1. The preparation method of the near-infrared laser ignition energetic material is characterized by comprising the following steps of: dissolving an energy-containing metal organic framework material into water at a certain temperature, and then adding CHNO high-energy explosive crystals; standing for 1-2 days at room temperature to obtain a novel energetic material with a layer of energetic metal organic framework material grown on the surface of the CHNO high-energy explosive crystal, and obtaining the target energetic material.

2. The preparation method of the near-infrared laser ignition energetic material as claimed in claim 1, wherein the preparation method of the energetic metal-organic framework material is as follows: reacting bistetrazolylamine (H) at room temperature₂BTA) is added into water, then NaOH is added, reflux is carried out, and organic cation chloride is added after reactants are completely dissolved; after the reaction solution is completely clarified, quickly adding transition metal salt, and carrying out secondary reflux for 10 minutes; and filtering while the solution is hot, standing the filtrate at room temperature, and obtaining the crystals of the energy-containing metal organic framework material after 1-2 days.

3. The method for preparing the near-infrared laser ignition energetic material according to claim 1, wherein the certain temperature is room temperature to 90 ℃.

4. The method for preparing the near-infrared laser ignition energetic material according to claim 1, wherein the CHNO high explosive comprises but is not limited to RDX, HMX and CL-20.

5. The preparation method of the near-infrared laser ignition energetic material according to claim 1, wherein the mass ratio of the energetic metal-organic framework material to the CHNO high-energy explosive crystal is 1: (0.2-5).

6. The method for preparing the near-infrared laser ignition energetic material according to claim 2, wherein the reflux temperature is 60-80 ℃.

7. The method for preparing the near-infrared laser ignition energetic material according to claim 2, wherein the refluxing time is 10-30 minutes.

8. The method for preparing the near-infrared laser ignition energetic material according to claim 2, wherein the secondary reflux temperature is 60-80 ℃.

9. The method for preparing the near-infrared laser ignition energetic material according to claim 2, wherein the refluxing time is 5-10 minutes.

10. A near-infrared laser ignition energetic material, which is prepared by the preparation method of any one of claims 1 to 9.

Background

The laser ignition mechanism of the energetic material can be divided into a photothermal effect mechanism and a laser direct dissociation mechanism. The photothermal effect mechanism is that energetic material molecules instantly generate high-energy heat by absorbing laser photon energy, so that the energetic material is ignited. The laser direct dissociation mechanism means that energetic material molecules absorb laser photons with specific frequency and dissociate to generate high-activity molecular fragments, so that chemical chain reaction is initiated to realize ignition of the energetic material. Most laser ignition belongs to photo-thermal ignition, and laser direct dissociation ignition is possible only when laser energy is matched with the photoactivation energy of energetic material molecules. The near infrared pulse diode laser light source has the advantages of small device, low price and the like, and is the most suitable power supply for the miniature laser ignition device.

However, the light quantum energy of the near-infrared laser is small, which is not enough to excite the electronic transition of the traditional explosive, so that the laser direct dissociation ignition of the energetic material is difficult to realize, and the near-infrared laser ignition is mainly photo-thermal ignition. Whether the laser ignition technology can be practically applied to weaponry or not is mainly determined by the development level of the laser technology and laser ignition energetic materials. In recent years, laser technology has been dramatically developed. Currently, a wide variety of lasers are commercialized, wherein the near infrared laser is well suited for the application requirements of weaponry. However, energetic materials with laser ignition properties are developing very slowly, which severely hampers the development of laser ignition technology.

The traditional CHNO explosive generally has the problem of low or basically no laser absorption capability, so that the traditional CHNO explosive does not have the laser ignition performance. Materials such as carbon black, organic dye and metal nanoparticles are used as photosensitizers and doped into the CHNO explosive, so that the laser absorption capacity of the composite energetic material can be improved, and the laser ignition performance of the CHNO explosive is realized. However, the composite energetic material prepared by the method has the defects of unstable performance, poor safety of the preparation process and the like. Meanwhile, the addition of harder components (metal nano-ions) in the explosive also increases the mechanical sensitivity of the target composite material and reduces the safety performance of the target composite material. Therefore, the development of a new method for preparing the composite energetic material with the laser ignition performance has important value for promoting the development of the laser ignition technology.

The invention provides a new method for constructing a near-infrared laser ignition energetic material by directionally growing an energetic metal organic framework material with strong laser absorption performance on the surface of the existing high-energy explosive crystal. The novel energetic material provided by the invention can promote the rapid development of a laser ignition technology, and also provides a new idea for the preparation of the novel laser ignition energetic material.

Disclosure of Invention

The method aims at the current situation that the existing near-infrared laser ignition energetic materials are rare in types and the development of the near-infrared laser ignition technology is seriously hindered. The invention provides an energetic material with near-infrared laser ignition performance and a preparation method thereof.

In order to realize the purpose of the invention, the invention provides the following technical scheme:

a preparation method of a near-infrared laser ignition energetic material comprises the following steps: dissolving an energy-containing metal organic framework material into water at a certain temperature, and then adding CHNO high-energy explosive crystals; standing for 2-3 days at room temperature to obtain a novel energetic material with a layer of energetic metal organic framework material grown on the surface of the CHNO high-energy explosive crystal, and obtaining the target energetic material.

In some embodiments, the energetic metal-organic framework material is prepared by a method comprising: reacting bistetrazolylamine (H) at room temperature₂BTA) is added into water, then NaOH is added, reflux is carried out, and after reactants are completely dissolved, organic nitrogen-rich cation chloride is added; after the reaction solution is completely clarified, quickly adding transition metal salt, and carrying out secondary reflux for 10 minutes; and filtering while the solution is hot, standing the filtrate at room temperature, and obtaining the crystals of the energy-containing metal organic framework material after 1-2 days.

In some embodiments, the certain temperature is between room temperature and 90 ℃.

In some embodiments, CHNO-based high explosive includes, but is not limited to, RDX, HMX, and CL-20.

In some embodiments, the energetic metal organic framework material and the CHNO-based high energy explosive crystal are present in a mass ratio of 1: (0.2-5).

In some embodiments, the reflux temperature is 60 ℃ to 80 ℃.

In some embodiments, the reflux time is 10-30 minutes.

In some embodiments, the secondary reflux temperature is 60 ℃ to 80 ℃.

In some embodiments, the reflux time is 5-10 minutes.

The invention also provides a near-infrared laser ignition composite energetic material prepared by any one of the preparation methods.

Compared with the prior art, the invention has the beneficial effects that:

the invention provides a composite energetic material with near-infrared laser ignition performance, aiming at the problem that the types of the existing near-infrared laser ignition materials are rare. CHNO high-energy explosive does not usually have near-infrared laser initiation performance, and the invention constructs a novel composite energetic material with near-infrared laser ignition performance by growing a layer of energetic MOFs with strong laser absorption performance on the surface of a crystal and utilizing the synergistic effect of the energetic MOFs and the MOFs. The content of energetic MOFs of the composite energetic material is 10-90%.

Drawings

For a clearer explanation of the embodiments or technical solutions in the prior art of the present application, the drawings used in the description of the embodiments or prior art will be briefly described below, it is obvious that the drawings in the following description are only references to some embodiments in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.

FIG. 1 is a schematic diagram of a synthetic route of an energetic material according to an embodiment of the present invention.

FIG. 2 is a single crystal view of an energetic metal-organic framework 1 according to an embodiment of the present invention.

Fig. 3 is a graph of a near-infrared laser ignition experiment of the energetic material 1 of an embodiment of the present invention.

Detailed Description

The present invention will be further described with reference to the following examples, which are intended to illustrate only some, but not all, of the embodiments of the present invention. Based on the embodiments of the present invention, other embodiments used by those skilled in the art without any creative effort belong to the protection scope of the present invention.

The technical scheme adopted by the invention is as follows:

1) designing and synthesizing an energy-containing metal organic framework material which has excellent solubility in a polar solvent and strong absorption capacity to near-infrared laser; 2) directionally growing the energy-containing metal organic framework material on the surface of the CHNO high-energy elementary explosive crystal; 3) the near-infrared laser ignition performance of the target energetic material is realized by utilizing the synergistic effect between the energetic metal organic framework material and the high-energy explosive.

The synthesis route of the energy-containing metal-organic framework material is shown in figure 1, wherein:

M：Fe²⁺、Cu²⁺、Co²⁺an iso-transition metal cation;

n: guanidine, triaminoguanidine, and like organic cations.

The specific synthesis method comprises the following steps:

reacting bistetrazolylamine (H) at room temperature₂BTA) was added to water, then NaOH was added, refluxing at 80 ℃ for 0.5 hour, and after the reactants were completely dissolved, organic cationic chloride salt was added. After the reaction solution is completely clarified, the transition metal salt is rapidly added, and the mixture is refluxed for 10 minutes at 80 ℃. And (4) filtering while heating, standing the filtrate at room temperature, and obtaining the crystals of the energy-containing metal organic framework material after 1-2 days.

NaOH in the above synthesis method may be other bases such as KOH;

bistetrazolylamines (H) in the above synthesis₂BTA) and NaOH in a molar ratio of 1: (1.8-2.1); h₂The molar ratio of BTA to organic nitrogen-rich cationic chloride salt is 1: (1.0-3.0); h₂The molar ratio of BTA to transition metal salt is 1: (0.25 to 0.75); the reflux temperature may be, but is not limited to, 80 ℃; the reflux time may be, but is not limited to, 10 minutes.

2) Preparation of novel energetic material:

at a certain temperature, the synthesized energy-containing metal organic framework material is dissolved in water, and then CHNO high-energy explosive crystals are added. Standing for 2-3 days at room temperature to obtain a novel energetic material with a layer of energetic metal organic framework material growing on the surface of the CHNO high-energy explosive crystal. It is compounded by energetic metal organic frame material and CHNO high-energy explosive. The energy-containing metal organic framework material is constructed by organic cations, transition metal ions and energy-containing ligands, has better solubility in polar solvents such as water, methanol, dimethylformamide and the like, and has stronger absorption capacity for visible light and near infrared light. The near infrared laser is directly irradiated on the target energetic material, so that the target energetic material is detonated or exploded.

The certain temperature range in the preparation method is room temperature to 90 ℃;

the high explosive in the preparation method can be, but is not limited to RDX, HMX and CL-20;

the mass ratio of the energy-containing metal organic framework material to the high-energy single-substance explosive in the preparation method is 1: (0.2-5).

The present invention will be further described with reference to the following specific examples.

Example 1 preparation of energetic Metal-organic framework Material-1

To a 100mL round bottom flask, at room temperature, was added 100mL of water, 1.56g of bistetrazolylamine (H)₂BTA), 0.8g NaOH, heated to 80 ℃ and refluxed for 10 minutes. Wait for H₂After the BTA and NaOH were completely dissolved, 2.24g of triaminoguanidine hydrochloride was added and refluxed for 5 minutes. And after the aminoguanidine hydrochloride is completely dissolved, adding 0.56g of copper chloride trihydrate, refluxing for 10 minutes, filtering, and standing the filtrate at room temperature for 1-3 days to obtain the green crystal energetic metal organic framework-1 material.

Example 2 preparation of energetic Metal-organic framework Material-1

To a 100mL round bottom flask, at room temperature, was added 100mL of water, 1.56g of bistetrazolylamine (H)₂BTA), 1.12g KOH, heated to 80 ℃ and refluxed for 10 minutes. Wait for H₂After the BTA and KOH were completely dissolved, 2.24g of triaminoguanidine hydrochloride was added and refluxed for 5 minutes. And after the aminoguanidine hydrochloride is completely dissolved, adding 0.78g of cobalt chloride hexahydrate, refluxing for 10 minutes, filtering, and standing the filtrate at room temperature for 1-3 days to obtain the green crystal energetic metal organic framework material-1.

FIG. 2 is a single crystal diagram of an energetic metal-organic framework material-1;

in the structure of the energy-containing metal-organic framework material, each copper ion and two deprotonated bistetrazolylamine anions (BTA)^2-) Coordinates, each BTA^2-The anion is coordinated with a copper ion in a chelating coordination mode. Through the coordination mode between the metal ions and the ligands, the structureNegatively charged Cu (BTA)₂ ^2-And (4) ion clusters. Triaminoguanidine cation (TAG) acts as charge balance and is distributed in Cu (BTA)₂ ^2-Around the ion cluster, so as to construct the crystal structure of the energy-containing metal organic framework material-1.

EXAMPLE 3 preparation of novel energetic Material (1)

At room temperature, 0.2g of energetic metal organic framework material-1, 20mL of water are added into a 100mL single-neck flask, the mixture is heated to 60 ℃ for reflux, after a clear solution is formed, 0.6g of CL-20 crystals are added into the solution, the solution is cooled to room temperature and stands for 2 days, and the target energetic material 1 is obtained.

EXAMPLE 4 preparation of novel energetic Material (2)

At room temperature, 0.2g of energetic metal organic framework material-1, 20mL of water is added into a 100mL single-neck flask, the mixture is heated to 60 ℃ for reflux, after a clear solution is formed, 0.6g of HMX crystal is added into the solution, the solution is cooled to room temperature and stands for 2 days, and the target energetic material 2 is obtained.

EXAMPLE 7 preparation of novel energetic Material (3)

At room temperature, 0.2g of energetic metal organic framework material-1, 20mL of water is added into a 100mL single-neck flask, the mixture is heated to 60 ℃ for reflux, after a clear solution is formed, 0.6g of RDX crystal is added into the solution, and the solution is cooled to room temperature and stands for 2 days to obtain the target energetic material 3.

EXAMPLE 8 laser ignition Performance of novel energetic materials

At room temperature, 0.1g of the composite energetic material 1 is pressed into a sheet shape under the pressure of 0.1MPa, a 1064nm laser is adopted to irradiate a sample, and a high-speed camera is used for shooting the whole ignition experiment process.

Fig. 3 is a graph of a near-infrared laser ignition experiment of the energetic material 1 of an embodiment of the present invention.

The energetic material 1 which is made into a sheet structure is placed on a sample stage of a laser ignition performance testing device, near-infrared laser of 1064nm is adopted to irradiate a sample, and a high-speed camera (1000 frames per second) is adopted to shoot the whole experimental process. The time interval between the laser just contacting the sample and the first observation of a burning flame is the material ignition delay time. As can be seen from fig. 3, the material starts to gasify after the laser is irradiated on the energetic material 1 for 6 ms; at 65ms, a distinct combustion flame was observed. Therefore, the near infrared laser ignition delay time of the energetic material 1 is 65 ms.

Although the present invention has been described herein with reference to the illustrated embodiments thereof, which are intended to be preferred embodiments of the present invention, it is to be understood that the invention is not limited thereto, and that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.