Spherical flower cluster 4, 4 ', 6, 6'-tetraazido hydrazine-1, 3, 5-triazine particles and preparation method of spherical flower cluster 4, 4 ', 6, 6'-tetraazido hydrazine-1, 3, 5-triazine particles

Abstract

The invention discloses a spherical flower cluster 4, 4 ', 6, 6'-tetraazido hydrazine-1, 3, 5-triazine particle and a preparation method thereof.A one-step simple solvent-anti-solvent method is adopted, 4, 4 ', 6, 6'-tetraazido hydrazine-1, 3, 5-triazine is dissolved in an organic solvent, and a triazine solution is obtained; the method comprises the following steps: adding a triazine solution and a surfactant solution into water to obtain a turbid liquid; and filtering, washing and drying the turbid liquid to obtain the spherical flower cluster 4, 4 ', 6, 6'-tetraazido hydrazine-1, 3, 5-triazine particles. According to the invention, a solvent-anti-solvent crystal morphology regulation and control method is combined with the surfactant, and the adsorption effect of the crystal surface of the surfactant is utilized to inhibit the growth of the crystal on one hand, inhibit the coalescence of the crystal on the other hand, avoid the further agglomeration of the formed spherical flower cluster and promote the stable dispersion of the crystal. The spherical flower cluster TAHT prepared by the method is consistent in morphology, uniform in particle size and free of agglomeration, and the preparation method is simple and easy for industrial production.

Description

Technical Field

[0001] This invention belongs to the field of energetic materials technology, and specifically relates to a spherical flower cluster 4,4',6,6'-tetraazidohydrazine-1,3,5-triazine particle and its preparation method. Technical Background

[0002] 4,4',6,6'-Tetraazidohydrazine-1,3,5-triazine (TAHT) is a novel high-nitrogen energetic material. Its molecular structure contains four azido groups and two triazine rings, with a nitrogen content of 79.2%. It exhibits a single crystal form, high energy (thermal decomposition exothermic up to 2021 J / g), good thermal stability (decomposition temperature >180℃), non-hygroscopicity, low sensitivity, and good compatibility with commonly used energetic materials. It can be applied to propellants, gas generators, propellants, and pyrotechnics, significantly improving burning rate, reducing burning temperature, and increasing gas production without reducing the energy of the formulation system [1-4]. TAHT has inexpensive and widely available raw materials, and can be synthesized in high yield through a simple two-step aqueous phase reaction. In recent years, with in-depth research and optimization by researchers, the synthesis route of TAHT has gradually matured, achieving a synthesis yield of kilograms, and the production process is green and environmentally friendly [5,6]. However, currently synthesized TAHT has irregular morphology and a wide particle size distribution (see...). Figure 1 This makes it prone to forming local hot spots under external forces, which can lead to accidental detonation of the material and reduce its safety, thus affecting its application in propellants and explosives.

[0003] References:

[0004] [1]My Hang V.Huynh,Michael A.Hiskey,et al.Polyazido high-nitrogencompounds:hydrazo-and azo-1,3,5-triazine[J].Angewandte Chemie,International Edition,2004,43(37):4924-4927.

[0005] [2]Li Xiaotong,Li Shenghua,Pang Siping,Li,et al.A new efficient route for the synthesis of 4,4'6,6'-tetra(azido)azo-1,3,5-triazine[J].ChineseChemical Letters,2007,18(9):1037.

[0006] [3] Li Xiaotong, Pang Siping, Yu Yongzhong, et al. Synthesis of high-nitrogen compound 4,4',6,6'-tetraazidoazo-1,3,5-triazine [J]. Energetic Materials, 2007, 15(5):485-489.

[0007] [4] Li Yuchuan, Zhang Xuejiao, Fu Geng, et al. Synthesis, characterization and thermal decomposition of 4,4',6,6'-tetraazidoazo-1,3,5-triazine (TAAT) [J]. Organic Chemistry, 2011, 31(9): 1484-1489.

[0008] [5]Tang Ruimin, Wang Chen, Zhu Maoguo, et al. Pyrolysis behavior and mechanism of high nitrogen compound 4,4',6,6'-tetra(azido)hydrazine-1,3,5-triazine[J]. Energetic Materials Frontiers, 2025, 6(2): 195-201.

[0009] [6] Yang Jianxing, Tang Ruimin, Xiao Yijie, et al. Compatibility of nitrogen-rich energetic materials TAHT and GZT with propellant matrix materials [J]. Explosive Materials, 2025, 54(3):1-7. Summary of the Invention

[0010] To overcome the problems of TAHT in the prior art having no fixed morphology and uneven particle size, the present invention aims to provide spherical flower cluster 4,4',6,6'-tetraazidohydrazine-1,3,5-triazine particles and a preparation method thereof. The spherical flower cluster TAHT obtained by this preparation has a uniform particle size, is evenly dispersed, and has no agglomeration.

[0011] To achieve the above objectives, the present invention employs the following technical solution:

[0012] A method for preparing spherical flower cluster 4,4',6,6'-tetraazidohydrazine-1,3,5-triazine particles includes the following steps:

[0013] 4,4',6,6'-tetraazidohydrazine-1,3,5-triazine was dissolved in an organic solvent to obtain a triazine solution;

[0014] A suspension was obtained by adding a triazine solution and a surfactant solution to water.

[0015] The suspension was filtered, washed, and dried to obtain spherical flower clusters of 4,4',6,6'-tetraazidohydrazine-1,3,5-triazine particles.

[0016] Furthermore, the organic solvent is dimethyl sulfoxide.

[0017] Furthermore, the dissolution of 4,4',6,6'-tetraazidohydrazine-1,3,5-triazine in an organic solvent was carried out at 25–45°C and a stirring speed of 600–800 r / min.

[0018] Furthermore, the surfactant is polyvinylpyrrolidone.

[0019] Furthermore, the concentration of the surfactant solution is 0.02 wt% to 0.05 wt%.

[0020] Furthermore, the triazine solution and surfactant solution are added to the water. Specifically, the triazine solution and surfactant solution are added dropwise to the water at 25–35°C and a stirring speed of 500–1000 r / min.

[0021] Furthermore, the dropping rate was 5–10 mL / min, and the mixture was stirred for 30 min after the dropping was completed.

[0022] Furthermore, the ratio of 4,4',6,6'-tetraazidohydrazine-1,3,5-triazine to organic solvent is 100–400 mg: 5 mL.

[0023] Furthermore, the mass ratio of organic solvent to water is 1:(2-4).

[0024] A spherical flower cluster 4,4',6,6'-tetraazidohydrazine-1,3,5-triazine particle, wherein the particle size ranges from 7 μm to 40 μm.

[0025] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0026] This invention uses TAHT as a raw material and employs a simple solvent-antisolvent crystal morphology control method. Using surfactants and organic solvents, spherical TAHT particles with different morphologies and particle sizes can be prepared. The solvent-antisolvent method utilizes the difference in solubility of substances in different solutions to instantly create a high and uniform spatial supersaturation, causing TAHT to precipitate as ultrafine crystals. Simultaneously, the shear force from the high-speed rotation of the solution causes the crystal particles to aggregate into a regular morphology. Furthermore, this invention combines the solvent-antisolvent crystal morphology control method with surfactants. The adsorption effect of surfactants on the crystal surface inhibits crystal growth and aggregation, preventing further agglomeration of the formed spherical clusters and promoting stable crystal dispersion.

[0027] Furthermore, PVP is used as the surfactant. Because PVP contains a strongly polar lactam group in its molecular structure, it has good solubility in water and dimethyl sulfoxide, making it an ideal surfactant.

[0028] The spherical TAHT particles obtained by this invention have the characteristics of uniform morphology and adjustable particle size. At the same time, the spherical structure formed by the interlacing of plates has a high specific surface area and abundant sites on the surface, providing good conditions for subsequent surface modification and doping. Attached Figure Description

[0029] Figure 1 Here is a SEM image of the raw material TAHT;

[0030] Figure 2 Here is a SEM image of the spherical flower cluster TAHT from Example 1;

[0031] Figure 3 for Figure 2 Enlarged view of a section of the THAT spherical flower cluster;

[0032] Figure 4 SEM images of TAHT crystallized at different temperatures; where a is an SEM image of TAHT in spherical flower clusters from Example 2; b is an SEM image of TAHT in spherical flower clusters from Example 2.

[0033] Figure 5 The image shown is a DSC diagram of the spherical flower cluster TAHT from Example 7.

[0034] Figure 6 The images are SEM images of TAHT obtained in Comparative Example 1 and Comparative Example 2, where a is the SEM image of TAHT obtained in Comparative Example 1 and b is the SEM image of TAHT obtained in Comparative Example 2. Specific implementation methods

[0035] To facilitate understanding of the present invention, a more complete description will be given below with reference to the accompanying drawings. Preferred embodiments of the invention are shown in the drawings. However, the invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of the invention.

[0036] This invention proposes a method for preparing spherical flower clusters 4,4',6,6'-tetraazidohydrazine-1,3,5-triazine particles. The method utilizes a solvent-antisolvent approach, using dimethyl sulfoxide as the solvent, water as the antisolvent, and PVP as the surfactant to synthesize spherical flower clusters TAHT.

[0037] Specifically, the preparation method of the present invention is as follows: the raw material TAHT (prepared according to the method in the reference: Tang Ruimin, Wang Chen, Zhu Maoguo, et al. Pyrolysis behavior and mechanism of highnitrogen compound 4,4',6,6'-tetra(azido)hydrazine-1,3,5-triazine[J]. Energetic Materials Frontiers, 2025, 6(2): 195-201.) is dissolved in an organic solvent, and stirred under constant temperature water bath heating until TAHT is completely dissolved. After filtering out impurities and undissolved particles in the solution, solution A is obtained; wherein, the organic solvent is dimethyl sulfoxide; the constant temperature is 25-45℃, and the stirring speed is 600-800r / min.

[0038] The surfactant PVP was dispersed in water and mixed evenly under stirring and ultrasonic vibration to obtain solution B, with a PVP mass fraction of 0.02wt% to 0.05wt%.

[0039] Solution A and solution B were simultaneously added dropwise to water using a syringe pump to obtain a suspension. During the addition, the mixture was continuously stirred and kept at a constant temperature. After addition, the suspension was filtered, washed, and dried to obtain spherical flower clusters of 4,4',6,6'-tetraazidohydrazine-1,3,5-triazine particles. The stirring speed and temperature were crucial to the crystal morphology. The dropping rate should be controlled at 5–10 mL / min, the constant temperature at 25–35 °C, the stirring speed at 500–1000 r / min, and the stirring time after addition for 30 min to allow for complete crystal separation. Overall, the ratio of 4,4',6,6'-tetraazidohydrazine-1,3,5-triazine to organic solvent was 100–400 mg:5 mL, and the mass ratio of organic solvent to water was 1:(2–4). Excess antisolvent (water) ensured sufficient particle dispersion and reduced agglomeration.

[0040] The spherical flower clusters TAHT prepared according to the above method have a particle size range of 7μm to 40μm, which is adjustable, and the particle size is uniform and evenly dispersed.

[0041] The following are specific examples.

[0042] Example 1

[0043] (1) Add 100 mg of raw material TAHT to 5 mL of dimethyl sulfoxide, and stir in a constant temperature water bath at 40 °C for 30 min at a stirring speed of 700 r / min to dissolve it completely. Filter the solution with a long-necked funnel to remove impurities and obtain TAHT solution. Place the solution in a 10 mL syringe.

[0044] (2) Add 25 mg PVP to 50 mL of water, stir for 30 min, and sonicate for 10 min to obtain an aqueous solution of PVP; take 10 mL of PVP aqueous solution and put it into a 10 mL syringe;

[0045] (3) Fix the two syringes to the injection pump and add the two solutions at a rate of 6 mL / min. Add the two solutions to a beaker containing 10 mL of water at the same time. During the addition process, make sure that the droplets of the two solutions are mixed at the needle tip before being added to the beaker. Stir continuously at a speed of 800 r / min and keep the temperature constant at 25°C. After the addition is completed, continue stirring for 30 min to allow TAHT to be fully extracted and evenly dispersed.

[0046] (4) The obtained suspension was filtered and washed thoroughly with water three times to remove dimethyl sulfoxide. The prepared sample was dried in a vacuum oven at 40°C to obtain spherical TAHT flower cluster particles.

[0047] Depend on Figure 2 and Figure 3 It can be seen that the spherical TAHT particles prepared under these conditions are formed by interlacing sheet-like structures, with high sphericity, uniform size, no agglomeration, and an average particle size of 9.15 μm, with a yield of 97.89%.

[0048] Example 2

[0049] (1) Add 100 mg of raw material TAHT to 5 mL of dimethyl sulfoxide, and stir in a constant temperature water bath at 40 °C for 30 min at a stirring speed of 700 r / min to dissolve it completely. Filter the solution with a long-necked funnel to remove impurities and obtain TAHT solution. Place the solution in a 10 mL syringe.

[0050] (2) Add 25 mg PVP to 50 mL of water, stir for 30 min, and sonicate for 10 min to obtain an aqueous solution of PVP; take 10 mL of PVP aqueous solution and put it into a 10 mL syringe;

[0051] (3) Fix the two syringes to the injection pump and add them at a rate of 6 mL / min. Add the two solutions to a beaker containing 10 mL of water at the same time. During the addition, make sure that the droplets of the two solutions are mixed at the needle tip before they fall into the beaker. Stir continuously at a speed of 800 r / min and keep the temperature constant at 30°C. After the addition is finished, continue stirring for 30 min to allow TAHT to be fully extracted and evenly dispersed.

[0052] (4) The obtained suspension was filtered and washed thoroughly with water three times to remove dimethyl sulfoxide. The prepared sample was dried in a vacuum oven at 40°C to obtain spherical TAHT flower cluster particles.

[0053] Depend on Figure 4 As can be seen from a, the spherical flower cluster TAHT particles prepared under these conditions have an average particle size of 13.43 μm, and their structure is still formed by interlacing sheets, consistent with the morphology of Example 1, with a yield of 96.34%.

[0054] Example 3

[0055] (1) Add 200 mg of raw material TAHT to 5 mL of dimethyl sulfoxide, and stir in a constant temperature water bath at 40 °C for 30 min at a stirring speed of 700 r / min to fully dissolve it. Filter the solution with a long-necked funnel to remove impurities and obtain TAHT solution. Place the solution in a 10 mL syringe.

[0056] (2) Add 25 mg PVP to 50 mL of water, stir for 30 min, and sonicate for 10 min to obtain an aqueous solution of PVP; take 10 mL of PVP aqueous solution and put it into a 10 mL syringe;

[0057] (3) Fix the two syringes to the injection pump and drop at a rate of 6 mL / min. Drop the two solutions into a beaker containing 10 mL of water at the same time. During the drop, ensure that the droplets of the two solutions are mixed at the needle tip before dropping into the beaker. Stir continuously at a speed of 800 r / min and keep the temperature constant at 35°C. After the drop is finished, continue stirring for 30 min to allow TAHT to be fully extracted and evenly dispersed.

[0058] (4) The obtained suspension was filtered and washed thoroughly with water three times to remove dimethyl sulfoxide. The prepared sample was dried in a vacuum oven at 40°C to obtain spherical TAHT flower cluster particles.

[0059] Depend on Figure 4 As shown in Figure b, the spherical TAHT flower cluster particles prepared under these conditions have an average particle size of 39.07 μm. Their structure is still formed by interlacing plates, but the interlacing is more compact, the crystal surface is smoother, and the yield is 95.12%.

[0060] Example 4

[0061] (1) Add 250 mg of raw material TAHT to 5 mL of dimethyl sulfoxide, and stir in a constant temperature water bath at 40 °C for 30 min at a stirring speed of 700 r / min to fully dissolve it. Filter the solution with a long-necked funnel to remove impurities and obtain TAHT solution. Place the solution in a 10 mL syringe.

[0062] (2) Add 25 mg PVP to 50 mL of water, stir for 30 min, and sonicate for 10 min to obtain an aqueous solution of PVP; take 10 mL of PVP aqueous solution and put it into a 10 mL syringe;

[0063] (3) Fix the two syringes to the injection pump and add the two solutions at a rate of 6 mL / min. Add the two solutions to a beaker containing 10 mL of water at the same time. During the addition process, make sure that the droplets of the two solutions are mixed at the needle tip before being added to the beaker. Stir continuously at a speed of 800 r / min and keep the temperature constant at 25°C. After the addition is completed, continue stirring for 30 min to allow TAHT to be fully extracted and evenly dispersed.

[0064] (4) The obtained suspension was filtered and washed thoroughly with water three times to remove dimethyl sulfoxide. The prepared sample was dried in a vacuum oven at 40°C to obtain spherical TAHT flower cluster particles.

[0065] The spherical TAHT flower cluster particles prepared under these conditions had an average particle size of 23.52 μm and a yield of 95.12%.

[0066] Example 5

[0067] (1) Add 300 mg of raw material TAHT to 5 mL of dimethyl sulfoxide, and stir in a constant temperature water bath at 40 °C for 30 min at a stirring speed of 700 r / min to dissolve it completely. Filter the solution with a long-necked funnel to remove impurities and obtain TAHT solution. Place the solution in a 10 mL syringe.

[0068] (2) Add 25 mg PVP to 50 mL of water, stir for 30 min, and sonicate for 10 min to obtain an aqueous solution of PVP; take 10 mL of PVP aqueous solution and put it into a 10 mL syringe;

[0069] (3) Fix the two syringes to the injection pump and add the two solutions at a rate of 6 mL / min. Add the two solutions to a beaker containing 10 mL of water at the same time. During the addition process, make sure that the droplets of the two solutions are mixed at the needle tip before being added to the beaker. Stir continuously at a speed of 800 r / min and keep the temperature constant at 25°C. After the addition is completed, continue stirring for 30 min to allow TAHT to be fully extracted and evenly dispersed.

[0070] (4) The obtained suspension was filtered and washed thoroughly with water three times to remove dimethyl sulfoxide. The prepared sample was dried in a vacuum oven at 40°C to obtain spherical TAHT flower cluster particles.

[0071] The yield of spherical flower cluster TAHT particles prepared under these conditions was 98.56%.

[0072] Example 6

[0073] (1) Add 400 mg of raw material TAHT to 5 mL of dimethyl sulfoxide, and stir in a constant temperature water bath at 40 °C for 30 min at a stirring speed of 700 r / min to fully dissolve it. Filter the solution with a long-necked funnel to remove impurities and obtain TAHT solution. Place the solution in a 10 mL syringe.

[0074] (2) Add 25 mg PVP to 50 mL of water, stir for 30 min, and sonicate for 10 min to obtain an aqueous solution of PVP; take 10 mL of PVP aqueous solution and put it into a 10 mL syringe;

[0075] (3) Fix the two syringes to the injection pump and add the two solutions at a rate of 6 mL / min. Add the two solutions to a beaker containing 10 mL of water at the same time. During the addition process, make sure that the droplets of the two solutions are mixed at the needle tip before being added to the beaker. Stir continuously at a speed of 800 r / min and keep the temperature constant at 25°C. After the addition is completed, continue stirring for 30 min to allow TAHT to be fully extracted and evenly dispersed.

[0076] (4) The obtained suspension was filtered and washed thoroughly with water three times to remove dimethyl sulfoxide. The prepared sample was dried in a vacuum oven at 40°C to obtain spherical TAHT flower cluster particles.

[0077] The yield of spherical flower cluster TAHT particles prepared under these conditions was 96.78%.

[0078] Example 7

[0079] (1) Add 200 mg of raw material TAHT to 5 mL of dimethyl sulfoxide, and stir in a constant temperature water bath at 40 °C for 30 min at a stirring speed of 700 r / min to fully dissolve it. Filter the solution with a long-necked funnel to remove impurities and obtain TAHT solution. Place the solution in a 10 mL syringe.

[0080] (2) Add 25 mg PVP to 50 mL of water, stir for 30 min, and sonicate for 10 min to obtain an aqueous solution of PVP; take 10 mL of PVP aqueous solution and put it into a 10 mL syringe;

[0081] (3) Fix the two syringes to the injection pump and add them at a rate of 5 mL / min. Add the two solutions to a beaker containing 10 mL of water at the same time. During the addition, make sure that the droplets of the two solutions are mixed at the needle tip before being added to the beaker. Stir continuously at a speed of 800 r / min and keep the temperature constant at 25°C. After the addition is finished, continue stirring for 30 min to allow TAHT to be fully extracted and evenly dispersed.

[0082] (4) The obtained suspension was filtered and washed thoroughly with water three times to remove dimethyl sulfoxide. The prepared sample was dried in a vacuum oven at 40°C to obtain spherical TAHT flower cluster particles.

[0083] Depend on Figure 5 It can be seen that the DSC diagram of the spherical flower clusters TAHT prepared under these conditions is consistent with the results in the literature [Dong Jiahao. Synthesis, structure and properties of nitrogen-rich heterocyclic compounds [D]. Northwest University, 2022.001229.], with a yield of 97.23%.

[0084] Example 8

[0085] (1) Add 200 mg of raw material TAHT to 5 mL of dimethyl sulfoxide, and stir in a constant temperature water bath at 40 °C for 30 min at a stirring speed of 700 r / min to fully dissolve it. Filter the solution with a long-necked funnel to remove impurities and obtain TAHT solution. Place the solution in a 10 mL syringe.

[0086] (2) Add 25 mg PVP to 50 mL of water, stir for 30 min, and sonicate for 10 min to obtain an aqueous solution of PVP; take 10 mL of PVP aqueous solution and put it into a 10 mL syringe;

[0087] (3) Fix the two syringes to the injection pump and add them at a rate of 10 mL / min. Add the two solutions to a beaker containing 10 mL of water at the same time. During the addition, make sure that the droplets of the two solutions are mixed at the needle tip before being added to the beaker. Stir continuously at a speed of 800 r / min and keep the temperature constant at 25°C. After the addition is finished, continue stirring for 30 min to allow TAHT to be fully extracted and evenly dispersed.

[0088] (4) The obtained suspension was filtered and washed thoroughly with water three times to remove dimethyl sulfoxide. The prepared sample was dried in a vacuum oven at 40°C to obtain spherical TAHT flower cluster particles.

[0089] The yield of spherical flower cluster TAHT particles prepared under these conditions was 96.78%.

[0090] Example 9

[0091] (1) Add 200 mg of raw material TAHT to 5 mL of dimethyl sulfoxide, and stir in a constant temperature water bath at 40 °C for 30 min at a stirring speed of 700 r / min to fully dissolve it. Filter the solution with a long-necked funnel to remove impurities and obtain TAHT solution. Place the solution in a 10 mL syringe.

[0092] (2) Add 25 mg PVP to 50 mL of water, stir for 30 min, and sonicate for 10 min to obtain an aqueous solution of PVP; take 10 mL of PVP aqueous solution and put it into a 10 mL syringe;

[0093] (3) Fix the two syringes to the injection pump and add them at a rate of 6 mL / min. Add the two solutions to a beaker containing 10 mL of water at the same time. During the addition, make sure that the droplets of the two solutions are mixed at the needle tip before being added to the beaker. Stir continuously at a speed of 1000 r / min and keep the temperature constant at 25°C. After the addition is finished, continue stirring for 30 min to allow TAHT to be fully extracted and evenly dispersed.

[0094] (4) The obtained suspension was filtered and washed thoroughly with water three times to remove dimethyl sulfoxide. The prepared sample was dried in a vacuum oven at 40°C to obtain spherical TAHT flower cluster particles.

[0095] The yield of spherical flower cluster TAHT particles prepared under these conditions was 97.55%.

[0096] Example 10

[0097] (1) Add 200 mg of raw material TAHT to 5 mL of dimethyl sulfoxide, and stir in a constant temperature water bath at 40 °C for 30 min at a stirring speed of 700 r / min to fully dissolve it. Filter the solution with a long-necked funnel to remove impurities and obtain TAHT solution. Place the solution in a 10 mL syringe.

[0098] (2) Add 25 mg PVP to 50 mL of water, stir for 30 min, and sonicate for 10 min to obtain an aqueous solution of PVP; take 10 mL of PVP aqueous solution and put it into a 10 mL syringe;

[0099] (3) Fix the two syringes to the injection pump and add the two solutions at a rate of 6 mL / min. Add the two solutions to a beaker containing 10 mL of water at the same time. During the addition process, make sure that the droplets of the two solutions are mixed at the needle tip before adding them to the beaker. Stir continuously at a speed of 500 r / min and keep the temperature constant at 25°C. After the addition is completed, continue stirring for 30 min to allow TAHT to be fully extracted and evenly dispersed.

[0100] (4) The obtained suspension was filtered and washed thoroughly with water three times to remove dimethyl sulfoxide. The prepared sample was dried in a vacuum oven at 40°C to obtain spherical TAHT flower cluster particles.

[0101] The yield of spherical flower cluster TAHT particles prepared under these conditions was 96.01%.

[0102] Example 11

[0103] (1) Add 200 mg of raw material TAHT to 5 mL of dimethyl sulfoxide, and stir in a constant temperature water bath at 25 °C for 30 min at a stirring speed of 700 r / min to fully dissolve it. Filter the solution with a long-necked funnel to remove impurities and obtain TAHT solution. Place the solution in a 10 mL syringe.

[0104] (2) Add 10 mg PVP to 50 mL of water, stir for 30 min, and sonicate for 10 min to obtain an aqueous solution of PVP; take 10 mL of PVP aqueous solution and put it into a 10 mL syringe;

[0105] (3) Fix the two syringes to the injection pump and add them at a rate of 6 mL / min. Add the two solutions to a beaker containing 15 mL of water at the same time. During the addition, make sure that the droplets of the two solutions are mixed at the needle tip before being added to the beaker. Stir continuously at a speed of 800 r / min and keep the temperature constant at 25°C. After the addition is finished, continue stirring for 30 min to allow TAHT to be fully extracted and evenly dispersed.

[0106] (4) The obtained suspension was filtered and washed thoroughly with water three times to remove dimethyl sulfoxide. The prepared sample was dried in a vacuum oven at 40°C to obtain spherical TAHT flower cluster particles.

[0107] The yield of spherical flower cluster TAHT particles prepared under these conditions was 95.41%.

[0108] Example 12

[0109] (1) Add 200 mg of raw material TAHT to 5 mL of dimethyl sulfoxide, and stir in a constant temperature water bath at 45°C for 30 min at a stirring speed of 700 r / min to fully dissolve it. Filter the solution with a long-necked funnel to remove impurities and obtain TAHT solution. Place the solution in a 10 mL syringe.

[0110] (2) Add 20 mg PVP to 50 mL of water, stir for 30 min, and sonicate for 10 min to obtain an aqueous solution of PVP; take 10 mL of PVP aqueous solution and put it into a 10 mL syringe;

[0111] (3) Fix the two syringes to the injection pump and add the two solutions at a rate of 6 mL / min. Add the two solutions to a beaker containing 20 mL of water at the same time. During the addition process, make sure that the droplets of the two solutions are mixed at the needle tip before adding them to the beaker. Stir continuously at a speed of 800 r / min and keep the temperature constant at 25°C. After the addition is completed, continue stirring for 30 min to allow TAHT to be fully extracted and evenly dispersed.

[0112] (4) The obtained suspension was filtered and washed thoroughly with water three times to remove dimethyl sulfoxide. The prepared sample was dried in a vacuum oven at 40°C to obtain spherical TAHT flower cluster particles.

[0113] The yield of spherical flower cluster TAHT particles prepared under these conditions was 98.12%.

[0114] Comparative Example 1

[0115] (1) Add 200mg of raw material TAHT to 5mL of N,N-dimethylformamide solution, and stir in a 40℃ constant temperature water bath for 30min to fully dissolve it. Filter the solution with a long-necked funnel to remove impurities and obtain TAHT solution. Place the solution in a 10mL syringe.

[0116] (2) Add 250 mg PVP to 50 mL of water, stir for 30 min, and sonicate for 10 min to obtain an aqueous solution of PVP; take 10 mL of PVP aqueous solution and put it into a 10 mL syringe;

[0117] (3) Fix the two syringes to the injection pump and add the two solutions at a rate of 6 mL / min. Add the two solutions to a beaker containing 10 mL of water at the same time. During the addition process, make sure that the droplets of the two solutions are mixed at the needle tip before being added to the beaker. Stir continuously at a speed of 800 r / min and keep the temperature constant at 25°C. After the addition is completed, continue stirring for 30 min to allow TAHT to be fully extracted and evenly dispersed.

[0118] (4) The obtained suspension was filtered and washed three times with water to remove N,N-dimethylformamide. The prepared sample was dried in a vacuum oven at 40°C to obtain spherical flower cluster TAHT particles.

[0119] Depend on Figure 6 As shown in section a, the TAHT crystals prepared using N,N-dimethylformamide as an organic solvent exhibit a snowflake-like appearance, lacking a complete spherical structure and showing signs of aggregation.

[0120] Comparative Example 2

[0121] (1) Add 200mg of raw material TAHT to 5mL of dimethyl sulfoxide, and stir in a 40℃ constant temperature water bath for 30min to fully dissolve it. Filter the solution with a long-necked funnel to remove impurities and obtain TAHT solution. Place the solution in a 10mL syringe.

[0122] (2) Add 200 mg PVP to 50 mL of water, stir for 30 min, and sonicate for 10 min to obtain an aqueous solution of PVP; take 10 mL of PVP aqueous solution and put it into a 10 mL syringe;

[0123] (3) Fix the two syringes to the injection pump and add the two solutions at a rate of 6 mL / min. Add the two solutions to a beaker containing 10 mL of water at the same time. During the addition process, make sure that the droplets of the two solutions are mixed at the needle tip before adding them to the beaker. Stir continuously at a speed of 800 r / min and keep the temperature constant at 15℃. After the addition is completed, continue stirring for 30 min to allow TAHT to be fully extracted and evenly dispersed.

[0124] (4) The obtained suspension was filtered and washed thoroughly with water three times to remove dimethyl sulfoxide. The prepared sample was dried in a vacuum oven at 40°C to obtain spherical TAHT flower cluster particles.

[0125] Depend on Figure 6 As shown in b, at lower temperatures, the crystal growth of TAHT is inhibited, the particle size is smaller, with an average particle size of 3.92 μm, but the structure is snowflake-like and agglomeration often occurs.

[0126] As can be seen from Comparative Examples 1 and 2, dimethyl sulfoxide is required as the optimal organic solvent in this invention, and the temperature range during the crystallization process is 25°C to 35°C; otherwise, agglomeration is likely to occur.

[0127] This invention employs a solvent-antisolvent method, combined with an emulsifier, to prepare spherical clusters of 4,4',6,6'-tetraazidohydrazine-1,3,5-triazine particles. Dimethyl sulfoxide is used as the organic solvent, water as the antisolvent, and PVP as the surfactant. Ultrafine crystals are instantaneously precipitated by simultaneous dropwise addition of the solution and antisolvent. Mechanical stirring then causes the crystals to coalesce into a plate-like, interwoven spherical structure. This method is simple to operate, easily scaled up continuously, and operates under mild reaction conditions, making it an ideal and efficient method for preparing spherical energetic materials. Furthermore, the surfactant disperses the particles, resulting in uniform particle size and dispersion. Compared to irregular morphologies, the spherical particles synthesized in this invention achieve the densest packing, significantly enhancing the material's energy output. Simultaneously, the uniform size and morphology improve combustion or detonation stability and reduce pressure fluctuations.

[0128] The above description is only of the preferred embodiment of the present invention and should not be construed as limiting the scope of the claims. The present invention is not limited to the above embodiments, and variations in its specific structure are permitted. All modifications made within the scope of the independent claims of the present invention are also within the scope of protection of the present invention.

[0129] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

Claims

1. A method for preparing spherical flower cluster 4,4',6,6'-tetraazidohydrazine-1,3,5-triazine particles, characterized in that, Includes the following steps: 4,4',6,6'-tetraazidohydrazine-1,3,5-triazine was dissolved in an organic solvent to obtain a triazine solution; A suspension is obtained by adding a triazine solution and a surfactant solution to water. The suspension was filtered, washed, and dried to obtain spherical flower clusters of 4,4',6,6'-tetraazidohydrazine-1,3,5-triazine particles.

2. The method for preparing spherical flower cluster 4,4',6,6'-tetraazidohydrazine-1,3,5-triazine particles according to claim 1, characterized in that, The organic solvent is dimethyl sulfoxide.

3. The method for preparing spherical flower cluster 4,4',6,6'-tetraazidohydrazine-1,3,5-triazine particles according to claim 1, characterized in that, The dissolution of 4,4',6,6'-tetraazidohydrazine-1,3,5-triazine in an organic solvent was carried out at 25–45 °C and a stirring speed of 600–800 r / min.

4. The method for preparing spherical flower cluster 4,4',6,6'-tetraazidohydrazine-1,3,5-triazine particles according to claim 1, characterized in that, The surfactant is polyvinylpyrrolidone.

5. The method for preparing spherical flower cluster 4,4',6,6'-tetraazidohydrazine-1,3,5-triazine particles according to claim 1 or 4, characterized in that, The concentration of the surfactant solution is 0.02 wt% to 0.05 wt%.

6. The method for preparing spherical flower cluster 4,4',6,6'-tetraazidohydrazine-1,3,5-triazine particles according to claim 1, characterized in that, The triazine solution and surfactant solution are added to the water. Specifically, the triazine solution and surfactant solution are added dropwise to the water at a temperature of 25–35°C and a stirring speed of 500–1000 r / min.

7. The method for preparing spherical flower cluster 4,4',6,6'-tetraazidohydrazine-1,3,5-triazine particles according to claim 6, characterized in that, The dropping rate is 5-10 mL / min, and the mixture is stirred for 30 min after the dropping is completed.

8. The method for preparing spherical flower cluster 4,4',6,6'-tetraazidohydrazine-1,3,5-triazine particles according to claim 1, characterized in that, The ratio of 4,4',6,6'-tetraazidohydrazine-1,3,5-triazine to organic solvent is 100–400 mg: 5 mL.

9. The method for preparing spherical flower cluster 4,4',6,6'-tetraazidohydrazine-1,3,5-triazine particles according to claim 1, characterized in that, The mass ratio of organic solvent to water is 1:(2-4).

10. A spherical flower cluster 4,4',6,6'-tetraazidohydrazine-1,3,5-triazine particle prepared by the method according to any one of claims 1-9, characterized in that, The particle size range is 7μm to 40μm.

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