An energetic eutectic compound and its preparation method

Abstract

The present invention relates to a novel energetic eutectic compound and a preparation method thereof, belonging to the technical field of energetic materials. The structural formula of the energetic eutectic compound is as follows, the space group is P 1 21 / c 1, and the unit cell parameters are α = 90°, β = 104.978(2)°, γ = 90°; the present invention also provides a preparation method of the novel energetic eutectic compound: at room temperature, the ammonium salt of 1,3,5-trinitro-2,4,6-trinitrobenzene and ammonium nitrate are dispersed into a eutectic solvent in a molar ratio of 2:1 to 1:2, and the eutectic solvent is a mixed solution of methanol and ethanol with a volume ratio of 4:1 to 1:1; ultrasonic dissolution and stirring are carried out for more than 24 h to obtain a eutectic solution, which is filtered and the filtrate is completely volatilized at 5-10 °C to obtain the compound.

Description

Technical Field

[0001] The present invention relates to a novel energetic eutectic compound and a preparation method thereof, and particularly to an energetic eutectic compound of ammonium salt of 1,3,5-trinitro-2,4,6-trinitroamino benzene and ammonium nitrate, belonging to the technical field of energetic materials. Background Art

[0002] Polynitrobenzene is a kind of high energy density material (HEDMs), which can rapidly release energy through the redox reaction occurring by itself. Among them, the benzene ring can serve as a fuel component, and the nitro group can serve as an oxidant. The most representative polynitrobenzenes are 2,4,6-trinitrotoluene (TNT) and hexanitrobenzene (HNB). Among them, hexanitrobenzene has an extremely high heat of explosion (6993 kJ·kg -1 )), but its chemical stability is very low, and chemical reactions can occur even in humid air, so its application is greatly limited. 1,3,5-Trinitro-2,4,6-trinitroamino benzene (TNTNB) is a novel energetic material, which is obtained by substituting the nitro groups at the 2, 4, and 6 positions in hexanitrobenzene (HNB) with nitroamino groups. While obtaining a higher heat of explosion than hexanitrobenzene, its stability has also been greatly improved. However, compared with insensitive explosives, 1,3,5-trinitro-2,4,6-trinitroamino benzene still has the disadvantage of high sensitivity. Its impact sensitivity (IS) is 1 J, and its friction sensitivity (FS) is 5 N. Making 1,3,5-trinitro-2,4,6-trinitroamino benzene into an ammonium salt has improved its disadvantages to a certain extent, reducing the impact sensitivity (2 J) and friction sensitivity (10 N), but there is still room for improvement.

[0003] Energetic eutectic compounds refer to energetic compounds formed by multiple ions with different charges through physical and chemical interactions. Such compounds mainly have the following advantages: (1) High energy density: Energetic eutectic compounds have a very high energy density, so more energy can be stored in the same volume; (2) Simple preparation method: The preparation process of energetic eutectic compounds is very simple and can be prepared by methods such as direct mixing and ball milling; (3) Good stability: Energetic eutectic compounds can stably exist at room temperature for a long time and usually do not undergo self-decomposition. In summary, the advantages of energetic eutectic compounds such as high density, easy preparation, and good stability make them have broad application prospects in the military, aerospace and other fields.

[0004] However, at present, the growth conditions of energetic eutectic compounds are relatively complex. The selection of ligand compounds, the types and ratios of eutectic solvents are all influencing factors for eutectic growth, and they are not easy to prepare. Summary of the Invention

[0005] In order to overcome the defects existing in the prior art, one of the purposes of the present invention is to provide a novel energetic eutectic compound, and the energetic eutectic compound is an ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene and an ammonium nitrate energetic eutectic compound, and the energetic eutectic compound has a relatively high energy density and good stability;

[0006] Another purpose of the present invention is to provide a preparation method of a novel energetic eutectic compound, and the method realizes the preparation of the energetic eutectic compound with a high yield through the selection of ligand compounds, the selection of types of eutectic solvents, and the regulation of ratios.

[0007] The purpose of the present invention is achieved through the following technical solutions.

[0008] A novel energetic eutectic compound, and the molecular formula of the novel energetic eutectic compound is C 6 H 16 N 14 O 15 , and the structural formula is as follows:

[0009]

[0010] The space group of the novel energetic eutectic compound is P1 21 / c 1, and the unit cell parameters are α = 90°, β = 104.978(2)°, γ = 90°.

[0011] A preparation method of the novel energetic eutectic compound according to the present invention, and the steps of the method are as follows:

[0012] (1) At room temperature, disperse the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene and ammonium nitrate into a eutectic solvent, ultrasonically dissolve it completely, and stir it at room temperature for more than 24 h to obtain a eutectic solution of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene and ammonium nitrate;

[0013] The eutectic solvent is a mixed solution of methanol and ethanol, and the volume ratio of methanol to ethanol is 4:1 to 1:1;

[0014] The molar ratio of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene to ammonium nitrate is 2:1 to 1:2;

[0015] (2) Filter the eutectic solution obtained in step (1) using an organic filter membrane, and slowly evaporate the obtained filtrate completely at 5°C to 10°C to obtain the novel energetic eutectic compound.

[0016] Preferably, the molar ratio of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene to ammonium nitrate is 1:1.

[0017] Preferably, the volume ratio of methanol to ethanol in the eutectic solvent is 3:1.

[0018] Preferably, the structural formula of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene is as follows:

[0019]

[0020] Preferably, the organic filter membrane is made of nylon 66 (NYLNO 66) and has a pore size of 0.45 μm.

[0021] Beneficial effects

[0022] (1) The present invention provides a novel energetic eutectic compound, which is an energetic eutectic compound of ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene and ammonium nitrate. Compared with the precursor of this energetic eutectic compound, which is the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene, the energetic eutectic compound has a higher oxygen balance, decomposition temperature and sensitivity, superior energy density, thermal stability and mechanical stability, and can be widely used as an energetic material in military, aerospace and other fields.

[0023] (2) The present invention provides a preparation method of a novel energetic eutectic compound. The method realizes the efficient growth of the energetic eutectic compound of ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene and ammonium nitrate by screening the types of ligands, regulating the molar ratio of ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene to ammonium nitrate, screening the types of eutectic solvents and the volume ratio between the components of the eutectic solvent; the method is simple and efficient, the reaction conditions are relatively mild, the product yield is relatively high, and no toxic and harmful gases are generated, which is relatively friendly to the environment.

[0024] (3) The present invention provides a preparation method of a novel energetic eutectic compound. Preferably, the molar ratio of ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene to ammonium nitrate is 1:1, and the eutectic solvent is a mixed solution with a volume ratio of methanol to ethanol of 3:1; the yield of the energetic eutectic compound prepared under such conditions can reach 76.6%, the friction sensitivity is 4 J, the impact sensitivity is 48 N, and the decomposition temperature can reach 191 °C, showing excellent thermal stability and mechanical stability. Description of the drawings

[0025] Figure 1 It is the crystal structure diagram of the final product described in Example 1;

[0026] Figure 2 It is the crystal cell packing diagram of the final product described in Example 1. Detailed implementation manners

[0027] Next, in conjunction with the accompanying drawings and specific embodiments, the technical solutions of the present invention will be clearly and completely described. The methods are conventional methods unless otherwise specified, and the raw materials can be obtained from public commercial channels unless otherwise specified.

[0028] In the following examples, the calculation method of the yield is as follows:

[0029] Yield of the final product (%) = Molar amount of the final product / Molar amount of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene × 100%.

[0030] The organic filter membrane is a filter membrane produced by Jinlong Company with a pore size of 0.45 μm and a material of NYLNO66.

[0031] Example 1

[0032] A preparation method of a novel energetic cocrystal compound, the method steps are as follows:

[0033] (1) At room temperature, 0.500 mmol of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene and 0.500 mmol of ammonium nitrate are dispersed into the cocrystal solvent, ultrasonically dissolved until completely dissolved, and stirred at room temperature for 24 h to obtain a cocrystal solution of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene and ammonium nitrate;

[0034] The structural formula of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene is as follows:

[0035]

[0036] The cocrystal solvent is a mixed solution of 7.5 mL of methanol and 2.5 mL of ethanol, where the volume ratio of methanol to ethanol is 3:1;

[0037] The molar ratio of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene to ammonium nitrate is 1:1;

[0038] (2) Filter the cocrystal solution obtained in step (1) using the organic filter membrane, and place the obtained filtrate in a glass bottle with a diameter of 2 cm and slowly volatilize it at 5 °C to 10 °C for one week to obtain 201 mg (0.383 mmol) of the final product, with a yield of 76.6%.

[0039] Example 2

[0040] A preparation method of a novel energetic cocrystal compound, the method steps are as follows:

[0041] (1) At room temperature, 0.500 mmol of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene and 0.250 mmol of ammonium nitrate were dispersed into a eutectic solvent, ultrasonicated to completely dissolve, and stirred at room temperature for 24 h to obtain a eutectic solution of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene and ammonium nitrate;

[0042] The structural formula of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene is as follows:

[0043]

[0044] The eutectic solvent is a mixed solution of 7.5 mL of methanol and 2.5 mL of ethanol, and the volume ratio of methanol to ethanol is 3:1;

[0045] The molar ratio of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene to ammonium nitrate is 2:1;

[0046] (2) The eutectic solution obtained in step (1) was filtered using an organic filter membrane, and the resulting filtrate was placed in a glass bottle with a diameter of 2 cm and slowly volatilized at 5 °C to 10 °C for one week to obtain 29.0 mg (0.056 mmol) of the final product, with a yield of 11.2%.

[0047] Example 3

[0048] A preparation method of a novel energetic eutectic compound, the method steps are as follows:

[0049] (1) At room temperature, 0.500 mmol of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene and 1.000 mmol of ammonium nitrate were dispersed into a eutectic solvent, ultrasonicated to completely dissolve, and stirred at room temperature for 24 h to obtain a eutectic solution of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene and ammonium nitrate;

[0050] The structural formula of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene is as follows:

[0051]

[0052] The eutectic solvent is a mixed solution of 7.5 mL of methanol and 2.5 mL of ethanol, and the volume ratio of methanol to ethanol is 3:1;

[0053] The molar ratio of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene to ammonium nitrate is 1:2;

[0054] (2) Filter the eutectic solution obtained in step (1) using an organic filter membrane. Place the resulting filtrate in a glass bottle with a 2-cm diameter and slowly evaporate it at 5°C - 10°C for one week to obtain 24.4 mg (0.047 mmol) of the final product, with a yield of 9.4%.

[0055] Example 4

[0056] A preparation method of a novel ionic energetic eutectic compound, the method steps are as follows:

[0057] (1) At room temperature, disperse 0.500 mmol of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene and 0.500 mmol of ammonium nitrate into the eutectic solvent, ultrasonically dissolve it completely, and stir it at room temperature for 24 h to obtain a eutectic solution of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene and ammonium nitrate;

[0058] The structural formula of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene is as follows:

[0059]

[0060] The eutectic solvent is a mixed solution of 8.0 mL of methanol and 2.0 mL of ethanol, and the volume ratio of methanol to ethanol is 4:1;

[0061] The molar ratio of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene to ammonium nitrate is 1:2;

[0062] (2) Filter the eutectic solution obtained in step (1) using an organic filter membrane. Place the resulting filtrate in a glass bottle with a 2-cm diameter and slowly evaporate it at 5°C - 10°C for one week to obtain 13.4 mg (0.026 mmol) of the final product, with a yield of 5.1%.

[0063] Example 5

[0064] A preparation method of a novel energetic eutectic compound, the method steps are as follows:

[0065] (1) At room temperature, disperse 0.500 mmol of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene and 0.500 mmol of ammonium nitrate into the eutectic solvent, ultrasonically dissolve it completely, and stir it at room temperature for 24 h to obtain a eutectic solution of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene and ammonium nitrate;

[0066] The structural formula of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene is as follows:

[0067]

[0068] The eutectic solvent is a mixed solution of 5.0 mL of methanol and 5.0 mL of ethanol, and the volume ratio of methanol to ethanol is 1:1;

[0069] The molar ratio of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene to ammonium nitrate is 1:1;

[0070] (2) Filter the eutectic solution obtained in step (1) using an organic filter membrane. Place the obtained filtrate in a glass bottle with a diameter of 2 cm and slowly evaporate it at 5 °C to 10 °C for one week to obtain 17.9 mg (0.034 mmol) of the final product, and the yield is 6.8%.

[0071] Perform X-ray single crystal diffraction analysis on the final product prepared in Example 1 to confirm its crystal structure, and obtain the crystal structure diagram ( Figure 1 ), the crystal cell packing diagram ( Figure 2 ) and the crystal cell parameter table (Table 1). The test results show that the final product described in Example 1 is the novel energetic eutectic compound described in the present invention, and the structural formula is as follows:

[0072]

[0073] Table 1 Crystal cell parameter table of the final product described in Example 1

[0074]

[0075] The X-ray single crystal diffraction results of the final products prepared in Examples 2 to 5 are similar to those in Example 1, indicating that the method realizes the growth and preparation of the novel energetic eutectic compound by selecting ligand compounds, selecting the types of eutectic solvents and optimizing the ratio. The reaction formula of the method is as follows:

[0076]

[0077] The level of oxygen balance (oxygen content) is one of the important indicators for measuring the energy density of energetic materials. That is, when other properties remain unchanged, the higher the oxygen balance, the higher the energy density of the energetic material. The oxygen balance calculation formula is as follows: where n O , n C , n H are the numbers of oxygen atoms, carbon atoms, and hydrogen atoms respectively, and M is the molar mass;

[0078] For the novel energetic eutectic compound described in the present invention, n O = 15, n C = 6, n H = 16, M = 524. Substituting into the formula for calculation, the oxygen balance is -15.3%, which is higher than that of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene (nO = 12, n C = 6, n H = 12, M = 444) has an oxygen balance of -21.6%, indicating that the novel energetic eutectic compound described in the present invention has a high energy density.

[0079] Differential scanning calorimetry (DSC) tests were carried out on the novel energetic eutectic compounds prepared in Examples 1 to 5. From the test results, it can be seen that the initial decomposition temperatures of the novel energetic eutectic compounds prepared in Examples 1 to 5 are 191 °C, 190 °C, 192 °C, 189 °C, and 191 °C, respectively.

[0080] Friction sensitivity and impact sensitivity tests were carried out on the novel energetic eutectic compounds prepared in Examples 1 to 5, and the results are shown in Table 2:

[0081] Table 2 Friction sensitivity and impact sensitivity tests of the end products described in Examples 1 to 5

[0082]

[0083] The above test results show that the energetic eutectic compound has the advantages of high density, good mechanical stability and thermal stability, and a simple preparation method, and has broad application prospects in the fields of military, aerospace, etc.

[0084] Comparative Example 1

[0085] In Comparative Example 1, only on the basis of Example 1, "7.5 mL of methanol and 2.5 mL of ethanol (volume ratio 3:1)" was replaced with "8.35 mL of methanol and 1.67 mL of ethanol (5:1)", and other conditions remained unchanged, and no crystals were obtained.

[0086] Comparative Example 2

[0087] In Comparative Example 2, only on the basis of Example 1, "7.5 mL of methanol and 2.5 mL of ethanol (volume ratio 3:1)" was replaced with "3.33 mL of methanol and 6.66 mL of ethanol (1:2)", and other conditions remained unchanged, and no crystals were obtained.

[0088] Comparative Example 3

[0089] In Comparative Example 3, only on the basis of Example 1, "0.500 mmol of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitroaminobenzene and 0.500 mmol of ammonium nitrate (molar ratio 1:1)" was replaced with "0.500 mmol of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitroaminobenzene and 0.167 mmol of ammonium nitrate (molar ratio 3:1)", and other conditions remained unchanged, and no crystals were obtained.

[0090] Comparative Example 4

[0091] Comparative Example 4 only based on Example 1, replaced "0.500 mmol of ammonium salt of 1,3,5-trinitro-2,4,6-trinitroaminobenzene and 0.500 mmol of ammonium nitrate (molar ratio 1:1)" with "0.500 mmol of ammonium salt of 1,3,5-trinitro-2,4,6-trinitroaminobenzene and 1.50 mmol of ammonium nitrate (molar ratio 1:3)", with other conditions remaining unchanged, and no crystals were obtained.

[0092] Comparative Example 5

[0093] Comparative Example 5 only based on Example 1, replaced "0.500 mmol of ammonium salt of 1,3,5-trinitro-2,4,6-trinitroaminobenzene and 0.500 mmol of ammonium nitrate (molar ratio 1:1)" with "0.500 mmol of ammonium salt of 1,3,5-trinitro-2,4,6-trinitroaminobenzene and 0.500 mmol of ammonium sulfate (molar ratio 1:1)", with other conditions remaining unchanged, and no crystals were obtained.

[0094] Comparative Example 6

[0095] Comparative Example 6 only based on Example 1, replaced "7.5 mL of methanol and 2.5 mL of ethanol (volume ratio 3:1)" with "10 mL of ethyl acetate", with other conditions remaining unchanged, and no crystals were obtained.

[0096] Comparative Example 7

[0097] Comparative Example 7 only based on Example 1, replaced "7.5 mL of methanol and 2.5 mL of ethanol (volume ratio 3:1)" with "10 mL of dichloromethane", with other conditions remaining unchanged, and no crystals were obtained.

[0098] From Comparative Examples 1 - 7 and Examples 1 - 5, it can be seen that the growth conditions of the novel energetic cocrystal compounds of the present invention are relatively complex. The selection of ligand compounds, the type of cocrystal solvent, and the volume ratio between the components of the cocrystal solvent will all affect the formation and yield of the novel energetic cocrystal compounds.

[0099] The above specific description further details the purpose, technical solution, and beneficial effects of the invention. It should be understood that the above is only the specific embodiment of the present invention and does not limit the protection scope of the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention should be included within the protection scope of the present invention.

Claims

1. An energetic eutectic compound, characterized in that: The molecular formula of the energetic eutectic compound is C 6 H 16 N 14 O 15 , and its structural formula is as follows: The space group of the energetic eutectic compound is P1 21 / c 1, and the unit cell parameters are α = 90°, β = 104.978(2)°, γ = 90°.

2. A preparation method of the energetic eutectic compound according to claim 1, characterized in that: The steps of the method are as follows: (1) At room temperature, disperse the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene and ammonium nitrate into a eutectic solvent, ultrasonically dissolve it completely, and stir it at room temperature for more than 24 h to obtain a eutectic solution of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene and ammonium nitrate; The eutectic solvent is a mixed solution of methanol and ethanol, wherein the volume ratio of methanol to ethanol is 4:1 to 1:1; The molar ratio of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene to ammonium nitrate is 2:1 to 1:2; The structural formula of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene is as follows: (2) Filter the eutectic solution with an organic filter membrane, and slowly volatilize the obtained filtrate completely at 5 °C to 10 °C to obtain the energetic eutectic compound.

3. According to the preparation method of the energetic eutectic compound described in claim 2, characterized in that: The molar ratio of the ammonium salt of 1,3,5-trinitro-2,4,6-trinitraminobenzene to ammonium nitrate is 1:1; the volume ratio of methanol to ethanol in the eutectic solvent is 3:

1.

4. According to the preparation method of the energetic eutectic compound described in any one of claims 2 to 3, characterized in that: The organic filter membrane is made of nylon 66 and has a pore size of 0.45 μm.

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