3, 3 '-diazido ethoxy-4, 4'-azofurazan compound as well as preparation method and application thereof

Abstract

The invention discloses a 3, 3 '-diazido ethoxy-4, 4'-azofurazan compound as well as a preparation method and application thereof, and belongs to the technical field of energetic materials, and the molecular structural formula of the 3, 3 '-diazido ethoxy-4, 4'-azofurazan compound is shown as (I). According to the preparation method, 3, 3 '-dinitro-4, 4'-azofurazan and 2-azidoethanol are used as raw materials, the temperature is raised to 35-37 DEG C, and the 3, 3 '-diazido ethoxy-4, 4'-azofurazan compound is prepared through a reaction, and the compound belongs to insensitive energetic materials, has the advantages of being low in sensitivity, good in thermal stability and the like and is mainly used in the fields of solid propellants, propellant powder and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of energetic materials, and particularly relates to an insensitive energetic material, namely a 3,3'-diazideethoxy-4,4'-azofurazan compound, and a preparation method and application thereof. Background Art

[0002] Azo and oxyazofurazan compounds have many advantages, such as high energy density, high formation enthalpy, good oxygen balance, and excellent heat resistance, and are currently one of the hot topics in the field of energetic materials research. Aleksei B. Sheremetev, Boris V. Lyalin, and Andrei M. Kozeev et al., in the article "A Practical Anodic Oxidation of Aminofurazans to Azofurazans: an environmentally friendly route" (RSC Advances, 2015, 5: 37617-37625), disclosed the azidoazofurazan 3,3'-diazido-4,4'-azofurazan (3,3'-diazidoazofurazan) compound and its properties. Its structure is shown in (II):

[0003]

[0004] The decomposition temperature (DSC) of this compound is 68°C, and its stability is extremely poor, so it cannot be used as a high-safety explosive. Summary of the Invention

[0005] In view of the defects or shortcomings of the prior art, the present invention provides a 3,3'-diazideethoxy-4,4'-azofurazan compound. The structural formula of the compound is shown in (I):

[0006]

[0007] The present invention also provides a method for preparing the above-mentioned 3,3'-diazideethoxy-4,4'-azofurazan compound, which comprises: heating a reaction system consisting of an alkaline catalyst, 2-azidoethanol, 3,3'-dinitro-4,4'-azofurazan and an organic solvent to 35-37° C. and then reacting to prepare the 3,3'-diazideethoxy-4,4'-azofurazan compound.

[0008] An optional solution is that the heating time is 5 to 10 minutes and the reaction time is 2 to 4 hours.

[0009] Alternatively, the base catalyst is selected from potassium hydroxide, sodium hydroxide or potassium carbonate.

[0010] Alternatively, the organic solvent is selected from dichloromethane, acetonitrile or DMF.

[0011] An optional solution is that the molar ratio of 3,3'-dinitro-4,4'-azofurazan, the base catalyst, and 2-azidoethanol is 1.0:2.0:2.0-2.5.

[0012] In a further embodiment, the method further comprises: after the reaction is completed, washing with water, separating the liquids, drying and concentrating under reduced pressure to recover the product 3,3'-diazideethoxy-4,4'-azofuroxan compound.

[0013] The compound of the present invention is composed of a furazan ring and an azidoethoxy group, with a nitrogen content of 50.0% and a high energy level. The compound of the present invention has a low sensitivity, with an impact sensitivity of 50J; high thermal stability, with a thermal decomposition temperature (DSC) of 250.6°C, while the thermal decomposition temperature of existing 3,3'-diazide-4,4'-azofurazan is 68°C; and a density of 1.59g / cm 3 ; The preparation process is simple, safe and reliable. DETAILED DESCRIPTION

[0014] Unless otherwise specified, the scientific and technical terms used herein are understood according to the knowledge of ordinary technicians in the relevant fields.

[0015] The following are embodiments given by the inventor. It should be noted that these embodiments are preferred examples and are mainly used to understand the present invention, but the present invention is not limited to these embodiments.

[0016] Example 1:

[0017] 2.18 g (0.025 mol) of 2-azidoethanol, 1.40 g (0.025 mol) of potassium hydroxide, 2.560 g (0.010 mol) of 3,3'-dinitro-4,4'-azofuroxan and 50 mL of dichloromethane were added to a reaction flask, and the temperature was heated to 35-37°C for 5 minutes. After reflux reaction at this temperature for 3 hours, the reactant was washed with water, separated, dried and concentrated under reduced pressure to obtain a light yellow liquid, i.e., 3,3'-diazideethoxy-4,4'-azofuroxan, 2.87 g, with a yield of 85.5%.

[0018] Product structure identification:

[0019] Infrared spectrum:

[0020] IR(KBr):v=2997,2949,2138,2108,2061,1580,1500,1454,1284,1034,890,658cm -1 ;

[0021] NMR spectroscopy:

[0022] 1 H NMR (DMSO, 500MHz), δ: 4.59~4.61(t,2H,CH2), 3.75~3.77(t,2H,CH2), 2.51(p,H,DMSO)

[0023] 13 C NMR (DMSO, 125MHz), δ: 158.63 (N=CO), 155.63 (N=CO), 72.60 (CH2), 49.52 (CH2), 39.82~40.16 (m, C, DMSO).

[0024] Elemental analysis: molecular formula C8H8N 12 O4

[0025] Theoretical value (%): C 28.58, H 2.40, N 49.99;

[0026] Found (%): C 29.36, H 2.39, N 48.51.

[0027] It was confirmed that the substance obtained by the above preparation method was 3,3'-diazideethoxy-4,4'-azofurazan, with the molecular formula C8H8N 12 O4.

[0028] Performance analysis of 3,3'-diazideethoxy-4,4'-azofurazan:

[0029] (1) Physical and chemical properties: Appearance: orange-yellow solid; Solubility: soluble in acetone, dichloromethane, ethyl acetate, dimethyl sulfoxide, dimethylformamide and other organic solvents, insoluble in water, ethanol, etc.; Density: 1.59 g / cm 3 (Single crystal-XRD).

[0030] (2) Melting point and decomposition temperature: The melting point of 3,3'-diazideethoxy-4,4'-azofurazan is 121.83°C (DSC method), and the decomposition temperature is 250.58°C (DSC method).

[0031] (3) Impact sensitivity: 50 J; test conditions: 10 kg drop weight, 30 mg charge; under the same test conditions, the impact sensitivity of 3,3'-diazide-4,4'-azofurazan is less than 5 J.

[0032] This shows that the 3,3'-diazideethoxy-4,4'-azofurazan compound obtained in the present invention has the characteristics of low sensitivity, good thermal stability and high nitrogen content, and can be used as an insensitive energetic material in propellants, propellants and mixed explosives.

[0033] Example 2:

[0034] This embodiment differs from Example 1 in that 1.74 g (0.020 mol) of 2-azidoethanol, 1.12 g (0.020 mol) of potassium hydroxide, 2.560 g (0.010 mol) of 3,3'-dinitro-4,4'-azofuroxan and 50 mL of dichloromethane are added to a reaction flask, and the temperature is heated to 35-37° C. for 10 min; 2.65 g of 3,3'-diazideethoxy-4,4'-azofuroxan is obtained, with a yield of 79.0%.

[0035] Example 3:

[0036] This embodiment differs from embodiment 1 in that the reaction time is 4 h, and 2.50 g of 3,3'-diazideethoxy-4,4'-azofuroxan is obtained with a yield of 74.3%.

[0037] Example 4:

[0038] This embodiment differs from the embodiment in that 2.61 g (0.030 mol) of 2-azidoethanol, 1.68 g (0.030 mol) of potassium hydroxide, 2.560 g (0.010 mol) of 3,3'-dinitro-4,4'-azofuroxan and 50 mL of dichloromethane are added to a reaction flask; 2.73 g of 3,4-diazideethoxyfuroxan is obtained, with a yield of 81.2%.

Claims

1. A 3,3'-diazideethoxy-4,4'-azofuroxan compound, characterized in that: Its structural formula is shown in (I):

2. The method for preparing the 3,3'-diazideethoxy-4,4'-azofurazan compound according to claim 1, characterized in that: The method comprises: heating a reaction system consisting of a base catalyst, 2-azidoethanol, 3,3'-dinitro-4,4'-azofuroxan and an organic solvent to 35-37° C. and then reacting to prepare a 3,3'-diazideethoxy-4,4'-azofuroxan compound.

3. The preparation method according to claim 2, characterized in that The heating time is 5 to 10 minutes, and the reaction time is 2 to 4 hours.

4. The preparation method according to claim 2, characterized in that The base catalyst is selected from potassium hydroxide, sodium hydroxide or potassium carbonate.

5. The preparation method according to claim 2, characterized in that The organic solvent is selected from dichloromethane, acetonitrile or DMF.

6. The preparation method according to claim 2, characterized in that The molar ratio of 3,3'-dinitro-4,4'-azofurazan, the base catalyst and 2-azidoethanol is 1.0:2.0:2.0-2.

5.

7. The preparation method according to claim 2, characterized in that The method further comprises: after the reaction is completed, washing with water, separating the liquids, drying and concentrating under reduced pressure to recover the product 3,3'-diazideethoxy-4,4'-azofuroxan compound.

8. Use of the 3,3'-diazideethoxy-4,4'-azofurazan according to claim 1 as an energetic material.

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