Anti-solvent synthesis method of ammonium perchlorate triethylene diamine perchlorate double salt
The synthesis of ammonium perchlorate triethylenediamine perchlorate double salt by antisolvent method solves the complex reaction control problem caused by water sensitivity in the existing technology, and improves the yield and purity of DAP-4.
Patent Information
- Application Number
- CN202511136691.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-14
- Publication Date
- 2025-11-18
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
The existing methods for preparing DAP-4 are sensitive to the amount of water used, which leads to complex reaction process control and unstable yield.
The triethylenediamine perchlorate double salt of ammonium perchlorate was synthesized by an antisolvent method. The reaction was carried out by mixing an organic solvent solution of triethylenediamine with an aqueous solution of perchloric acid at room temperature to form a precipitate, which was then mixed with an organic solvent solution of ammonium perchlorate and an antisolvent. The mass ratio of the precipitate to ammonium perchlorate was controlled, and organic solvents such as ethyl acetate or diethyl ether and antisolvents were used to optimize the reaction conditions.
The synthesis process was simplified, the yield of DAP-4 was improved, and higher product purity and yield were achieved.
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Abstract
Description
Technical Field
[0001] This invention relates to the synthesis of the perovskite energetic compound ammonium perchlorate triethylenediamine perchlorate complex salt (H2dabacoNH4(ClO4), DAP-4), specifically to the antisolvent synthesis method of DAP-4. Background Technology
[0002] In 2018, Academician Chen Xiaoming's team synthesized for the first time a perovskite energetic compound, DAP-4 (H2dabcoNH4(ClO4)3, with the structural formula shown in (I)), using triethylenediamine (dabco) as the A-site ion and perchlorate as the X-site ion. The compound has a density of 1.87 g / cm³. 3 It has a thermal decomposition temperature above 350℃, a detonation velocity of 8.81km / s, a detonation pressure of 35.2Gpa, an impact sensitivity of 23J, and a friction sensitivity of 36N. Compared with traditional CHON energetic compounds, DAP-4 has the advantages of low raw material price and high thermal decomposition temperature.
[0003]
[0004] Subsequently, the Xi'an Institute of Modern Chemistry developed a heat-resistant explosive based on DAP-4. Experiments showed that DAP-4's overall performance was comparable to RDX and superior to existing ultra-high temperature heat-resistant energetic compounds like HNS. In room-temperature steel target penetration tests, the DAP-4-based heat-resistant explosive achieved a detonation velocity of 7597 m / s, a penetration depth of 233 mm, and a perforation diameter >11.1 mm, exceeding the HNS-based S992 explosive (detonation velocity of 6879 m / s, penetration depth of 182 mm, and perforation diameter of 10.3 mm), demonstrating excellent performance. Furthermore, after prolonged ultra-high temperature holding (210℃ for 170 hours), the DAP-4-based heat-resistant explosive still achieved a penetration depth of 214 mm and a perforation diameter of 13.2 mm, exceeding national petroleum industry standards, indicating that DAP-4 can be applied to high-temperature / ultra-high temperature oil perforation scenarios.
[0005] In existing technologies, DAP-4 is prepared via a one-pot aqueous solution method (Science China Materials, 2018, 61(8):1123-1128). The yield of DAP-4 in this method is highly sensitive to the amount of water added during the reaction, and excessive water during filtration and washing will also reduce the yield (Journal of Explosives and Pyrotechnics, 2022, 5(4):479-485). Therefore, the amount of water used must be strictly controlled, making the reaction process control quite complex. Summary of the Invention
[0006] To address the deficiencies or shortcomings of existing technologies, this invention provides an antisolvent synthesis method for ammonium perchlorate triethylenediamine perchlorate complex salt.
[0007] Therefore, the synthesis method provided by the present invention includes:
[0008] Step 1: At room temperature, an organic solvent 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. The molar ratio of triethylenediamine to perchloric acid is 1:(2-3).
[0009] Step 2: Under room temperature conditions, the precipitate obtained in Step 1, the organic solvent solution of ammonium perchlorate, and the antisolvent are mixed and reacted to prepare ammonium perchlorate triethylenediamine perchlorate double salt; wherein the mass ratio of precipitate to ammonium perchlorate is (2-3):1.
[0010] Alternatively, the perchloric acid aqueous solution may have a mass percentage concentration of 70% to 72%.
[0011] Alternatively, the organic solvent in step one can be ethyl acetate or diethyl ether.
[0012] Alternatively, the antisolvent in step two may be one or a mixture of two or more of diethyl ether, ethyl acetate, and acetone.
[0013] An alternative approach is to add an antisolvent in step two in a volume greater than or equal to four times the volume of the organic solvent used in step two.
[0014] An alternative approach is to obtain the product by centrifugation, washing, and drying after the reaction in step two is completed.
[0015] Alternatively, the organic solvent in step two can be dimethyl sulfoxide or N,N-dimethylformamide (DMF).
[0016] The synthesis method of this invention is simple to control and has a higher yield. Detailed Implementation
[0017] Unless otherwise specified, the scientific and technical terms used in this article are intended for understanding by those skilled in the art.
[0018] The present invention will be further described in detail below with reference to the 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. The raw materials used in the following embodiments are all commercially available products.
[0019] Example 1:
[0020] Step 1: Dissolve 112 mg of triethylenediamine in 20 mL of ethyl acetate and add 500 μL 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 (yield 96.23%).
[0021] Step 2: Then, 313 mg of the white precipitate prepared by the method in Step 1 above 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 added and stirred vigorously to obtain white crystals. The white crystals were centrifuged, washed three times with ethyl acetate, and dried to obtain the product with a yield of 95.32%.
[0022] The product structure was identified as follows:
[0023] Powder X-ray diffraction analysis: 2θ = 12.18°, 21.19°, 24.52°, and 36.55° belong to the (200), (222), (400), and (531) crystal planes of DAP-4, respectively.
[0024] FTIR analysis (KBr, cm -1 ): 3317, 3172, 3045, 2783, 2499, 2009, 1475, 1425, 1326, 1068, 885, 846, 802, 626.
[0025] Structural identification data confirmed that the substance obtained by the preparation method in the above embodiments is DAP-4.
[0026] Comparative Examples 1-3:
[0027] The comparative example uses a one-pot aqueous solution method to prepare DAP-4. The specific method is as follows: 112 mg of triethylenediamine, 117 mg of ammonium perchlorate, and 500 μL of perchloric acid aqueous solution (mass percentage concentration of 70%) were added to 10 mL, 20 mL, and 30 mL of water, respectively. The mixture was stirred at room temperature for 30 min, washed three times with ethyl acetate, dried, and the product was collected.
[0028] In the comparative examples, the yield was 91.24% when 10 mL of water was added, 75.95% when 20 mL was added, and 40.31% when 30 mL was added. This shows that the total amount of water added has a significant impact on the yield, and the total amount of water added must be strictly controlled when using the one-pot aqueous solution method.
Claims
1. A method for the antisolvent synthesis of ammonium perchlorate triethylenediamine perchlorate double salt, characterized in that the method... include: Step 1: At room temperature, an organic solvent 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. The molar ratio of triethylenediamine to perchloric acid is 1:(2-3). Step 2: Under room temperature conditions, the precipitate obtained in Step 1, the organic solvent solution of ammonium perchlorate, and the antisolvent are mixed and reacted 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, The antisolvent in step two is one or a mixture of two or more of diethyl ether, ethyl acetate, and acetone.
5. The synthesis method according to claim 1, characterized in that, The volume of antisolvent added in step two is greater than or equal to four times the volume of organic solvent used in step two.
6. 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.
7. The synthesis method according to claim 1, characterized in that, The organic solvent in step two is dimethyl sulfoxide or N,N-dimethylformamide.