CN112358370A

CN112358370A - CL-20 and NTO eutectic explosive and preparation method thereof

Info

Publication number: CN112358370A
Application number: CN202010991284.0A
Authority: CN
Inventors: 杜君宜; 刘吉平; 杨威威
Original assignee: Beijing Institute of Technology BIT
Current assignee: Beijing Institute of Technology BIT
Priority date: 2020-09-20
Filing date: 2020-09-20
Publication date: 2021-02-12

Abstract

The invention relates to a CL-20 and NTO (nitrotoluene) eutectic explosive and a preparation method thereof, in particular to a hexanitrohexaazaisowurtzitane (CL-20) and 3-nitro-1, 2, 4-triazole-5-ketone (NTO) eutectic explosive and a preparation method thereof, belonging to the field of energetic materials. The CL-20/NTO eutectic explosive is prepared by taking CL-20 and NTO as raw materials and adopting a solvent volatilization method. The CL-20/NTO eutectic explosive prepared by the invention has greatly reduced melting point and is more suitable for being used as a fusion casting matrix explosive; the crystal density is obviously improved (6.1%); the detonation velocity is improved by 9.7 percent, and good detonation performance is shown. The preparation method has the advantages of mild preparation conditions, simple process and convenient operation. The eutectic explosive is a novel high-energy low-sensitivity fusion-cast matrix explosive and has a good application prospect.

Description

CL-20 and NTO eutectic explosive and preparation method thereof

Technical Field

The invention relates to a hexanitrohexaazaisowurtzitane (CL-20) and 3-nitro-1, 2, 4-triazole-5-ketone (NTO) eutectic explosive and a preparation method thereof, belonging to the technical field of energetic materials.

Background

The existing fusion-cast matrix explosives have inherent defects, such as low charge density of 2,4, 6-trinitrotoluene (TNT), unsatisfactory detonation performance and easy oil leakage in long-term storage; 2, 4-Dinitroanisole (DNAN) has poor detonation performance; the melting point of 3, 4-dinitrofurazan-based furazan (DNTF) is too high, and the DNTF is volatile when a fused cast medicine is prepared; 1,3, 3-Trinitroazetidine (TNAZ) is too costly to be produced in large quantities; the synthetic route of 1-methyl-2, 4, 5-trinitroimidazole (MTNI) is complicated, and the cost is high. The traditional fusion-cast matrix explosive cannot meet the requirements of modern weapons on the performance of energetic materials. Therefore, the research on the preparation of the novel fusion-cast matrix explosive is not slow enough.

The eutectic technology is a new technology developed in recent years, is widely applied to the field of energetic materials, and can essentially and effectively improve the properties of the energetic materials, such as melting point, sensitivity, thermal stability, solubility, hygroscopicity and the like from a molecular level. The CL-20 explosive name hexanitrohexaazaisowurtzitane is a newly developed high explosive for military use. The explosion energy and mechanical sensitivity of the CL-20 explosive are higher than that of HMX, and the heat resistance is similar to that of RDX. NTO (chemical name is 3-nitro-1, 2, 4-triazole-5-ketone) is a high-energy low-sensitivity single-substance explosive with excellent performance, the crystal density is 1.93g/cm3, and the theoretical detonation velocity is 8670 m/s; the degree of friction sensitivity was 8% (3.92MPa, 90 ℃ swing angle), the characteristic drop height H50 was 102.3cm (5kg drop weight), and the degree of impact sensitivity was 16% (10kg drop weight, 25cm drop height). The NTO energy is close to that of hexogen, has higher thermal stability and chemical stability, has excellent X-ray and ultraviolet radiation resistance, and can be used as a insensitive coating agent of sensitive explosives. At present, there is no report on a literature disclosing a cocrystal explosive of hexanitrohexaazaisowurtzitane (CL-20) and 3-nitro-1, 2, 4-triazol-5-one (NTO) and a preparation method thereof.

Disclosure of Invention

The invention aims to provide a CL-20 and NTO eutectic explosive and a preparation method thereof, wherein the crystal density of the eutectic explosive is obviously improved (6.1%); the detonation velocity is improved by 9.7 percent, and good detonation performance is shown.

In order to solve the technical problems, the invention is realized by the following technical scheme.

CL-20 and NTO eutectic explosive, wherein CL-20 molecules, NTO molecules and H in the eutectic explosive₂The molar ratio of O molecules is 1:1: 1. The molecular formula of the eutectic is C₅H₈N₈O₆Belonging to the orthorhombic system, P2₁2₁2₁Space group with crystal density up to 1.909g/cm³。

A preparation method of a CL-20 and NTO eutectic explosive comprises the following specific steps:

step one, preparation of CL-20 and NTO saturated solution

Dissolving sufficient CL-20 in a solvent at the temperature of 35-65 ℃, and dissolving and filtering to obtain a saturated CL-20 solution; adding sufficient NTO into the NTO saturated solution for dissolving and filtering to obtain CL-20 and NTO saturated solution;

step two, preparation of CL-20 and NTO eutectic explosive

And (3) transferring the CL-20 and NTO saturated solution prepared in the step one into a container, standing the container in a thermostat, slowly volatilizing the solvent at the temperature of 35-65 ℃, slowly forming crystals, filtering and drying to obtain the CL-20/NTO eutectic explosive.

In the step one, the solvent is one or a mixture of industrial ethyl acetate, industrial isopropanol and industrial dimethyl sulfoxide.

Advantageous effects

1. Compared with CL-20, the CL-20/NTO eutectic explosive prepared by the invention has greatly reduced DSC melting peak and is more suitable for being used as a fusion casting matrix explosive.

2. Compared with NTO, the crystal density of the CL-20/NTO eutectic explosive prepared by the invention is obviously improved (6.1%); the detonation velocity is improved by 9.7 percent, and good detonation performance is shown.

3. The preparation method has the advantages of mild preparation conditions, simple process and convenient operation.

Drawings

FIG. 1 is a flow chart of the preparation of the CL-20/NTO eutectic explosive of the invention.

FIG. 2 is a CL-20/NTO eutectic explosive through infrared (FT-IR) diagram

FIG. 3 is a powder diffraction graph of CL-20/NTO eutectic explosive passing PXRD test

FIG. 4 is an SEM image of CL-20 (non-transcrystallized, a), NTO, and CL-20/NTO eutectic (c, d, e)

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more clearly apparent, the present invention will be described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

FIG. 1 shows a preparation flow chart of a hexa-3, 4-diaminofurazan and 3, 4-dinitropyrazole (CL-20/NTO) eutectic explosive. The preparation process of the CL-20/NTO eutectic explosive is as follows:

(1) preparation of CL-20 and NTO solution

Dissolving sufficient CL-20 in a solvent, dissolving at 35-65 ℃, and filtering to obtain a saturated CL-20 solution; adding sufficient NTO into the saturated CL-20 solution, and filtering to obtain saturated CL-20 and NTO solution.

(2) Preparation of CL-20 and NTO eutectic explosive

Transferring the CL-20/NTO solution into a beaker, standing the beaker in a thermostat, slowly volatilizing the solvent at a certain temperature, filtering and drying to obtain the CL-20/NTO eutectic explosive.

FIGS. 2, 3 and 4 show the molecular structure diagrams of CL-20/NTO eutectic explosive confirmed by FT-IR and PXRD tests. From the analysis results of the above figures, it can be seen that: CL-20 molecules, NTO molecules and H in the eutectic explosive₂The molar ratio of O molecules is 1:1: 1. The molecular formula of the eutectic is C₅H₈N₈O₆Belonging to the orthorhombic system, P2₁2₁2₁Space group with crystal density up to 1.909g/cm³And the improvement is remarkably higher than NTO (6.1%).

Table 1 shows the explosive properties of the CL-20/NTO eutectic explosive of the invention. The table shows that the detonation velocity of the CL-20/NTO eutectic explosive is respectively improved by 9.7 percent compared with NTO, and the CL-20/NTO eutectic explosive shows good detonation performance. From table 1, it can also be seen that the physicochemical properties of the explosive can be effectively adjusted by means of eutectic.

Table 2 shows the DSC melting peak temperature (the temperature rise rate is 10 k/min) of the CL-20/NTO eutectic explosive of the invention. As can be seen from Table 2, the high melting point of CL-20 forms a eutectic with the low melting point of NTO through intermolecular forces, significantly lowering the melting point of the pure component CL-20.

TABLE 1 detonation performance of CL-20/NTO eutectic explosives and component samples

TABLE 2 DSC melting peak temperatures of CL-20/NTO eutectic explosives and component samples

Specific examples of the preparation of the CL-20/NTO eutectic explosive of the invention are described in detail below.

Example 1

Adding 10ml of industrial ethyl acetate into a three-neck flask at 20 ℃, adding enough CL-20, starting stirring, dissolving and filtering to obtain a saturated CL-20 solution. Then adding sufficient NTO into the solution, stirring, dissolving, and filtering to obtain saturated solution of CL-20 and NTO. And transferring the CL-20 and NTO saturated solution into a beaker, slowly volatilizing the solvent in a constant temperature box at 20 ℃, separating out crystals, filtering and drying to obtain the CL-20/NTO eutectic explosive.

Example 2

At 30 ℃, 20ml of industrial acetonitrile is added into a three-mouth bottle, sufficient CL-20 is added, stirring is started, and saturated CL-20 solution is obtained through dissolution and filtration. Then adding sufficient NTO into the solution, stirring, dissolving, and filtering to obtain saturated solution of CL-20 and NTO. And transferring the CL-20 and NTO saturated solution into a beaker, slowly volatilizing the solvent in a constant temperature box at 30 ℃, separating out crystals, filtering and drying to obtain the CL-20/NTO eutectic explosive.

Example 3

Adding 3ml of industrial product dimethyl sulfoxide into a three-neck flask at 40 ℃, adding enough CL-20, starting stirring, dissolving and filtering to obtain a saturated CL-20 solution. Then adding sufficient NTO into the solution, stirring, dissolving, and filtering to obtain saturated solution of CL-20 and NTO. And transferring the CL-20 and NTO saturated solution into a beaker, slowly volatilizing the solvent in a constant temperature box at 50 ℃, separating out crystals, filtering and drying to obtain the CL-20/NTO eutectic explosive.

Example 4

Adding enough CL-20 into a bottle of 20ml industrial ethyl acetate and acetonitrile (volume ratio is 1:1) at 50 ℃, starting stirring, dissolving and filtering to obtain a saturated CL-20 solution. Then adding sufficient NTO into the solution, stirring, dissolving, and filtering to obtain saturated solution of CL-20 and NTO. And transferring the CL-20 and NTO saturated solution into a beaker, slowly volatilizing the solvent in a constant temperature box at 50 ℃, separating out crystals, filtering and drying to obtain the CL-20/NTO eutectic explosive.

Example 5

At 25 ℃, 20ml of industrial dimethyl sulfoxide and acetonitrile (volume ratio is 1:1) are added into a three-mouth bottle, sufficient CL-20 is added, stirring is started, and the saturated CL-20 solution is obtained by dissolution and filtration. Then adding sufficient NTO into the solution, stirring, dissolving, and filtering to obtain saturated solution of CL-20 and NTO. And transferring the CL-20 and NTO saturated solution into a beaker, slowly volatilizing the solvent in a constant temperature box at 25 ℃, separating out crystals, filtering and drying to obtain the CL-20/NTO eutectic explosive.

Example 6

Adding 15ml of industrial ethyl acetate and dimethyl sulfoxide (volume ratio is 1:1) into a three-necked bottle at 35 ℃, adding enough CL-20, stirring, dissolving, and filtering to obtain a saturated CL-20 solution. Then adding sufficient NTO into the solution, stirring, dissolving, and filtering to obtain saturated solution of CL-20 and NTO. And transferring the CL-20 and NTO saturated solution into a beaker, slowly volatilizing the solvent in a constant temperature box at 50 ℃, separating out crystals, filtering and drying to obtain the CL-20/NTO eutectic explosive.

The above detailed description is intended to illustrate the objects, aspects and advantages of the present invention, and it should be understood that the above detailed description is only exemplary of the present invention and is not intended to limit the scope of the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims

1. A CL-20 and NTO eutectic explosive is characterized in that: CL-20 molecules, NTO molecules and H in the eutectic explosive₂The molar ratio of O molecules is 1:1: 1; the molecular formula of the eutectic is C₅H₈N₈O₆Belonging to the orthorhombic system, P2₁2₁2₁Space group with crystal density up to 1.909g/cm³。

2. A method of making a CL-20 and NTO eutectic explosive according to claim 1, wherein: the method comprises the following specific steps:

step one, preparation of CL-20 and NTO saturated solution

step two, preparation of CL-20 and NTO eutectic explosive

3. The method of claim 2, wherein: in the step one, the solvent is one or a mixture of industrial ethyl acetate, industrial isopropanol and industrial dimethyl sulfoxide.