Molecular perovskite energetic material NP-1 and preparation method thereof

Abstract

The invention provides a molecular perovskite energetic material NP-1 and a preparation method thereof. The molecular formula of the molecular perovskite energetic material NP-1 is (C14H32N4) [NH4 (ClO4) 3]. The invention also relates to a preparation method of the molecular perovskite energetic material NP-1. The preparation method comprises the following steps: step 1, dissolving cycleanine in deionized water to form a solution A; step 2, adding perchloric acid into the solution A to form a solution B; step 3, slowly heating the solution B, and keeping the temperature; step 4, pouring the solution B into a beaker, cooling, precipitating and filtering to obtain a precipitate; and step 5, freezing the precipitate, and freeze-drying to obtain white NP-1 powder. The raw materials 1, 4, 7, 10-tetraazacyclododecane and dilute perchloric acid are adopted as the raw materials, the interaction between the two is milder and more stable, and the molecular perovskite energetic material NP-1 with the advantages of high yield, high density, low sensitivity and the like is prepared.

Description

Technical Field

[0001] The invention belongs to the technical field of explosives and firearms, and in particular relates to a molecular perovskite energetic material NP-1 and a preparation method thereof. Background Art

[0002] Molecular perovskite energetic materials featuring the ABX3 framework have received extensive attention in the past five years due to their simple synthesis methods and remarkable efficacy. In 2018, Academician Chen Xiaoming took the lead in designing and synthesizing high-energy compounds of this molecular structure. In his study, the triethylenediamine cation (H2dabco) with protonated A site was used to synthesize the high-energy perovskite energetic materials. 2+ , designated as C6H 14 N2 2+ ) is occupied, while the B site can accommodate various cations, including NH4 + , K + 、Na + or Ag + . X site is ClO4 - 、NO3 - or IO4 - In the molecular structure of ABX3 high energy materials, fuel (H2dabc 2+ ) and oxidant (ClO4 - ) are ionically bonded together, thus establishing optimal conditions for their redox reactions. In particular, when B is an ammonium cation (NH4 + ) due to NH4 + There are no metal particles in it, so it is similar to ClO4 - The reaction between them will also release a lot of heat and gas. Therefore, (H2dabco)[NH4(ClO4)3] (abbreviated as DAP-4) has become the most popular molecular perovskite energetic material currently being studied.

[0003] H2dabco in DAP-4 2+ Similarly, 1,4,7,10-tetraazacyclododecane (Chinese name: cyclocyclotengning, C8H 20 N4) has not been reported as an organic fuel in perovskite-type energetic materials. 2+ More economical. For production, reducing costs without affecting production capacity is the best way to improve economic benefits. It is meaningful to produce molecular perovskite energetic material NP-1 from 1,4,7,10-tetraazacyclododecane and dilute perchloric acid. Summary of the invention

[0004] The purpose of the present invention is to provide a molecular perovskite energetic material NP-1 and a preparation method thereof.

[0005] The present invention is achieved through the following technical solutions:

[0006] The present invention relates to a molecular perovskite energetic material NP-1, the molecular formula of which is: (C 14 H 32 N4)[NH4(ClO4)3], the structural formula is shown in (I):

[0007]

[0008] The present invention also relates to a method for preparing the aforementioned molecular perovskite energetic material NP-1, comprising the following steps:

[0009] Step 1, completely dissolving 3.46 g of cyclopentane in 60 mL of deionized water to form solution A;

[0010] Step 2, adding 19 mL of perchloric acid to solution A to form solution B;

[0011] Step 3, slowly heating solution B under stirring and keeping the temperature constant;

[0012] Step 4, remove the water bath, pour solution B into a 200 mL beaker, cool to 0-5°C, filter the white precipitate in the beaker, and wash it twice with ice distilled water to obtain a precipitate;

[0013] If the cooling temperature is higher than 5°C, a large amount of the product NP-1 will dissolve in water. If filtered at this time, the yield of the product NP-1 will be greatly reduced; if the temperature is lower than 0°C, a large amount of by-products will precipitate from the solution, resulting in a decrease in the purity of the main product NP-1. The present invention has been tested many times and the results show that the cooling temperature is controlled at 0 to 5°C as the best temperature, that is, under this temperature control, the final yield of the main product NP-1 is also the highest, and almost no by-products are doped in the main product NP-1.

[0014] Step 5, freezing the precipitate in a -45°C refrigerator, placing it in a freeze dryer precooled to -50°C, sealing it, evacuating it, and freeze drying it to obtain a white NP-1 powder with good dispersibility;

[0015] In step 5, if the freezing temperature in the refrigerator is higher than -45°C, the product NP-1 will have poor dispersibility after freeze-drying, especially uneven particle size, and a large amount of agglomeration. Only when the refrigerator temperature is -45°C or slightly lower, can the NP-1 powder with good dispersibility and no agglomeration be obtained.

[0016] The reaction principle of the preparation process is as follows:

[0017]

[0018] Preferably, in step 1, the cyclopentane is 1,4,7,10-tetraazacyclododecane. 20 N4,CAS NO.:294-90-6.

[0019] Preferably, in step 2, the perchloric acid has a mass fraction of 35 wt.%.

[0020] Preferably, in step 3, the heating temperature is 60° C. and the insulation time is 1 hour;

[0021] If the temperature is higher than 60°C, the molecules of the raw material cyclopentane will be completely cleaved in the solution, and the predetermined product cannot be obtained; if the temperature is lower than 60°C, the molecules of cyclopentane will not be cleaved at all, and the molecules will not be rearranged, resulting in the failure to obtain the predetermined product. The present invention has been tested many times, and the final results show that the predetermined product can be obtained by controlling the reaction temperature to 60°C and keeping it warm for 1 hour.

[0022] Preferably, in step 5, the freezing time is 24 hours.

[0023] The present invention has the following advantages:

[0024] (1) The raw materials 1,4,7,10-tetraazacyclododecane and dilute perchloric acid used in the present invention are both low-cost raw materials. The interaction between the two is more gentle and stable, and the heat generated can be ignored.

[0025] (2) The preparation method of the present invention has mild conditions, high safety factor, and has the prospect of batch production and large-scale production.

[0026] (3) The present invention uses 1,4,7,10-tetraazacyclododecane as an organic fuel and reacts it with an oxidant HClO4 to synthesize the single-substance explosive NP-1, which can be used as a high explosive in wartime emergencies.

[0027] (4) The molecular perovskite energetic material NP-1 prepared by the method of the present invention has the advantages of high yield, high density and low sensitivity. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is a schematic diagram of the reaction for preparing NP-1 in Example 1 of the present invention;

[0029] Figure 2 This is a test result diagram of single crystal diffraction of NP-1 prepared in an embodiment of the present invention;

[0030] Figure 3 is an X-ray diffraction (XRD) test result diagram of NP-1 prepared in an embodiment of the present invention;

[0031] Figure 4It is a comparison chart of the differential scanning calorimetry (DSC) test results of NP-1 prepared in the examples of the present invention. DETAILED DESCRIPTION

[0032] The present invention is described in detail below in conjunction with specific embodiments. It should be noted that the following embodiments are only further descriptions of the present invention, but the protection scope of the present invention is not limited to the following embodiments.

[0033] Example 1

[0034] This embodiment relates to a method for preparing a molecular perovskite energetic material NP-1, see Figure 1 As shown, the specific steps are as follows:

[0035] Step 1, completely dissolving 3.46 g of cyclopentane in 60 mL of deionized water to form solution A;

[0036] Step 2, adding 19 mL of 35 wt.% perchloric acid to solution A to form solution B;

[0037] Step 3, slowly heating solution B to 60°C under stirring and keeping the temperature for 1 hour;

[0038] Step 4, remove the water bath, pour the heated solution into a 200 mL beaker, and when the solution in the beaker cools to 0-5°C, filter out the white precipitate in the beaker and wash it twice with ice distilled water;

[0039] Step 5, put the filtered precipitate into a -45°C refrigerator, keep it in a frozen state for 24 hours, then put it into a freeze dryer that has been pre-cooled to -50°C, seal it and evacuate it, and freeze-dry it for 48 hours to obtain NP-1 white powder with good dispersibility.

[0040] As shown in Table 1: The elemental analysis (EA) test results of NP-1 show that the measured element percentages of the raw material cyclopentane and the prepared NP-1 are consistent with the theoretical percentages, which indicates that the single crystal diffraction test results are accurate.

[0041] Table 1

[0042] sample N(％) C(％) H(％) O(％) S(％) NP-1 test results 12.98 28.89 6.16 32.98 0 Theoretical value of NP-1 12.20 29.40 6.30 33.50 0 Cyclotrimethylenetetramine test results 31.94 55.07 11.27 0 0 Theoretical value of cyclopentane 32.60 55.80 11.60 0 0

[0043] The crystal structure parameters and structure correction data of NP-1 prepared in this example are shown in Table 2. Figure 2 As shown in Table 2 and Figure 2 As can be seen, the chemical formula of NP-1 is (C 14 H 32 N4)[NH4(ClO4)3], it belongs to the orthorhombic system, Pnma space group, each unit cell consists of 8 molecules of C14 N4H 34 and 8 molecules of NH4 + Then add 24 molecules of perchlorate (ClO4 - ) is formed by ionic bonding, the unit cell parameters α=β=γ=90°.

[0044] Table 2

[0045]

[0046] See Figure 3 As shown, the X-ray diffraction (XRD) test result diagram of NP-1 prepared in Example; Figure 3 The XRD spectrum of NP-1 shows that the measured XRD spectrum of NP-1 is basically consistent with the XRD spectrum of NP-1 fitted by the single crystal diffraction results, which once again proves the accuracy of the single crystal diffraction test results.

[0047] From Table 3 (DSC test results of NP-1) and Figure 4 (The left figure (a) is the DSC spectrum at different heating rates, and the right figure (b) is the Kissinger equation fitting diagram); the thermal analysis data show that the activation energy of the thermal decomposition reaction of NP-1 (E K ) is very close to that of DAP-4, which is the result of their similar molecular structures. However, the thermal decomposition rate constant (k) of NP-1 is significantly greater than that of DAP-4, which means that at the same temperature, the thermal decomposition rate of NP-1 is higher than that of DAP-4. The activation enthalpy (ΔH ≠ ) is similar to the activation enthalpy of DAP-4, indicating that NP-1 and DAP-4 need to absorb almost the same amount of heat from the ground state to the activated state. The activation free energy (ΔG ≠ ) are all positive numbers, indicating that their activation processes are not spontaneous and must absorb a certain amount of energy to reach the activated state from the ground state. The DSC spectrum generally shows that the thermal decomposition process of NP-1 is more intense than that of DAP-4, which further proves an advantage of NP-1 over traditional products.

[0048] Table 3

[0049]

[0050] In Table 3: ΔH ≠ is the activation enthalpy, ΔG ≠ is the activation free energy, ΔS ≠ is the activation entropy, E K is the activation energy of thermal decomposition calculated using the Kissinger equation, A K is the pre-exponential factor calculated by the Kissinger equation, k is the rate constant, k = AK Exp[-E K / (T p ·R)], the calculation methods of all data in Table 3 are derived from the following literature:

[0051] (1)Yi Wang, Xiaolan Song, Dan Song. Synthesis, thermolysis, and sensitivities of HMX / NC energetic nanocomposites[J]. Journal of HazardousMaterials, 2016, 312: 73-83.

[0052] (2)Yi Wang, Xiaolan Song, Dan Song. Mechanism investigation for remarkable decreases in sensitivities from micron to nano nitroamine[J]. Nanomaterials and Nanotechnology, 2016, 6: 1-10.

[0053] (3)Yong Kou, Yi Wang, Xiaolan Song. Iron / aluminum nanocompositesprepared by one-step reduction method and their effects on thermaldecomposition of AP and AN[J].Defence Technology, 2023,22:74-87.

[0054] The performance of NP-1 prepared by the method of this embodiment is compared with the existing product, as shown in Table 4:

[0055] Table 4

[0056]

[0057] The data in Table 4 show that NP-1 has the characteristics of high density, low sensitivity, low thermal decomposition temperature, easy availability of raw materials, simple preparation process, and low cost. Therefore, NP-1 is very suitable for large-scale production in wartime to make up for the shortage of major explosives.

[0058] NP-1 in Table 4 is the NP-1 synthesized in the embodiment, i.e. (C 14 H 32N4) [NH4 (ClO4) 3]; DAP-4, TNT, RDX, HMX and CL-20 refer to the following literature:

[0059] (Chen Kangyu, Song Xiaolan, Wang Yi, Yu Zhihong, Kou Yong, An Chongwei. Characterization and performance study of molecular perovskite energetic material DAP-4[J]. Journal of Explosives and Propellants, 2024, 47(9): 786-796.)

[0060] In Table 4: ρ is the theoretical density, ΔH f is the enthalpy of formation, Q D The explosion heat calculated by EXPLO5 software, v D The detonation velocity, P, was calculated using EXPLO5 software. C-J The explosion pressure calculated by EXPLO5 software, T p The exothermic peak temperature of the DSC curve at a heating rate of 10℃ / min, I sp is the standard specific impulse calculated by NASA-CEA2 software, IS is the measured impact sensitivity, FS is the measured friction sensitivity, OB is the measured friction sensitivity, CO2 It is the oxygen balance when all carbon elements are oxidized to CO2. The calculation method can be found in the following literature:

[0061] Shao-Li Chen, Zi-Run Yang, Bin-Jie Wang, et al. Molecular perovskitehigh-energetic materials [J]. Science China Materials, 2018, 61(8): 1123-1128.

[0062] In summary, the raw materials 1,4,7,10-tetraazacyclododecane and dilute perchloric acid used in the present invention are used as raw materials, and the interaction between the two is more gentle and stable, so that a molecular perovskite energetic material NP-1 with the advantages of high yield, high density, low sensitivity, etc. is prepared.

[0063] The above describes the specific embodiments of the present invention. It should be understood that the present invention is not limited to the above specific embodiments, and those skilled in the art may make various modifications or variations within the scope of the claims, which will not affect the essence of the present invention.

Claims

1. A molecular perovskite energetic material NP-1, characterized in that: The molecular formula is: (C 14 H 32 N4)[NH4(ClO4)3].

2. The molecular perovskite energetic material NP-1 according to claim 1, characterized in that: The structural formula is as follows:

3. A method for preparing the molecular perovskite energetic material NP-1 as claimed in claim 1, characterized in that: The following steps are involved: Step 1, completely dissolving 3.46 g of cyclopentane in 60 mL of deionized water to form solution A; Step 2, adding 19 mL of perchloric acid to solution A to form solution B; Step 3, slowly heating solution B under stirring and keeping the temperature constant; Step 4, remove the water bath, pour solution B into a 200 mL beaker, cool to 0-5°C, filter the white precipitate in the beaker, and wash it twice with ice distilled water to obtain a precipitate; Step 5, freeze the precipitate in a -45°C refrigerator, put it into a freeze dryer precooled to -50°C, seal it, evacuate it, and freeze-dry it to obtain NP-1 white powder.

4. The method for preparing the molecular perovskite energetic material NP-1 according to claim 3, characterized in that: In step 1, the cyclopentane is 1,4,7,10-tetraazacyclododecane.

5. The method for preparing the molecular perovskite energetic material NP-1 according to claim 3, characterized in that: In step 2, the perchloric acid has a mass fraction of 35 wt.%.

6. The method for preparing the molecular perovskite energetic material NP-1 according to claim 3, characterized in that: In step 3, the heating temperature is 60° C. and the insulation time is 1 hour.

7. The method for preparing the molecular perovskite energetic material NP-1 according to claim 3, characterized in that: In step 5, the freezing time is 24 hours.

8. The method for preparing the molecular perovskite energetic material NP-1 according to claim 3, characterized in that: In step 5, the freeze-drying time is 48 hours.

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