Energetic 3D metal-organic framework materials and their preparation methods and applications

Abstract

The present invention discloses an energetic 3D metal organic framework material, which includes a metal ion, an organic ligand and an explosive component; wherein the metal ion is a silver ion; the organic ligand is a 1,2,4-oxadiazolone compound, and the explosive component is a perchlorate ion. The energetic 3D metal organic framework material has a three-dimensional crystal structure, high oxygen balance, excellent thermal stability, and low-sensitivity metal organic framework materials in the fields of detonators, propellants, and high explosives. The present invention also discloses a preparation method of an energetic 3D metal organic framework material, in which water is used instead of an organic solvent in the preparation, which is environmentally friendly and pollution-free, and has a simple preparation process. The energetic 3D metal organic framework material of the present invention wraps the explosive component in the framework through its unique three-dimensional structure, and improves stability while increasing the oxygen content and oxygen balance of the molecule.

Description

Technical Field

[0001] The present invention relates to the technical field of energetic materials, and in particular to energetic 3D metal organic framework materials and preparation methods and applications thereof. Background Art

[0002] Metal-organic framework materials are a class of materials composed of metal ions or metal clusters coordinated with organic ligands. Due to their highly porous structure, they show great application prospects in gas storage, catalytic chemistry, optics, biomedical engineering and other fields. In recent years, metal-organic framework materials have gradually emerged in the field of energetic materials, including applications in explosive monitoring and the preparation of high-energy and low-sensitivity energetic materials. Energetic metal-organic framework materials can be introduced into energetic components through a simple self-assembly process. However, due to the difficult-to-control coordination bond number and coordination mode of metal ions during the self-assembly process, it is very difficult to form metal-organic framework materials with special 3D structures. Finding suitable metal ions, organic ligands and reaction conditions to form energetic 3D metal-organic framework materials has been the goal pursued by researchers. Summary of the invention

[0003] An object of the present invention is to solve at least the above problems and / or disadvantages and to provide at least the advantages which will be described hereinafter.

[0004] Another object of the present invention is to provide an energetic 3D metal-organic framework material, which utilizes 1,2,4-oxadiazolone as an organic ligand and metal ions to wrap explosive components in the framework through its unique three-dimensional structure. It is a metal-organic framework material with a three-dimensional crystal structure, high oxygen balance, excellent thermal stability, and low sensitivity, and shows application potential in the fields of detonators, propellants, and high explosives.

[0005] Another object of the present invention is to provide a method for preparing an energetic 3D metal organic framework material, which uses water instead of an organic solvent, is environmentally friendly and pollution-free, and has simple synthesis steps.

[0006] In order to achieve these objects and other advantages according to the present invention, there is provided an energetic 3D metal organic framework material comprising metal ions, organic ligands and an explosive component;

[0007] Among them, the metal ion is silver ion, the organic ligand is 1,2,4-oxadiazolone compound, and the explosive component is perchlorate ion.

[0008] Preferably, the 1,2,4-oxadiazolone compound has the following structure:

[0009]

[0010] Among them, R1 , R 2 A nitrogen-containing group.

[0011] Preferably, the 3D metal organic framework material is monoclinic, has a P21 / n space group, and a unit cell parameter of α=90°, β=99.443°, γ=90°.

[0012] Preferably, wherein R 1 , R 2 All are amino groups.

[0013] The purpose of the present invention can also be further achieved by a method for preparing an energetic 3D metal-organic framework material, which comprises the steps of: dispersing the ligand in water, heating, adding acid dropwise, and continuing to stir for 30 minutes after all the solids are dissolved, adding an aqueous solution of the corresponding acid silver salt, heating the system again and maintaining it for 30 minutes, cooling to room temperature, standing, filtering, washing with water, and vacuum drying to obtain the 3D metal-organic framework material.

[0014] Preferably, the heating temperature is 60°C and the temperature is raised to 60°C again.

[0015] Preferably, the acid is perchloric acid and the silver salt is silver perchlorate.

[0016] Preferably, the ligand is diamino 1,2,4-oxadiazolone, and the molar ratio of the ligand to the silver salt is 1:2.

[0017] Preferably, the standing time is 5 hours.

[0018] The purpose of the present invention can be further achieved by using the energetic 3D metal organic framework material as an energetic oxidant.

[0019] The present invention has at least the following beneficial effects:

[0020] 1. The energetic 3D metal organic framework material of the present invention is a metal organic framework material with a three-dimensional crystal structure, high oxygen balance, excellent thermal stability and low sensitivity, and shows application potential in the fields of detonators, propellants, and high explosives.

[0021] 2. The energetic 3D metal organic framework material of the present invention utilizes 1,2,4-oxadiazolone as an organic ligand and metal ions to wrap explosive components in the framework through its unique three-dimensional structure, which can increase energy while reducing sensitivity.

[0022] 3. The preparation method of the present invention uses water instead of organic solvent, is environmentally friendly and pollution-free, and has simple synthesis steps.

[0023] Other advantages, objectives and features of the present invention will be embodied in part through the following description, and in part will be understood by those skilled in the art through study and practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is a single crystal structure diagram of the energetic 3D metal organic framework material in Example 1 of the present invention;

[0025] Figure 2 This is a crystal stacking diagram of the energetic 3D metal organic framework material in Example 1 of the present invention;

[0026] Figure 3 This is a three-dimensional framework diagram of the energetic 3D metal organic framework material in Example 1 of the present invention;

[0027] Figure 4 This is an optical image of the energetic 3D metal organic framework material in Example 1 of the present invention;

[0028] Figure 5 This is the DSC graph of the energetic 3D metal organic framework material in Example 1 of the present invention. DETAILED DESCRIPTION

[0029] The present invention is further described in detail below in conjunction with the accompanying drawings so that those skilled in the art can implement the invention with reference to the description.

[0030] It should be understood that terms such as “having”, “including” and “comprising” used herein do not specify the existence or addition of one or more other elements or combinations thereof.

[0031] It should be noted that the experimental methods described in the following embodiments are conventional methods unless otherwise specified, and the reagents and materials can be obtained from commercial channels unless otherwise specified.

[0032] <Example 1>

[0033] Energetic 3D metal organic framework material, its monomer structure formula is as follows:

[0034]

[0035] The specific synthetic route is as follows:

[0036]

[0037] The specific synthesis steps are as follows:

[0038] Diamino 1,2,4-oxadiazolone (1mmol, 0.2g) was dispersed in 3mL of water, heated to 60℃, and 2ml of 72% perchloric acid was added dropwise, and all the solids were dissolved. After stirring for 30 minutes, 3mL of silver perchlorate (2mmol, 0.42g) was added. After the system was heated to 60℃ again and maintained for 30 minutes, it was cooled to room temperature and allowed to stand for 5 hours. After filtering, it was washed with 1mL of water and dried in vacuo to obtain 56mg of perchloric acid·tris(diamino 1,2,4-oxadiazolone)·silver, colorless needle-shaped crystals, with a yield of 41%.

[0039] Among them, the synthesis reference of diamino-1,2,4-oxadiazolone is: Chemical Engineering Journal, 2023, 467, 143527.

[0040] Among them, the single crystal structure diagram of energetic 3D metal organic framework materials is shown in Figure 1 , the crystal packing diagram is shown in Figure 2 , see the three-dimensional framework diagram Figure 3 ; Optical diagram see Figure 4 ;DSC diagram see Figure 5 .

[0041] Through crystal analysis, it can be found that each silver atom in perchloric acid·tris(diamino 1,2,4-oxadiazolone)·silver forms five coordination bonds with two nitrogen atoms on the 1,2,4-oxadiazole ring, two amino nitrogen atoms and one carbonyl oxygen atom, thereby building a strong three-dimensional framework to wrap the perchlorate ion in the hole. The reasonable selection of organic ligands, inorganic metal salts and reaction conditions plays a positive role in the structure of energetic metal organic frameworks.

[0042] <Example 2>

[0043] Performance comparison of the energetic 3D metal organic framework material of Example 1 of the present invention, conventional detonating explosives lead azide (LA) and lead styphnate (LS).

[0044] The performance comparison of energetic 3D metal organic framework materials, LA, and LS is shown in Table 1.

[0045] Table 1. Performance comparison of energetic 3D metal organic framework materials, LA, and LS

[0046]

[0047] It can be seen from the above table that energetic 3D metal-organic framework materials have good thermal stability and high density. Compared with traditional explosives LA and LS, they show better mechanical stability, which can greatly avoid safety issues during the use, transportation and storage of energetic materials.

[0048] The energetic 3D metal-organic framework material of the present invention forms a 3D metal-organic framework to encapsulate the sensitive component perchlorate, thereby increasing the oxygen content and oxygen balance of the molecule while improving stability. The perchloric acid·tris(diamino-1,2,4-oxadiazolone)·silver 3D energetic metal-organic framework material prepared by the present invention exhibits an ultra-high crystal density (2.612 g cm at 170 K). -3 ), excellent thermal stability (240℃), and ideal mechanical sensitivity (impact sensitivity 7J, friction sensitivity 40N). The energetic 3D metal organic framework material of diamino 1,2,4-oxadiazolone is not only expected to replace detonators such as lead azide, but also provide a new perspective for the development of a new generation of high-energy and low-sensitivity energetic materials.

[0049] Although the embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the specification and the embodiments. It can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily realized. Therefore, without departing from the general concept defined by the claims and equivalent scope, the present invention is not limited to the specific details and the illustrations shown and described here.

Claims

1. An energetic 3D metal organic framework material comprising metal ions, organic ligands and explosive components; in, The metal ion is a silver ion, the organic ligand is a 1,2,4-oxadiazolone compound, the explosive component is a perchlorate ion, and the monomer structure of the energetic 3D metal organic framework material is as follows: 。 2. The energetic 3D metal organic framework material according to claim 1, in, The 3D metal organic framework material is monoclinic, with a P21 / n space group, and unit cell parameters of a=8.2276Å, b=10.5623Å, c=12.0855Å, α=90º, β=99.443º, and γ=90º.

3. A method for preparing the energetic 3D metal organic framework material according to claim 1 or 2, comprising the steps of: dispersing the ligand in water, heating, adding acid dropwise, stirring for 30 min after all the solids are dissolved, adding an aqueous solution of the corresponding acid silver salt, heating the system again and maintaining the temperature for 30 min, cooling to room temperature, standing, filtering, washing with water, and vacuum drying to obtain the 3D metal organic framework material.

4. The method according to claim 3, in, The heating temperature was 60°C and the temperature was raised to 60°C again.

5. The method according to claim 3, in, The acid is perchloric acid and the silver salt is silver perchlorate.

6. The method according to claim 3, in, The ligand is diamino 1,2,4-oxadiazolone, and the molar ratio of the ligand to the silver salt is 1:

2.

7. The method according to claim 3, in, The standing time is 5 h.

8. Use of the energetic 3D metal organic framework material as claimed in claim 1 as an energetic material.

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