CN114133306B

CN114133306B - CL-20 and 3,4-MDNP supermolecular explosive and preparation method thereof

Info

Publication number: CN114133306B
Application number: CN202111399583.6A
Authority: CN
Inventors: 杨宗伟; 黄辉; 李洪珍; 郝世龙
Original assignee: Institute of Chemical Material of CAEP
Current assignee: Institute of Chemical Material of CAEP
Priority date: 2021-11-19
Filing date: 2021-11-19
Publication date: 2023-05-02
Anticipated expiration: 2041-11-19
Also published as: CN114133306A

Abstract

The invention discloses a CL-20 and 3,4-MDNP supermolecular explosive and a preparation method thereof, wherein the preparation method comprises the following steps: step one, preparation of an assembly solution of CL-20 and 3, 4-MDNP: adding CL-20 and 3,4-MDNP into an assembly solvent, stirring at 30-40 ℃, fully dissolving, and filtering to obtain an assembly solution for later use; preparing CL-20/3,4-MDNP supermolecular explosive: and placing the CL-20 and 3,4-MDNP assembly solution in a crystallizer with a tail pipe, adjusting the vacuum degree of the assembly system to 80-500mbar, volatilizing and extracting the solvent at room temperature, and rapidly combining and assembling crystals, growing and separating out crystals to obtain the CL-20/3,4-MDNP supermolecular explosive. The invention provides a novel CL-20/3,4-MDNP supramolecular explosive, and the preparation method is simple and efficient, and the CL-20/3,4-DNP supramolecular explosive is rapidly prepared through decompression auxiliary assembly, so that the preparation with high flux is convenient, and an effective way is provided for the preparation of the novel supramolecular explosive. The CL-20/3,4-MDNP supermolecular explosive has higher energy density and lower sensitivity, and has potentially better application prospect in the aspect of high-energy low-sensitivity explosive.

Description

CL-20 and 3,4-MDNP supermolecular explosive and preparation method thereof

Technical Field

The invention belongs to the field of energetic materials, and particularly relates to a preparation method of a hexanitrohexaazaisowurtzitane (CL-20) and a 1-methyl-3, 4-dinitropyrazole (3, 4-MDNP) supermolecular explosive. The invention has better application prospect in high-energy low-sensitivity explosive.

Background

Supermolecular explosive mainly refers to two or more explosive molecules which are microscopically combined together through intermolecular interaction to form molecular crystals with specific compositions and structures, and is characterized in that a new microstructure is formed, and macroscopic properties different from components are generated. Therefore, the supermolecular explosive is taken as a novel mode for constructing a novel energetic material and regulating and controlling the performance of the novel energetic material, and has important significance for promoting the research and development of the energetic material.

As is well known, the structure and the performance of substances are closely related, and for the field of energetic materials, the density, the melting point, the decomposition temperature, the sensitivity, the detonation and other performances of the explosive can be effectively regulated and controlled through the formation of the supermolecular structure explosive.

Disclosure of Invention

The invention provides a CL-20 and 3,4-MDNP supramolecular explosive and a preparation method thereof, so that the preparation method is simple and efficient, is convenient for high-flux preparation, and provides an effective way for preparing novel supramolecular explosive.

In view of the high-energy high-sensitivity and low-energy low-sensitivity characteristics of the CL-20 and the 3,4-MDNP, the invention adopts a supermolecule assembly strategy, and the vacuum degree of an assembly system is controlled by decompression auxiliary assembly, so that CL-20 molecules and 3,4-MDNP molecules are assembled to form the CL-20/3,4-MDNP supermolecule explosive, and the performance complementation of the CL-20 and the 3,4-MDNP is hopefully realized, and the energy and the safety are better matched. In addition, the invention changes the traditional assembly mode which depends on slow volatilization of the solvent into the low-pressure rapid assembly mode by decompression assistance, shortens the preparation time, improves the preparation efficiency, is easy for high-flux preparation, and provides an effective way for screening and preparing the supermolecular explosive. At present, no published literature report exists about the preparation of CL-20/3,4-MDNP supermolecular explosive.

The technical scheme adopted by the invention is as follows: the preparation method of the CL-20 and 3,4-MDNP supramolecular explosive comprises the following steps:

step one, preparation of CL-20 and 3,4-MDNP Assembly solution

Adding CL-20 and 3,4-MDNP into an assembly solvent, stirring at 30-40 ℃, fully dissolving, and filtering to obtain an assembly solution for later use;

step two, preparation of CL-20/3,4-MDNP supermolecular explosive

And placing the CL-20 and 3,4-MDNP assembly solution in a crystallizer with a tail pipe, adjusting the vacuum degree of the assembly system to 80-500mbar, volatilizing and extracting the solvent at room temperature, and rapidly combining and assembling crystals, growing and separating out crystals to obtain the CL-20/3,4-MDNP supermolecular explosive.

As a preferred mode of the preparation method of the CL-20 and 3,4-MDNP supermolecular explosive, the assembling solvent in the first step is one or more of methanol, acetone and acetonitrile.

As a preferred mode of the preparation method of the CL-20 and 3,4-MDNP supermolecular explosive, the CL-20 and 3,4-MDNP molecules are assembled and combined according to the molar ratio of 1:1 to form the explosive.

The invention also provides the CL-20 and 3,4-MDNP supramolecular explosive, which is prepared by the preparation method of the CL-20 and 3,4-MDNP supramolecular explosive.

As a preferable mode of the CL-20 and 3,4-MDNP supermolecular explosive, the CL-20/3,4-MDNP supermolecular explosive belongs to monoclinic system, P21/c space group and has crystal density of 1.833g/cm ³ Unit cell parameters:

α＝90°,β＝110.7350(10)°,γ＝90°。

the beneficial effects of the invention are as follows:

1) And preparing the CL-20/3,4-MDNP supermolecular explosive for the first time by adopting an independent loading strategy.

2) The preparation method is simple and efficient, the CL-20/3,4-DNP supermolecular explosive is rapidly prepared through decompression auxiliary assembly, the process is simple, the preparation efficiency is high, the high-flux preparation is convenient, and an effective way is provided for the preparation of novel supermolecular explosive.

3) The CL-20/3,4-MDNP supermolecular explosive is not reported in the literature, has higher energy density and better safety, and has better application prospect in high-energy low-sensitivity explosive.

Drawings

FIG. 1 is a flow chart of the preparation process of the CL-20 and 3,4-MDNP supramolecular explosive disclosed by the invention.

FIG. 2 is a diagram showing the structure of the crystal structure of the CL-20/3,4-MDNP supramolecular explosive disclosed by the invention.

FIG. 3 is a unit cell stacking diagram of the CL-20/3,4-MDNP supramolecular explosive disclosed in the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings, but embodiments of the present invention are not limited thereto.

As shown in FIG. 1, FIG. 1 shows a process flow diagram of the preparation of CL-20 and 3,4-MDNP supramolecular explosives of the present embodiment. The preparation process of the CL-20/3,4-MDNP supramolecular explosive of the embodiment is as follows:

step one, preparation of CL-20 and 3,4-MDNP Assembly solution

step two, preparation of CL-20/3,4-MDNP supermolecular explosive

And placing the CL-20 and 3,4-MDNP assembly solution in a crystallizer with a tail pipe, adjusting the vacuum degree of an assembly system to 80-500mbar, volatilizing and extracting the solvent at room temperature, and rapidly combining, assembling, growing and separating out crystals to obtain the CL-20/3,4-MDNP supermolecular explosive.

Specifically, the following details specific embodiments of the preparation method of the CL-20/3,4-MDNP supramolecular explosive according to the present invention.

Example 1

100ml of methanol was added to a three-necked flask, followed by 0.876g of CL-20 and 0.688g of 3,4-MDNP, stirred under slight heat (30-40 ℃ C.) to sufficiently dissolve the CL-20 and 3,4-MDNP, and then filtered to obtain an assembly solution. And placing the assembly solution in a crystallizer with a tail pipe, adjusting the vacuum degree of the assembly system to 500mbar, volatilizing and extracting the solvent at room temperature, and rapidly combining, assembling, growing and separating out crystals to obtain the CL-20/3,4-MDNP supermolecular explosive.

Example 2

50ml of acetone was added to a three-necked flask, followed by adding 2.19g of CL-20 and 1.72g of 3,4-MDNP, stirring under slight heat (30-40 ℃ C.) to sufficiently dissolve the CL-20 and 3,4-MDNP, and filtering to obtain an assembly solution. And placing the assembly solution in a crystallizer with a tail pipe, adjusting the vacuum degree of the assembly system to 400mbar, volatilizing and extracting the solvent at room temperature, and rapidly combining, assembling, growing and separating out crystals to obtain the CL-20/3,4-MDNP supermolecular explosive.

Example 3

100ml of acetonitrile was added to a three-necked flask, followed by 1.752g of CL-20 and 1.376g of 3,4-MDNP, stirred under slight heat (30-40 ℃ C.) to sufficiently dissolve the CL-20 and 3,4-MDNP, and then filtered to obtain an assembly solution. And placing the assembly solution in a crystallizer with a tail pipe, adjusting the vacuum degree of the assembly system to 80mbar, volatilizing and extracting the solvent at room temperature, and rapidly combining, assembling, growing and separating out crystals to obtain the CL-20/3,4-MDNP supermolecular explosive.

Example 4

50ml of methanol and 10ml of acetone (5:1 volume ratio) were added to a three-necked flask, 1.314g of CL-20 and 0.516g of 3,4-MDNP were then added thereto, stirred under slight heat (30-40 ℃ C.) to dissolve CL-20 and 3,4-MDNP sufficiently, and then filtered to obtain an assembly solution. And placing the assembly solution in a crystallizer with a tail pipe, adjusting the vacuum degree of the assembly system to 250mbar, volatilizing and extracting the solvent at room temperature, and rapidly combining, assembling, growing and separating out crystals to obtain the CL-20/3,4-MDNP supermolecular explosive.

Example 5

50ml of methanol and 25ml of acetone (2:1 volume ratio) were added to a three-necked flask, followed by 1.533g of CL-20 and 1.204g of 3,4-MDNP, stirred under slight heat (30-40 ℃ C.) to sufficiently dissolve the CL-20 and the 3,4-MDNP, and then filtered to obtain an assembly solution. And placing the assembly solution in a crystallizer with a tail pipe, adjusting the vacuum degree of the assembly system to 300mbar, volatilizing and extracting the solvent at room temperature, and rapidly combining, assembling, growing and separating out crystals to obtain the CL-20/3,4-MDNP supermolecular explosive.

Example 6

50ml of methanol and 50ml of acetonitrile (1:1 volume ratio) were added to a three-necked flask, followed by 2.409g of CL-20 and 1.892g of 3,4-MDNP, stirring under slight heat (30-40 ℃ C.) to sufficiently dissolve the CL-20 and the 3,4-MDNP, and then filtering to obtain an assembly solution. And placing the assembly solution in a crystallizer with a tail pipe, adjusting the vacuum degree of the assembly system to 200mbar, volatilizing and extracting the solvent at room temperature, and rapidly combining, assembling, growing and separating out crystals to obtain the CL-20/3,4-MDNP supermolecular explosive.

Example 7

25ml of acetonitrile and 25ml of acetone (1:1 volume ratio) were added to a three-necked flask, followed by 1.839g of CL-20 and 1.445g of 3,4-MDNP, stirred under slight heat (30-40 ℃ C.) to sufficiently dissolve the CL-20 and the 3,4-MDNP, and then filtered to obtain an assembly solution. And placing the assembly solution in a crystallizer with a tail pipe, adjusting the vacuum degree of the assembly system to 150mbar, volatilizing and extracting the solvent at room temperature, and rapidly combining, assembling, growing and separating out crystals to obtain the CL-20/3,4-MDNP supermolecular explosive.

As shown in fig. 2 and 3, according to another embodiment of the present invention, the present embodiment discloses CL-20/3,4-MDNP supramolecular explosives prepared by the methods for preparing CL-20 and 3,4-MDNP supramolecular explosives of the above embodiments. FIGS. 2 and 3 show the crystal structure and unit cell packing diagrams of CL-20/3,4-MDNP supramolecular explosives of the present invention. As can be seen from FIGS. 2 and 3, the CL-20/3,4-MDNP supramolecular explosive of the embodiment is formed by combining and assembling CL-20 molecules and 3,4-MDNP molecules according to a molar ratio of 1:1, belongs to monoclinic systems, P21/c space groups and has a crystal density of 1.833g/cm ³ Unit cell parameters:

α＝90°,β＝110.7350(10)°,γ＝90°。/>

the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be appreciated by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

The preparation method of the CL-20 and 3,4-MDNP supermolecular explosive is characterized by comprising the following steps:

step one, preparation of CL-20 and 3,4-MDNP Assembly solution

Adding CL-20 and 3,4-MDNP into an assembly solvent, stirring at 30-40 ℃, fully dissolving, and filtering to obtain an assembly solution for later use; CL-20 molecules and 3,4-MDNP molecules are assembled and combined according to a molar ratio of 1:1 to form;

step two, preparation of CL-20/3,4-MDNP supermolecular explosive

Placing the CL-20 and 3,4-MDNP assembly solution in a crystallizer with a tail pipe, adjusting the vacuum degree of the assembly system to 80-500mbar, volatilizing and extracting the solvent at room temperature, and quickly combining and assembling crystals, growing and separating out crystals to obtain the CL-20/3,4-MDNP supermolecular explosive;

the CL-20/3,4-MDNP supermolecular explosive belongs to monoclinic system, P21/c space group and has crystal density of 1.833g/cm ³ Unit cell parameters:
α＝90°,β＝110.7350(10)°,γ＝90°。
2. the method for preparing the CL-20 and 3,4-MDNP supramolecular explosive according to claim 1, wherein the method is characterized in that: the assembly solvent in the first step is one or more of methanol, acetone and acetonitrile.
3. A CL-20 and 3,4-MDNP supermolecular explosive, which is characterized in that: the CL-20 and 3,4-MDNP supramolecular explosive is prepared by the preparation method of the CL-20 and 3,4-MDNP supramolecular explosive according to any one of claims 1 or 2.