Preparation method and application of 3, 4-diazido ethoxy furazanyl furazan

Abstract

The invention discloses a preparation method and application of 3, 4-diazido ethoxy furazan furazan, dichloromethane, potassium hydroxide and 2-azido ethanol are respectively added into a reaction flask, reaction is carried out for 15 minutes at the temperature of 25-30 DEG C, then 3, 4-dinitrofurazan furazan is added, the temperature is raised to 35-38 DEG C, reflux reaction is carried out for 2-4 hours under the ultrasonic condition, after the reaction is finished, the reaction is carried out for 2-4 hours, and the 3, 4-diazido ethoxy furazan furazan is obtained. And carrying out water washing, drying and vacuum concentration, and recrystallizing by using carbon tetrachloride to obtain the 3, 4-diazido ethoxy furazanyl furazan. The compound disclosed by the invention belongs to an energetic plasticizer, has the characteristics of relatively good thermal stability, relatively low sensitivity and the like, and is mainly applied to the fields of solid propellants, propellant powder and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of energetic materials and relates to a preparation method and application of an energetic plasticizer - 3,4-diazideethoxyfuroxanyl furazan oxide. Background Art

[0002] Energetic plasticizers are indispensable functional additives in explosives and pyrotechnics. Their application can expand the use temperature range of explosives and pyrotechnics, improve the overall energy level, improve processing technology, improve low-temperature mechanical properties, and greatly reduce their fragility. Organic azide compounds are a class of excellent energetic materials that have been widely used in energetic adhesives, energetic plasticizers, oxidants, and many other aspects. They are an important way to improve the energy level and technical performance of energetic materials.

[0003] Research results over the past half century have shown that when designing high-energy density compounds composed of carbon, hydrogen, oxygen, and nitrogen elements, the furazan ring is a very effective structural unit, which is extremely meaningful for significantly increasing the energy of low-signal propellants and clean propellants. Furazan plasticizers have good physical, chemical and detonation properties, such as high density, high thermal stability, good impact sensitivity, good oxygen balance, high explosion pressure and detonation velocity. In terms of thermal stability, density, sensitivity and detonation parameters, it is far superior to nitroglycerin. As a potential high-energy dense structure, furazan-based furazan oxide has broad application prospects and great research and application value as an energetic plasticizer compound skeleton in propellant formulations. However, in the prior art, there are problems such as long synthesis reaction time and low yield in the synthesis method of furazan-based furazan oxide plasticizers. Summary of the invention

[0004] In view of the deficiencies in the prior art, the purpose of the present invention is to provide a preparation method and application of 3,4-diazideethoxyfurazanyl furazan oxide, so as to overcome the problems of long synthesis reaction time and low yield of 3,4-diazideethoxyfurazanyl furazan oxide in the prior art. The present invention is a synthesis method with simple reaction, short reaction time and high yield.

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

[0006] A method for preparing 3,4-diazideethoxyfurazanyl furazan oxide is disclosed. The method uses 3,4-dinitrofurazanyl furazan oxide, potassium hydroxide and 2-azidoethanol as raw materials and dichloromethane as solvent to prepare 3,4-diazideethoxyfurazanyl furazan oxide. The azide group in the prepared 3,4-diazideethoxyfurazanyl furazan oxide is connected to a high-energy furazanyl furazan oxide skeleton through an ethyl ether chain.

[0007] The present invention 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, reacting at a temperature of 25°C to 30°C for 15 minutes, adding 3,4-dinitrofurazanyl furazan oxide, heating to 35°C to 38°C, and reflux reacting for 2h to 4h under ultrasonic conditions. After the reaction is completed, washing with water, drying and concentrating under reduced pressure, and recrystallizing with carbon tetrachloride, 3,4-diazideethoxyfurazanyl furazan oxide is obtained.

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

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

[0011] The 3,4-diazideethoxyfurazanyl furazan oxide prepared by the 3,4-diazideethoxyfurazanyl furazan oxide preparation method is used as an energetic plasticizer in propellants and projectiles.

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

[0013] The 3,4-diazideethoxyfuroxanyl oxide furazan synthesis method of the present invention has simple reaction, short reaction time and high yield. Compared with other synthesis methods in the prior art, the reaction time is reduced to 3 hours, the yield is increased to 89.9%, and no phase transfer catalyst is required.

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

[0015] The 3,4-diazideethoxyfurazanyl furazan oxide of the present invention is used as an energetic plasticizer, GAP is used as an adhesive, and a formula containing 3,4-diazideethoxyfurazanyl furazan oxide has a higher specific impulse and characteristic velocity. 3,4-diazideethoxyfurazanyl furazan oxide as an energetic plasticizer component has good performance in the propulsion formula. DETAILED DESCRIPTION

[0016] The invention provides a preparation method and application of 3,4-diazonioethoxyfurazanyl furazan oxide. The preparation method uses 3,4-dinitrofurazanyl furazan oxide, potassium hydroxide and 2-azidoethanol as raw materials, and dichloromethane as solvent. During the preparation process, the rate-controlling step of the reaction is that 2-azidoethanol removes protons under alkaline conditions to form 2-azidoethoxy anions, and then undergoes aromatic nucleophilic substitution reaction with a nitro group on furazan. The aromatic nucleophilic substitution reaction belongs to an Ar-SN2 reaction mechanism, and an alkaline environment can be provided by using potassium hydroxide with a strong alkalinity to effectively remove hydroxyl protons in 2-azidoethanol to form 2-azidoethoxy anions, while promoting charge transfer activation of the nitro group of the furazan ring. According to the above mechanism, the present invention designs a more efficient reaction route. First, 2-azidoethanol and potassium hydroxide are reacted for 15 minutes to make the reaction system produce 2-azidoethoxy anions with sufficient concentration. Then, ultrasonic cavitation and shock waves and microjets formed in the solution are used to improve dispersibility, so that the 2-azidoethoxy anions attack the carbon atoms connected to the furazan ring and the nitro group with high frequency and high efficiency, and at the same time, intermolecular etherification side reactions are avoided to complete the aromatic nucleophilic substitution reaction, so that the yield is significantly improved.

[0017] Specifically, the process comprises the following steps: adding dichloromethane, potassium hydroxide and 2-azidoethanol to a reaction bottle respectively, reacting at a temperature of 25°C to 30°C for 15 minutes, adding 3,4-dinitrofurazanyl furazan oxide, heating to 35°C to 38°C, using ultrasonic conditions, reflux reaction for 2h to 4h, preferably 3h, washing with water, drying and concentrating under reduced pressure after the reaction, and recrystallizing with carbon tetrachloride to obtain 3,4-diazideethoxyfurazanyl furazan oxide. The molar ratio of 3,4-dinitrofurazanyl furazan oxide, 2-azidoethanol and potassium hydroxide is 1:2 to 3:2 to 3, preferably 1:2.5 to 2.5.

[0018] The structural formula of the above 3,4-dinitrofurazanyl furazan oxide is:

[0019]

[0020] The azide group in the obtained 3,4-diazideethoxyfurazanyl furazan oxide is connected to the high-energy furazanyl furazan oxide skeleton through an ethyl ether chain. The structural formula of 3,4-diazideethoxyfurazanyl furazan oxide is:

[0021]

[0022] The synthetic route of the preparation method of the present invention is:

[0023]

[0024] The 3,4-diazideethoxyfuroxanyl oxide furoxan compound prepared by the invention is used as an energetic plasticizer in propellants and projectiles.

[0025] Specific embodiments of the present invention are given below. It should be noted that the present invention is not limited to the following specific embodiments, and all equivalent changes made on the basis of the technical solution of this application fall within the protection scope of the present invention.

[0026] Embodiment 1:

[0027] The present embodiment provides a method for preparing 3,4-diazideethoxyfurazanyl 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 bottle, and the mixture is heated to 25° C. to 30° C. with stirring, 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. to 38° C., and refluxed for 3 h under ultrasonic conditions. After the reaction is completed, the mixture is washed with water, dried, concentrated under reduced pressure, and recrystallized using carbon tetrachloride to obtain a white crystalline solid, i.e., 3,4-diazideethoxyfurazanyl furazan oxide, 3.52 g, with a yield of 89.9%.

[0028] Structure identification:

[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] NMR spectrum: 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 value (%): C 30.62, H 2.06, N 42.85;

[0034] Found (%): C 30.65, H 2.26, N 43.07.

[0035] It was confirmed that the substance obtained by the above preparation method was 3,4-diazideethoxyfuroxanyloxyfuroxan, with the molecular formula C 10 H8N 12 O6.

[0036] Embodiment 2:

[0037] The present embodiment provides a method for preparing 3,4-diazideethoxyfurazanyl 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 bottle, and the mixture is heated to 25° C. to 30° C. with stirring, 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. to 38° C., and refluxed for 3 h under ultrasonic conditions. After the reaction is completed, the mixture is washed with water, dried, concentrated under reduced pressure, and recrystallized using carbon tetrachloride to obtain a white crystalline solid, i.e., 3,4-diazideethoxyfurazanyl furazan oxide, 3.02 g, with a yield of 77.0%.

[0038] Embodiment 3:

[0039] The present embodiment provides a method for preparing 3,4-diazideethoxyfurazanyl 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 bottle, and the mixture is heated to 25° C. to 30° C. with stirring, 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. to 38° C., and refluxed for 3 h under ultrasonic conditions. After the reaction is completed, the mixture is washed with water, dried, concentrated under reduced pressure, and recrystallized using carbon tetrachloride to obtain a white crystalline solid, i.e., 3,4-diazideethoxyfurazanyl furazan oxide, 3.27 g, with a yield of 83.4%.

[0040] Embodiment 4:

[0041] The present embodiment provides a method for preparing 3,4-diazideethoxyfurazanyl 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 bottle, and the mixture is heated to 25° C. to 30° C. with stirring, and reacted at this temperature for 15 minutes. Then, 3.12 g (0.010 mol) of 3,4-dinitrofurazanyl furazan oxide is added, and the mixture is heated to 35° C. to 38° C., and refluxed for 3 hours under ultrasonic conditions. After the reaction is completed, the mixture is washed with water, dried, concentrated under reduced pressure, and recrystallized using carbon tetrachloride to obtain a white crystalline solid, i.e., 3,4-diazideethoxyfurazanyl furazan oxide, 2.89 g, with a yield of 73.7%.

[0042] Embodiment 5:

[0043] The present embodiment provides a method for preparing 3,4-diazideethoxyfurazanyl 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 bottle, and the mixture is heated to 25° C. to 30° C. with stirring, 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. to 38° C., and refluxed for 4 h under ultrasonic conditions. After the reaction is completed, the mixture is washed with water, dried, concentrated under reduced pressure, and recrystallized using carbon tetrachloride to obtain a white crystalline solid, i.e., 3,4-diazideethoxyfurazanyl furazan oxide, 3.45 g, with a yield of 88.0%.

[0044] Application of 3,4-diazideethoxyfuroxanyl oxide furazan of the present invention

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

[0046] Table 1 Performance of simulated formulation of 3,4-diazideethoxyfuroxanyl oxide furazan

[0047] Plasticizers and GAP Curing agent (%) Al(％) AP(%) HMX(%) <![CDATA[I sp (s) [a] ]]> <![CDATA[C* [b] ]]> <![CDATA[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-diazideethoxyfuroxanyl furazan oxide; the curing agent is TDI, H100; %, mass fraction; [a] specific impulse (s); [b] characteristic velocity (m·s -1 ); [c] Pressure index.

[0049] The 3,4-diazideethoxyfurazanyl furazan oxide of the present invention is used as an energetic plasticizer and GAP is used as a binder. A propellant formula is designed and performance simulation calculations are performed, wherein the mixed system of 3,4-diazideethoxyfurazanyl furazan oxide and GAP accounts for 20.8% of the total mass of the formula. The results are shown in Table 1. The results show that the formula containing 3,4-diazideethoxyfurazanyl furazan oxide has a higher specific impulse and characteristic velocity, indicating that 3,4-diazideethoxyfurazanyl furazan oxide has good performance as an energetic plasticizer component in the propellant formula.

Claims

1. A method for preparing 3,4-diazideethoxyfuroxanyl oxide furazan, characterized in that: The preparation method uses 3,4-dinitrofurazanyl furazan oxide, potassium hydroxide and 2-azidoethanol as raw materials and dichloromethane as solvent to prepare 3,4-diazideethoxyfurazanyl furazan oxide, wherein the azide group in the prepared 3,4-diazideethoxyfurazanyl furazan oxide is connected to a high-energy furazanyl furazan oxide skeleton through an ethyl ether chain.

2. The method for preparing 3,4-diazideethoxyfuroxanyl oxide furazan according to claim 1, characterized in that: The following steps are involved: Add dichloromethane, potassium hydroxide and 2-azidoethanol into the reaction bottle respectively, react at 25℃~30℃ for 15 minutes, then add 3,4-dinitrofurazanyl furazan oxide, raise the temperature to 35℃~38℃, and reflux for 2h~4h under ultrasonic conditions. After the reaction, wash with water, dry and concentrate under reduced pressure, and recrystallize with carbon tetrachloride to obtain 3,4-diazideethoxyfurazanyl furazan oxide.

3. The method for preparing 3,4-diazideethoxyfuroxanyl oxide furazan according to claim 2, characterized in that: The molar ratio of the 3,4-dinitrofurazanyl oxide furazan, 2-azidoethanol and potassium hydroxide is 1:2-3:2-3.

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

5.

5. The 3,4-diazideethoxyfurazanyl furazan oxide prepared by the method for preparing 3,4-diazideethoxyfurazanyl furazan oxide according to claim 2 is used as an energetic plasticizer in propellants and projectiles.

Images