CN114292150B - CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance, preparation method and application - Google Patents
CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance, preparation method and application Download PDFInfo
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Abstract
The invention provides a low-mechanical-sensitivity high-detonation-performance CL-20/DFTNAN eutectic explosive, a preparation method and application, wherein the eutectic explosive is prepared from CL-20 and DFTNAN, and the molar ratio of the CL-20 to the DFTNAN is 1; the weakening degree of the eutectic explosive relative to the mechanical sensitivity of CL-20 is 194%; the eutectic of the eutectic explosive belongs to monoclinic system, P2 1 A/c space group; in the eutectic explosive, CL-20 molecules and DFTNAN molecules are combined through intermolecular hydrogen bonds. Compared with CL-20, the low-mechanical-sensitivity high-detonation-performance CL-20/DFTNAN eutectic explosive disclosed by the invention has the advantages that the mechanical sensitivity is greatly reduced, and meanwhile, the detonation performance is excellent. The preparation method has simple process flow and mild reaction conditions, can complete preparation under the condition of 0-18 ℃, and the prepared eutectic explosive has good detonation performance and safety and can be used as an insensitive main explosive to be applied to mixed explosives.
Description
Technical Field
The invention belongs to the technical field of energetic materials, relates to CL-20 eutectic explosives, and particularly relates to a CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance, a preparation method and application.
Background
As the CL-20 type explosive in the prior art is difficult to consider both high detonation performance and low mechanical sensitivity, the application of the CL-20 type explosive as an insensitive main explosive in mixed explosives is limited.
In recent years, in the research and development aspect of insensitive high-energy explosives, two main ideas exist: one method is to design and synthesize new single-compound explosive molecules, and the method can adjust the contradiction between high energy density and safety from the aspect of molecular design, but has the defects of high research and development cost, long period, low yield of most parts and complex process; the other method is to modify the existing high-energy density explosive. Common modification means include: first, energetic materials are nanocrystallized and nanostructured; secondly, coating and compounding energetic material molecules; thirdly, the crystallization process is improved through crystal engineering, and measures such as adding additives are used in the recrystallization process, so as to achieve the purpose of improving the crystal quality.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance, a preparation method and application thereof, and solve the technical problem that the CL-20 eutectic explosive in the prior art cannot give consideration to both low mechanical sensitivity and high detonation performance.
In order to solve the technical problems, the invention adopts the following technical scheme:
a CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance is prepared from CL-20 and DFTNAN.
The invention also has the following technical characteristics:
specifically, the molar ratio of CL-20 to DFTNAN is 1.
Specifically, the mechanical sensitivity of the eutectic explosive relative to CL-20 is weakened to 194%.
Specifically, the eutectic of the eutectic explosive belongs to monoclinic system, P2 1 The/c space group.
Specifically, in the eutectic explosive, CL-20 molecules and DFTNAN molecules are combined through intermolecular hydrogen bonds.
The invention also provides a preparation method of the CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance, which comprises the following steps:
adding CL-20 and DFTNAN into a crystallization solvent, and carrying out constant temperature reaction at 0-18 ℃ to prepare a crude mixture; filtering the crude mixture to prepare a mixed saturated crystallization solution; dropwise adding the mixed saturated crystallization solution into water to prepare a mixed eutectic; and filtering and drying the mixed eutectic in sequence to prepare the CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance.
Specifically, the crystallization solvent is methanol, dichloromethane, acetone, ethyl acetate, tetrahydrofuran or acetonitrile.
Specifically, the volume ratio of the mixed saturated crystallization solution to water is 1 (2-10).
The CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance is applied to mixed explosives as a insensitive main explosive.
Compared with the prior art, the invention has the following technical effects:
compared with CL-20, the low mechanical sensitivity and high detonation performance CL-20/DFTNAN eutectic explosive disclosed by the invention has the advantages that the mechanical sensitivity is greatly reduced, and meanwhile, the detonation performance is excellent.
The invention discloses a preparation method of a CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance for the first time, and the preparation method has simple process flow and mild reaction conditions, and can complete the preparation under the condition of 0-18 ℃.
(III) the CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance has good detonation performance and safety, and can be used as an insensitive main explosive to be applied to mixed explosives.
Drawings
FIG. 1 is a single crystal diffraction diagram of a CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance.
FIG. 2 is a process flow schematic diagram of a preparation method of a CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance.
The present invention will be explained in further detail with reference to examples.
Detailed Description
CL-20, namely hexanitrohexaazaisowurtzitane, is a high-energy-content compound which has the highest energy density and is produced in large scale industrially, but due to the high mechanical sensitivity and electrostatic spark sensitivity, if other components are added, the mechanical sensitivity is reduced, and the related detonation performance (such as detonation velocity and detonation pressure) of the CL-20 type explosive is easily reduced greatly.
DFTNAN, 3, 5-difluoro-2, 4, 6-trinitroanisole, is a novel energetic compound with a melting point of82-83 ℃ and the density of 1.81g cm -3 The detonation velocity is 8540 m.s -1 The peak temperature of thermal decomposition was 265 ℃. Furthermore, the mechanical sensitivity of DFTNAN is comparable to TNT. The mixed eutectic explosive prepared from the DFTNAN and the CL-20 can effectively reduce the mechanical sensitivity of the CL-20 eutectic explosive, simultaneously can keep higher high explosive performance of the CL-20 eutectic explosive, and realizes the organic combination of high energy and low feeling, and no published literature report about the CL-20/DFTNAN eutectic explosive exists in the prior art.
The eutectic is essentially a molecular self-assembly behavior, weak interaction force of non-covalent bonds is formed among different molecules through molecular recognition, eutectic thermodynamics and kinetic effects, host molecules and guest molecules are connected into a special molecular configuration, and the molecular configuration is orderly arranged and assembled to finally form eutectic particles. The intermolecular forces that assemble the host and guest are mainly hydrogen bonds, pi stacking, halogen bonds, and van der waals forces. The bond energy of the intermolecular secondary bond is far lower than that of the covalent bond or the ionic bond in the host ligand, so that the chemical properties of the components cannot be influenced after the host and the guest form a eutectic. The eutectic technology is utilized to modify the energetic material, so that the preparation process is simple, economic and practical, and becomes a research hotspot in recent years.
Based on the analysis and the current situation, the invention discloses a CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance, a preparation method and application for the first time, so that the CL-20 eutectic explosive can still maintain excellent detonation performance while reducing the mechanical sensitivity, and the application prospect of the CL-20 eutectic explosive is widened.
In the invention, the detonation performance test and the mechanical sensitivity test of the CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance both adopt a test mode and test equipment known in the prior art.
The molecular formula of eutectic of the eutectic explosive prepared in the invention is C 13 H 9 N 15 O 19 F 2 。
In the present invention, the degree of attenuation of mechanical sensitivity is calculated according to the following formula:
W＝(Ms 1 -Ms 2 )+Ms 2 ；
in the formula:
w represents the degree of attenuation of mechanical sensitivity in units of%;
Ms 1 the mechanical sensitivity of the CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance is shown, and the unit is N/m;
Ms 2 represents the mechanical sensitivity of CL-20, with the unit of N/m.
The present invention is not limited to the following embodiments, and equivalent changes made on the basis of the technical solutions of the present invention fall within the scope of the present invention.
Example 1:
the embodiment discloses a preparation method of a CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance, as shown in FIG. 2, the preparation method specifically comprises the following steps:
0.876g of CL-20 and 0.558g of DFTNAN were added to 50mL of a crystallization solvent, which was methanol, and reacted in a constant temperature bath at 5 ℃ for 24 hours to prepare a crude mixture; filtering the crude mixture to prepare a mixed saturated crystallization solution; placing the mixed saturated crystallization solution into a dropping funnel, quickly dropping the mixed saturated crystallization solution into 300mL of deionized water, and immediately separating out fine mixed eutectic; and filtering and drying the mixed eutectic to obtain the CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance.
Example 2:
the embodiment discloses a preparation method of a CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance, which is basically the same as that in embodiment 1, and is characterized in that the isothermal reaction temperature is 0 ℃, the crystallization solvent is dichloromethane, the volume of the crystallization solvent is 40mL, and the volume of deionized water is 80mL.
Example 3:
the embodiment discloses a preparation method of a CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance, which is basically the same as the embodiment 1, and is characterized in that the temperature of the isothermal reaction is 10 ℃, the crystallization solvent is acetone, and the volume of the crystallization solvent is 30mL.
Example 4:
the embodiment discloses a preparation method of a CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance, which is basically the same as that in embodiment 1, and is characterized in that the temperature of isothermal reaction is 18 ℃, the crystallization solvent is ethyl acetate, and the volume of deionized water is 250mL.
Example 5:
this example discloses a method for preparing a CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance, which is substantially the same as example 1 except that the isothermal reaction temperature is 15 ℃, the crystallization solvent is tetrahydrofuran, and the volume of the crystallization solvent is 40mL.
Example 6:
the embodiment discloses a preparation method of a CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance, which is basically the same as that in embodiment 1, and is characterized in that the temperature of isothermal reaction is 10 ℃, the crystallization solvent is acetonitrile, and the volume of deionized water is 400mL.
Example 7:
the embodiment discloses a CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance, which is prepared by adopting the preparation method of the CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance in the embodiment 1. The eutectic explosive is prepared from CL-20 and DFTNAN.
In this example, the mechanical sensitivity of the eutectic explosive relative to CL-20 is weakened to 194%.
In this example, the molecular structure of the eutectic explosive was confirmed by single crystal diffraction analysis, as shown in fig. 1. In the eutectic explosive, the molar ratio of CL-20 to DFTNAN is 1. The eutectic of the eutectic explosive belongs to monoclinic system, P2 1 The/c space group. In the eutectic explosive, CL-20 molecules and DFTNAN molecules are combined through intermolecular hydrogen bonds.
In the embodiment, the detonation performance and the mechanical sensitivity of the CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance are tested by adopting a known technical means commonly used in the field, and the mechanical sensitivity test adopts a 2kg drop weight and the drop height is 50cm. The test results are shown in table 1.
TABLE 1 detonation Properties and mechanical sensitivities of Low mechanical sensitivity high detonation Performance CL-20/DFTNAN eutectic explosives and component samples
As can be seen from table 1:
the low mechanical sensitivity and high detonation performance CL-20/DFTNAN eutectic explosive has the mechanical sensitivity of 53N/m; the low-mechanical-sensitivity high-detonation-performance CL-20/DFTNAN eutectic explosive has the following specific detonation performance: the energy density is 1.952g/cm 3 The detonation velocity is 9086m/s, and the detonation pressure is 40.76GPa.
Compared with CL-20, the low mechanical sensitivity and high detonation performance CL-20/DFTNAN eutectic explosive has the mechanical sensitivity reduced by 194%; compared with CL-20, the detonation velocity is reduced by only 3.2%, the detonation pressure is reduced by only 10.6%, and the energy density is reduced by only 4.7%.
The analysis shows that compared with CL-20, the low-mechanical-sensitivity high-detonation-performance CL-20/DFTNAN eutectic explosive disclosed by the invention has greatly reduced mechanical sensitivity and excellent detonation performance.
Claims (6)
1. A CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance is characterized by being prepared from CL-20 and DFTNAN; the molar ratio of CL-20 to DFTNAN is 1;
the eutectic of the eutectic explosive belongs to monoclinic system, P2 1 A/c space group;
in the eutectic explosive, CL-20 molecules and DFTNAN molecules are combined through intermolecular hydrogen bonds.
2. The CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance of claim 1, wherein the mechanical sensitivity of the eutectic explosive relative to CL-20 has a degree of attenuation of 194%.
3. The preparation method of the CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance as claimed in any one of claims 1 or 2, which is characterized by comprising the following steps:
adding CL-20 and DFTNAN into a crystallization solvent, and carrying out constant temperature reaction at 0-18 ℃ to prepare a crude mixture; filtering the crude mixture to prepare a mixed saturated crystallization solution; dropwise adding the mixed saturated crystallization solution into water to prepare a mixed eutectic; and filtering and drying the mixed eutectic to obtain the CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance.
4. The method for preparing the CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation property according to claim 3, wherein the crystallization solvent is methanol, dichloromethane, acetone, ethyl acetate, tetrahydrofuran or acetonitrile.
5. The method for preparing the CL-20/DFTNAN eutectic explosive with low mechanical sensitivity and high detonation performance as claimed in claim 3, wherein the volume ratio of the mixed saturated crystallization solution to water is 1 (2-10).
6. Use of a low mechanical sensitivity high detonation performance CL-20/DFTNAN co-crystal explosive according to any one of claims 1 or 2 as a passive primary explosive in a mixed explosive.
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