Ternary component potassium-based supramolecular energetic material as well as preparation method and application thereof

Abstract

The invention discloses a ternary component potassium-based supramolecular energetic material as well as a preparation method and application thereof, and belongs to the technical field of energetic material development. The preparation method comprises the following steps: 1) adding 4, 5-dinitrobenzo-18-crown-6, potassium nitrate and nitro potassium into a solvent according to a molar ratio of 1: 1: 1, and stirring and filtering to obtain an assembly solution; and 2) adjusting the gas pressure to 0.1-0.5 Mpa and the temperature to 70-90 DEG C, pumping the assembled solution into a spray head through a feed pump, dispersing the assembled solution into fine fog drops under the action of high-pressure hot air flow, rapidly volatilizing the solvent, and rapidly combining, assembling and gathering crystals to form the dry 4, 5-dinitrobenzo 18-crown-6 / potassium nitrate / nitrate imitated potassium supramolecular energetic material. The invention provides the novel ternary component supramolecular energetic material, the preparation method is simple and rapid, the 4, 5-dinitrobenzo 18-crown-6 / potassium nitrate / nitrate imitated potassium supramolecular energetic material can be rapidly prepared through pressure-assisted assembly, the process is simple and easy to operate, the preparation efficiency is high, and continuous preparation is easy.

Description

Technical Field

[0001] This invention belongs to the field of energetic materials development technology, specifically relating to a ternary potassium-based supramolecular energetic material, its preparation method, and its application. Background Technology

[0002] Potassium salts can inhibit the chain reaction of free radicals in the combustible gases of propellants and solid propellants, and suppress the generation of secondary flames. They are very effective in eliminating muzzle flash of gun propellants and secondary combustion of rocket propellants, and therefore have good application prospects in propellants and solid propellants. At present, the potassium salts used in actual formulations are mainly inorganic potassium salts such as potassium carbonate and potassium sulfate. Although they can solve the smoke and flame problem to a certain extent, inorganic potassium salts have the following defects that need to be solved: (1) Inorganic potassium salts have strong hygroscopicity, which affects the stability of performance; (2) They do not have energy and cannot provide energy assistance to the formulation, and may even reduce the energy of the formulation, making it difficult to meet the high demand for energy levels.

[0003] Currently, the research and development cycle for synthesizing novel energetic potassium salts is long and the cost is high. Modification of existing energetic potassium salts, such as potassium nitrate, has become a research focus. Although existing methods such as coating can reduce their hygroscopicity, the coating layer is prone to peeling and failure under external shear forces in actual formulations. Therefore, it is necessary to explore and research new modification technologies to develop new materials.

[0004] Supramolecular energetic materials primarily rely on intermolecular interactions and microscopic assembly to form multi-component materials with novel crystal stacking structures and macroscopic properties. The main characteristic of supramolecular energetic materials lies in forming molecular energetic materials with new crystal structures without destroying the original molecular structure. This aims to effectively overcome the drawbacks of the original component molecules, endowing the novel energetic materials with specific properties, and thus effectively regulating the physicochemical, safety, and energy properties of energetic materials.

[0005] However, how to develop new energetic materials and solve the problems of potassium salts in eliminating smoke and flame has become an urgent technical problem to be solved. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention provides a ternary supramolecular energetic material consisting of 4,5-dinitrobenzo18crown6 / potassium nitrate / potassium nitroform, along with its preparation method and applications. This method achieves a simple, rapid, and efficient preparation process that is easy to implement continuously, providing an efficient method for the preparation of novel supramolecular energetic materials and effectively solving the problems associated with inorganic potassium salts.

[0007] To achieve the above-mentioned technical objectives, the technical solution adopted by the present invention is as follows: This invention first provides a method for preparing a potassium-based supramolecular energetic material with a ternary component of 4,5-dinitrobenzo18crown6 / potassium nitrate / potassium nitroform, comprising the following steps: Step 1: Preparation of the assembly solution of 4,5-dinitrobenzo18 crown 6 with potassium nitrate and potassium nitroform Add 4,5-dinitrobenzo18crown6, potassium nitrate, and potassium nitroform in a molar ratio of 1:1:1 to the assembly solvent. Stir at 20-35℃ until fully dissolved, then filter to obtain the assembly solution for later use. Step 2: Preparation of 4,5-dinitrobenzo18 crown 6 with potassium nitrate and potassium nitroform supramolecular energetic materials Adjust the gas pressure to 0.1-0.5 MPa and the temperature to 70-90°C. Pump the 4,5-dinitrobenzo18crown6, potassium nitrate, and potassium nitroform assembly solution into the nozzle via a feed pump. Under the action of high-pressure hot gas flow, the solution is dispersed into fine droplets, the solvent evaporates rapidly, and the crystals quickly combine, assemble, and aggregate to form a dry 4,5-dinitrobenzo18crown6 / potassium nitrate / potassium nitroform ternary supramolecular energetic material.

[0008] The preparation method provided by this invention combines the energetic and hydrophobic properties of 4,5-dinitrobenzo18-crown 6 with the high oxygen content of potassium nitrate and potassium nitroform. Through a supramolecular assembly strategy, a ternary supramolecular energetic material of 4,5-dinitrobenzo18-crown 6 / potassium nitrate / potassium nitroform is assembled. This preparation method achieves a good match between oxygen supply and hydrophobic properties, providing a new approach for the synthesis and performance regulation of novel energetic materials, while also enriching the types and numbers of supramolecular energetic materials. Furthermore, this invention changes the traditional method of free assembly of solute molecules in solution to forced assembly assisted by external pressure, thereby significantly shortening the preparation cycle and improving the preparation efficiency, providing a rapid and efficient method for the preparation of supramolecular energetic materials. Currently, there are no published reports on the preparation of ternary supramolecular energetic materials of 4,5-dinitrobenzo18-crown 6 / potassium nitrate / potassium nitroform; therefore, this invention develops a novel potassium-based supramolecular energetic material.

[0009] In a preferred method for preparing a ternary supramolecular energetic material of 4,5-dinitrobenzo18crown6 / potassium nitrate / potassium nitroform, the assembly solvent in step one is any one or a mixture of several of methanol, ethanol, acetone, tetrahydrofuran, and ethyl acetate.

[0010] This invention also discloses a ternary supramolecular energetic material consisting of 4,5-dinitrobenzo18crown6 / potassium nitrate / potassium nitroform, which is prepared by the above-described preparation method for the ternary supramolecular energetic material consisting of 4,5-dinitrobenzo18crown6 / potassium nitrate / potassium nitroform.

[0011] The 4,5-dinitrobenzo18-crown 6 / potassium nitrate / potassium nitroform ternary supramolecular energetic material of the present invention belongs to the monoclinic crystal system, space group P121 / n1, and has a crystal density of 1.574 g / cm³. 3 Cell parameters: α=90°, β=97.296(2)°, γ=90°.

[0012] The beneficial effects of this invention are as follows: (1) Using a supramolecular assembly strategy, a potassium-based supramolecular energetic material with a ternary component of 4,5-dinitrobenzo18crown6 / potassium nitrate / potassium nitroform was prepared for the first time.

[0013] (2) The preparation method of the present invention is simple and quick. The ternary potassium-based supramolecular energetic material of 4,5-dinitrobenzo18crown6 / potassium nitrate / potassium nitroform can be quickly prepared by pressure-assisted assembly. The process is simple and easy to operate, with high preparation efficiency and easy to be prepared continuously, providing an efficient method for the preparation of novel supramolecular energetic materials.

[0014] (3) The ternary potassium-based supramolecular energetic material of 4,5-dinitrobenzo18crown6 / potassium nitrate / potassium nitroform is a new material with excellent moisture resistance, high energy and good safety, and has good application prospects in energetic materials. Attached Figure Description

[0015] Figure 1 This is a process flow diagram for preparing the 4,5-dinitrobenzo18crown6 / potassium nitrate / potassium nitroform ternary potassium-based supramolecular energetic material of the present invention.

[0016] Figure 2 The crystal structure diagram of the potassium-based supramolecular energetic material of the ternary component 4,5-dinitrobenzo18crown6 / potassium nitrate / potassium nitroform of the present invention is shown.

[0017] Figure 3 This is a cell packing diagram of the potassium-based supramolecular energetic material of the ternary component 4,5-dinitrobenzo18crown6 / potassium nitrate / potassium nitroform of the present invention. Detailed Implementation

[0018] The present invention will be specifically described below through embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above-described invention are still within the scope of protection of the present invention.

[0019] like Figure 1 As shown, Figure 1 The flowchart of the preparation process of the ternary supramolecular energetic material of 4,5-dinitrobenzo18crown6 / potassium nitrate / potassium nitroform in this embodiment is shown.

[0020] The preparation process of the ternary supramolecular energetic material of 4,5-dinitrobenzo18 crown 6 / potassium nitrate / potassium nitroform in this embodiment is as follows: Step 1: Preparation of the assembly solution of 4,5-dinitrobenzo18 crown 6 with potassium nitrate and potassium nitroform. 4,5-dinitrobenzo18crown6 was added to the assembly solvent along with potassium nitrate and potassium nitroform (C(NO2)3K) in a molar ratio of 1:1:1. The solution was heated and stirred at 20-35℃ until fully dissolved, and then filtered to obtain the assembly solution for later use. Step 2: Preparation of 4,5-dinitrobenzo18-crown 6 / potassium nitrate / potassium nitroform ternary supramolecular energetic materials Adjust the gas pressure to 0.1-0.5 MPa and the temperature to 70-90°C. Pump the 4,5-dinitrobenzo18crown6, potassium nitrate, and potassium nitroform assembly solution into the nozzle via a feed pump. Under the action of high-pressure hot gas flow, the solution is dispersed into fine droplets, the solvent evaporates rapidly, and the crystals quickly combine, assemble, and aggregate to form a dry 4,5-dinitrobenzo18crown6 / potassium nitrate / potassium nitroform ternary supramolecular energetic material.

[0021] Specifically, the following details several specific embodiments of the preparation method of the 4,5-dinitrobenzo18crown6 / potassium nitrate / potassium nitroform ternary supramolecular energetic material of the present invention. Example

[0022] 30 ml of methanol was added to a three-necked flask, followed by 0.402 g of 4,5-dinitrobenzo18-crown 6, 0.101 g of potassium nitrate, and 0.189 g of potassium nitroform. The mixture was stirred at 35°C. After the 4,5-dinitrobenzo18-crown 6, potassium nitrate, and potassium nitroform were fully dissolved, the mixture was filtered to obtain the assembly solution. The gas pressure was adjusted to 0.1 MPa and the temperature to 70°C. The assembly solution was then pumped into a nozzle using a feed pump. Under the action of a high-pressure hot gas flow, the solution was dispersed into fine droplets. The solvent evaporated rapidly, and the supramolecular energetic material crystals quickly combined, assembled, and aggregated to form a dry ternary supramolecular energetic material of 4,5-dinitrobenzo18-crown 6 / potassium nitrate / potassium nitroform. Example

[0023] 80 ml of ethanol was added to a three-necked flask, followed by 0.402 g of 4,5-dinitrobenzo18-crown 6, 0.101 g of potassium nitrate, and 0.189 g of potassium nitroform. The mixture was stirred at 40 °C. After the 4,5-dinitrobenzo18-crown 6, potassium nitrate, and potassium nitroform were fully dissolved, the mixture was filtered to obtain the assembly solution. The gas pressure was adjusted to 0.3 MPa and the temperature to 80 °C. The assembly solution was pumped into a nozzle using a feed pump. Under the action of a high-pressure hot gas flow, the solution was dispersed into fine droplets. The solvent evaporated rapidly, and the supramolecular energetic material crystals quickly combined, assembled, and aggregated to form a dry ternary supramolecular energetic material of 4,5-dinitrobenzo18-crown 6 / potassium nitrate / potassium nitroform. Example

[0024] 40 ml of acetone was added to a three-necked flask, followed by 2.01 g of 4,5-dinitrobenzo18-crown 6, 0.505 g of potassium nitrate, and 0.945 g of potassium nitroform. The mixture was stirred at 25 °C. After the 4,5-dinitrobenzo18-crown 6, potassium nitrate, and potassium nitroform were completely dissolved, the mixture was filtered to obtain the assembly solution. The gas pressure was adjusted to 0.4 MPa and the temperature to 70 °C. The assembly solution was then pumped into a nozzle using a feed pump. Under the action of a high-pressure hot gas flow, the solution was dispersed into fine droplets. The solvent evaporated rapidly, and the crystals quickly combined, assembled, and aggregated to form a dry ternary supramolecular energetic material of 4,5-dinitrobenzo18-crown 6 / potassium nitrate / potassium nitroform. Example

[0025] 30 ml of methanol and 30 ml of acetone (1:1, volume ratio) were added to a three-necked flask, followed by 2.01 g of 4,5-dinitrobenzo18-crown 6, 0.505 g of potassium nitrate, and 0.945 g of potassium nitroform. The mixture was stirred at 30°C. After the 4,5-dinitrobenzo18-crown 6, potassium nitrate, and potassium nitroform were completely dissolved, the mixture was filtered to obtain the assembly solution. The gas pressure was adjusted to 0.2 MPa and the temperature to 70°C. The assembly solution was pumped into a nozzle using a feed pump. Under the action of a high-pressure hot gas flow, the solution was dispersed into fine droplets. The solvent evaporated rapidly, and the supramolecular energetic material crystals quickly combined, assembled, and aggregated to form a dry ternary supramolecular energetic material of 4,5-dinitrobenzo18-crown 6 / potassium nitrate / potassium nitroform. Example

[0026] Add 50 ml of ethanol and 20 ml of ethyl acetate (5:2, volume ratio) to a three-necked flask, then add 0.804 g of 4,5-dinitrobenzo18-crown 6, 0.202 g of potassium nitrate, and 0.378 g of potassium nitroform. Stir at 30°C. After the 4,5-dinitrobenzo18-crown 6, potassium nitrate, and potassium nitroform are completely dissolved, filter to obtain the assembled solution.

[0027] Adjust the gas pressure to 0.5 MPa and the temperature to 90°C, and pump the assembly solution into the nozzle via a feed pump. Under the action of high-pressure hot gas flow, the solution is dispersed into fine droplets, the solvent evaporates rapidly, and the crystals quickly combine, assemble, and aggregate to form a dry 4,5-dinitrobenzo18crown6 / potassium nitrate / potassium nitroform ternary supramolecular energetic material. Example

[0028] 50 ml of methanol and 25 ml of ethyl acetate were added to a three-necked flask, followed by 2.01 g of 4,5-dinitrobenzo18-crown 6, 0.505 g of potassium nitrate, and 0.945 g of potassium nitroform. The mixture was stirred at 30°C. After the 4,5-dinitrobenzo18-crown 6, potassium nitrate, and potassium nitroform were completely dissolved, the mixture was filtered to obtain the assembly solution. The gas pressure was adjusted to 0.35 MPa and the temperature to 80°C. The assembly solution was then pumped into a nozzle using a feed pump. Under the action of a high-pressure hot gas flow, the solution was dispersed into fine droplets. The solvent evaporated rapidly, and the crystals quickly combined, assembled, and aggregated to form a dry ternary supramolecular energetic material of 4,5-dinitrobenzo18-crown 6 / potassium nitrate / potassium nitroform.

[0029] like Figure 2 and Figure 3 As shown, the preparation method of the above-mentioned 4,5-dinitrobenzo18crown6 with potassium nitrate and potassium nitroform supramolecular energetic material discloses the ternary component supramolecular energetic material of 4,5-dinitrobenzo18crown6 / potassium nitrate / potassium nitroform prepared by the above-mentioned method. Figure 2 and Figure 3 The crystal structure and unit cell packing diagram of the ternary supramolecular energetic material of the present invention, consisting of 4,5-dinitrobenzo18crown6 / potassium nitrate / potassium nitroform, are shown.

[0030] Depend on Figure 2 and Figure 3 It can be seen that the ternary supramolecular energetic material of 4,5-dinitrobenzo18crown6 / potassium nitrate / potassium nitroform in this embodiment is formed by the assembly of 4,5-dinitrobenzo18crown6 molecules with potassium nitrate and potassium nitroform molecules in a 1:1:1 molar ratio. It belongs to the monoclinic crystal system, space group P121 / n1, and has a crystal density of 1.574 g / cm³. 3 Cell parameters: α=90°, β=97.296(2)°, γ=90°.

[0031] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a ternary potassium-based supramolecular energetic material, characterized in that, Includes the following steps: Step 1: Preparation of the assembly solution: Add 4,5-dinitrobenzo18crown6, potassium nitrate and potassium nitroform to the solvent in a molar ratio of 1:1:1, stir at 20-35℃ until fully dissolved, and then filter to obtain the assembly solution for later use. Step 2: Preparation of the ternary potassium-based supramolecular energetic material: Adjust the gas pressure to 0.1-0.5 MPa and the temperature to 70-90℃. Pump the assembly solution containing 4,5-dinitrobenzo18crown6, potassium nitrate, and potassium nitroform into the nozzle via a feed pump. Under the action of high-pressure hot gas flow, the solution is dispersed into fine droplets, the solvent evaporates rapidly, and the crystals quickly combine, assemble, and aggregate to form a dry ternary supramolecular energetic material of 4,5-dinitrobenzo18crown6 / potassium nitrate / potassium nitroform.

2. The preparation method according to claim 1, characterized in that: The solvent mentioned in step one is any one or a mixture of several of methanol, ethanol, acetone, tetrahydrofuran, and ethyl acetate.

3. A ternary potassium-based supramolecular energetic material, characterized in that: The ternary potassium-based supramolecular energetic material is prepared by the method described in claim 1 or 2.

4. The ternary potassium-based supramolecular energetic material according to claim 3, characterized in that: The aforementioned ternary potassium-based supramolecular energetic material belongs to the monoclinic crystal system, space group P121 / n1, and has a crystal density of 1.574 g / cm³. 3 Cell parameters: α=90°, β=97.296(2)°, γ=90°.

5. The application of the ternary potassium-based supramolecular energetic material according to claim 3 or 4 in propellants and solid propellants.

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