Nitrogen-rich energetic ionic salt compound based on bis-(5-aminotetrazole) boron

Abstract

The invention discloses a nitrogen-rich energetic ionic salt compound based on bis-(5-aminotetrazole) boron. The nitrogen-rich energetic ionic salt compound comprises bis-(5-aminotetrazole) boric acid guanidine salt (I), bis-(5-aminotetrazole) boric acid aminoguanidine salt (II) and bis-(5-aminotetrazole) borane perchlorate (III), the structural formulas of the compounds are shown as (I)-(III). The compound can be used for mixed explosives and fuel-rich propellants.

Description

Technical Field

[0001] This invention belongs to the field of energetic materials and relates to a class of nitrogen-rich energetic ionic salt compounds based on bis-(5-aminotetrazolium)boron. Background Technology

[0002] Extensive research has been conducted on energetic azole-boron compounds. However, limitations in the selection of azoles result in synthesized energetic azole-boron compounds with low nitrogen content and few detonating groups, leading to poor detonation performance. Nitro-containing azole-boron compounds, on the other hand, have poor sensitivity, making them difficult to apply in practical applications. Energetic ionic compounds, as an important branch of high-energy materials, are rich in high-energy chemical bonds such as CN, NN, or N=N in their molecular structure, exhibiting significant positive enthalpy of formation. These compounds not only possess excellent detonation velocity performance but also have more environmentally friendly explosion products. Notably, the delocalized distribution of negative charges in ionic salt molecules provides a structural basis for the design of desensitizing molecules: by uniformly dispersing the charge into the chemical bond network connected to the detonating group, the shear resistance of the molecular skeleton can be effectively enhanced, thereby significantly improving safety performance. Using bis-(5-aminotetrazole)borane as a precursor, synthesized in the prior art, this compound has a low density (1.50 g / cm³). 3 The detonation performance was calculated using EXPLO5, with a theoretical detonation velocity of 7050 m / s and a theoretical detonation pressure of 17.5 GPa. The energy level is low and the combustion efficiency is poor, which limits its application in the field of fuel-rich propellants. Summary of the Invention

[0003] To address the shortcomings of existing technologies, the present invention aims to provide a nitrogen-rich energetic ionic salt compound based on bis-(5-aminotetrazole)borane, overcoming the inherent defects of energetic compounds such as low density and insufficient detonation pressure and velocity.

[0004] To solve the above-mentioned technical problems, the present invention adopts the following technical solution: Nitrogen-rich energetic ionic salt compounds based on bis-(5-aminotetrazole)boron include bis-(5-aminotetrazole)boronic acid guanidine salt (I), bis-(5-aminotetrazole)boronic acid aminoguanidine salt (II), and bis-(5-aminotetrazole)borane perchlorate (III); their structural formulas are shown in (I) to (III): .

[0005] The method for synthesizing nitrogen-rich energetic ionic salt compounds based on bis-(5-aminotetrazolium)boron, specifically the method for synthesizing bis-(5-aminotetrazolium)boron guanidine salt (I): Deionized water is added to a single-necked flask, barium bis(5-aminotetrazolium)boron is dissolved in it, and then guanidine sulfate is slowly added dropwise while stirring for 30 min; the clear liquid is filtered and allowed to air dry naturally in a petri dish to obtain a white powder.

[0006] The present invention also includes the following technical features: Specifically, the ratio of deionized water, barium bis(5-aminotetrazolium)borate, and guanidine sulfate is 2 ml: 1 mmol: 1 mmol.

[0007] The method for synthesizing nitrogen-rich energetic ionic salt compounds based on bis-(5-aminotetrazazole)boron is characterized by the following method for synthesizing bis-(5-aminotetrazazole)boronic acid aminoguanidine salt (II): at 25°C, deionized water is added to a single-necked flask, barium bis(5-aminotetrazazole)boron is dissolved in it, and then aminoguanidine salt sulfate is slowly added dropwise while stirring; the clear liquid is filtered and naturally dried in a petri dish to obtain a white powder.

[0008] Specifically, the ratio of deionized water, bis(5-aminotetrazolium)barium borate, and aminoguanidine sulfate is 2 ml: 1 mmol: 1 mmol.

[0009] The method for synthesizing nitrogen-rich energetic ionic salt compounds based on bis-(5-aminotetrazazole)boron is characterized by the following method for synthesizing bis-(5-aminotetrazazole)borane perchlorate (III): at 25°C, anhydrous ethanol is added to a single-necked flask, bis(5-aminotetrazazole)boron is dissolved in it, and then HClO4 is slowly added dropwise while stirring for 30 min; after adding deionized water, the mixture is directly filtered, and the clear liquid is dried to obtain a white solid.

[0010] Specifically, the ratio of anhydrous ethanol, bis(5-aminotetrazolium)boron, and HClO4 is 2 ml: 2 mmol: 2 mmol.

[0011] Compared with the prior art, the present invention has the following technical effects: The two bis-(5-aminotetrazazole)borate guanidine energetic ionic salt compounds and one bis-(5-aminotetrazazole)borane perchlorate compound of this invention exhibit significantly improved density and detonation performance compared to their precursors. Compound (III) shows the highest improvement, with a 15.33% increase in density, a 25.88% increase in detonation pressure, and a 68% increase in detonation velocity, while maintaining good sensitivity. Laser ignition tests revealed a combustion time of only 68 ms, significantly lower than the 726 ms of its precursor, demonstrating a substantial increase in combustion efficiency. These compounds are primarily intended for use in heat-resistant explosives and fuel-rich propellants.

[0012] In terms of synthesis, since bis-(5-aminotetrazazole)borane itself contains a -BH2 group, it is not suitable for traditional silver salt ion conversion. This invention uses an aqueous solution of the corresponding nitrogen-rich explosive group hydrochloride to directly react with it to obtain two nitrogen-rich energetic ionic salts (amines), avoiding the high sensitivity drawback of the intermediate silver salt. Simultaneously, by strictly controlling the mass fraction of the perchloric acid aqueous solution, the oxidizing properties of perchloric acid are prevented from damaging the -BH2 explosive group. Detailed Implementation

[0013] This invention provides a class of nitrogen-rich energetic ionic salt compounds based on bis-(5-aminotetrazazole)boron, comprising: two bis-(5-aminotetrazazole)borates (guanidines) and one bis-(5-aminotetrazazole)borane perchlorate; specifically including: bis-(5-aminotetrazazole)boronic acid guanidine salt (I), bis-(5-aminotetrazazole)boronic acid aminoguanidine salt (II), and bis-(5-aminotetrazazole)borane perchlorate (III), the structural formulas of which are shown in (I) to (III):

[0014] This invention selects bis-(5-aminotetrazole)borane synthesized in the prior art as a precursor. This neutral compound has unique acid-base response characteristics: it can be protonated to form a cationic salt under acidic conditions and deprotonated to form an anionic salt in an alkaline environment, exhibiting excellent derivatization potential; its structure is shown in (IV): .

[0015] The synthetic route for nitrogen-rich energetic ionic salt compounds based on bis-(5-aminotetrazolium)boron in this invention is as follows: .

[0016] 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.

[0017] Example 1: This embodiment provides a method for synthesizing bis(5-aminotetrazazole)borate guanidine salt (I): 2 ml of deionized water was added to a 10 ml single-necked flask, and 500 mg (1 mmol) of barium bis(5-aminotetrazazole)borate was dissolved in it. Then, 157 mg (1 mmol) of guanidine sulfate was slowly added dropwise while stirring for 30 min. The supernatant was filtered and allowed to air dry in a petri dish to obtain 296 mg of white powder, with a yield of 61.7%.

[0018] Structural assessment: Bis-(5-aminotetrazole)borate guanidine salt (I): Infrared spectrum: IR(KBr),v (cm -1 ): 3446, 3348, 3168, 2476, 1637, 1562, 1458, 1296, 1228, 1145, 1085, 827, 767, 634, 516 Nuclear magnetic resonance spectroscopy:

[0019] Elemental analysis: Molecular formula: C3H 12 N 13 B Theoretical values: C 14.95, H 5.02, N 75.50; Measured values: C 14.38, H 5.25, N 75.22.

[0020] Properties of bis-(5-aminotetrazole)borate guanidine salt (I): (1) Physical and chemical properties Density: 1.55 g / cm³ 3 Gaussian 09 program B3LYP / 6-31G** method Thermal decomposition initiation temperature: 251 ℃ (DSC method) (2) Detonation performance Detonation velocity: density is 1.55 g / cm³ 3 The calculated detonation velocity is 8.69 km / s (EXPLO5 6.04). Explosion pressure: density is 1.55 g / cm³ 3 The calculated burst pressure is 25.0 GPa (EXPLO5 6.04). Heat of combustion: density 1.55 g / cm³ 3 The heat of combustion was 16432 kJ / kg, as tested by the oxygen bomb tester. Enthalpy of formation: density 1.55 g / cm³ 3 The enthalpy of formation was calculated to be 406 kJ / mol using the Gaussian 09 program B3LYP / 6-31G** method. (3) Safety performance Impact sensitivity: >40 JWL-1 type impact sensitivity meter Friction sensitivity: >360 NWM-1 friction sensitivity meter Example 2: This embodiment provides a method for synthesizing bis-(5-aminotetrazazole)borate aminoguanidine salt (II): At 25°C, 2 ml of deionized water was added to a 10 ml single-necked flask, and 500 mg (1 mmol) of barium bis(5-aminotetrazazole)borate was dissolved in it. Then, 246 mg (1 mmol) of aminoguanidine salt sulfate was slowly added dropwise while stirring for 30 min. The supernatant was filtered and allowed to air dry in a petri dish to obtain 271 mg of white powder, with a yield of 53.1%.

[0021] Structural assessment: Bis-(5-aminotetrazolium)borate aminoguanidine salt (II): Infrared spectrum: IR(KBr), v (cm -1 ): 3431, 3374, 3297, 2482, 1687, 1560, 1467, 1282, 1145, 1091, 1002, 860, 765, 632, 501 Nuclear magnetic resonance spectroscopy:

[0022] Elemental analysis: Molecular formula: C3H 13 N 14 B Theoretical values: C 14.07, H 5.12, N 76.59; Measured values: C 14.22, H 5.43, N 76.72.

[0023] Properties of bis-(5-aminotetrazolium)borate aminoguanidine salt (II): (1) Physical and chemical properties Density: 1.56 g / cm³ 3 Gaussian 09 program B3LYP / 6-31G** method Thermal decomposition initiation temperature: 227 ℃ (DSC method) (2) Detonation performance Detonation velocity: density is 1.56 g / cm³ 3 The calculated detonation velocity is 8.73 km / s (EXPLO5 6.04). Explosion pressure: density is 1.56 g / cm³ 3 The calculated burst pressure is 26.9 GPa (EXPLO5 6.04). Heat of combustion: density 1.56 g / cm³ 3 The heat of combustion was 20842 kJ / kg, as tested by the oxygen bomb tester. Enthalpy of formation: density 1.56 g / cm³ 3The enthalpy of formation was calculated to be 603 kJ / mol using the Gaussian 09 program B3LYP / 6-31G** method. (3) Safety performance Impact sensitivity: >40 JWL-1 type impact sensitivity meter Friction sensitivity: >360 NWM-1 friction sensitivity meter Example 3: This embodiment provides a method for synthesizing bis-(5-aminotetrazazole)borane perchlorate (III): At 25°C, 2 ml of anhydrous ethanol was added to a 10 ml single-necked flask, and 362 mg (2 mmol) of bis(5-aminotetrazazole)borane 3 was dissolved in it. Then, 200 mg (2 mmol) of HClO4 was slowly added dropwise while stirring for 30 min. After adding 2 ml of deionized water, the mixture was filtered directly, and the supernatant was dried to obtain 298 mg of a white solid, with a yield of 71.3%.

[0024] Structural assessment: Bis-(5-aminotetrazole)borane perchlorate (III): Infrared spectrum: IR(KBr), v (cm -1 ): 3467, 3427, 3373, 2447, 1670, 1550, 1473, 1346, 1205, 1141, 1053, 987, 808, 738, 624, 464 Nuclear magnetic resonance spectroscopy:

[0025] Elemental analysis: Molecular formula: C2H6N 10 O4BCl Theoretical values: C 8.57, H 2.16, N 49.95; Measured values: C 9.08, H 2.73, N 49.27.

[0026] Properties of bis-(5-aminotetrazolium)borane perchlorate (III): (1) Physical and chemical properties Density: 1.73 g / cm³ 3 Gaussian 09 program B3LYP / 6-31G** method Thermal decomposition initiation temperature: 198 ℃ (DSC method) (2) Detonation performance Detonation velocity: density is 1.73 g / cm³ 3 The calculated detonation velocity is 8.94 km / s (EXPLO5 6.04). Explosion pressure: density is 1.73 g / cm³ 3 The calculated burst pressure is 29.4 GPa (EXPLO5 6.04). Heat of combustion: density 1.73 g / cm³ 3 The heat of combustion was 16678 kJ / kg, as tested by the oxygen bomb tester. Enthalpy of formation: density 1.73 g / cm³ 3 The enthalpy of formation was calculated to be 354 kJ / mol using the Gaussian 09 program B3LYP / 6-31G** method. (3) Safety performance Impact sensitivity: = 38 JWL-1 type impact sensitivity meter Friction sensitivity: >360 NWM-1 friction sensitivity meter The two bis-(5-aminotetrazazole)borate (guanidines) and one bis-(5-aminotetrazazole)borane perchlorate compounds synthesized in this invention can be used in the fields of heat-resistant explosives and fuel-rich propellants.

Claims

1. Nitrogen-rich energetic ionic salt compound based on bis-(5-aminotetrazole) boron characterized in that, The guanidine salt of bis-(5-amino tetrazole)boric acid (I), the aminoguanidine salt of bis-(5-amino tetrazole)boric acid (II), and the perchloric acid salt of bis-(5-amino tetrazole)borane (III) have the structural formulae as shown in (I)-(III). 。 2. The process for the synthesis of the double-(5-amino tetrazole) boron based nitrogen-rich energetic ionic salt compound of claim 1, characterized in that, The guanidine salt of bis-(5-amino tetrazole)boric acid (I) is synthesized by adding deionized water into a single-necked flask, dissolving barium bis-(5-amino tetrazole)borate in the deionized water, slowly adding guanidine sulfate, and stirring for 30 min; filtering the clear solution, and naturally drying the white powder in a petri dish.

3. The method of synthesis of double-(5-amino tetrazole) boron based nitrogen rich energetic ionic salt compounds as claimed in claim 2 wherein, The deionized water, barium bis-(5-amino tetrazole)borate, and guanidine sulfate are used in a ratio of 2 ml: 1 mmol: 1 mmol.

4. The process for the synthesis of the double-(5-amino tetrazole) boron based nitrogen-rich energetic ionic salt compound of claim 1, characterized in that, The aminoguanidine salt of bis-(5-amino tetrazole)boric acid (II) is synthesized by adding deionized water into a single-necked flask at 25 DEG C, dissolving barium bis-(5-amino tetrazole)borate in the deionized water, slowly adding aminoguanidine sulfate, and stirring; filtering the clear solution, and naturally drying the white powder in a petri dish.

5. The method of synthesis of double-(5-amino tetrazole) boron based nitrogen rich energetic ionic salt compounds as claimed in claim 4 wherein, The deionized water, barium bis-(5-amino tetrazole)borate, and aminoguanidine sulfate are used in a ratio of 2 ml: 1 mmol: 1 mmol.

6. The method of synthesis of the double-(5-amino tetrazole) boron based nitrogen-rich energetic ionic salt compound of claim 1, characterized in that, The perchloric acid salt of bis-(5-amino tetrazole)borane (III) is synthesized by adding anhydrous ethanol into a single-necked flask at 25 DEG C, dissolving bis-(5-amino tetrazole)borane in the anhydrous ethanol, slowly adding HClO4, and stirring for 30 min; filtering the clear solution after adding deionized water, and drying the white solid.

7. The method of synthesis of double-(5-amino tetrazole) boron based nitrogen rich energetic ionic salt compounds as claimed in claim 6 wherein, The anhydrous ethanol, bis-(5-amino tetrazole)borane, and HClO4 are used in a ratio of 2 ml: 2 mmol: 2 mmol.

Images