Preparation method of modified ammonium perchlorate triethylene diamine perchloric acid double salt

Abstract

The invention discloses a preparation method of modified ammonium perchlorate triethylene diamine perchloric acid double salt. According to the disclosed scheme, K < + > or NO3 <-> is doped in DAP-4, so that the sensitivity of DAP-4 is reduced, and the modified ammonium perchlorate triethylene diamine perchloric acid double salt is prepared. The doped perovskite energetic compound DAP-4 belongs to a heat-resistant explosive, and plays an important role in the fields of oil exploration and civil industry.

Description

Technical Field

[0001] This invention relates to the doping synthesis of perovskite energetic compound ammonium perchlorate triethylenediamine perchlorate complex salt (H2dabacoNH4(ClO4), DAP-4), specifically to the antisolvent synthesis of DAP-4, belonging to the field of energetic materials. Background Technology

[0002] In 2018, Academician Chen Xiaoming's team synthesized the first perovskite energetic compound DAP-4 (H2dabcoNH4(ClO4)3) with triethylenediamine (dabco) as the A-site ion and perchlorate as the X-site ion, with a density of 1.87 g / cm³. 3 It has a thermal decomposition temperature above 350℃, a detonation velocity of 8.81 km / s, a detonation pressure of 35.2 GPa, an impact sensitivity of 23 J, and a friction sensitivity of 36 N. Compared to traditional CHON energetic compounds, DAP-4 has the advantages of low raw material cost and high thermal decomposition temperature, thus it has wide applications in high-temperature / ultra-high-temperature oil perforation scenarios. However, its high sensitivity limits the further application of DAP-4. Summary of the Invention

[0003] The technical problem to be solved by the present invention is to provide a method that can effectively reduce the sensitivity of the perovskite energetic compound DAP-4, which is a shortcoming of high sensitivity.

[0004] This invention provides a novel method for reducing the sensitivity of perovskite energetic compound ammonium perchlorate triethylenediamine perchlorate complex salt (H2dabacoNH4(ClO4)3, DAP-4), by doping DAP-4 with K. + Or NO3 - The sensitivity of DAP-4 is reduced. The perovskite energetic compound DAP-4 used in this invention is a heat-resistant explosive that plays an important role in oil exploration and civilian industries. Detailed Implementation Unless otherwise specified, the scientific and technical terms used in this article are intended for understanding by those skilled in the art.

[0005] The present invention will be further described in detail below with reference to embodiments. It should be noted that the embodiments are preferred examples and are mainly used to understand the present invention, but the present invention is not limited to the embodiments.

[0006] Example 1 (K) + The molar amount of potassium perchlorate donor added is 20% of the molar amount of triethylenediamine perchlorate. Weigh 150 mg (0.0006 mol) of triethylenediamine and dissolve it in 50 mL of ethyl acetate. Add 1 mL of perchloric acid aqueous solution (mass percentage concentration of 70%, molar amount of perchloric acid of 0.007 mol) to obtain a white precipitate. Centrifuge the white precipitate, wash it three times with ethyl acetate, and then air dry it for later use. Take 313 mg of the white precipitate obtained in the above steps (the white precipitate is triethylenediamine perchlorate, molar amount 0.001 mol) and add it to 2 mL of dimethyl sulfoxide. Then add 94 mg of ammonium perchlorate (0.0008 mol) and 28 mg of potassium perchlorate (0.0002 mol). Stir until dissolved, then quickly add 10 mL of the antisolvent ethyl acetate and stir vigorously to obtain white crystals. Centrifuge the white crystals, wash them three times with ethyl acetate, and dry them to obtain a white precipitate, which is K. + Doped DAP-4.

[0007] K was prepared using the method described in this example. + The molar amount of potassium perchlorate donor added is 5% and 10% of the molar amount of triethylenediamine perchlorate, respectively, and K is added. + Doped DAP-4.

[0008] Example 2 (NO3) - The total molar amount of the donor triethylenediamine nitrate and ammonium nitrate is 50% of the molar amount of triethylenediamine perchlorate. Weigh 150 mg (0.0006 mol) of triethylenediamine and dissolve it in 50 mL of ethyl acetate. Add 1 mL of perchloric acid aqueous solution (mass percentage concentration of 70% and molar amount of perchloric acid of 0.007 mol) to obtain white precipitate 1. Centrifuge white precipitate 1, wash it three times with ethyl acetate, and then air dry it for later use. Weigh 150 mg of triethylenediamine and dissolve it in 50 mL of ethyl acetate. Add 1 mL of nitric acid solution (60% concentration, 0.0095 mol of nitric acid) to obtain white precipitate 2. Centrifuge the white precipitate 2, wash it three times with ethyl acetate, and then dry it for later use. Take 250 mg of the white precipitate 1 obtained in the above steps (white precipitate 1 is triethylenediamine perchlorate, molar amount 0.0008 mol) and 48 mg of white precipitate 2 (white precipitate 2 is triethylenediamine nitrate, molar amount 0.0002 mol) and add them to 2 mL of dimethyl sulfoxide. Then add 94 mg of ammonium perchlorate (0.0008 mol) and 16 mg of ammonium nitrate (0.0002 mol). Stir until dissolved, then quickly add 10 mL of the antisolvent ethyl acetate and stir vigorously to obtain white crystals. Centrifuge the white crystals, wash them three times with ethyl acetate, and air dry to obtain a white precipitate, which is NO3. - Doped DAP-4.

[0009] NO3 was prepared using the methods described in this example. - The donor addition amount is 5% and 10% of the molar amount of triethylenediamine perchlorate, and NO3. - Doped DAP-4.

[0010] Comparative Example 1: Weigh 150 mg of triethylenediamine and dissolve it in 50 mL of ethyl acetate. Add 1 mL of perchloric acid aqueous solution (70% by mass) to obtain a white precipitate. Centrifuge the white precipitate, wash it three times with ethyl acetate, and then air dry it for later use.

[0011] The white precipitate obtained in the above steps was added to 2 mL of dimethyl sulfoxide, followed by 117 mg of ammonium perchlorate. After stirring until dissolved, 10 mL of the antisolvent ethyl acetate was quickly added and stirred vigorously to obtain white crystals. The white crystals were centrifuged, washed three times with ethyl acetate, and dried to obtain a white precipitate, which was DAP-4.

[0012] Comparative Example 2: This comparative example uses the traditional aqueous solution method to prepare K. + The specific method for doping DAP-4 is as follows: Weigh 150 mg of triethylenediamine, 94 mg of ammonium perchlorate and 28 mg of potassium perchlorate and add them to 5 mL of deionized water. After they are completely dissolved, slowly add 1 mL of perchloric acid aqueous solution (mass percentage concentration of 70%) and stir until a white precipitate is formed. Filter, wash with water and dry to obtain a white precipitate.

[0013] Comparative Example 3: This comparative example uses the traditional DAP-4 preparation process to prepare NO3. - The specific method for doping DAP-4 is as follows: Weigh 150 mg of triethylenediamine, 94 mg of ammonium perchlorate and 16 mg of ammonium nitrate and add them to 5 mL of deionized water. After they are completely dissolved, slowly add 1 mL of nitric acid solution (60% concentration) and stir until a white precipitate is formed. Filter, wash with water and dry to obtain a white precipitate.

[0014] The structure of DAP-4 prepared in the above examples is identified as follows: 20%K + Powder X-ray diffraction analysis of the doped powder: 2θ = 21.32°, 24.66°, and 36.81° belong to the (222), (400), and (531) crystal planes of DAP-4, respectively.

[0015] 20% NO3 -Powder X-ray diffraction analysis of the doped powder: 2θ = 21.27°, 24.60°, and 36.71° belong to the (222), (400), and (531) crystal planes of DAP-4, respectively.

[0016] The structure of the white precipitate in Comparative Example 1 was identified as follows: 2θ = 21.19°, 24.52°, and 36.55° belong to the (222), (400), and (531) crystal planes of DAP-4, respectively.

[0017] The white precipitate structure of Comparative Example 2 was identified as follows: 2θ = 21.19°, 24.52°, and 36.55° belong to the (222), (400), and (531) crystal planes of DAP-4, respectively.

[0018] The white precipitate structure of Comparative Example 3 was identified as follows: 2θ = 21.19°, 24.52°, and 36.55° belong to the (222), (400), and (531) crystal planes of DAP-4, respectively.

[0019] Structural identification data confirmed that the substances obtained in Comparative Examples 1, 2, and 3 were DAP-4, and the diffraction peak positions of the three samples did not shift. Examples 1 and 2 were also DAP-4, but compared to the comparative examples, the diffraction peak positions shifted. According to Bragg's equation: 2dsinθ = nλ, changes in lattice spacing cause shifts in the diffraction peak positions. For the comparative examples, the absence of peak shift indicates that K... + and NO3 - The doping did not enter the DAP-4 lattice, meaning that the traditional one-step aqueous solution method cannot achieve doping. Furthermore, in the example, the diffraction peak positions shifted, which is attributed to K... + and NO3 - This is caused by entering the DAP-4 lattice. Due to K + With NO3 - The different ionic radii cause different shifts in the diffraction peak positions. In summary, traditional one-step aqueous solution methods cannot achieve doping, while the two-step antisolvent method can.

[0020] The sensitivity of the above embodiments was further tested, wherein the impact sensitivity was tested using the impact sensitivity test method in GJB770A-97; and the friction sensitivity was tested using the friction sensitivity test method in GJB770A-97. The sensitivity test results are shown in Table 1.

[0021] Table 1

[0022] Sensitivity test results show that doping can effectively improve the safety of DAP-4 and reduce its sensitivity, thereby obtaining modified ammonium perchlorate triethylenediamine perchlorate complex salt.

Claims

1. A method for preparing a modified ammonium perchlorate triethylenediamine perchlorate double salt, characterized in that the method... include: Step 1: At room temperature, the organic solvent A solution of triethylenediamine is mixed with an aqueous solution of perchloric acid to produce a precipitate. After the reaction is complete, the precipitate is collected as triethylenediamine perchlorate. The molar ratio of triethylenediamine to perchloric acid is 1:(2~12). Step 2: At room temperature, an antisolvent is added to an organic solvent B solution containing triethylenediamine perchlorate, the dopant, and ammonium perchlorate to prepare modified ammonium perchlorate triethylenediamine perchlorate double salt; the dopant is potassium perchlorate or a mixture of triethylenediamine nitrate and ammonium nitrate, and the triethylenediamine nitrate is a precipitate produced by the reaction of a triethylenediamine organic solvent C solution with nitric acid.

2. The method for preparing modified ammonium perchlorate triethylenediamine perchlorate double salt according to claim 1, characterized in that, The mass ratio of triethylenediamine perchlorate, ammonium perchlorate, and potassium perchlorate is (2-3):1:(0.2-0.5).

3. The method for preparing the modified ammonium perchlorate triethylenediamine perchlorate double salt according to claim 1, characterized in that, The mass ratio of triethylenediamine perchlorate, ammonium perchlorate, triethylenediamine nitrate, and ammonium nitrate is (2-3):1:(0.4-0.6):(0.1-0.3).

4. The method for preparing modified ammonium perchlorate triethylenediamine perchlorate double salt according to claim 1, characterized in that, In step two, the amount of potassium perchlorate added accounts for 20% of the amount of triethylenediamine perchlorate.

5. The method for preparing the modified ammonium perchlorate triethylenediamine perchlorate double salt according to claim 1, characterized in that, In step two, the total molar amount of triethylenediamine nitrate and ammonium nitrate accounts for 50% of the molar amount of triethylenediamine perchlorate.

6. The method for preparing modified ammonium perchlorate triethylenediamine perchlorate double salt according to claim 1, characterized in that, The organic solvent A used in step one is selected from ethyl acetate or diethyl ether.

7. The method for preparing the modified ammonium perchlorate triethylenediamine perchlorate double salt according to claim 1, characterized in that, Organic solvent B is selected from N,N-dimethylformamide or dimethyl sulfoxide.

8. The method for preparing the modified ammonium perchlorate triethylenediamine perchlorate double salt according to claim 1, characterized in that, Organic solvent C is selected from ethyl acetate or diethyl ether.

9. The method for preparing the modified ammonium perchlorate triethylenediamine perchlorate double salt according to claim 1, characterized in that, The antisolvent is selected from ethyl acetate, acetone, or diethyl ether.

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