CN116986958A - Energy-containing 3D metal organic framework material and preparation method and application thereof - Google Patents
Energy-containing 3D metal organic framework material and preparation method and application thereof Download PDFInfo
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- CN116986958A CN116986958A CN202310928147.6A CN202310928147A CN116986958A CN 116986958 A CN116986958 A CN 116986958A CN 202310928147 A CN202310928147 A CN 202310928147A CN 116986958 A CN116986958 A CN 116986958A
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- 239000000463 material Substances 0.000 title claims abstract description 54
- 239000013273 3D metal–organic framework Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 11
- 239000013110 organic ligand Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical group [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims abstract description 5
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 4
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical group N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000000284 resting effect Effects 0.000 claims 1
- 239000002360 explosive Substances 0.000 abstract description 12
- 239000013078 crystal Substances 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000012621 metal-organic framework Substances 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 239000003380 propellant Substances 0.000 abstract description 3
- 238000010586 diagram Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 4
- -1 diamino-1, 2, 4-oxadiazolone Chemical compound 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 3
- BXTWRMNZAGYXQQ-UHFFFAOYSA-N 1,2,4-oxadiazol-3-one Chemical compound O=C1N=CON1 BXTWRMNZAGYXQQ-UHFFFAOYSA-N 0.000 description 2
- 150000001540 azides Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- BBVIDBNAYOIXOE-UHFFFAOYSA-N 1,2,4-oxadiazole Chemical group C=1N=CON=1 BBVIDBNAYOIXOE-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000003378 silver Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B29/00—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0008—Compounding the ingredient
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/006—Stabilisers (e.g. thermal stabilisers)
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
- C06B45/18—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component
- C06B45/30—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component the component base containing an inorganic explosive or an inorganic thermic component
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
Abstract
The invention discloses an energy-containing 3D metal organic framework material, which comprises metal ions, organic ligands and explosion-causing components; wherein, the metal ion is silver ion; the organic ligand is a bi-1, 2, 4-oxadiazolone compound, the explosion-causing component is perchlorate ions, the energy-containing 3D metal organic framework material has a three-dimensional crystal structure, high oxygen balance, excellent thermal stability and low sensitivity, and the metal organic framework material has application potential in the fields of primary explosive, propellant, high explosive and the like. The invention also discloses a preparation method of the energy-containing 3D metal organic framework material, wherein water is used for replacing an organic solvent in the preparation, and the preparation method is environment-friendly and pollution-free and has a simple preparation process. The energetic 3D metal organic framework material disclosed by the invention wraps explosive components in the framework through a unique three-dimensional structure, so that the oxygen content and the oxygen balance of molecules are improved, and meanwhile, the stability is improved.
Description
Technical Field
The invention relates to the technical field of energetic materials, in particular to an energetic 3D metal organic framework material and a preparation method and application thereof.
Background
The metal organic framework material is a material formed by coordination of metal ions or metal clusters and organic ligands, and has a huge application prospect in the fields of gas storage, catalytic chemistry, optics, biomedical engineering and the like due to a highly porous structure. In recent years, metal-organic framework materials have been increasingly used in the field of energetic materials at a brand-new angle, including in explosive monitoring and the preparation of high-energy low-inductance energetic materials. The energetic metal-organic framework material may be incorporated with the energetic component by a simple self-assembly process. However, it is very difficult for metal organic framework materials to form special 3D structures due to the difficult controlled number of coordination bonds and coordination patterns of metal ions during self-assembly. Finding suitable metal ions, organic ligands and reaction conditions to form energetic 3D metal-organic framework materials is a continuing goal pursued by researchers.
Disclosure of Invention
It is an object of the present invention to address at least the above problems and/or disadvantages and to provide at least the advantages described below.
It is still another object of the present invention to provide an energetic 3D metal-organic framework material, which uses bi-1, 2, 4-oxadiazolone as an organic ligand and metal ions to encapsulate explosive components in a framework through its unique three-dimensional structure, and is a metal-organic framework material having a three-dimensional crystal structure, high oxygen balance, excellent thermal stability, low sensitivity, and exhibiting application potential in the fields of primary explosive, propellant, high explosive, etc.
Still 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 environment-friendly and pollution-free, and has simple synthesis steps.
To achieve these objects and other advantages and in accordance with the purpose of the invention, there is provided an energetic 3D metal-organic framework material comprising metal ions, an organic ligand, and an explosion-causing component;
wherein the metal ion is silver ion, the organic ligand is a bi-1, 2, 4-oxadiazolone compound, and the explosion-causing component is perchlorate ion.
Preferably, the bi-1, 2, 4-oxadiazolone compound has the structure shown in the following formula (I):
wherein R is 1 、R 2 Is a nitrogen-containing group.
Preferably, the 3D metal organic framework material is monoclinic, the P21/n space group is provided with unit cell parameters ofα＝90°，β＝99.443°，γ＝90°。
Preferably, wherein R 1 、R 2 All are amino groups.
The object of the invention is further achieved by a method for preparing an energetic 3D metal-organic framework material comprising the steps of: dispersing the ligand in water, heating, dropwise adding acid, continuously stirring for 30min after the solid is completely dissolved, adding aqueous solution of corresponding silver acid salt, heating and maintaining the system for 30min again, cooling to room temperature, standing, filtering, washing with water, and vacuum drying to obtain the 3D metal organic frame material.
Preferably, the heating temperature is 60 ℃, and the temperature is raised to 60 ℃ again.
Preferably, the acid is perchloric acid and the silver salt is silver perchlorate.
Preferably, the ligand is diamino-1, 2, 4-oxadiazolone, and the molar ratio of the ligand to silver salt is 1:2.
Preferably, the rest time is 5h.
The object of the invention can be further achieved by the use of an energetic 3D metal organic framework material as an energetic oxidant.
The invention at least comprises the following beneficial effects:
1. the energy-containing 3D metal organic framework material has a three-dimensional crystal structure, high oxygen balance, excellent thermal stability and low sensitivity, and has application potential in the fields of primary explosive, propellant, high explosive and the like.
2. The energetic 3D metal organic framework material disclosed by the invention has the advantages that the 1,2, 4-oxadiazolone serving as an organic ligand and metal ions are used for wrapping explosive components in the framework through a unique three-dimensional structure, so that the energy can be improved, and the sensitivity can be reduced.
3. The preparation method of the invention uses water to replace organic solvent, is environment-friendly and pollution-free, and has simple synthesis steps.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a single crystal structure of the energetic 3D metal-organic framework material of example 1 of the present invention;
FIG. 2 is a crystal stacking diagram of the energetic 3D metal-organic framework material of example 1 of the present invention;
FIG. 3 is a three-dimensional frame diagram of an energetic 3D metal-organic framework material according to example 1 of the present invention;
FIG. 4 is an optical view of the energetic 3D metal organic framework material of example 1;
fig. 5 is a DSC diagram of the energetic 3D metal-organic framework material in example 1 of the present invention.
Detailed Description
The present invention is described in further detail below with reference to the drawings to enable those skilled in the art to practice the invention by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
The experimental methods described in the following embodiments are conventional methods unless otherwise indicated, and the reagents and materials are commercially available.
Example 1 ]
The monomer structure formula of the energy-containing 3D metal organic framework material is as follows:
the specific synthetic route is as follows:
the specific synthesis steps are as follows:
diamino-1, 2, 4-oxadiazolone (1 mmol,0.2 g) was dispersed in 3mL of water and after heating to 60℃2mL of 72% perchloric acid was added dropwise, the solid was completely dissolved. After stirring for a further 30 minutes, a 3mL aqueous solution of silver perchlorate (2 mmol,0.42 g) was added. After the system was again warmed to 60℃and held for 30 minutes, cooled to room temperature and left to stand for 5 hours, filtered and washed with 1mL of water, and dried under vacuum, 56mg of perchloric acid tris (diaminobi 1,2, 4-oxadiazolone) silver was obtained in the form of colorless needle crystals with a yield of 41%.
Among them, diamino-bis-1, 2, 4-oxadiazolone synthesis references: chemical Engineering Journal,2023,467,143527.
The monocrystal structure diagram of the energy-containing 3D metal organic framework material is shown in fig. 1, the crystal stacking diagram is shown in fig. 2, and the three-dimensional framework diagram is shown in fig. 3; the optical diagram is shown in fig. 4; the DSC chart is shown in FIG. 5.
The method can obtain five coordination bonds formed by each silver atom in perchloric acid and tris (diamino-1, 2, 4-oxadiazolone) and silver, two nitrogen atoms on the 1,2, 4-oxadiazole ring, two nitrogen atoms of amino groups and an oxygen atom of a carbonyl group through crystal analysis, so that a strong three-dimensional framework is constructed, and perchlorate is wrapped in a hole. The reasonable selection of organic ligand, inorganic metal salt and reaction condition plays a positive role in the structure of the energy-containing metal organic frame.
Example 2 ]
Performance comparison of the energetic 3D metal organic framework material, conventional initiating explosive Lead Azide (LA), lead Stevenate (LS) of example 1 of the present invention.
The performance of the energetic 3D metal-organic framework material, LA, LS is compared to table 1 below.
TABLE 1 comparison of Performance of energetic 3D Metal organic framework materials, LA, LS
From the above table, the energetic 3D metal organic framework material has good thermal stability and high density, and compared with the traditional primary explosive LA and LS, the material has better mechanical stability, and can greatly avoid the safety problem in the process of using, transporting and storing the energetic material.
The energy-containing type 3D metal organic framework material disclosed by the invention wraps the sensitive component perchlorate in the 3D metal organic framework, so that the oxygen content and the oxygen balance of molecules are improved, and meanwhile, the stability is improved. The perchloric acid-tris (diamino-bi-1, 2, 4-oxadiazolone) -silver 3D energetic metal-organic framework material prepared by the invention shows ultra-high crystal density (2.612 g cm at 170K) -3 ) Excellent thermal stability (240 ℃) and ideal mechanical sensitivity (impact sensitivity 7J, friction sensitivity 40N). The energy-containing 3D metal organic framework material of the diamino-1, 2, 4-oxadiazolone is hopeful to replace detonators such as lead azide and the like, and provides a new view for the development of new generation high-energy low-sense energy-containing materials.
Although embodiments of the invention have been disclosed above, they are not limited to the use listed in the specification and embodiments. It can be applied to various fields suitable for the present invention. Additional modifications will readily occur to those skilled in the art. Therefore, the invention is not to be limited to the specific details and illustrations shown and described herein, without departing from the general concepts defined in the claims and their equivalents.
Claims (10)
1. An energetic 3D metal-organic framework material comprising metal ions, organic ligands, and an explosion-causing component;
wherein the metal ion is silver ion, the organic ligand is a bi-1, 2, 4-oxadiazolone compound, and the explosion-causing component is perchlorate ion.
2. The energetic-type 3D metal-organic framework material of claim 1, wherein the bis-1, 2, 4-oxadiazolone compound has the structure of formula (I):
wherein R is 1 、R 2 Is a nitrogen-containing group.
3. The energetic-type 3D metal-organic framework material of claim 1, wherein the 3D metal-organic framework material is monoclinic, P21/n space group, unit cell parameters areα＝90°，β＝99.443°，γ＝90°。
4. The energetic 3D metal-organic framework material of claim 2 wherein R 1 、R 2 All are amino groups.
5. A method of preparing the energetic 3D metal-organic framework material of any one of claims 1 to 4, comprising the steps of: dispersing the ligand in water, heating, dropwise adding acid, continuously stirring for 30min after the solid is completely dissolved, adding aqueous solution of corresponding silver acid salt, heating and maintaining the system for 30min again, cooling to room temperature, standing, filtering, washing with water, and vacuum drying to obtain the 3D metal organic frame material.
6. The method of claim 5, wherein the heating temperature is 60 ℃, and the temperature is raised again to 60 ℃.
7. The method of claim 5, wherein the acid is perchloric acid and the silver salt is silver perchlorate.
8. The method of claim 5, wherein the ligand is diamino-bis-1, 2, 4-oxadiazolone having a molar ratio to silver salt of 1:2.
9. The method of claim 5, wherein the resting time is 5 hours.
10. Use of the energetic 3D metal-organic framework material of claim 1 as an energetic material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310928147.6A CN116986958A (en) | 2023-07-27 | 2023-07-27 | Energy-containing 3D metal organic framework material and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310928147.6A CN116986958A (en) | 2023-07-27 | 2023-07-27 | Energy-containing 3D metal organic framework material and preparation method and application thereof |
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| CN116986958A true CN116986958A (en) | 2023-11-03 |
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|---|---|---|---|
| CN202310928147.6A Pending CN116986958A (en) | 2023-07-27 | 2023-07-27 | Energy-containing 3D metal organic framework material and preparation method and application thereof |
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| Country | Link |
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| CN (1) | CN116986958A (en) |
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2023
- 2023-07-27 CN CN202310928147.6A patent/CN116986958A/en active Pending
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