A method for preparing and using 3,4-diazidoethyloxyfuroxan

Abstract

This invention discloses a method for preparing and applying 3,4-diazidoethoxyfurazanyl furazan oxide. Dichloromethane, potassium hydroxide, and 2-azidoethanol are added to a reaction flask, and the mixture is reacted at 25℃–30℃ for 15 minutes. Then, 3,4-dinitrofurazanyl furazan oxide is added, and the temperature is raised to 35℃–38℃. The mixture is then refluxed under ultrasonic conditions for 2–4 hours. After the reaction, the mixture is washed with water, dried, and concentrated under reduced pressure. It is then recrystallized using carbon tetrachloride to obtain 3,4-diazidoethoxyfurazanyl furazan oxide. The compound involved in this invention belongs to the category of energetic plasticizers, exhibiting good thermal stability and low sensitivity. It is mainly used in solid propellants, propellants, and other fields.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of energetic materials, and relates to a preparation method and application of an energetic plasticizer, 3,4-diazidoethyloxy furazanyl oxofurazan. BACKGROUND

[0002] Energetic plasticizer is an indispensable functional additive in explosive products, and its application can expand the use temperature range of explosive products, improve the overall energy level, improve the processing technology, improve the low-temperature mechanical properties, and greatly reduce the vulnerability. Organic azide compound is an excellent energetic material, which has been widely used in energetic binder, energetic plasticizer, oxidant and many other aspects, and is an important way to improve the energy level and technical performance of energetic materials.

[0003] The research results in the past half century show that when designing high-energy density compounds composed of carbon, hydrogen, oxygen and nitrogen elements, furazan ring is a very effective structural unit, and is extremely meaningful for greatly improving the energy of low characteristic signal propellant and clean propellant. The furazan plasticizer has good physical and chemical properties and detonation performance, such as high density, high thermal stability, good impact sensitivity, good oxygen balance, high explosion pressure and high detonation velocity. It is far superior to nitroglycerin in thermal stability, density, sensitivity and detonation parameters. As a potential high-energy dense structure, furazanyl oxofurazan has a broad application prospect as an energetic plasticizer compound skeleton in propellant formulations and has great research and application value. However, in the prior art, the synthesis method of furazanyl oxofurazan plasticizer has problems of long synthesis reaction time and low yield. SUMMARY

[0004] In view of the problems in the prior art, the purpose of the present application is to provide a preparation method and application of 3,4-diazidoethyloxy furazanyl oxofurazan, which overcomes the problems of long synthesis reaction time and low yield of 3,4-diazidoethyloxy furazanyl oxofurazan in the prior art. The present application is a simple synthesis method with short reaction time and high yield.

[0005] In order to solve the above technical problems, the present application adopts the following technical solutions:

[0006] A preparation method of 3,4-diazidoethyloxy furazanyl oxofurazan, which uses 3,4-dinitro furazanyl oxofurazan, potassium hydroxide and 2-azidoethanol as raw materials, and dichloromethane as a solvent to prepare 3,4-diazidoethyloxy furazanyl oxofurazan. The azido group in the prepared 3,4-diazidoethyloxy furazanyl oxofurazan is connected to the high-energy furazanyl oxofurazan skeleton through an ethyl ether chain.

[0007] The present application also includes the following technical features:

[0008] Specifically, the method comprises the following steps: adding dichloromethane, potassium hydroxide and 2-azidoethanol into a reaction bottle respectively, adding 3,4-dinitrofurazanyloxy furazan at 25-30 DEG C for 15 min, increasing the temperature to 35-38 DEG C, and refluxing for 2-4 h under ultrasonic condition, and then washing with water, drying, concentrating under reduced pressure, recrystallizing with carbon tetrachloride to obtain 3,4-dinitrofurazanyloxy furazan.

[0009] Specifically, the molar ratio of 3,4-dinitrofurazanyloxy furazan, 2-azidoethanol and potassium hydroxide is 1:2-3:2-3.

[0010] Specifically, the molar ratio of 3,4-dinitrofurazanyloxy furazan, 2-azidoethanol and potassium hydroxide is 1:2.5:2.5.

[0011] The 3,4-dinitrofurazanyloxy furazan prepared by the method can be used as an energetic plasticizer in propellants and gun propellants.

[0012] Compared with the prior art, the method has the following technical effects:

[0013] The method for synthesizing 3,4-dinitrofurazanyloxy furazan has the advantages of simple reaction, short reaction time and high yield, and compared with other synthesis methods in the prior art, the reaction time is reduced to 3 h, the yield is increased to 89.9%, and no phase transfer catalyst is needed.

[0014] The compound is an energetic plasticizer, has the characteristics of good thermal stability and low sensitivity, and can be used in the fields of solid propellants and gun propellants.

[0015] As an energetic plasticizer, 3,4-dinitrofurazanyloxy furazan has high specific impulse and characteristic velocity in a formula containing 3,4-dinitrofurazanyloxy furazan as an adhesive, and has good performance as an energetic plasticizer component in a propellant formula. Specific embodiments

[0016] The application provides a preparation method and application of 3,4-diazidoethyloxyfuroxan, which is prepared from 3,4-dinitrofuroxan, potassium hydroxide and 2-azidoethanol as raw materials and dichloromethane as a solvent. In the preparation process, the speed control step of the reaction is that 2-azidoethanol is deprotonated to form 2-azidoethyloxy anion under alkaline conditions, and then an aromatic nucleophilic substitution reaction occurs with the nitro group on furoxan. The aromatic nucleophilic substitution reaction belongs to the Ar-SN2 reaction mechanism. The alkaline potassium hydroxide can provide an alkaline environment to effectively remove the hydroxyl protons in 2-azidoethanol to form 2-azidoethyloxy anion, and promote the charge transfer activation of the nitro group on the furoxan ring. According to the above mechanism, a more efficient reaction route is designed. The 2-azidoethanol and potassium hydroxide are reacted for 15 min to generate 2-azidoethyloxy anion with sufficient concentration in the reaction system. The ultrasonic cavitation effect, the shock wave and microjet flow formed in the solution are used to improve the dispersibility, so that the 2-azidoethyloxy anion attacks the carbon atom connected with the nitro group on the furoxan ring at a high frequency and high efficiency, the intermolecular etherification side reaction is avoided, the aromatic nucleophilic substitution reaction is completed, and the yield is obviously improved.

[0017] Specifically, the following steps are included: dichloromethane, potassium hydroxide and 2-azidoethanol are added into a reaction bottle, 3,4-dinitrofuroxan is added after reaction for 15 min at a temperature of 25 DEG C to 30 DEG C, the temperature is increased to 35 DEG C to 38 DEG C, ultrasonic conditions are adopted, and reflux reaction is carried out for 2 h to 4 h, preferably 3 h. After the reaction is completed, water washing, drying and reduced pressure concentration are carried out, carbon tetrachloride recrystallization is used, and 3,4-diazidoethyloxyfuroxan is obtained. The molar ratio of 3,4-dinitrofuroxan, 2-azidoethanol and potassium hydroxide is 1:2 to 3:2 to 3, and preferably 1:2.5:2.5.

[0018] The structural formula of the above 3,4-dinitrofuroxan is as follows:

[0019]

[0020] The azido group in the prepared 3,4-diazidoethyloxyfuroxan is connected with the high-energy furoxan skeleton through an ethyl ether chain, and the structural formula of the 3,4-diazidoethyloxyfuroxan is as follows:

[0021]

[0022] The synthesis route of the preparation method is as follows:

[0023]

[0024] The 3,4-diazidoethyloxyfuroxan compound prepared by the application is used as an energetic plasticizer in propellants and gun propellants.

[0025] The following are specific embodiments of the present invention. It should be noted that the present invention is not limited to the following specific embodiments. All equivalent modifications made based on the technical solutions of this application fall within the protection scope of the present invention.

[0026] Example 1:

[0027] This embodiment provides a method for preparing 3,4-diazidoethoxyfurazanyl furazan oxide. 2.18 g (0.025 mol) of 2-azidoethanol, 1.40 g (0.025 mol) of potassium hydroxide, and 50 mL of dichloromethane are added to a reaction flask. The mixture is stirred and heated to 25°C–30°C and reacted at this temperature for 15 min. Then, 3.12 g (0.010 mol) of 3,4-dinitrofurazanyl furazan oxide is added, and the mixture is heated to 35°C–38°C and refluxed under ultrasonic conditions for 3 h. After the reaction is complete, the mixture is washed with water, dried, and concentrated under reduced pressure. Recrystallization using carbon tetrachloride yields a white crystalline solid, 3.52 g, of 3,4-diazidoethoxyfurazanyl furazan oxide, with a yield of 89.9%.

[0028] Structural assessment:

[0029] Infrared spectrum: IR (KBr, cm -1 ),υ:2970,2930(-CH2-),2158,2118(-N3),1633,1552,1480,1328

[0030] (-C=N),1159,1100,1060,1009(-COC-)

[0031] Nuclear magnetic resonance spectroscopy: 1 H NMR (DMSO, 500MHz), δ: 3.57~3.59(t,2H,CH2), 3.69~3.71(t,2H,CH2), 4.47~4.49(t,2H,CH2), 4.56~4.58(t,2H,CH2)2.51(p,H,DMSO); 13 C NMR (DMSO, 500MHz), δ: 163.68, 163.50 (N=CO), 144.01, 136.85, 134.30 (N=C) 103.96 (N=C→O), 72.63, 72.57 (CH2), 49.54 (CH2), 39.82~40.16 (m, C, DMSO);

[0032] Elemental analysis: Molecular formula C 10 H8N 12 O6

[0033] Theoretical values ​​(%): C 30.62, H 2.06, N 42.85;

[0034] Measured values ​​(%): C 30.65, H 2.26, N 43.07.

[0035] The substance obtained by the above preparation method is confirmed to be 3,4-diazidoethoxyfurazanyloxyfurazan, with the molecular formula C2. 10 H8N 12 O6.

[0036] Example 2:

[0037] This embodiment provides a method for preparing 3,4-diazidoethoxyfurazanyl furazan oxide. 1.74 g (0.020 mol) of 2-azidoethanol, 1.12 g (0.020 mol) of potassium hydroxide, and 50 mL of dichloromethane are added to a reaction flask. The mixture is stirred and heated to 25°C–30°C and reacted at this temperature for 15 min. Then, 3.12 g (0.010 mol) of 3,4-dinitrofurazanyl furazan oxide is added, and the mixture is heated to 35°C–38°C and refluxed under ultrasonic conditions for 3 h. After the reaction is complete, the mixture is washed with water, dried, and concentrated under reduced pressure. Recrystallization using carbon tetrachloride yields a white crystalline solid, 3.02 g, of 3,4-diazidoethoxyfurazanyl furazan oxide, with a yield of 77.0%.

[0038] Example 3:

[0039] This embodiment provides a method for preparing 3,4-diazidoethoxyfurazanyl furazan oxide. 2.61 g (0.030 mol) of 2-azidoethanol, 1.68 g (0.030 mol) of potassium hydroxide, and 50 mL of dichloromethane are added to a reaction flask. The mixture is stirred and heated to 25°C–30°C and reacted at this temperature for 15 min. Then, 3.12 g (0.010 mol) of 3,4-dinitrofurazanyl furazan oxide is added, and the mixture is heated to 35°C–38°C and refluxed under ultrasonic conditions for 3 h. After the reaction is complete, the mixture is washed with water, dried, and concentrated under reduced pressure. Recrystallization using carbon tetrachloride yields a white crystalline solid, 3.27 g of 3,4-diazidoethoxyfurazanyl furazan oxide, with a yield of 83.4%.

[0040] Example 4:

[0041] This embodiment provides a method for preparing 3,4-diazidoethoxyfurazanyl furazan oxide. 2.18 g (0.025 mol) of 2-azidoethanol, 1.68 g (0.030 mol) of potassium hydroxide, and 50 mL of dichloromethane are added to a reaction flask. The mixture is stirred and heated to 25°C–30°C and reacted at this temperature for 15 min. Then, 3.12 g (0.010 mol) of 3,4-dinitrofurazanyl furazan oxide is added, and the mixture is heated to 35°C–38°C and refluxed under ultrasonic conditions for 3 h. After the reaction is complete, the mixture is washed with water, dried, and concentrated under reduced pressure. Recrystallization using carbon tetrachloride yields a white crystalline solid, 2.89 g, of 3,4-diazidoethoxyfurazanyl furazan oxide, with a yield of 73.7%.

[0042] Example 5:

[0043] This embodiment provides a method for preparing 3,4-diazidoethoxyfurazanyl furazan oxide. 2.18 g (0.025 mol) of 2-azidoethanol, 1.40 g (0.025 mol) of potassium hydroxide, and 50 mL of dichloromethane are added to a reaction flask. The mixture is stirred and heated to 25°C–30°C and reacted at this temperature for 15 min. Then, 3.12 g (0.010 mol) of 3,4-dinitrofurazanyl furazan oxide is added, and the mixture is heated to 35°C–38°C and refluxed under ultrasonic conditions for 4 h. After the reaction is complete, the mixture is washed with water, dried, and concentrated under reduced pressure. Recrystallization using carbon tetrachloride yields a white crystalline solid, 3.45 g, of 3,4-diazidoethoxyfurazanyl furazan oxide, with a yield of 88.0%.

[0044] Application of 3,4-diazidoethoxyfurazanyl oxyfurazanyl in this invention

[0045] The 3,4-diazidoethoxyfurazanyloxyfurazan compound of the present invention has the characteristics of low sensitivity, good thermal stability and high nitrogen content, and can be widely used as a plasticizer in propellants, propellants and mixed explosives.

[0046] Table 1. Performance of simulated formulations of 3,4-diazidoethoxyfurazanyl-oxidized furazan.

[0047] Plasticizer with GAP Curing agent (%) Al(％) AP (%) HMX (%) I sp (s) [a] ]]> C* [b] ]]> ηB [c] ]]> 20.8 1.2 14 27 37 269.36 1627 0.508 20.8 1.2 16 27 35 269.88 1625 0.512 20.8 1.2 18 27 33 269.32 1617 0.492 20.8 1.2 18 30 30 269.29 1617 0.512 20.8 1.2 18 35 25 268.84 1613 0.539

[0048] In Table 1, the plasticizer is 3,4-diazidoethoxyfurazanyloxyfurazan; the curing agent is TDI,H100; % by mass fraction; [a] specific impulse (s); [b] characteristic velocity (m·s) -1 );[c] Stress index.

[0049] Using 3,4-diazidoethoxyfurazanyl furazan oxide as an energetic plasticizer and GAP as a binder, a propellant formulation was designed and its performance was simulated. The mixture of 3,4-diazidoethoxyfurazanyl furazan oxide and GAP accounted for 20.8% of the total mass of the formulation. The results are shown in Table 1. The results show that the formulation containing 3,4-diazidoethoxyfurazanyl furazan oxide has a higher specific impulse and characteristic velocity, indicating that 3,4-diazidoethoxyfurazanyl furazanyl furazan oxide has good performance as an energetic plasticizer component in the propellant formulation.

Claims

1. A method for preparing 3,4-diazidoethoxyfurazanyl-oxidized furazan, characterized in that, The preparation method uses 3,4-dinitrofuzanyl furazan oxide, potassium hydroxide and 2-azidoethanol as raw materials and dichloromethane as solvent to prepare 3,4-diazidoethoxyfuzanyl furazan oxide. In the prepared 3,4-diazidoethoxyfuzanyl furazan oxide, the azido group is linked to the high-energy furazanyl furazan oxide skeleton through an ethyl ether chain. The process includes the following steps: Dichloromethane, potassium hydroxide, and 2-azidoethanol are added to a reaction flask, and the mixture is reacted at 25℃~30℃ for 15 min. Then, 3,4-dinitrofurazanyloxyfurazan is added, and the temperature is raised to 35℃~38℃. The mixture is then refluxed under ultrasonic conditions for 2 h~4 h. After the reaction is completed, the mixture is washed with water, dried, and concentrated under reduced pressure. It is then recrystallized using carbon tetrachloride to obtain 3,4-diazidoethoxyfurazanyloxyfurazan.

2. The method for preparing 3,4-diazidoethoxyfurazanyl-oxidized furazan according to claim 1, characterized in that, The molar ratio of 3,4-dinitrofurazanyloxyfurazan, 2-azidoethanol, and potassium hydroxide is 1:2~3:2~3.

3. The method for preparing 3,4-diazidoethoxyfurazanyl-oxidized furazan according to claim 2, characterized in that, The molar ratio of 3,4-dinitrofurazanyloxyfurazan, 2-azidoethanol, and potassium hydroxide is 1:2.5:2.5.

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