Ultrasonic synthesis method of ammonium perchlorate triethylene diamine perchlorate double salt

Abstract

The invention discloses an ultrasonic synthesis method of ammonium perchlorate triethylene diamine perchloric acid double salt, which comprises the following steps: mixing an organic solvent solution of triethylene diamine with a perchloric acid aqueous solution at room temperature, reacting to generate a precipitate, and collecting the precipitate after the reaction is completed; and reacting the obtained white precipitate with ammonium perchlorate in anhydrous acetonitrile at room temperature under ultrasonic conditions to prepare ammonium perchlorate triethylene diamine perchlorate double salt. The method disclosed by the invention is simple to control and relatively high in yield.

Description

TECHNICAL FIELD

[0001] The present application relates to the synthesis of ammonium perchlorate triethylenediamine perchlorate complex salt (H2dabacoNH4(ClO4)3, DAP-4), in particular the synthesis of DAP-4 by ultrasonic method. BACKGROUND

[0002] The molecular perovskite energetic compound H2dabcoNH4(ClO4)3 (DAP-4) has a structural formula as shown in (I), which is a new energetic compound with triethylenediamine (dabco) as A-site ion, ammonium ion as B-site ion, and perchlorate as X-site ion. The density of the substance is 1.87 g / cm 3 , the detonation velocity is 8.81 km / s, the detonation pressure is 35.2 Gpa, the impact sensitivity is 23 J, the friction sensitivity is 36 N, and the thermal decomposition temperature is higher than 350℃. DAP-4 has the advantages of low raw material price, simple preparation process, and high thermal decomposition temperature. At present, researchers have applied DAP-4 to high-temperature / ultra-high-temperature oil perforating bullets. It is found that when used as a heat-resistant explosive, its comprehensive performance can be comparable to that of hexogen, and is superior to the existing high-temperature heat-resistant explosive HNS. According to the report, after being kept at 210℃ for 170 hours, the penetration depth and hole diameter of the DAP-4-based heat-resistant explosive can reach 214 mm and 13.2 mm respectively, which exceeds the national oil industry standard.

[0003]

[0004] (I) In the prior art, DAP-4 is prepared by one-pot method in aqueous solution (Science China Materials, 2018, 61(8): 1123-1128). In this method, the yield of DAP-4 is sensitive to the amount of water added during the reaction process, and too much water during the filtration and washing process will also reduce the yield (Chinese Journal of Explosives and Propellants, 2022, 5(4): 479-485). Therefore, the amount of water needs to be strictly controlled, resulting in complex reaction process control. SUMMARY

[0005] In view of the defects or deficiencies of the prior art, the present application provides an ultrasonic synthesis method of ammonium perchlorate triethylenediamine perchlorate complex salt.

[0006] Therefore, the synthesis method provided by the present application comprises: Step one, under room temperature, the organic solvent solution of triethylenediamine is mixed with perchloric acid aqueous solution to produce a precipitate, and the precipitate is collected after the reaction is completed; wherein the mass ratio of triethylenediamine to perchloric acid is 1: (2-12), and specifically can be 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12 and any ratio between the above two values; Step two, under room temperature and ultrasonic conditions, the precipitate obtained in step one is reacted with ammonium perchlorate in anhydrous acetonitrile to prepare ammonium perchlorate triethylenediamine perchlorate; wherein the mass ratio of the precipitate to ammonium perchlorate is (2-3):1.

[0007] Optionally, the mass percentage concentration of the perchloric acid aqueous solution is 70%-72%.

[0008] Optionally, the organic solvent in step one is ethyl acetate or diethyl ether.

[0009] Optionally, the ultrasonic power in step two is 400w, and the ultrasonic time is greater than or equal to 3h.

[0010] Optionally, the product is obtained after centrifugation, washing and air drying after the reaction in step two is completed.

[0011] The synthetic method of the application has simple control operation and high yield. DETAILED DESCRIPTION

[0012] Unless otherwise specified, the scientific and technical terms in this document are understood according to the understanding of the relevant field of ordinary skill.

[0013] The application will be further described in detail below in combination with examples. It should be noted that the examples are preferred examples, mainly for understanding the application, but the application is not limited to the examples.

[0014] Example 1: 112 mg (0.0005 mol) of triethylenediamine was dissolved in 20 mL of ethyl acetate, and 500 μL of perchloric acid aqueous solution (mass percentage of 70%, 0.0035 mol of perchloric acid) was added to obtain a white precipitate, which was centrifuged, washed with ethyl acetate for 3 times and then air dried for standby (yield of 96.23%); 313 mg of the white precipitate obtained in the above step was taken and mixed with 117 mg of ammonium perchlorate in anhydrous acetonitrile, and ultrasonic treatment (power 400W) was carried out at room temperature for 3h. After centrifugation, ethyl acetate washing and air drying, a white solid was obtained, which was DAP-4, and the yield was 92.59%.

[0015] The structure of DAP-4 prepared in the above examples is identified as follows: Powder X-ray diffraction analysis: 2θ = 12.21°, 21.24°, 24.58°, 27.51°, 36.66° belong to (200), (222), (400), (420), (531) crystal face of DAP-4 respectively. The structure identification data confirmed that the material obtained by ultrasonic synthesis method was DAP-4.

[0016] Comparative Examples 1-3: This comparative example used aqueous one-pot method to prepare DAP-4, and the specific method was as follows: 112 mg of triethylenediamine, 117 mg of ammonium perchlorate, and 500 μL of aqueous perchloric acid (70% by mass) were added to 10 mL, 20 mL, and 30 mL of water respectively, and after stirring at room temperature for 30 min, ethyl acetate was used for washing three times, and the product was collected after drying; The yield was 91.24% when the amount of water added in each comparative example was 10 mL, the yield was 75.95% when the amount of water added was 20 mL, and the yield was 40.31% when the amount of water added was 30 mL. Thus, it was shown that the total amount of water added had a great influence on the yield, and the total amount of water added needed to be strictly controlled when using the aqueous one-pot method.

Claims

1. An ultrasonic synthesis method for ammonium perchlorate triethylenediamine perchlorate double salt, characterized in that the method... include: Step 1: At room temperature, a solution of triethylenediamine in an organic solvent is mixed with an aqueous solution of perchloric acid to produce a precipitate. After the reaction is complete, the precipitate is collected. The molar ratio of triethylenediamine to perchloric acid is 1:(2~12). Step 2: Under room temperature and ultrasonic conditions, the precipitate obtained in Step 1 is reacted with ammonium perchlorate in anhydrous acetonitrile to prepare ammonium perchlorate triethylenediamine perchlorate double salt; wherein the mass ratio of precipitate to ammonium perchlorate is (2-3):

1.

2. The synthesis method according to claim 1, characterized in that, The perchloric acid aqueous solution has a mass percentage concentration of 70% to 72%.

3. The synthesis method according to claim 1, characterized in that, The organic solvent in step one is ethyl acetate or diethyl ether.

4. The synthesis method according to claim 1, characterized in that, Step 2: The ultrasonic power is 400W, and the ultrasonic duration is greater than or equal to 3 hours.

5. The synthesis method according to claim 1, characterized in that, After the reaction in step two is completed, the product is obtained by centrifugation, washing, and drying.

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