A cl-20 co-crystal energetic material

Abstract

The application discloses a kind of Cl-20 eutectic energetic materials, belongs to the field of energetic materials, the preparation method of the disclosed Cl-20 eutectic energetic materials includes: at 15-30 ℃, Cl-20 and azofurazan tetra ring are dissolved in organic solvent, and the precipitate is collected after standing 12-36 h, to obtain Cl-20 eutectic energetic material.The Cl-20 eutectic energetic material preparation method of the application is simple in operation, the highest yield is 64.1%, and the Cl-20 eutectic energetic material obtained has high thermal stability, excellent safety performance, the thermal decomposition temperature is 245 ℃ (10 ℃ / min), the impact sensitivity is 15 J, and the friction sensitivity is >360N.

Description

Technical Field

[0001] This invention relates to the field of energetic materials, specifically to a Cl-20 eutectic energetic material. Background Technology

[0002] Hexanitrohexaazaisowulzane (chemical formula C6H6N) 12 O 12 HNIW (abbreviated as HNIW, commonly known as CL20, with the structural formula shown below) is a high-density (≈2.0 g•cm³) synthesized in recent years. -3 CL20 is a cage-like compound with high oxygen balance (-10.95%), high energy, high explosive pressure, and high explosive velocity, and is the highest-energy single-element explosive ever used. However, CL20 has high mechanical sensitivity, with a friction sensitivity of 100% and an impact sensitivity of 96-100% (10 kg drop hammer, 25 cm drop height), which severely limits its engineering applications.

[0003]

[0004] Co-crystallization technology has been developed and applied in the field of energetic materials. Co-crystallization involves altering the composition and crystal structure of energetic materials without destroying their molecular chemical structure, thereby improving properties such as density and sensitivity. Driven by weak intermolecular interactions, the formation of a co-crystallization between CL20 and insensitive molecules can effectively reduce the sensitivity of energetic materials and improve their safety performance. In 2011, Bolton et al. synthesized a cosmic energetic material with a 1:1 molar ratio of CL20 to trinitrotoluene, achieving a density of 1.92 g·cm³. -3, Its burst speed is slightly lower than the CL20, but its sensitivity is much lower than the CL20. Angew. Chem. Int. Ed. 2011, 50, 8960). Bolton et al. prepared a eutectic energetic material with a molar ratio of CL20 and HMX of 2:1 (Cryst. Growth Des. 2012, 12, 4311). The sensitivity of the eutectic explosive was close to that of HMX, and its detonation velocity was superior to that of HMX. After years of development, various CL20 eutectic materials have been synthesized, but problems such as the difficulty in obtaining single crystals of CL20-energetic compounds still exist. Summary of the Invention

[0005] In view of the defects and shortcomings of the existing technology, the present invention provides a Cl-20 eutectic energetic material.

[0006] Therefore, the preparation method of Cl-20 eutectic energetic material provided by the present invention includes the following steps: at 15-30℃, Cl-20 and TATF are dissolved in an organic solvent, and after standing for 12-36 h, the crystals precipitated in the reaction system are collected to obtain Cl-20 eutectic energetic material.

[0007] An alternative is to use a molar ratio of Cl-20 to TATF of 1:0.5~2.

[0008] Alternatively, the organic solvent may be ethyl acetate, dichloromethane, or chloroform.

[0009] In some preferred embodiments, the density of the material is 1.88 g / cm³. 3 .

[0010] In some preferred embodiments, the thermal decomposition temperature of the material is 245°C at a heating rate of 10°C / min.

[0011] Some preferred embodiments include a material with an impact sensitivity of 15 J and a friction sensitivity of >360 N.

[0012] In some preferred embodiments, the single-crystal parameters of the material are:

[0013]

[0014] Based on the advantages of azofuran tetra-membered ring (TATF, structural formula shown below), such as high density, good oxygen balance, high standard enthalpy of formation, and good detonation performance, this invention achieves effective desensitization of CL20 materials by preparing related Cl-20 eutectic energetic materials.

[0015]

[0016] The method for preparing Cl-20 eutectic energetic material of the present invention is simple to operate and has a maximum yield of 64.1%. The Cl-20 eutectic energetic material obtained has high thermal stability and excellent safety performance, with a thermal decomposition temperature of 245℃ (10℃ / min), an impact sensitivity of 15 J, and a friction sensitivity of >360N. Attached Figure Description

[0017] Figure 1 The single crystal structure of the Cl-20 eutectic energetic material prepared in Example 1 is shown.

[0018] Figure 2 The crystal structure of the Cl-20 eutectic energetic material prepared in Example 1 is shown.

[0019] Figure 3 The image shows a SEM image of the Cl-20 eutectic energetic material prepared in Example 1.

[0020] Figure 4 The DSC curves of the Cl-20 eutectic energetic material prepared in Example 1 at different heating rates (5, 10, 15, 20 °C / min) are shown. Detailed Implementation

[0021] Unless otherwise specified, the scientific and technical terms used in this article are based on the understanding of those skilled in the art.

[0022] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Operating methods not specifically specified in the following embodiments are generally performed under conventional conditions or as recommended by the manufacturer.

[0023] Example 1: At 20 °C, Cl-20 (43.8 mg, 0.10 mmol) and TATF (38.4 mg, 0.10 mmol) were dissolved in 4 mL of ethyl acetate, allowed to evaporate naturally, and allowed to stand for 24 h to obtain 52.7 mg of bulk eutectic material with a yield of 64.1%.

[0024] X-ray single-crystal diffraction analysis revealed the single-crystal structure of the prepared Cl-20 eutectic energetic material as shown in the figure. Figure 1 The crystal data are shown in Table 1.

[0025] Table 1

[0026] The mechanical sensitivity of the Cl-20 eutectic energetic material was tested using a drop hammer impact sensitivity meter and a friction sensitivity tester: measured impact sensitivity 10 J, measured friction sensitivity > 360 N; (measured impact sensitivity of Cl-20 is 0.75 J, measured friction sensitivity is 120 N; measured impact sensitivity of TATF is 15 J, measured friction sensitivity is > 360 N).

[0027] The density of the prepared Cl-20 eutectic energetic material is 1.88 g / cm³. 3 (The density of Cl-20 is 2.04 g / cm³) 3 ).

[0028] The theoretically calculated detonation velocity of the prepared Cl-20 eutectic energetic material is 9188 m / s and the detonation pressure is 38.71 GPa (the theoretically calculated detonation velocity of Cl-20 is 9380 m / s and the detonation pressure is 42.0 GPa; the theoretically calculated detonation velocity of TATF is 8000 m / s and the detonation pressure is 29.5 GPa).

[0029] Example 2: At 25°C, Cl-20 (43.8 mg, 0.10 mmol) and TATF (57.6 mg, 0.15 mmol) were dissolved in 4 mL of dichloromethane, allowed to evaporate naturally, and allowed to stand for 36 h to obtain 21.9 mg of bulk eutectic material with a yield of 26.6%.

[0030] Example 3: At 20°C, Cl-20 (65.7 mg, 0.15 mmol) and TATF (38.4 mg, 0.10 mmol) were dissolved in 4 mL of chloroform, allowed to evaporate naturally, and allowed to stand for 24 h to obtain 47.7 mg of bulk eutectic material with a yield of 58.0%.

[0031] Example 4: At 15 °C, Cl-20 (43.8 mg, 0.10 mmol) and TATF (38.4 mg, 0.10 mmol) were dissolved in 4 mL of ethyl acetate, allowed to evaporate naturally, and allowed to stand for 36 h to obtain 35.5 mg of bulk eutectic material with a yield of 43.2%.

Claims

1. A Cl-20 eutectic energetic material, characterized in that, The preparation method of the Cl-20 eutectic energetic material includes the following steps: at 15-30℃, Cl-20 and TATF are dissolved in an organic solvent, and after standing for 12-36 h, the crystals precipitated from the reaction system are collected to obtain the Cl-20 eutectic energetic material.

2. The Cl-20 eutectic energetic material according to claim 1, characterized in that, The molar ratio of Cl-20 to TATF is 1:0.5~2.

3. The Cl-20 eutectic energetic material according to claim 1, characterized in that, The organic solvent is ethyl acetate, dichloromethane, or chloroform.

4. The Cl-20 eutectic energetic material according to claim 1, characterized in that, The density of the material is 1.88 g / cm³. 3 .

5. The Cl-20 eutectic energetic material according to claim 1, characterized in that, The thermal decomposition temperature of the material is 245°C at a heating rate of 10°C / min.

6. The Cl-20 eutectic energetic material according to claim 1, characterized in that, The material has an impact sensitivity of 15J and a friction sensitivity of >360N.

7. The Cl-20 eutectic energetic material according to claim 1, characterized in that, The single-crystal parameters of the material are: 。

Images