Tetrazine ring and guanidinium salt-based porous aromatic framework energetic material, and preparation method and application thereof

Abstract

The application provides a preparation method and application of a porous aromatic framework energetic material based on a tetrazine ring and guanidine salt, and belongs to the technical field of energetic materials; wherein the porous aromatic framework material EPAF-8 is formed by polymerization of 3,6-dichloro-1,2,4,5-tetrazine and an energetic monomer triaminoguanidine hydrochloride, and the porous aromatic framework energetic material EPAF-9 is formed by polymerization of 3,6-dichloro-1,2,4,5-tetrazine and an energetic monomer triaminoguanidine NTO salt. The porous aromatic framework EPAF-8 and / or EPAF-9 material provided by the application has high energy density and thermal stability, and has low sensitivity at the same time, and the preparation of a high-energy low-sensitivity energetic material is realized.

Description

Technical Field

[0001] This invention belongs to the field of energetic materials technology, and relates to porous aromatic framework energetic materials based on tetrazine rings and guanidine salts, their preparation methods and applications. Background Technology

[0002] Explosives, as a typical energetic material, have wide applications in both military and civilian fields. However, high-energy explosives are often very sensitive to external stimuli, and safety issues severely restrict their practical application. To address these issues, researchers have made great efforts to make high energy and low sensitivity compatible in energetic materials, including: (1) molecular-level design, including the introduction of functional groups (such as nitro, amino, etc.), merging of various nitrogen heterocycles, salt formation, stereochemical effects of molecular structure, hydrogen bonding strategies, etc.; (2) eutectic design of energetic material molecules; (3) preparation of energetic composite materials based on polymer or other substances coating; (4) development of new energetic materials, including energetic ionic liquids, energetic polymers, etc. These research strategies have achieved certain results and greatly enriched the types of energetic materials. However, the complex synthesis steps, yield and cost, crystallization difficulty, dispersion uniformity, etc., have greatly increased the difficulty of research work. At the same time, the coating of non-energetic components will also reduce the energy density and detonation performance of energetic materials.

[0003] Therefore, exploring design and research approaches for high-energy, low-sensitivity energetic materials to advance the field of energetic materials is of significant scientific importance. In recent years, domestic and international experts and scholars have conducted research on porous materials and other energetic materials. Majano et al. packed the high-density energetic material FOX-7 into the pores of pure silica MFI-type zeolite nanocrystals, preventing FOX-7 from decomposing explosively at temperatures approximately 100°C above the explosion temperature. In 2013, Professor Pang Siping's team at Beijing Institute of Technology reported for the first time a cationic energetic metal-organic framework material with a three-dimensional structure; its excellent detonation performance gives it great potential application value in the field of energetic materials. In 2016, Professor Wang Bo's research group and collaborators used the classic MOF (HKUST-1) as a conductive framework precursor. The porous carbon material formed after carbonization was combined with in-situ synthesized copper azide, solving the problem of high electrostatic sensitivity of copper azide, while exhibiting good flame sensitivity, high density, high positive heat of formation, and excellent initiation capability. Furthermore, in 2019, Titi et al. proposed a strategy to induce the spontaneous combustion behavior of MOFs. By introducing acetylene or ethylene substituents into ZIFs as triggers for spontaneous combustion, they were able to achieve and adjust the ability to spontaneously combust, making spontaneously combustible MOFs a promising candidate for safer and more environmentally friendly propellants. It is evident that porous materials play a crucial role in the development of energetic materials and possess significant research value.

[0004] Porous aromatic frameworks (PAFs) are a new type of porous material composed of aromatic building blocks, and have experienced rapid development over the past decade. Aromatic building blocks exhibit a rich variety of structures and good chemical reactivity. By designing the structural units and modifying the PAF framework, the structure and pore properties of PAFs can be controlled, resulting in different properties and applications in various fields. For example, existing technologies such as CN113278162A have conducted preliminary research on porous aromatic framework energetic materials (EPAFs) and their preparation methods. However, there is still room for improvement in the specific detonation performance of the prepared materials. Furthermore, how to further improve the preparation process of porous aromatic framework energetic materials to make production more convenient and faster, while also achieving both economic efficiency and practicality, is a consistent goal pursued by the industry. Summary of the Invention

[0005] In view of this, the present invention provides porous aromatic framework energetic materials based on tetrazine rings and guanidine salts, their preparation methods, and applications. Using tetrazine rings and guanidine salts as raw materials, porous aromatic framework energetic materials EPAF-8 and / or EPAF-9 are synthesized. The resulting products exhibit high energy density and thermal stability, while also possessing low sensitivity, thus realizing the preparation of high-energy, low-sensitivity energetic materials. Furthermore, the preparation process has been optimized and improved, simplifying the steps to obtain the final products. The entire preparation process is characterized by mild conditions and simple operation, demonstrating strong potential for industrial application.

[0006] To achieve the above effects, the first aspect of the present invention provides a method for preparing a porous aromatic framework energetic material based on a tetrazine ring and a guanidine salt. The porous aromatic framework energetic material is formed by polymerization of a tetrazine ring and a guanidine salt. The method comprises the following specific steps: S1: Weigh a certain amount of a tetrazine ring and a guanidine salt into a double-necked flask, add a solvent and N,N-diisopropylethylamine to obtain a mixed solution, and sonicate the mixed solution; S2: Under nitrogen protection, stir the ultrasonically treated mixed solution obtained in S1 in an oil bath at 60-180°C for 2-4 days, and filter the obtained product; S3: Wash and dry the filtered product obtained in S2 to obtain the porous aromatic framework material.

[0007] Optionally, the tetrazine ring in S1 is 3,6-dichloro-1,2,4,5-tetrazine; and the guanidine salt is triaminoguanidine hydrochloride or triaminoguanidine NTO salt.

[0008] Optionally, the guanidine salt is triaminoguanidine hydrochloride, and the mass ratio of 3,6-dichloro-1,2,4,5-tetraazine to triaminoguanidine hydrochloride is 23:14; or, the guanidine salt is triaminoguanidine NTO salt, and the mass ratio of 3,6-dichloro-1,2,4,5-tetraazine to triaminoguanidine NTO salt is 23:24.

[0009] Optionally, the solvent in S1 is at least one of toluene, mesitylene, o-dichlorobenzene, or N,N-dimethylacetamide.

[0010] Optionally, the solvent in S1 is mesitylene, and the volume ratio of mesitylene to N,N-diisopropylethylamine in the mixed solution is 5:1.

[0011] Optionally, the washing and drying process of the product obtained by filtration in S2 described in S3 specifically includes: washing the product obtained by filtration in S2 with dichloromethane, ethanol, and purified water in sequence, and then vacuum drying at 80°C overnight.

[0012] In a second aspect, the present invention provides a porous aromatic framework energetic material based on a tetrazine ring and a guanidine salt, wherein the porous aromatic framework energetic material is EPAF-8, and its specific structure is as follows:

[0013]

[0014] A third aspect of the present invention provides another porous aromatic framework energetic material based on a tetrazine ring and a guanidine salt, wherein the porous aromatic framework energetic material is EPAF-9, and its specific structure is as follows:

[0015]

[0016] Optionally, the porous aromatic framework energetic material of the tetrazine ring and guanidine salt is prepared by the above preparation method.

[0017] In a fourth aspect, the present invention provides an application of one or more porous aromatic framework energetic materials based on tetrazine rings and guanidine salts in the field of energetic materials.

[0018] The beneficial effects of this invention are as follows:

[0019] (1) The porous aromatic framework energetic materials EPAF-8 and / or EPAF-9 based on tetrazine ring and guanidine salt have cationic charge characteristics, high energy density, high thermal stability and stability, and are energetic materials with great application potential.

[0020] (2) The conditions for preparing porous aromatic framework materials are mild, the process is simple and easy to operate, which optimizes the existing preparation process and ensures a high yield of the final product, meeting the requirements of actual industrial production.

[0021] Furthermore, additional advantages, objects, and features of the invention will be set forth in part in the description which follows, and will also become apparent in part to those skilled in the art upon studying the following text, or may be learned by practice of the invention. The objects and other advantages of the invention can be realized and obtained by means of the structures and method steps specifically pointed out in the written description, claims, and drawings.

[0022] Those skilled in the art will understand that the objectives and advantages achievable with the present invention are not limited to those specifically described above, and that the above and other objectives achievable with the present invention will become clearer from the following detailed description. Attached Figure Description

[0023] The accompanying drawings, which are provided to further illustrate the invention and form part of this application, are not intended to limit the scope of the invention.

[0024] Figure 1 The Fourier transform infrared (IR) spectrum of the energetic material EPAF-8 prepared in Example 1 of this invention is shown below.

[0025] Figure 2 This is a TG-DSC curve of the energetic material EPAF-8 prepared in Example 1 of the present invention.

[0026] Figure 3 The Fourier transform infrared (IR) spectrum of the energetic material EPAF-9 prepared in Example 5 of this invention is shown.

[0027] Figure 4 This is a TG-DSC curve of the energetic material EPAF-9 prepared in Example 5 of the present invention. Detailed Implementation

[0028] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the embodiments and accompanying drawings. The illustrative embodiments and descriptions of this invention are used to explain the invention, but are not intended to limit the invention. It should also be noted that, in order to avoid obscuring the invention with unnecessary details, only structures and / or processing steps closely related to the solutions according to the invention are shown in the accompanying drawings, while other details not closely related to the invention are omitted.

[0029] It should be emphasized that the term "including / comprises" as used herein refers to the presence of a feature, element, step, or component, but does not exclude the presence or addition of one or more other features, elements, steps, or components.

[0030] This invention provides a first aspect of a method for preparing a porous aromatic framework energetic material based on a tetrazine ring and a guanidine salt. The porous aromatic framework energetic material is formed by the polymerization of a tetrazine ring and a guanidine salt. The method comprises the following specific steps: S1: Weigh a certain amount of a tetrazine ring and a guanidine salt into a double-necked flask, add a solvent and N,N-diisopropylethylamine to obtain a mixed solution, and then sonicate the mixed solution; S2: Under nitrogen protection, stir the ultrasonically treated mixed solution obtained in S1 in an oil bath at 60-180°C for 2-4 days, and filter the obtained product; S3: Wash and dry the filtered product obtained in S2 to obtain the porous aromatic framework material.

[0031] Tetraazine rings, as typical high-nitrogen, low-carbon-hydrogen materials, exhibit excellent performance in terms of energy density and combustion efficiency. Tetraazine rings have multiple synthetic routes, simple synthesis processes, short reaction times, and are environmentally friendly with low production costs. Furthermore, tetraazine rings possess high reactivity and readily covalently combine with other substances, giving them greater flexibility and versatility in the preparation of energetic materials. The choice of guanidine salts to react with tetraazine rings fully considers their high-energy characteristics. During the preparation of the target product of this invention, a co-precipitation reaction can occur fully with the tetraazine ring material, allowing for better control of the reactant composition and structure, thus achieving precise preparation.

[0032] Furthermore, it should be noted that existing preparation techniques often involve first obtaining a porous aromatic framework energetic material through a reaction, and then performing a composite reaction between the porous aromatic framework energetic material and a single-element explosive (such as NTO) to form a composite energetic material. In this case, the porous aromatic framework energetic material is an intermediate product, and its preparation purpose is often aimed at improving the high sensitivity and strong corrosion characteristics of existing single-element explosives, not the final product. The preparation method proposed in this invention, however, uses a direct composite reaction between a tetrazine ring and a guanidine salt. Through a more convenient reaction process, it directly prepares a composite energetic material with similar functions to existing porous aromatic framework energetic composite materials, and even with superior energy density and combustion / explosion performance. This undoubtedly simplifies the existing preparation process and is beneficial for the industrial application of related materials.

[0033] Optionally, the tetrazine ring in S1 is 3,6-dichloro-1,2,4,5-tetrazine; the guanidine salt is triaminoguanidine hydrochloride or triaminoguanidine NTO salt.

[0034] Optionally, the guanidine salt is triaminoguanidine hydrochloride, with a mass ratio of 3,6-dichloro-1,2,4,5-tetraazine to triaminoguanidine hydrochloride of 23:14; or, the guanidine salt is triaminoguanidine NTO salt, with a mass ratio of 3,6-dichloro-1,2,4,5-tetraazine to triaminoguanidine NTO salt of 23:24.

[0035] Optionally, the solvent in S1 is preferably a high-boiling-point solvent with good solubility. It can be used alone or in combination to achieve the preparation. The specific solvent component can be at least one of toluene, mesitylene, o-dichlorobenzene or N,N-dimethylacetamide.

[0036] Optionally, the solvent in S1 is mesitylene, and the volume ratio of mesitylene to N,N-diisopropylethylamine in the mixed solution is 5:1. N,N-diisopropylethylamine is used here as an "acid-binding agent," its main function being to neutralize the acid produced in the reaction, allowing the reaction to proceed in the forward direction and thus promoting the synthesis. Similarly, if toluene, o-dichlorobenzene, or N,N-dimethylacetamide or one or more of these are chosen to participate in the reaction, their roles in the reaction process are essentially the same or similar to those of mesitylene.

[0037] Optionally, the washing and drying process of the product obtained from the filtration in S2 in S3 specifically includes: washing the product obtained from the filtration in S2 with dichloromethane, ethanol, and purified water in sequence, and then vacuum drying at 80°C overnight.

[0038] It is worth noting that a certain order should be followed when using different solvents for washing. A reasonable expectation is to use dichloromethane to remove the tetrazine monomer, ethanol to remove the remaining dichloromethane solvent from the previous step, and finally water to remove the guanidine salt monomer. The dichloromethane and water must be separated by ethanol due to their immiscibility. In reality, the actual impact of the washing order on yield and other results is unclear; the main effect is on the purity of the product after the washing process. Based on the aforementioned point, the porous aromatic framework energetic material prepared by this invention is a final product, not an intermediate product. To achieve industrial production, a high purity of the product is required, making the above-mentioned washing sequence essential.

[0039] In a second aspect, the present invention provides a porous aromatic framework energetic material based on a tetrazine ring and a guanidine salt, wherein the porous aromatic framework energetic material is EPAF-8, and its specific structure is as follows:

[0040]

[0041] A third aspect of the present invention provides another porous aromatic framework energetic material based on a tetrazine ring and a guanidine salt, wherein the porous aromatic framework energetic material is EPAF-9, and its specific structure is as follows:

[0042]

[0043] Optionally, the porous aromatic framework energetic material of tetrazine ring and guanidine salt is prepared by the above preparation method.

[0044] In a fourth aspect, the present invention provides an application of one or more porous aromatic framework energetic materials based on tetrazine rings and guanidine salts in the field of energetic materials.

[0045] The present invention will be further described in detail below through specific embodiments. The following embodiments are merely descriptive and not limiting, and should not be used to limit the scope of protection of the present invention.

[0046] Furthermore, this invention aims to design and synthesize novel energetic porous aromatic frameworks (EPAFs) materials. Utilizing the properties of PAFs, the resulting products exhibit diverse high-porosity structures, ultra-high chemical stability, and the ability to withstand various harsh conditions such as strong acids, strong alkalis, solvents, heat, and humidity. This provides technical and theoretical reserves for the future development of energetic and porous materials chemistry, and has great potential application value.

[0047] Example 1

[0048] This invention discloses the synthetic route and structure of EPAF-8, a porous aromatic framework energetic material, using the energetic monomers triaminoguanidine hydrochloride and 3,6-dichloro-1,2,4,5-tetraazine as raw materials:

[0049]

[0050] 2.3 g of 3,6-dichloro-1,2,4,5-tetraazine (15.0 mmol) and 1.4 g of triaminoguanidine hydrochloride (10.0 mmol) were weighed into a 250 mL double-necked flask, and 50 mL of mesitylene and 10 mL of N,N-diisopropylethylamine (DIPEA) were added. The mixture was sonicated for a period of time. Under nitrogen protection, the mixture was stirred in an oil bath at 180 °C for 2 days. The product was filtered. The filtered product was washed with dichloromethane, ethanol, and purified water, respectively, and dried under vacuum at 80 °C overnight to obtain the porous aromatic skeleton EPAF-8 material with a yield of 87.5%.

[0051] Fourier transform infrared spectroscopy analysis was performed on the porous aromatic framework energetic material EPAF-8 prepared in Example 1, see... Figure 1 .

[0052] Depend on Figure 1 It can be seen that the peak at 880 cm⁻¹ is related to the stretching vibration of C-Cl on 3,6-dichloro-1,2,4,5-tetraazine, while the peaks at 3320 cm⁻¹ and 3200 cm⁻¹ belong to the characteristic vibrations of the amino group on triaminoguanidine hydrochloride. The disappearance of these characteristic peaks in the product indicates that the monomer has reacted sufficiently, proving the successful synthesis of EPAF-8.

[0053] TG-DSC analysis was performed on the porous aromatic framework energetic material EPAF-8 prepared in Example 1. The results are shown in the figure. Figure 2 .

[0054] The TG-DSC curve analysis results show that EPAF-8 has excellent thermal stability and exhibits a clear exothermic signal peak, which has potential application value in the field of energetic materials.

[0055] Table 1 shows the impact sensitivity and calculated theoretical detonation performance of the energetic material EPAF-8 prepared according to Example 1 of this invention. As can be seen from the table, the energetic material EPAF-8 exhibits low sensitivity and very good energetic characteristics. Compared with the prior art, the energetic material EPAF-8 produced using the preparation method of this invention shows a significant improvement in key detonation performance aspects. This is due to the excellent properties of its reactants and the effective improvement of related preparation processes.

[0056] Table 1. Impact sensitivity and calculated theoretical detonation performance of the energetic material EPAF-8 in Example 1

[0057]

[0058] Example 2

[0059] 2.3 g of 3,6-dichloro-1,2,4,5-tetraazine (15.0 mmol) and 1.4 g of triaminoguanidine hydrochloride (10.0 mmol) were weighed into a 250 mL double-necked flask, and 50 mL of mesitylene and 10 mL of N,N-diisopropylethylamine (DIPEA) were added. The mixture was sonicated for a period of time. Under nitrogen protection, the mixture was stirred in an oil bath at 150 °C for 2 days. The product was filtered. The filtered product was washed with dichloromethane, ethanol, and purified water, respectively, and dried under vacuum at 80 °C overnight to obtain the porous aromatic framework EPAF-8 material with a yield of 85.5%.

[0060] Example 3

[0061] 2.3 g of 3,6-dichloro-1,2,4,5-tetraazine (15.0 mmol) and 1.4 g of triaminoguanidine hydrochloride (10.0 mmol) were weighed into a 250 mL double-necked flask, and 50 mL of mesitylene and 10 mL of N,N-diisopropylethylamine (DIPEA) were added. The mixture was sonicated for a period of time. Under nitrogen protection, the mixture was stirred in an oil bath at 180 °C for 3 days. The product was filtered. The filtered product was washed with dichloromethane, ethanol, and purified water, respectively, and dried under vacuum at 80 °C overnight to obtain the porous aromatic framework EPAF-8 material with a yield of 89.5%.

[0062] Example 4

[0063] 4.6 g of 3,6-dichloro-1,2,4,5-tetraazine (30.0 mmol) and 2.8 g of triaminoguanidine hydrochloride (20.0 mmol) were weighed into a 250 mL double-necked flask, and 50 mL of mesitylene and 10 mL of N,N-diisopropylethylamine (DIPEA) were added. The mixture was sonicated for a period of time. Under nitrogen protection, the mixture was stirred and reacted in an oil bath at 150 °C for 2 days. The product was filtered. The filtered product was washed with dichloromethane, ethanol, and purified water, respectively, and dried under vacuum at 80 °C overnight to obtain the porous aromatic framework EPAF-8 material with a yield of 83.0%.

[0064] Example 5

[0065] This invention presents the synthetic route and structure of EPAF-9, a porous aromatic framework energetic material, synthesized from energetic monomers triaminoguanidine (NTO) and 3,6-dichloro-1,2,4,5-tetraazine.

[0066]

[0067] 2.3 g of 3,6-dichloro-1,2,4,5-tetraazine (15.0 mmol) and 2.4 g of triaminoguanidine NTO salt (10.0 mmol) were weighed into a 250 mL double-necked flask. 50 mL of mesitylene and 10 mL of N,N-diisopropylethylamine (DIPEA) were added, and the mixture was sonicated for a period of time. Under nitrogen protection, the mixture was stirred and reacted in an oil bath at 180 °C for 2 days. The product was filtered, washed with dichloromethane, ethanol, and purified water, respectively, and dried under vacuum at 80 °C overnight to obtain the porous aromatic skeleton EPAF-9 material with a yield of 84.5%.

[0068] Fourier transform infrared spectroscopy analysis was performed on the porous aromatic framework energetic material EPAF-9 prepared in Example 5, see... Figure 3 .

[0069] Depend on Figure 3 It can be seen that 880cm -1 The peak at 3320 cm⁻¹ is related to the stretching vibration of C-Cl on 3,6-dichloro-1,2,4,5-tetraazine, while the peak at 3320 cm⁻¹ is related to the stretching vibration of C-Cl on 3,6-dichloro-1,2,4,5-tetraazine. -1 3200cm -1 The peaks at [specific location] are attributed to the characteristic vibrations of the amino group on the triaminoguanidine NTO salt. The disappearance of these characteristic peaks in the product indicates that the monomer has reacted sufficiently, confirming the successful synthesis of EPAF-9.

[0070] TG-DSC analysis was performed on the porous aromatic framework energetic material EPAF-9 prepared in Example 5, see [the results are missing in the original text]. Figure 4 .

[0071] The TG-DSC curve analysis results show that EPAF-9 has excellent thermal stability and exhibits a clear exothermic signal peak, which has potential application value in the field of energetic materials.

[0072] Table 2 shows the impact sensitivity and calculated theoretical detonation performance of the energetic material EPAF-9 prepared in Example 5 of this invention. As can be seen from the table, the energetic material EPAF-9 exhibits low sensitivity and very good energetic characteristics. Compared with the prior art, the energetic material EPAF-9 produced using the preparation method of this invention shows a significant improvement in key detonation performance aspects. This is due to the excellent properties of its reactants and the effective improvement of related preparation processes.

[0073] Table 2. Impact sensitivity and calculated theoretical detonation performance of energetic material EPAF-9 in Example 5

[0074]

[0075] Example 6

[0076] 2.3 g of 3,6-dichloro-1,2,4,5-tetraazine (15.0 mmol) and 2.4 g of triaminoguanidine NTO salt (10.0 mmol) were weighed into a 250 mL double-necked flask. 50 mL of mesitylene and 10 mL of N,N-diisopropylethylamine (DIPEA) were added, and the mixture was sonicated for a period of time. Under nitrogen protection, the mixture was stirred and reacted in an oil bath at 150 °C for 2 days. The product was filtered, washed with dichloromethane, ethanol, and purified water, respectively, and dried under vacuum at 80 °C overnight to obtain the porous aromatic framework EPAF-9 material with a yield of 82.0%.

[0077] Example 7

[0078] 2.3 g of 3,6-dichloro-1,2,4,5-tetraazine (15.0 mmol) and 2.4 g of triaminoguanidine NTO salt (10.0 mmol) were weighed into a 250 mL double-necked flask. 50 mL of mesitylene and 10 mL of N,N-diisopropylethylamine (DIPEA) were added, and the mixture was sonicated for a period of time. Under nitrogen protection, the mixture was stirred and reacted in an oil bath at 180 °C for 3 days. The product was filtered, washed with dichloromethane, ethanol, and purified water, respectively, and dried under vacuum at 80 °C overnight to obtain the porous aromatic framework EPAF-9 material with a yield of 86.0%.

[0079] Example 8

[0080] 4.6 g of 3,6-dichloro-1,2,4,5-tetraazine (30.0 mmol) and 4.8 g of triaminoguanidine NTO salt (20.0 mmol) were weighed into a 250 mL double-necked flask. 50 mL of mesitylene and 10 mL of N,N-diisopropylethylamine (DIPEA) were added, and the mixture was sonicated for a period of time. Under nitrogen protection, the mixture was stirred and reacted in an oil bath at 150 °C for 2 days. The product was filtered, washed with dichloromethane, ethanol, and purified water, respectively, and dried under vacuum at 80 °C overnight to obtain the porous aromatic skeleton EPAF-9 material with a yield of 81.0%.

[0081] Aromatic building blocks possess a rich variety of structures and excellent chemical reactivity. By designing the building blocks and modifying the PAF framework, the structure and pore properties of PAFs can be controlled, resulting in different properties applicable to various fields. Therefore, designing and synthesizing novel energetic porous aromatic frameworks (EPAFs) can provide technical and theoretical reserves for the future development of energetic and porous materials chemistry. The EPAFs provided by this invention have diverse high-porosity structures and ultra-high chemical stability, capable of withstanding various harsh conditions such as strong acids, strong bases, solvents, heat, and humidity. The improved preparation process is simpler and easier to operate, enabling the convenient and rapid acquisition of energetic materials that meet purity standards. The yield meets expectations and can satisfy the requirements of actual industrial production. Furthermore, the synthesized materials exhibit significantly improved heat dissipation properties and possess great potential application value.

[0082] The above detailed description further illustrates the purpose, technical solution, and beneficial effects of the invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a porous aromatic framework energetic material based on a tetrazine ring and a guanidine salt, wherein the porous aromatic framework energetic material is formed by polymerization of a tetrazine ring and a guanidine salt, characterized in that, The specific steps include the following: S1: Weigh a certain amount of tetrazine ring and guanidine salt into a double-necked bottle, add solvent and N,N-diisopropylethylamine to obtain a mixed solution, and then sonicate the mixed solution. S2: Under nitrogen protection, the ultrasonically treated mixed solution obtained in S1 is stirred and reacted in an oil bath at 60-180℃ for 2-4 days, and the obtained product is filtered. S3: The product obtained from the filtration in S2 is washed and dried to obtain a porous aromatic framework material. The tetrazine ring in S1 is 3,6-dichloro-1,2,4,5-tetrazine; the guanidine salt is triaminoguanidine hydrochloride or triaminoguanidine NTO salt; The guanidine salt is triaminoguanidine hydrochloride, and the mass ratio of 3,6-dichloro-1,2,4,5-tetraazine to triaminoguanidine hydrochloride is 23:14; or, The guanidine salt is a triaminoguanidine NTO salt, and the mass ratio of the 3,6-dichloro-1,2,4,5-tetraazine to the triaminoguanidine NTO salt is 23:

24.

2. The preparation method according to claim 1, characterized in that: The solvent mentioned in S1 is at least one of toluene, mesitylene, o-dichlorobenzene, or N,N-dimethylacetamide.

3. The preparation method according to claim 2, characterized in that: The solvent in S1 is mesitylene, and the volume ratio of mesitylene to N,N-diisopropylethylamine in the mixed solution is 5:

1.

4. The preparation method according to claim 1, characterized in that: The washing and drying process of the product obtained from filtration in S2, as described in S3, specifically includes: The product obtained by filtration in S2 was washed sequentially with dichloromethane, ethanol, and purified water, and then dried under vacuum at 80°C overnight.

5. A porous aromatic framework energetic material based on a tetrazine ring and a guanidine salt, prepared by the preparation method according to any one of claims 1-4, characterized in that, The porous aromatic framework energetic material is EPAF-8, and its specific structure is as follows: EPAF-8.

6. A porous aromatic framework energetic material based on a tetrazine ring and a guanidine salt, prepared by the preparation method according to any one of claims 1-4, characterized in that, The porous aromatic framework energetic material is EPAF-9, and its specific structure is as follows: EPAF-9.

7. The application of a porous aromatic framework energetic material based on a tetrazine ring and a guanidine salt according to claim 5 or 6 in the field of energetic materials.

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