C-N triazole energetic compound as well as preparation method and application thereof

Abstract

The invention discloses a C-N triazole energetic compound, and belongs to the field of energetic material synthesis. In order to solve the technical problems that an existing triazole intermediate is low in density and poor in thermal stability due to a single structure, a synthesis process depends on a high-risk reagent, and functional modification sites are insufficient, the invention provides a novel high-nitrogen-content diazole compound which is constructed by taking 1, 3, 5-triazine as a mother nucleus and bridging a triazole ring through a C-N bond, and the synthesis comprises two steps: synthesizing 2, 3, 5-triazine into 2, 3, 5-triazine-1, 3, 5-triazine into 2, 3, 5-triazine-1, 3, 5-triazine-1, 3, 5-triazine; the preparation method comprises the following steps: carrying out hydrazinolysis on 2, 4-dichloro-1, 3, 5-triazine and hydrazine hydrate in methanol, and cyclizing with cyanogen bromide in a methanol / water / acetonitrile mixed solvent, thereby obtaining the 2, 4-dichloro-1, 3, 5-triazine derivative. And introducing a nitrogen-containing group through multi-site modification to form an energetic compound or energetic salt. The energetic compound and the energetic salt have high nitrogen content and excellent thermal stability and detonation performance, and are suitable for preparation of high-energy materials such as propellants and initiating explosives.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of energetic material design and synthesis. More particularly, the present application relates to a C-N linked triazole energetic compound and its preparation method and use. BACKGROUND

[0002] The efficient design and performance optimization of energetic materials highly depend on the development of new heterocyclic intermediates, especially triazole compounds with high nitrogen content, stable skeleton and multiple modification sites. Currently, the research on C-N linked triazole structure as energetic material precursor faces the following technical bottlenecks: 1. Insufficient design of fused ring structure and utilization of nitrogen atoms: The existing triazole intermediates are mostly based on single ring or simple bridged triazoles (such as 1,2,4-triazole or benzotriazole), which have sparse distribution of nitrogen atoms and limited extension of conjugated system. For example, single ring triazoles can only provide limited functionalization sites, and the introduction of multiple energetic groups (such as nitro, amino nitro) can easily lead to a decrease in molecular stability due to steric hindrance or electronic repulsion; and traditional double triazole structures (such as linked triazoles connected by single bonds) are difficult to balance the demand for high energy density and thermal stability due to the lack of rigid conjugated skeleton. In addition, the synthesis of such structures often relies on complex bridging strategies, resulting in a decrease in nitrogen atom utilization and limiting the further improvement of the energy density of energetic compounds.

[0003] 2. High risk and inefficiency of synthesis process: The existing preparation methods of C-N linked triazole intermediates generally have complicated steps, harsh conditions or safety hazards. For example, when constructing C-N bond through metal catalytic coupling (such as Buchwald-Hartwig reaction), noble metal catalysts (such as palladium) are needed, which not only has high cost, but also the residual metal may affect the purity and safety of energetic materials; and the method based on azide cycloaddition needs strict temperature control to avoid explosion risk. For triazole intermediates containing fused ring systems, existing technologies often require high-temperature dehydration condensation (such as phosphorus oxychloride-mediated ring closure reaction) or multi-step reactions in strong acid / strong base environment, resulting in complex by-products, difficult product separation, and high requirement for equipment corrosion resistance.

[0004] 3. Limited directionality and diversity of functional modification: The molecular design of existing triazole intermediates cannot be compatible with the directional modification of multiple sites and multiple types of energetic groups. For example, chloro triazole derivatives can introduce amino groups through nucleophilic substitution, but due to the influence of ring electron effect, the selectivity of subsequent nitration reaction is poor, and isomer mixture is easily generated; and nitro-substituted triazole intermediates are difficult to further introduce electron-donating groups (such as amino) under mild conditions due to the electron-deficient nature of the ring. Such limitations result in a single path for functional modification of energetic compounds, which cannot accurately regulate key performance indicators such as energy release rate, sensitivity and stability through molecular structure.

[0005] The above problems seriously restrict the development of C-N linked triazole energetic materials. Therefore, it is urgent to design a new type of C-N linked triazole intermediate, which needs to meet the following requirements: (1) high nitrogen density and extended conjugated system, providing multiple sites for the introduction of energetic groups; (2) can be prepared by an efficient and safe synthesis route, avoiding high-risk reagents and harsh conditions; (3) support flexible functional modification to realize the targeted optimization of the performance of energetic compounds. This technical gap has become a core problem that needs to be broken through in this field. SUMMARY

[0006] An object of the present application is to solve at least the above problems and to provide at least the advantages to be explained later.

[0007] Another object of the present application is to provide a C-N linked triazole compound having high nitrogen density and rigid conjugated skeleton, which significantly expands the distribution density of nitrogen atoms and the symmetry of the molecule, providing high active sites for multi-site nitration, amination and other energetic modifications; at the same time, the synthesis process uses mild conditions and conventional solvents, avoids high-risk reagents, has high yield and is easy to purify, and supports the scale production of energetic compounds.

[0008] Another object of the present application is to provide a C-N linked triazole energetic compound or energetic salt, which has high nitrogen density, excellent thermal stability and low sensitivity; the nitration product and perchlorate / nitrate salt thereof significantly improve the energy density through multi-site modification, and the preparation process is mild and efficient, suitable for safe and large-scale production.

[0009] In order to achieve these objects and other advantages according to the present application, a C-N linked triazole energetic compound is provided, which has a structure as shown in formula (I): (I).

[0010] The present application further claims a method for the C-N linked triazole compound, comprising: S1, dissolving 2,4-dichloro-1,3,5-triazine in methanol, adding 85% mass fraction of hydrazine hydrate, reacting at room temperature for 4-8 h, collecting the solid phase filter residue, washing with methanol, and drying to obtain white solid product 2,4-dihydrazino-1,3,5-triazine; wherein the molar volume ratio of 2,4-dichloro-1,3,5-triazine to hydrazine hydrate is 2-3:4 mol / L; S2, dissolving the solid product 2,4-dihydrazino-1,3,5-triazine obtained in step S1 in a mixed solvent of methanol and deionized water, adding cyanogen bromide acetonitrile solution, refluxing at 50°C for 10-20 h, rotary evaporation for 0.5 h, volatilizing the solid phase at room temperature, acetonitrile washing, and drying to obtain the C-N linked triazole compound; The molar ratio of 2,4-dihydrazino-1,3,5-triazine to cyanogen bromide is 1-3:5, and the volume ratio of methanol, deionized water and acetonitrile is 2:3:4.

[0011] The present invention further claims protection for the use of the CN-triazole compound in the preparation of energetic compounds.

[0012] The present invention further claims protection for a CN-triazole energetic compound or energetic salt, wherein the CN-triazole energetic compound or energetic salt is prepared using the CN-triazole compound as a raw material, and the CN-triazole energetic compound has a structure as shown in formula (II): (II); Wherein, R is a nitrogen-containing group.

[0013] Preferably, R is -NHNO2.

[0014] Preferably, R is an amino group and the energy-containing salt is a perchlorate or a nitrate.

[0015] The present invention further claims a method for preparing the CN-triazole energetic compound or energetic salt, wherein the CN-triazole energetic compound of formula (II) is obtained by reacting the CN-triazole compound of formula (I) under acidic conditions and then separating the reacted CN-triazole energetic compound.

[0016] Preferably, when R is an amino group and the energetic salt is a perchlorate, the specific preparation method comprises: completely dissolving the CN triazole compound of formula (I) in 70% by mass perchloric acid, reacting at room temperature for 0.5 h, filtering and then washing with water to obtain a white CN triazole energetic perchlorate; wherein the molar volume ratio of the CN triazole compound of formula (I) to perchloric acid is 1:10-15 mol / L; When R is an amino group and the energetic salt is a nitrate, the specific preparation method comprises: completely dissolving the CN triazole compound of formula (I) in 50% by mass nitric acid, reacting at room temperature for 0.5 h, filtering, and then washing with water to obtain a yellow CN triazole energetic nitrate; wherein the molar volume ratio of the CN triazole compound of formula (I) to nitric acid is 1:10-15 mol / L; Among them, the structural formula of CN triazole energetic perchlorate is ; The structural formula of CN triazole energetic nitrate is .

[0017] Preferably, when R is -NHNO2, the specific preparation method includes: At 0 DEG C, a C-N linked triazole compound of formula (I) is added into mass fraction 100% nitric acid, and the reaction is carried out for 0.5 h under ice bath, and after removing the ice bath, the reaction is carried out for 12 h at room temperature, the solid is precipitated by pouring into crushed ice, and after filtration and water washing, a C-N linked triazole energetic compound is obtained, and the structural formula is ; wherein the molar volume ratio of the C-N linked triazole compound of formula (I) to nitric acid is 1:2-4 mol / L.

[0018] The application further claims the use of the C-N linked triazole energetic compound or the energetic salt in the preparation of an energetic material.

[0019] The application at least has the following beneficial effects: Firstly, the C-N linked triazole compound (formula I) provided by the application takes 1,3,5-triazine as the core, forms a novel C-N linked triazole compound by bridging triazole rings through C-N bonds, has high molecular symmetry and an extended conjugated system, and has a significantly higher nitrogen atom distribution density than traditional monocyclic or simply linked ring triazoles; the structure of the C-N linked triazole compound provides multiple active sites for subsequent nitration, amination and other energetic modifications, and the novel C-N linked triazole compound has excellent thermal stability, solving the common problems of low nitrogen density and insufficient thermal stability of traditional triazole intermediates; Secondly, the synthesis process of the C-N linked triazole compound (formula I) and the C-N linked triazole energetic compound or the energetic salt (formula II) breaks through the limitation of traditional multi-step high-risk routes, wherein the C-N linked triazole compound (formula I) is efficiently constructed into a novel C-N linked triazole compound under mild conditions (50 DEG C, normal pressure) through two-step reactions (hydrazine hydrate substitution and cyanogen bromide cyclization), the solvent system (methanol / water / acetonitrile=2:3:4) is optimized for solubility and reaction selectivity, and high-risk reagents such as azide and heavy metal catalysts are avoided; the C-N linked triazole energetic compound or the energetic salt (formula II) is further based on the C-N linked triazole compound (formula I) to realize nitration, salification and other energetic modifications, and a single parent body can derive multiple types of high-energy compounds (such as nitramine and perchlorate), and the process is simple and safe; Thirdly, the functional modification is flexible and diverse, and R can be -NHNO2, an amino group or a salification group (perchlorate / nitrate), which indicates that the same parent body can introduce nitro groups, amino groups and other energetic groups through directional modification at different sites, significantly improving the energy density and oxygen balance, and the chemical compatibility of the modification sites, such as the stability of the amino group in strong acid (perchlorate salt) and the high selectivity of the nitration reaction (no by-products), realizes the balance between the adjustability of energetic performance and low sensitivity. Fourthly, the C-N linked triazole compound (Formula I) provided by the application is used as a new energetic material precursor, and the derivative (Formula II energetic compound and salt) has high energy and low sensitivity, and is suitable for propellants, primary explosives and other fields, and solves the technical bottleneck that the energy-safety of the existing energetic material is difficult to be optimized simultaneously.

[0020] Other advantages, objects, and features of the application will be understood by those skilled in the art from the following description, and will be understood by those skilled in the art from the following description. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 The nuclear magnetic resonance hydrogen spectrum of compound 2 in the embodiment 1 of the application is shown in the figure; Figure 2 The single crystal structure of the C-N linked triazole compound 3 in the embodiment 1 of the application is shown in the figure; Figure 3 The nuclear magnetic resonance hydrogen spectrum of the C-N linked triazole compound 3 in the embodiment 1 of the application is shown in the figure; Figure 4 The nuclear magnetic resonance carbon spectrum of the C-N linked triazole compound 3 in the embodiment 1 of the application is shown in the figure; Figure 5 The single crystal structure of the C-N linked triazole energetic perchlorate salt 4 in the embodiment 2 of the application is shown in the figure; Figure 6 The nuclear magnetic resonance hydrogen spectrum of the C-N linked triazole energetic perchlorate salt 4 in the embodiment 2 of the application is shown in the figure; Figure 7 The nuclear magnetic resonance carbon spectrum of the C-N linked triazole energetic perchlorate salt 4 in the embodiment 2 of the application is shown in the figure; Figure 8 The nuclear magnetic resonance hydrogen spectrum of the C-N linked triazole energetic nitrate salt 5 in the embodiment 3 of the application is shown in the figure; Figure 9 The nuclear magnetic resonance carbon spectrum of the C-N linked triazole energetic nitrate salt 5 in the embodiment 3 of the application is shown in the figure; Figure 10 The nuclear magnetic resonance hydrogen spectrum of the C-N linked triazole energetic compound 6 in the embodiment 4 of the application is shown in the figure; Figure 11 The nuclear magnetic resonance carbon spectrum of the C-N linked triazole energetic compound 6 in the embodiment 4 of the application is shown in the figure. DETAILED DESCRIPTION

[0022] The application will be further described in detail below with reference to the accompanying drawings, so that those skilled in the art can implement the application according to the description.

[0023] It should be understood that the terms such as "have", "contain" and "include" used herein do not exclude the presence or addition of one or more other elements or combinations thereof.

[0024] Example 1 CN triazole compound 3, its structural formula is: ; The specific synthetic route is as follows: ; The specific synthesis steps are: Compound 1 (0.9 g, 6.00 mmol, purchased from Anaiji) was added to 20 mL of methanol. Compound 1 dissolved rapidly. 85% hydrazine hydrate (8 mL) was quickly added, and the solution turned from clear to milky white. The reaction was stopped at room temperature for 5 h and filtered to obtain a white solid. This solid was washed with methanol (3 × 8 mL) and oven-dried to obtain compound 2 (0.687 g) with a yield of 81.1%. Compound 2 (0.56 g, 4 mmol) was dissolved in methanol (14 mL) and deionized water (21 mL). Acetonitrile (28 mL) containing cyanogen bromide (1.06 g, 10 mmol) was poured into the solution. The solution was heated to 50°C and refluxed for 12 h, until the solution became clear. After the reaction, the remaining aqueous solution was evaporated by rotary evaporation at room temperature, and crystals precipitated. This solid was washed with acetonitrile (3 × 20 mL) and oven-dried to obtain CN-triazole compound 3 (0.418 g) with a yield of 40%.

[0025] The H NMR spectrum of compound 2 is shown in Figure 1 The single crystal structure of CN triazole compound 3 is shown in Figure 2 As shown, the nuclear magnetic resonance hydrogen spectrum of CN triazole compound 3 is as follows Figure 3 As shown, the C NMR spectrum of CN triazole compound 3 is as follows Figure 4 shown.

[0026] Example 2 CN triazole energetic high chloride salt 4, its structural formula is: ; The specific synthetic route is as follows: ; The specific synthesis steps are: CN-triazole compound 3 (0.261 g, 1 mmol) was dissolved in 70% HClO4 (10 mL) until it was completely dissolved. After reacting at room temperature for 0.5 h, solid precipitated. After filtration and washing with water (3 × 10 mL), white CN-triazole energetic high chloride salt 4 (0.248 g) was obtained with a yield of 88%.

[0027] The single crystal structure of CN triazole energetic high chloride salt 4 is shown in the figure Figure 5 The nuclear magnetic resonance hydrogen spectrum of the C-N linked triazole energetic perchlorate salt 4 is shown in FIG. 4. Figure 6 The nuclear magnetic resonance carbon spectrum of the C-N linked triazole energetic perchlorate salt 4 is shown in FIG. 5. Figure 7

[0028] Example 3 The C-N linked triazole energetic nitrate salt 5 has the structural formula: The specific synthesis route is as follows: The specific synthesis steps are as follows: The C-N linked triazole compound 3 (0.261 g, 1 mmol) was dissolved in 50% HNO3(10 mL), completely dissolved, and reacted at room temperature for 0.5 h, after which a solid was precipitated, filtered, and washed with water (3 x 10 mL) to obtain the yellow C-N linked triazole energetic nitrate salt 5 (0.220 g) in a yield of 90%.

[0029] The nuclear magnetic resonance hydrogen spectrum of the C-N linked triazole energetic nitrate salt 5 is shown in FIG. 6. Figure 8 The nuclear magnetic resonance carbon spectrum of the C-N linked triazole energetic nitrate salt 5 is shown in FIG. 7. Figure 9

[0030] Example 4 The C-N linked triazole energetic compound 6 has the structural formula: The specific synthesis route is as follows: The specific synthesis steps are as follows: At 0°C, 100% HNO3(2 mL) was added, and the C-N linked triazole compound 3 (0.261 g, 1 mmol) was slowly added, completely dissolved, and reacted in an ice bath for 0.5 h, after which the ice bath was removed, and the reaction was carried out at room temperature for 12 h, and then the reaction mixture was poured into crushed ice, and a yellow solid was precipitated, which was washed with water (3 x 10 mL) to obtain the C-N linked triazole energetic compound 6 (0.174 g, 55%).

[0031] The nuclear magnetic resonance hydrogen spectrum of the C-N linked triazole energetic compound 6 is shown in FIG. 8. Figure 10 The nuclear magnetic resonance carbon spectrum of the C-N linked triazole energetic compound 6 is shown in FIG. 9. Figure 11

[0032] <Performance parameter comparison> ​​​​​​The performance comparison of the synthesized C-N linked triazole energetic perchlorate 4, C-N linked triazole energetic nitrate 5, C-N linked triazole energetic compound 6 and existing energetic compounds TNT and TATB is shown in Table 1.

[0033] a. Thermal performance index: thermal decomposition temperature (onset temperature). Differential scanning calorimetry (DSC) was used to monitor the heat flow change of the sample heating process under nitrogen protection (5 ℃ min -1 ) condition, and the initial thermal decomposition temperature was determined according to the thermal effect change.

[0034] b. Physical performance index: crystal density. X-ray diffraction method (theoretical density calculated according to crystal structure parameters) was used for measurement.

[0035] c. Thermodynamic performance index: enthalpy of formation. Quantum chemistry calculation software Gaussian 09 RsvisionE.01 was used to calculate the molecular structure by using density functional theory (DFT) method, to simulate the energy change of the molecular formation process, and to obtain the enthalpy of formation.

[0036] d. Composition performance index: nitrogen and oxygen content. Element analysis method was used to detect the signal strength of nitrogen and oxygen elements by instrument, and to calculate the mass percentage in the compound.

[0037] e. Detonation performance index: detonation velocity. Explo5 v6.05 software was used to simulate and calculate the detonation velocity according to the parameters of the energetic compound.

[0038] f. Detonation performance index: detonation pressure. Explo5 v6.05 software was used to input the composition and structure parameters of the energetic compound, to simulate the detonation process by the built-in model and to calculate the detonation pressure.

[0039] g. Safety performance index: impact sensitivity. Standard BAM drop hammer method was used, the sample was placed under the drop hammer device, the sample was impacted by drop hammer with different drop height, the probability of explosion or violent reaction of the sample was counted, and the impact sensitivity was determined.

[0040] h. Safety performance index: friction sensitivity. BAM friction tester was used, specific pressure and friction force were applied to the sample, and the reaction was observed to determine the friction sensitivity.

[0041] Table 1 Test and calculated performance of compounds 4, 5, 6 and TNT and TATB Note: T d a : thermal decomposition temperature (onset temperature) nitrogen protection (DSC, 5 ℃ min-1 ) ; ρ b : crystal density; ∆ f H c : enthalpy of formation, calculated with Gaussian 09 (Rsvision E.01); v D e : detonation velocity - Explo5 v6.05; P f : detonation pressure, Explo5 v6.05; IS g : impact sensitivity; FS h : friction sensitivity.

[0042] It can be seen from the above table that compared with TNT, CN-triazole energetic high chloride salt 4, CN-triazole energetic nitrate 5, and CN-triazole energetic compound 6 have high energy density and detonation performance. The detonation velocity (8011~8512 m / s) and detonation pressure (26.89~33.87 GPa) of CN-triazole energetic high chloride salt 4, CN-triazole energetic nitrate 5, and CN-triazole energetic compound 6 are significantly higher than those of TNT (6881 m / s, 19.50 GPa). The detonation velocity (8512 m / s) of CN-triazole energetic compound 6 even exceeds that of TATB (8200 m / s). This is because the high nitrogen content of the CN-triazole skeleton increases the molecular energy density, and the nitration modification and condensed ring conjugated system enhance the molecular lethality, thereby improving the detonation performance. The thermal decomposition temperatures of CN-triazole energetic high chloride salt 4 (307℃) and CN-triazole energetic nitrate 5 (321℃) are higher than that of TNT (295℃) and close to that of TATB (360℃). In addition, the formation enthalpies of CN-triazole energetic high chloride salt 4, CN-triazole energetic nitrate 5, and CN-triazole energetic compound 6 (325.1~541.5 kJ / mol) are significantly higher than those of TNT (-59.3kJ / mol). This is because the rigid fused ring skeleton of CN-triazole energetic high chloride salt 4, CN-triazole energetic nitrate 5, and CN-triazole energetic compound 6 endows the molecules with high thermal stability, and the amino or nitramine groups reduce the ring strain through the conjugation effect, thereby delaying thermal decomposition. The impact sensitivity of CN-triazole energetic high-chloride salt 4 and CN-triazole energetic nitrate 5 (both 40 J) is significantly lower than that of TATB (112 J). Their friction sensitivity (both 360 N) is comparable to that of TATB, demonstrating their combined high energy and low sensitivity. The detonation performance of CN-triazole energetic compound 6 (detonation velocity: 8512 m / s, detonation pressure: 33.87 GPa) surpasses that of TATB, and its sensitivity (IS: 20 J) is significantly superior to that of TNT (15 J), demonstrating a synergistic optimization of energy and safety.

[0043] In summary, the CN-triazole energetic compound of the present invention achieves comprehensive optimization of energy density, thermal stability, and sensitivity through a rigid fused-ring backbone design and multi-site energetic modification. Its detonation performance surpasses that of TNT, its thermal stability approaches that of TATB, and its sensitivity is significantly lower than that of traditional high-energy materials.

[0044] The number of equipment and processing scales described herein are intended to simplify the description of the present invention. Applications, modifications, and variations of the C-N triazole energetic compounds and their preparation methods of the present invention will be readily apparent to those skilled in the art.

[0045] Although the embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the description and implementation methods. They can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to the specific details and illustrations shown and described herein.

Claims

1. A CN triazole compound, characterized in that: The CN triazole compound has a structure as shown in formula (I): （Ⅰ）。 2. The method of claim 1, wherein the CN triazole compound include: S1. Dissolve 2,4-dichloro-1,3,5-triazine in methanol, add 85% by mass of hydrazine hydrate, and react at room temperature for 4-8 hours. Collect the solid residue by filtration, wash with methanol, and dry to obtain a white solid product, 2,4-dihydrazine-1,3,5-triazine; wherein the molar volume ratio of 2,4-dichloro-1,3,5-triazine to hydrazine hydrate is 2-3:4 mol / L; S2, dissolving the solid product 2,4-dihydrazino-1,3,5-triazine obtained in step S1 in a mixed solvent of methanol and deionized water, adding an acetonitrile solution of cyanogen bromide, and reacting at 50° C. under reflux for 10 to 20 hours, rotary evaporating for 0.5 hours, volatilizing at room temperature, collecting the solid phase, washing with acetonitrile, and drying to obtain the CN-triazole compound; The molar ratio of 2,4-dihydrazino-1,3,5-triazine to cyanogen bromide is 1-3:5, and the volume ratio of methanol, deionized water and acetonitrile is 2:3:

4.

3. Use of the CN triazole compound as claimed in claim 1 in the preparation of energetic compounds.

4. CN triazole energetic compound or energetic salt, characterized in that The CN triazole energetic compound or energetic salt is prepared using the CN triazole compound according to claim 1 as a raw material, and the CN triazole energetic compound has a structure as shown in formula (II): （Ⅱ）； Wherein, R is a nitrogen-containing group.

5. The CN triazole energetic compound or energetic salt according to claim 4, wherein: R is -NHNO2.

6. The CN triazole energetic compound or energetic salt according to claim 4, wherein: R is amino, and the energetic salts are perchlorate and nitrate.

7. The method for preparing the CN triazole energetic compound or energetic salt according to claim 4, wherein: The CN-triazole compound of formula (I) is reacted under acidic conditions and then separated to obtain the CN-triazole energetic compound of formula (II).

8. The method for preparing the CN triazole energetic compound or energetic salt according to claim 7, wherein: When R is an amino group and the energetic salt is a perchlorate, the specific preparation method comprises: completely dissolving the CN triazole compound of formula (I) in 70% by mass perchloric acid, reacting at room temperature for 0.5 h, filtering, and then washing with water to obtain a white CN triazole energetic perchlorate; the molar volume ratio of the CN triazole compound of formula (I) to perchloric acid is 1:10-15 mol / L; When R is an amino group and the energetic salt is a nitrate, the specific preparation method comprises: completely dissolving the CN triazole compound of formula (I) in 50% by mass nitric acid, reacting at room temperature for 0.5 h, filtering, and then washing with water to obtain a yellow CN triazole energetic nitrate; the molar volume ratio of the CN triazole compound of formula (I) to nitric acid is 1:10-15 mol / L; Among them, the structural formula of CN triazole energetic perchlorate is ; The structural formula of CN triazole energetic nitrate is .

9. The method for preparing the CN triazole energetic compound or energetic salt according to claim 7, wherein: When R is -NHNO2, the specific preparation method includes: At 0°C, add the CN triazole compound of formula (I) to 100% nitric acid by mass, react in an ice bath for 0.5 h, remove the ice bath and react at room temperature for 12 h, pour crushed ice into the solid, filter and wash with water to obtain the CN triazole energetic compound, whose structural formula is ; wherein the molar volume ratio of the CN-triazole compound of formula (I) to nitric acid is 1:2~4 mol / L.

10. Use of the CN-triazole energetic compound or energetic salt according to any one of claims 4 to 6 in the preparation of energetic materials.

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