of water. The mixture was acidified with hydrochloric acid to a pH ≤ 5 and extracted with ethyl acetate (50 mL x 4). The organic phases were combined, washed with saturated brine, and dried over anhydrous MgSO₄. After filtration, the mixture was concentrated under reduced pressure to a small amount of solvent, and two equivalents of aminoguanidine bicarbonate as a solid were added dropwise. The mixture was stirred at room temperature for 3 h, then concentrated to dryness and washed with a small amount of ethanol and petroleum ether to obtain the desired product 17 as a yellow solid in a yield of 59.8%.

[0165] 1H NMR (d6-DMSO): 8.65 (s, 1H, NH), 7.32 (s, 2H, NH2), 6.84 (s, 2H, NH2), 4.70 (s, 2H, NH2)ppm; 13 C NMR (d6-DMSO): 158.88, 150.38, 135.02, 126.76ppm; IR (KBr pellet): 3450, 3349, 3297, 2348, 2234, 1656, 1562, 1461, 1419, 1390, 1325, 1200, 1126, 1066, 1014, 986, 838, 813, 750, 678, 613, 458; Elemental analysis for C5H 14 N 14 O6(M W 366.23), calcd: C, 16.40; H, 3.85; N, 53.54. Found: C, 16.45; H, 4.00; N, 53.40.

[0166] Example 15

[0167] 5-Dinitromethyl-4-nitro-1,2,3-triazole ammonium salt (6)

[0168] Its structural formula is as follows:

[0169]

[0170] At room temperature, 5-dinitromethyl-4-nitro-1,2,3-triazole potassium salt (512 mg, 2 mmol) was added to a single-necked flask and dissolved in water. Silver nitrate aqueous solution (2 mmol) was added dropwise, and the mixture was stirred at room temperature for 1 hour. After filtering, a yellow solid (4-dinitromethyl-5-nitro-1,2,3-triazole silver salt) was obtained. The obtained solid was dispersed in 20 mL of water, and ammonium chloride aqueous solution (2 mmol) was added dropwise. The mixture was stirred at room temperature for 3 hours, and the filtrate was filtered and concentrated to obtain a yellow solid, which was the target product 6, with a yield of 94.1%.

[0171] 1 H NMR (500MHz, DMSO-d6, ppm): 7.32 (s, 4H, NH4 + ); 13 C NMR (500MHz, DMSO-d6, ppm): 148.60, 134.99, 127.00. Elemental analysis for C3H5N7O7(M W235.12), calcd: C, 15.33; H, 2.14; N, 41.70. Found: C, 15.30; H, 2.12; N, 41.65.

[0172] Example 16

[0173] 5-Dinitromethyl-4-nitro-1,2,3-triazolidine salt (7)

[0174] Its structural formula is as follows:

[0175]

[0176] At room temperature, 5-dinitromethyl-4-nitro-1,2,3-triazole potassium salt (512 mg, 2 mmol) was added to a single-necked flask and dissolved in water. Silver nitrate aqueous solution (2 mmol) was added dropwise, and the mixture was stirred at room temperature for 1 hour. After filtering, a yellow solid (5-dinitromethyl-4-nitro-1,2,3-triazole silver salt) was obtained. The obtained solid was dispersed in 20 mL of water, and hydrazine hydrochloride aqueous solution (2 mmol) was added dropwise. The mixture was stirred at room temperature for 3 hours, and the filtrate was filtered and concentrated to obtain a yellow solid, which was the target product 7, with a yield of 91.0%.

[0177] 1 H NMR(d6-DMSO): 7.09(s, 5H)ppm; 13 C NMR (d6-DMSO): 150.30, 135.1, 126.98ppm. Elemental analysis for C3H6N8O6(M W 250.13), calcd: C, 14.41; H, 2.42; N, 44.80. Found: C, 14.39; H, 2.43; N, 44.38.

[0178] Example 17

[0179] 5-Dinitromethyl-4-nitro-1,2,3-triazole hydroxylamine salt (8)

[0180] Its structural formula is as follows:

[0181]

[0182] At room temperature, 5-dinitromethyl-4-nitro-1,2,3-triazole potassium salt (512 mg, 2 mmol) was added to a single-necked flask and dissolved in water. Silver nitrate aqueous solution (2 mmol) was added dropwise, and the mixture was stirred at room temperature for 1 hour. After filtration, a yellow solid (5-dinitromethyl-4-nitro-1,2,3-triazole silver salt) was obtained. The obtained solid was dispersed in 20 mL of water, and hydroxylamine hydrochloride aqueous solution (2 mmol) was added dropwise. The mixture was stirred at room temperature for 3 hours. After filtration, the filtrate was directly concentrated to obtain a yellow solid, the target product 8, with a yield of 91.6%.

[0183] 1 H NMR (d6-DMSO): 9.92 (s, 4H, NH3OH)ppm; 13 C NMR (d6-DMSO): 156.10, 149.50, 133.12, 127.61ppm. Elemental analysis for C3H5N7O7(M W 251.12), calcd: C, 14.35; H, 2.01; N, 39.05. Found: C, 14.37; H, 1.99; N, 39.04.

[0184] Example 18

[0185] 5-Dinitromethyl-4-nitro-1,2,3-triazoleguanidine salt (9)

[0186] Its structural formula is as follows:

[0187]

[0188] At room temperature, 5-dinitromethyl-4-nitro-1,2,3-triazole potassium salt (512 mg, 2 mmol) was added to a single-necked flask and dissolved in water. Silver nitrate aqueous solution (2 mmol) was added dropwise, and the mixture was stirred at room temperature for 1 hour. After filtration, a yellow solid (4-dinitromethyl-5-nitro-1,2,3-triazole silver salt) was obtained. The obtained solid was dispersed in 20 mL of water, and guanidine hydrochloride aqueous solution (2 mmol) was added dropwise. The mixture was stirred at room temperature for 3 hours. After filtration, the filtrate was directly concentrated to obtain a yellow solid, the target product 9, with a yield of 89.3%.

[0189] 1H NMR (d6-DMSO): 7.02 (s, 6H, NH2) ppm; 13 C NMR (d6-DMSO): 158.98, 150.40, 135.12, 126.75ppm. Elemental analysis forC4H7N9O6(M W277.16), calcd: C, 17.33; H, 2.55; N, 45.48. Found: C, 17.30; H, 2.57; N, 44.47.

[0190] Example 19

[0191] 5-Dinitromethyl-4-nitro-1,2,3-triazole aminoguanidine salt (10)

[0192] Its structural formula is as follows:

[0193]

[0194] At room temperature, 5-dinitromethyl-4-nitro-1,2,3-triazole potassium salt (512 mg, 2 mmol) was added to a single-necked flask and dissolved in water. Silver nitrate aqueous solution (2 mmol) was added dropwise, and the mixture was stirred at room temperature for 1 hour. After filtration, a yellow solid (4-dinitromethyl-5-nitro-1,2,3-triazole silver salt) was obtained. The obtained solid was dispersed in 20 mL of water, and aminoguanidine hydrochloride aqueous solution (2 mmol) was added dropwise. The mixture was stirred at room temperature for 3 hours. After filtration, the filtrate was directly concentrated to obtain a yellow solid, the target product 10, with a yield of 89.3%.

[0195] 1 H NMR (d6-DMSO): 8.65 (s, 1H, NH), 7.32 (s, 2H, NH2), 6.84 (s, 2H, NH2), 4.70 (s, 2H, NH2)ppm; 13 C NMR (d6-DMSO): 158.98, 150.40, 135.12, 126.75ppm. Elemental analysis forC4H9N 10 O6(M W 293.18), calcd: C, 16.39; H, 3.09; N, 47.78. Found: C, 16.41; H, 3.07; N, 47.80.

[0196] Example 20

[0197] The calculation formula of nitrogen content (mass fraction of nitrogen element) is: nitrogen content = (relative atomic mass of nitrogen * number of nitrogen atoms) / relative molecular mass * 100%.

[0198] The detonation velocity was calculated using EXPLO5 V6.05 software.

[0199] The impact sensitivity test instrument is a BFH-10 drop hammer impact sensitivity tester manufactured by Edison, USA. The following steps are used: (1) Place the sample to be tested (20 ± 2 mg) in the impact column; (2) Continuously adjust the weight and height of the drop hammer to impact the sample to be tested (using a weight of a certain mass (e.g., 2 kg, 5 kg, 10 kg) to drop freely from a certain height and directly impact the sample) and observe whether it explodes (explosion determination: sample color change, explosion sound, and odor are all considered explosions); (3) Record the weight and height of the drop hammer for five consecutive times when no explosion occurs and calculate the impact sensitivity value.

[0200] Table 1 Properties of some energetic ion salts

[0201]

[0202]

[0203] As can be seen from Table 1, the energetic ion salts of the present invention exhibit high nitrogen content, high detonation velocity, and high impact sensitivity (high safety). The detonation velocity of potassium salt 4 is significantly higher than that of lead azide, a currently used heavy metal ion-containing primary explosive, making it suitable for use as a green primary explosive. Some energetic ion salts with organic nitrogen-rich structures as cations, such as compounds 6, 7, 14, and 15, exhibit nitrogen content and detonation velocity far superior to RDX, and are therefore suitable for use in mixed explosives, solid propellants, and gas generators.

Claims

1. A triazole compound ionic salt as shown in formula III-S-1 or III-S-2, characterized in that: The cation in the triazole compound ion salt is NH4 + 、 2. The triazole compound ionic salt of formula III-S-1 or III-S-2 according to claim 1, characterized in that: The triazole compound ion salt represented by formula III-S-1 or III-S-2 is any of the following compounds:

3. A method for preparing the triazole compound ionic salt represented by formula III-S-1 or III-S-2 according to claim 1, characterized in that: It is method 1 or 2; When the cation in the triazole compound ion salt is 1, it is method 1: The method 1 comprises the following steps: in an aqueous solution, performing a metathesis reaction on compound 5 and compound 5-1 to obtain compound III-S-1; Where R is NH4 + 、 X1 is a halogen; When the number of cations in the triazole compound ion salt is 2, it is method 2: The method 2 comprises the following steps: reacting a triazole compound as shown in formula III with compound 5-2 to obtain compound III-S-2; Where R is NH4 + 、 X2 is OH - 、CO3 2- 、HCO3 - 、SO3 2- 、S 2- or PO4 3- .

4. The method for preparing the triazole compound ion salt represented by formula III-S-1 or III-S-2 according to claim 3, wherein: It meets one or more of the following conditions: (1) In method 1, R is NH4 + 、 (2) In method 1, X1 is chlorine or iodine; (3) In method 1, the compound 5-1 is ammonium chloride, hydrazine hydrochloride, hydroxylamine hydrochloride, guanidine hydrochloride or aminoguanidine hydrochloride; (4) In method 1, the molar ratio of compound 5-1 to compound 5 is (0.8-1.2):1; (5) In method 1, the temperature of the metathesis reaction is room temperature; (6) In method 1, the metathesis reaction time is 1 to 5 hours; (7) In method 1, the metathesis reaction further includes post-treatment, and the post-treatment includes filtration and concentration; (8) In method 2, R is NH4 + 、 (9) In method 2, X2 is OH - 、CO3 2- or HCO3 - ; (10) In method 2, the compound 5-2 is ammonia water, hydroxylamine aqueous solution, hydrazine hydrate, guanidine carbonate or aminoguanidine bicarbonate; (11) In method 2, the molar ratio of the compound 5-2 to the triazole compound represented by formula III is (1-2):1; (12) In method 2, the reaction temperature is room temperature; (13) In method 2, the reaction time is 0.5 to 6 hours; (14) In method 2, the reaction further comprises post-treatment, and the post-treatment comprises concentration; (15) In method 2 described above, the reaction is carried out in an atmosphere of pH ≥ 7.

5. The method for preparing the triazole compound ionic salt represented by formula III-S-1 or III-S-2 according to claim 4, wherein: It meets one or more of the following conditions: (1) In method 1, X1 is chlorine; (2) In method 1, the molar ratio of compound 5-1 to compound 5 is 1:1; (3) In method 1, the metathesis reaction time is 3 h; (4) In method 2, the molar ratio of the compound 5-2 to the triazole compound represented by formula III is 1:1 or 2:1; (5) In method 2, the reaction time is 1 to 5 hours.

6. The method for preparing the triazole compound ionic salt represented by formula III-S-1 or III-S-2 according to claim 4, wherein: It meets the following conditions: in method 2, the reaction time is 1 h, 3 h or 5 h.

7. The method for preparing the triazole compound ionic salt represented by formula III-S-1 or III-S-2 according to claim 3, wherein: It satisfies the following conditions (1) and / or (2): (1) Method 1 further comprises the following steps: compound 4 undergoes a double decomposition reaction with a silver salt in an aqueous solution to obtain compound 5; (2) Method 2 further comprises the following steps: compound 4 is subjected to a protonation reaction with an acid to obtain a triazole compound as shown in formula III; 8. The method for preparing the triazole compound ionic salt represented by formula III-S-1 or III-S-2 according to claim 7, wherein: It meets one or more of the following conditions: (1) In method 1, the silver salt is silver nitrate or silver sulfate; (2) In method 1, the molar ratio of the silver salt to the compound 4 is (0.8-1.2):1; (3) In method 1, the temperature of the metathesis reaction is room temperature; (4) In method 1, the double decomposition reaction time is 0.5 to 1.5 hours; (5) In method 1, the metathesis reaction further includes post-treatment, and the post-treatment includes filtration; (6) In method 2, the acid is hydrochloric acid or sulfuric acid; (7) In method 2, the protonation reaction is carried out in an atmosphere with a pH of ≤ 5; (8) In method 2, the protonation reaction further includes post-treatment, and the post-treatment includes extraction.

9. The method for preparing the triazole compound ionic salt represented by formula III-S-1 or III-S-2 according to claim 8, wherein: It meets one or more of the following conditions: (1) In method 1, the silver salt is silver nitrate; (2) In method 1, the molar ratio of the silver salt to the compound 4 is 1:1; (3) In method 1, the metathesis reaction time is 1 h; (4) In method 2, the extraction solvent is an ester solvent and / or an ether solvent.

10. The method for preparing the triazole compound ionic salt represented by formula III-S-1 or III-S-2 according to claim 9, wherein: It meets the following conditions: in method 2, the extraction solvent is ethyl acetate and / or diethyl ether.

11. The method for preparing the triazole compound ionic salt represented by formula III-S-1 or III-S-2 according to claim 7, wherein: The method 1 and the method 2 independently further comprise the following steps: Step a: Compound 3 reacts with a nitrating agent to obtain a product; Step b: reacting the product obtained in step a with a potassium salt in an alcohol solvent to obtain compound 4; The nitrating agent is a mixture of fuming nitric acid and anhydride or a mixture of fuming nitric acid and concentrated sulfuric acid, and the anhydride is one or more of trifluoroacetic anhydride, acetic anhydride and nitric anhydride.

12. The method for preparing the triazole compound ionic salt represented by formula III-S-1 or III-S-2 according to claim 11, wherein: It meets one or more of the following conditions: (1) The nitrating agent is a mixture of fuming nitric acid and concentrated sulfuric acid; (2) In the step a, the volume ratio of the fuming nitric acid to the acid anhydride or concentrated sulfuric acid in the nitrating reagent is 1:1; (3) In step a, the preparation temperature of the nitrating reagent is -20 to 10°C; (4) In step a, the mass volume ratio of the compound 3 to the nitrating agent is 0.05 to 0.15 g / mL; (5) In step a, the reaction temperature is between -20°C and room temperature; (6) In step a, the reaction time is 4 to 20 hours; (7) In step a, the reaction further comprises post-treatment, and the post-treatment comprises quenching and extraction; (8) In step b, the potassium salt is potassium iodide, potassium hydroxide, potassium carbonate or potassium bicarbonate; (9) In step b, the alcohol solvent is methanol; (10) In the step b, the mass volume ratio of the compound 3 to the alcohol solvent is 0.02 to 0.04 g / mL; (11) In step b, the molar ratio of the potassium salt to the compound 3 is (2-4):1; (12) In step b, the reaction temperature is room temperature; (13) In step b, the reaction time is 10 to 20 hours; (14) In step b, the reaction further comprises post-treatment, and the post-treatment comprises filtration, washing and recrystallization.

13. The method for preparing the triazole compound ionic salt represented by formula III-S-1 or III-S-2 according to claim 12, wherein: It meets one or more of the following conditions: (1) In step a, the preparation temperature of the nitrating reagent is -15 to 5°C; (2) In step a, the mass volume ratio of the compound 3 to the nitrating agent is 0.1 g / mL; (3) In step a, the reaction temperature is -15°C to room temperature, -5°C to room temperature, or 5°C to room temperature; (4) In step a, the reaction time is 6 to 12 hours; (5) In the step a, the quenching solvent is ice water; (6) In step a, the extraction solvent is an organic chlorine-containing solvent and / or an ether solvent; (7) In step b, the potassium salt is potassium iodide; (8) In step b, the mass volume ratio of the compound 3 to the alcohol solvent is 0.03 g / mL; (9) In step b, the washing solvent is an alcohol solvent.

14. The method for preparing the triazole compound ionic salt represented by formula III-S-1 or III-S-2 according to claim 13, wherein: It meets one or more of the following conditions: (1) In step a, the preparation temperature of the nitrating reagent is -15°C, -5°C or 5°C; (2) In step a, the reaction time is 6 h, 9 h or 12 h; (3) In step a, the extraction solvent is chloroform and / or diethyl ether; (4) In step b, the washing solvent is methanol.

15. The method for preparing the triazole compound ionic salt represented by formula III-S-1 or III-S-2 according to claim 11, wherein: The method 1 and the method 2 independently further comprise the following steps: In a solvent, in the presence of an oxidant, compound 2 undergoes a substitution reaction with hydrochloric acid to obtain compound 3; 16. The method for preparing the triazole compound ionic salt represented by formula III-S-1 or III-S-2 according to claim 15, wherein: It meets one or more of the following conditions: (1) The hydrochloric acid is 37% hydrochloric acid; (2) The oxidant is one or more of sodium nitrite, isopropyl nitrite, isoamyl nitrite, and nitrosyl fluoroborate; (3) The solvent is one or more of water, methanol, ethanol and isopropanol; (4) The molar ratio of the hydrochloric acid to the compound 2 is (4-6):1; (5) The molar ratio of the oxidant to the compound 2 is (0.8-1.6):1; (6) The mass volume ratio of the compound 2 to the solvent is 0.06 to 0.09 g / mL; (7) The mass volume ratio of the oxidant to the solvent is 0.02 to 0.05 g / mL; (8) The oxidant is added at a temperature of about 0°C; (9) The temperature of the substitution reaction is 0°C to room temperature; (10) The time of the substitution reaction is 5 to 8 hours; (11) The substitution reaction further includes post-treatment, and the post-treatment includes extraction.

17. The method for preparing the triazole compound ionic salt represented by formula III-S-1 or III-S-2 according to claim 16, wherein: It meets one or more of the following conditions: (1) The oxidant is sodium nitrite; (2) The solvent is water; (3) The molar ratio of the hydrochloric acid to the compound 2 is 5:1; (4) The molar ratio of the oxidant to the compound 2 is 1.2:1; (5) The mass volume ratio of the compound 2 to the solvent is 0.073 g / mL; (6) The mass volume ratio of the oxidant to the solvent is 0.035 g / mL; (7) The oxidant is added at a temperature of -5 to 5°C; (8) The time of the substitution reaction is 6 to 7 hours; (9) The extraction solvent is an ester solvent and / or an ether solvent.

18. The method for preparing the triazole compound ionic salt represented by formula III-S-1 or III-S-2 according to claim 17, wherein: It meets one or more of the following conditions: (1) The substitution reaction time is 6 h or 7 h; (2) The extraction solvent is ethyl acetate and / or ether.

19. The method for preparing the triazole compound ionic salt represented by formula III-S-1 or III-S-2 according to claim 15, wherein: The method 1 and the method 2 independently further comprise the following steps: In a solvent, 5-cyano-4-nitro-1,2,3-triazole and hydroxylamine undergo an addition reaction to obtain compound 2; 20. The method for preparing the triazole compound ionic salt represented by formula III-S-1 or III-S-2 according to claim 19, wherein: It meets one or more of the following conditions: (1) The hydroxylamine is a hydroxylamine aqueous solution; (2) The solvent is one or more of water, alcohol solvent and tetrahydrofuran; (3) the molar ratio of the hydroxylamine to the 5-cyano-4-nitro-1,2,3-triazole is (0.8-1.2):1; (4) The mass volume ratio of the 5-cyano-4-nitro-1,2,3-triazole to the solvent is 0.4 to 0.5 g / mL; (5) The temperature of the addition reaction is 70-100°C; (6) The addition reaction time is 0.5 to 18 hours; (7) The addition reaction further includes post-processing, and the post-processing includes filtration.

21. The method for preparing the triazole compound ionic salt represented by formula III-S-1 or III-S-2 according to claim 20, wherein: It meets one or more of the following conditions: (1) The hydroxylamine is a 50% hydroxylamine aqueous solution; (2) The solvent is water; (3) the molar ratio of the hydroxylamine to the 5-cyano-4-nitro-1,2,3-triazole is 1:1; (4) The mass volume ratio of the 5-cyano-4-nitro-1,2,3-triazole to the solvent is 0.45 g / mL; (5) The temperature of the addition reaction is 100°C; (6) The addition reaction time is 1 to 12 hours.

22. The method for preparing the triazole compound ionic salt represented by formula III-S-1 or III-S-2 according to claim 21, wherein: It meets the following conditions: the addition reaction time is 1h, 6h or 12h.

23. A compound as shown in Formula 2 or Formula 3, 24. A high explosive or solid propellant, characterized in that: It includes the triazole compound ion salt represented by formula III-S-1 or III-S-2 as claimed in claim 1 or 2.

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