Bis-triazolotriazine fused ring nitrogen-rich compound ionic salt as well as construction method and application thereof

Abstract

The invention relates to a bis (triazolotriazine) fused ring nitrogen-rich compound ionic salt as well as a construction method and application thereof. The invention relates to a bis (triazolotriazine) fused ring nitrogen-rich compound ionic salt, which has a structural formula as shown in a formula I and / or a formula II, and a racemate, a stereoisomer or a tautomer of the bis (triazolotriazine) fused ring nitrogen-rich compound ionic salt. The invention also provides a construction method of the bis (triazolotriazine) fused ring nitrogen-rich compound ionic salt, which comprises the following steps: adding acid into a bis (triazolotriazine) fused ring nitrogen-rich compound solution and / or suspension, and stirring for reaction to obtain the bis (triazolotriazine) fused ring nitrogen-rich compound ionic salt or energetic ionic salt. The invention also provides an application of the bis (triazolotriazine) fused ring nitrogen-rich compound ion salt prepared by the construction method as an energetic material. The invention provides a novel fused ring nitrogen-rich compound ionic salt, and solves the problem of high construction difficulty of the existing fused ring compound ionic salt. # imgabs0 #

Description

Technical Field

[0001] The invention relates to the technical field of energetic materials, and in particular to a bistriazolotriazine fused-ring nitrogen-rich compound ion salt and a construction method and application thereof. Background Art

[0002] In the field of energetic materials research, scientists have been committed to designing and synthesizing compounds with both high energy density and high stability. The realization of this goal is crucial to the development of energetic materials with excellent detonation performance. Ideal energetic materials should have high formation enthalpy and high density, which together ensure efficient energy release in practical applications. At the same time, in order to ensure the safety and reliability of the material in various environments, the molecular structure of the compound should also have good insensitivity and excellent thermal stability by fine-tuning the molecular structure of the compound.

[0003] A fused ring compound refers to a compound containing two or more juxtaposed ring structures. Compared with their monocyclic or simple polycyclic homologues, such compounds generally exhibit more significant chemical stability, higher density and more chemical modification sites. In nature, a variety of fused ring compounds with important biological activities have been discovered, including heterocyclic fused ring compounds. In recent years, with the continuous advancement of chemical synthesis technology, the number of artificially synthesized nitrogen-containing fused ring compounds has also continued to increase. There are various synthesis methods for these compounds, including but not limited to intramolecular cyclization reactions, such as aromatic nucleophilic substitution reactions, intracyclic affinity substitution reactions, acyl nucleophilic substitution reactions, etc. However, the difficulty of constructing fused ring skeletons is generally greater, which leads to relatively few types of such compounds. Therefore, the continuous exploration and development of new synthesis strategies in order to obtain more fused ring compounds is the key to promoting the development of energetic materials. Summary of the invention

[0004] In view of this, the purpose of the present invention is to provide a bistriazolotriazine condensed ring nitrogen-rich compound ion salt and its construction method and application, so as to provide a new type of condensed ring nitrogen-rich compound ion salt and solve the problem that the existing condensed ring compound ion salt is difficult to construct.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0006] A bistriazolotriazine fused ring nitrogen-rich compound ion salt, the structural formula of which is a compound shown in Formula I and its racemate, stereoisomer or tautomer;

[0007]

[0008] In Formula I, X - Selected from Cl - 、F - ,

[0009] NO3 - 、ClO4 - 、N(NO2)2 - 、C(NO2)3 - 、1 / 2SO4 - and 1 / 3PO4 - At least one of .

[0010] A bistriazolotriazine fused ring nitrogen-rich compound ion salt, the structural formula of which is a compound shown in Formula II and its racemate, stereoisomer or tautomer;

[0011]

[0012] In Formula II, X - Selected from Cl - 、F - , NO3 - 、ClO4 - 、N(NO2)2 - 、C(NO2)3 - 、1 / 2SO4 - and 1 / 3PO4 - At least one of .

[0013] Preferably, the X - Selected from NO3 - 、ClO4 - or N(NO2)2 - .

[0014] The present invention also provides a method for constructing the bistriazolotriazine fused-ring nitrogen-rich compound ion salt as described in the present invention, comprising the following steps:

[0015] Acid is added to the solution and / or suspension of the bistriazolotriazine fused ring nitrogen-rich compound, and the mixture is stirred for reaction to obtain an ionic salt or energetic ionic salt of the bistriazolotriazine fused ring nitrogen-rich compound.

[0016] Preferably, the solution is a solution of a bistriazolotriazine fused ring nitrogen-rich compound and at least one of water and an alcohol having 1 to 6 carbon atoms;

[0017] And / or, the suspension is a suspension formed by an ionic salt of a bistriazolotriazine fused-ring nitrogen-rich compound and at least one of water and an alcohol having 1 to 6 carbon atoms.

[0018] Preferably, the bistriazol-triazine fused ring nitrogen-rich compound is selected from and / or

[0019] Preferably, the acid is selected from:

[0020] At least one of HNO3, HClO4, HN(NO2)2, HC(NO2)3, HCl, HF, H2SO4 and H3PO4.

[0021] Preferably, the stirring reaction temperature is 0°C to 50°C.

[0022] Preferably, the stirring reaction time is 2.6 h to 5 h.

[0023] Preferably, the method for constructing the bistriazolotriazine fused-ring nitrogen-rich compound ion salt further comprises the following steps:

[0024] The ionic salt of the bistriazolotriazine fused ring nitrogen-rich compound is subjected to double decomposition reaction to obtain the energetic ionic salt of the bistriazolotriazine fused ring nitrogen-rich compound.

[0025] Preferably, the method for constructing the ionic salt of the bistriazolotriazine fused ring nitrogen-rich compound further includes the following steps: exchanging the ionic salt of the bistriazolotriazine fused ring nitrogen-rich compound through a membrane to obtain an energetic ionic salt of the bistriazolotriazine fused ring nitrogen-rich compound.

[0026] Preferably, the bistriazol-triazine fused ring nitrogen-rich compound ion salt is a compound as shown in Formula I or Formula II, and X - Selected from Cl - 、1 / 2SO4 - and 1 / 3PO4 - At least one of .

[0027] Preferably, the bistriazol-triazine fused ring nitrogen-rich compound ion salt and M + X - Through double decomposition reaction, an energetic ion salt of a bistriazolotriazine fused ring nitrogen-rich compound is obtained;

[0028] The M + Selected from Ag + 、1 / 2Ca + 、1 / 2Pb + and 1 / 2Cu + At least one of;

[0029] The X - Selected from F - , NO3 - 、ClO4 - 、N(NO2)2- and C(NO2)3 - At least one of .

[0030] Preferably, the energetic ion salt of the bistriazol-triazine fused ring nitrogen-rich compound is a compound as shown in Formula I or Formula II, and X - Selected from F-, NO3 - 、ClO4 - 、N(NO2)2 - and C(NO2)3 - At least one of .

[0031] Preferably, the membrane is a polymer separation membrane.

[0032] Preferably, the polymer separation membrane includes a reverse osmosis membrane, a nanofiltration membrane, an ultrafiltration membrane, a microfiltration membrane, a gas separation membrane, a pervaporation membrane and an electrodialysis membrane.

[0033] Preferably, the temperature of the metathesis reaction is 0°C to 50°C;

[0034] Preferably, the double decomposition reaction time is 0.5h to 5h.

[0035] The present invention also provides an application of a bistriazolotriazine fused-ring nitrogen-rich compound ion salt prepared by the construction method of the present invention as an energetic material.

[0036] The present invention also provides an application of an energetic ion salt of a bistriazolotriazine fused-ring nitrogen-rich compound prepared by the construction method of the present invention as an energetic material.

[0037] Beneficial effects of the present invention:

[0038] The bistriazolotriazine fused ring nitrogen-rich skeleton of the present invention has the characteristics of a two-dimensional planar structure, rich nitrogen content and three amino groups, good stability, and can introduce specific functional groups in a targeted manner. The amino groups in the amino-substituted nitrogen-rich fused ring compound can directly form energetic ion salts, and can also be modified to obtain quaternary ammonium salts and substituted amine structures, and have potential application value in constructing new fused ring structures.

[0039] The method for constructing a bistriazolotriazine fused ring nitrogen-rich skeleton of the present invention obtains two mutually isomeric bistriazolotriazine fused ring nitrogen-rich skeletons by molecular rearrangement under acidic conditions, and verifies the rearrangement mechanism by combining experiments with theoretical calculations. The method is simple, has high preparation efficiency, and high product purity, and provides a basis for the subsequent design and synthesis of fused ring energetic molecules, etc., and has the advantages of being environmentally friendly, simple to operate, and excellent product performance. It has broad application prospects in the fields of energy, medicine, materials science, etc., and has promotion and application value in the field of organic compound technology. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 is the hydrogen nuclear magnetic resonance spectrum of compound 1-1 in Example 1 of the present invention;

[0041] Figure 2 is the carbon nuclear magnetic resonance spectrum of compound 1-1 in Example 1 of the present invention;

[0042] Figure 3 is the hydrogen nuclear magnetic resonance spectrum of compound 2-1 in Example 4 of the present invention;

[0043] Figure 4 is the carbon nuclear magnetic resonance spectrum of compound 2-1 in Example 4 of the present invention;

[0044] Figure 5 is a single crystal structure diagram of compound 1-1 in Example 1 of the present invention;

[0045] Figure 6 is a single crystal structure diagram of compound 2 in Example 2 of the present invention;

[0046] Figure 7 is a single crystal structure diagram of compound 2-1 in Example 4 of the present invention;

[0047] Figure 8 Detonators used in detonation tests;

[0048] Fig. 9 This is a top view of the detonator;

[0049] Fig.10 This is a schematic diagram of the detonation device;

[0050] Fig.11 This is a diagram showing the detonation effect of energetic ion salt 1-2. DETAILED DESCRIPTION

[0051] The following will describe the embodiments of the present invention with reference to the preferred embodiments, and those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present invention. It should be understood that the preferred embodiments are only for illustrating the present invention, not for limiting the scope of protection of the present invention.

[0052] The present invention intends to disclose a bistriazolotriazine condensed ring nitrogen-rich compound ion salt and a construction method and application thereof, so as to provide a novel condensed ring nitrogen-rich compound ion salt and solve the problem that the existing condensed ring compound ion salt is difficult to construct.

[0053] Among them, a bistriazolotriazine fused ring nitrogen-rich compound ion salt, whose structural formula is a compound shown in Formula I and its racemate, stereoisomer or tautomer;

[0054]

[0055] In Formula I, X - Selected from Cl - 、F - , NO3 - 、ClO4 - 、N(NO2)2 - 、C(NO2)3 - 、1 / 2SO4 - and 1 / 3PO4 - At least one of .

[0056] A bistriazolotriazine fused ring nitrogen-rich compound ion salt, the structural formula of which is a compound shown in Formula II and its racemate, stereoisomer or tautomer;

[0057]

[0058] In Formula II, X - Selected from Cl - 、F - ,

[0059] NO3 - 、ClO4 - 、N(NO2)2 - 、C(NO2)3 - 、1 / 2SO4 - and 1 / 3PO4 - At least one of .

[0060] For example, X - Selected from NO3 - 、ClO4 - or N(NO2)2 - .

[0061] In some embodiments, a method for constructing a bistriazolotriazine fused-ring nitrogen-rich compound ion salt is also provided, comprising the following steps:

[0062] Acid is added to the solution and / or suspension of the bistriazolotriazine fused ring nitrogen-rich compound, and the mixture is stirred for reaction to obtain an ionic salt or energetic ionic salt of the bistriazolotriazine fused ring nitrogen-rich compound.

[0063] In some embodiments, the solution is a solution formed by a bistriazolotriazine fused ring nitrogen-rich compound and at least one of water and an alcohol having 1 to 6 carbon atoms;

[0064] And / or, the suspension is a suspension formed by an ionic salt of a bistriazolotriazine fused-ring nitrogen-rich compound and at least one of water and an alcohol having 1 to 6 carbon atoms.

[0065] In some embodiments, the bistriazolotriazine fused ring nitrogen-rich compound is selected from and / or

[0066] In some embodiments, the acid is selected from:

[0067] At least one of HNO3, HClO4, HN(NO2)2, HC(NO2)3, HCl, HF, H2SO4 and H3PO4.

[0068] In some embodiments, the temperature of the stirring reaction is 0°C to 50°C.

[0069] In some embodiments, the stirring reaction time is 2.6 h to 5 h.

[0070] In some embodiments, the following steps are also included:

[0071] The ionic salt of the bistriazolotriazine fused ring nitrogen-rich compound is subjected to double decomposition reaction to obtain the energetic ionic salt of the bistriazolotriazine fused ring nitrogen-rich compound.

[0072] In some embodiments, the ion salt of the bistriazolotriazine fused ring nitrogen-rich compound is subjected to membrane exchange to obtain an energetic ion salt of the bistriazolotriazine fused ring nitrogen-rich compound.

[0073] In some embodiments, the bistriazol-triazine fused ring nitrogen-rich compound ion salt is a compound as shown in Formula I or Formula II, and X - Selected from Cl - 、1 / 2SO4 - and 1 / 3PO4 - At least one of;

[0074] In some embodiments, the bistriazolotriazine fused ring nitrogen-rich compound ion salt and M + X - Through double decomposition reaction, an energetic ion salt of a bistriazolotriazine fused ring nitrogen-rich compound is obtained;

[0075] M + Selected from Ag + 、1 / 2Ca + 、1 / 2Pb+ and 1 / 2Cu + At least one of;

[0076] X - Selected from F - ,

[0077] NO3 - 、ClO4 - 、N(NO2)2 - and C(NO2)3 - At least one of .

[0078] In some embodiments, the energetic ion salt of the bistriazolotriazine fused ring nitrogen-rich compound is a compound as shown in Formula I or Formula II, and X - Selected from F - ,

[0079] NO3 - 、ClO4 - 、N(NO2)2 - and C(NO2)3 - At least one of .

[0080] Exemplarily, the membrane is a polymer separation membrane.

[0081] Exemplarily, the polymer separation membranes include reverse osmosis membranes, nanofiltration membranes, ultrafiltration membranes, microfiltration membranes, gas separation membranes, pervaporation membranes, and electrodialysis membranes.

[0082] In some embodiments, the temperature of the metathesis reaction is 0°C to 50°C;

[0083] In some embodiments, the metathesis reaction time is 0.5 h to 5 h.

[0084] In some embodiments, a bistriazolotriazine fused-ring nitrogen-rich compound ion salt prepared by the construction method of any of the above embodiments is used as an energetic material.

[0085] In some embodiments, an energetic ion salt of a bistriazolotriazine fused ring nitrogen-rich compound prepared by the construction method of any of the above embodiments is used as an energetic material.

[0086] In order to make the technical problems, technical solutions and beneficial effects solved by the present application clearer, the construction method of the bistriazol and triazine fused ring nitrogen-rich compound ion salt of the present invention will be further described in detail in combination with specific embodiments and drawings. Obviously, the specific embodiments described are only part of the embodiments of the present application, not all of the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and is by no means a limitation to the present application and its application. Based on the specific embodiments in the present application, all other embodiments obtained by ordinary technicians in the field without creative work belong to the scope of protection of this application.

[0087] If no specific techniques or conditions are specified in the specific embodiments, the techniques or conditions described in the literature in the field or the product instructions are used. If no manufacturer is specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0088] Example 1

[0089] The bistriazolotriazine fused ring nitrogen-rich compound energetic ion salt 1-1 has the following structural formula:

[0090]

[0091] The specific synthetic route is:

[0092]

[0093] The construction method includes the following steps:

[0094] S1. Disperse compound 1 (0.206 g, 1 mmol) in 10 mL of deionized water to obtain a second solution;

[0095] S2, dropwise add 70% perchloric acid (HClO4) aqueous solution to the second solution until all the solid is dissolved, the amount of perchloric acid (HClO4) aqueous solution added is 3 mL, react at room temperature for 2.7 h, stop the reaction, let the solution stand at room temperature, wait for white solid to precipitate, and obtain a white solid;

[0096] S3. The white solid obtained in S2 was recrystallized and purified in a methanol / water mixed solution to obtain the bistriazolotriazine fused ring nitrogen-rich compound energetic ion salt 1-1 (0.294 g, 96%).

[0097] Wherein, the steps of preparing compound 1 are:

[0098] S1. Dissolve 2-amine-4,6-dichloro-1,3,5-triazine (0.165 g, 1 mmol) in methanol (10 mL) solution, add 80% hydrazine hydrate (10 mL) solution, a large amount of white solution appears, stir at room temperature for 12 h, filter, rinse with methanol, and vacuum dry to obtain the product 2-amine-4,6-dihydrazine-1,3,5-triazine (0.148 g, 95%).

[0099] S2. Add 2-amine-4,6-dihydrazino-1,3,5-triazine (0.312 g, 2 mmol) to an ethanol (15 mL) solution and stir at room temperature for 0.5 h. The solution becomes a white turbid liquid. Add cyanogen bromide (0.45 g, 4.2 mmol) to the solution and stir at room temperature for 3 d. After the reaction is complete, filter, wash with ethanol and dry in vacuum. Purify by crystallization in a mixed solution of methanol / water to obtain product 1 (0.323 g, 80%).

[0100] Wherein, the reaction equation for preparing compound 1 is:

[0101]

[0102] Example 2

[0103] The bistriazolotriazine fused ring nitrogen-rich compound ion salt 1-2 has the following structural formula:

[0104]

[0105] The specific synthetic route is:

[0106]

[0107] The construction method includes the following steps:

[0108] S1. Disperse compound 1 (0.206 g, 1 mmol) in 10 mL of deionized water to obtain a second solution;

[0109] S2. Add 68% nitric acid (HNO3) aqueous solution to the second solution until all the solids are dissolved. The amount of nitric acid (HNO3) aqueous solution added is 3 mL. After reacting at room temperature for 2.7 h, stop the reaction, air-dry, and obtain product 1-2 (0.234 g, 87%).

[0110] Example 3

[0111] Bistriazolotriazine fused ring nitrogen-rich compound 2, the structural formula of which is as follows:

[0112]

[0113] The specific synthetic route is as follows:

[0114]

[0115] The construction method includes the following steps:

[0116] S1. Disperse compound 1 (0.206 g, 1 mmol) in 10 mL of deionized water to obtain a second solution;

[0117] S2, dropwise add 70% perchloric acid (HClO4) aqueous solution to the second solution until all the solid is dissolved, the amount of perchloric acid (HClO4) aqueous solution added is 3 mL, the reaction is stopped after reacting at room temperature for 1 hour, the solution is allowed to stand at room temperature until a white solid precipitates, and a white solid is obtained;

[0118] S3. The white solid obtained in S2 was recrystallized and purified in hot water to obtain product 2 (0.192 g, 93%).

[0119] Example 4

[0120] The bistriazolotriazine fused ring nitrogen-rich compound energetic ion salt 2-1 has the following structural formula:

[0121]

[0122] The specific synthetic route is:

[0123]

[0124] The construction method includes the following steps:

[0125] S1. Disperse compound 2 (0.206 g, 1 mmol) in 10 mL of deionized water to obtain a second solution;

[0126] S2, dropwise add 70% perchloric acid (HClO4) aqueous solution to the second solution until all the solid is dissolved, the amount of perchloric acid (HClO4) aqueous solution added is 3 mL, the reaction is stopped after 3 h at room temperature, the solution is allowed to stand at room temperature until a white solid precipitates, and a white solid is obtained;

[0127] S3. The white solid obtained in S2 was recrystallized and purified in a mixed solution of methanol and water to obtain the bistriazolotriazine fused ring nitrogen-rich compound energetic ion salt 2-1 (0.379 g, 93%).

[0128] Example 5

[0129] The bistriazolotriazine fused ring nitrogen-rich compound ion salt 1-3 and the bistriazolotriazine fused ring nitrogen-rich compound energetic ion salt 1-2 have the following structural formulas:

[0130]

[0131] The specific synthetic route is:

[0132]

[0133] The construction method includes the following steps:

[0134] S1. Compound 1 (0.206 g, 1 mmol) was completely dissolved in a 36% hydrochloric acid (HCl) aqueous solution and blown dry to obtain compound 1-3;

[0135] S2, dissolving compound 1-3 (0.242 g, 1 mmol) in 10 mL of deionized water to obtain a third solution;

[0136] S3. Dissolve AgNO3 (0.170 g, 1 mmol) in ethanol (10 mL), and add AgNO3 ethanol solution to the third solution at a rate of 1 mL / min. A large amount of white precipitate will appear. After reacting at room temperature for 2.6 h, stop the reaction, filter, and air-dry the filtrate to obtain product 1-2 (0.234 g, 87%).

[0137] Example 6

[0138] The bistriazolotriazine fused ring nitrogen-rich compound energetic ion salt 1-1 has the following structural formula:

[0139]

[0140] The specific synthetic route is:

[0141]

[0142] The construction method includes the following steps:

[0143] S1. Compound 1 (0.206 g, 1 mmol) was completely dissolved in a 36% hydrochloric acid (HCl) aqueous solution and blown dry to obtain compound 1-3;

[0144] S2, dissolving compound 1-3 (0.242 g, 1 mmol) in 10 mL of deionized water to obtain a third solution;

[0145] S3. Dissolve AgClO4 (0.207 g, 1 mmol) in ethanol (10 mL), add AgClO4 aqueous solution to the third solution at a rate of 1 mL / min, and a large amount of white precipitate appears. After reacting at room temperature for 0.5 h, stop the reaction, filter, and air-dry the filtrate to obtain the product 1-1 (0.276 g, 90%).

[0146] Example 7

[0147] The bistriazolotriazine fused ring nitrogen-rich compound ion salt 2-2 has the following structural formula:

[0148]

[0149] The specific synthetic route is:

[0150]

[0151] The construction method includes the following steps:

[0152] S1. Disperse compound 2 (0.206 g, 1 mmol) in 10 mL of deionized water to obtain a second solution;

[0153] S2. Add 68% nitric acid (HNO3) aqueous solution to the second solution in an amount of 3 mL until the solid is completely dissolved. After reacting at room temperature for 3 h, stop the reaction, blow dry, and obtain the bistriazol-triazine fused ring nitrogen-rich compound ion salt 2-2 (0.254 g, 74%).

[0154] Example 8

[0155] The bistriazolotriazine fused ring nitrogen-rich compound ion salt 2-2 has the following structural formula:

[0156]

[0157] The specific synthetic route is:

[0158]

[0159] The construction method includes the following steps:

[0160] S1. Disperse compound 2 (0.206 g, 1 mmol) in 10 mL of 36% hydrochloric acid (HCl) solution, react at room temperature for 3 h, then stop the reaction, blow dry, and dry in air to obtain product 2-3;

[0161] S2. Disperse compound 2-3 (0.279 g, 1 mmol) in 10 mL of water, add AgNO3 (0.170 g, 1 mmol) to produce a large amount of white precipitate. Stir at room temperature for 0.5 h, filter, and dry the filtrate to obtain the bistriazol-triazine fused ring nitrogen-rich compound ion salt 2-2 (0.295 g, 89%).

[0162] Detection and analysis

[0163] 1) Nuclear magnetic resonance imaging

[0164] The bistriazolotriazine fused ring nitrogen-rich compound energetic ion salt 1-1 prepared in Example 1 and the bistriazolotriazine fused ring nitrogen-rich compound energetic ion salt 2-1 prepared in Example 4 were subjected to nuclear magnetic resonance detection using a Bruker AVANCE 400 nuclear magnetic resonance instrument. The results are as follows: Figures 1 to 4 shown.

[0165] Figure 1 is the nuclear magnetic resonance hydrogen spectrum, from Figure 1 From the analysis, it can be seen that the five peaks at chemical shifts of 6.7, 7.0, 8.58, 9.22, and 14.17 correspond to four different hydrogens in the energetic salt 1-1 of the bistriazolotriazine fused ring nitrogen-rich compound.

[0166] Figure 2 is the carbon NMR spectrum, from Figure 2 From the analysis, it can be seen that the peaks at chemical shifts of 143.66, 145.14, 146.41, and 163.76 correspond to four different carbons in the energetic salt 1-1 of the bistriazolotriazine fused ring nitrogen-rich compound.

[0167] Figure 3 is the nuclear magnetic resonance hydrogen spectrum, from Figure 3 From the analysis, we can see that the two peaks at chemical shifts of 8.8 and 9.6 correspond to two different hydrogens in the energetic salt 2-1 of the bistriazolotriazine fused ring nitrogen-rich compound.

[0168] Figure 4 is the carbon NMR spectrum, from Figure 4 From the analysis, it can be seen that the peak at the chemical shift of 146.18 corresponds to the carbon in the energetic salt 2-1 of the bistriazolotriazine fused ring nitrogen-rich compound.

[0169] 2) The single crystal structures of the bistriazolotriazine fused ring nitrogen-rich compound energetic ion salt 1-1 prepared in Example 1, the compound 2 prepared in Example 3, and the bistriazolotriazine fused ring nitrogen-rich compound energetic ion salt 2-1 prepared in Example 4 were determined using a Bruker smartApex single crystal diffractometer. The results are as follows: Figures 5 to 7 shown.

[0170] from Figure 5 It can be seen from the analysis that the energetic ion salt 1-1 of the bistriazolotriazine fused ring nitrogen-rich compound prepared in Example 1 is not combined with water molecules.

[0171] from Figure 6 From the analysis, it can be seen that the structure of compound 2 prepared in Example 3 is determined to be a two-dimensional planar shape.

[0172] from Figure 7 It can be seen from the analysis that the energetic salt 2-1 of the bistriazolotriazine fused ring nitrogen-rich compound prepared in Example 4 forms a eutectic with a water molecule.

[0173] 3) Detonation test

[0174] The bistriazolotriazine fused ring nitrogen-rich compound energetic ion salt 1-2 prepared in Example 5 is applied to a detonator.

[0175] The specific operation is: carefully inject 150g of melted TNT into the detonator, then quickly add 250g of bistriazolotriazine fused ring nitrogen-rich compound energetic ion salt 1-2 that has been ground into fine powder into the detonator, stir as evenly as possible, cool to room temperature, and then conduct a detonation test. The results are as follows Figures 8 to 11 shown.

[0176] from Figure 8 to Figure 11 From the analysis, it can be seen that TNT containing bistriazolotriazine fused ring nitrogen-rich compound ion salt 1-2 can penetrate a 12 mm steel plate.

[0177] The bistriazolotriazine fused ring nitrogen-rich compound energetic ion salt 1-1 prepared in Example 1 is used as an energetic material.

[0178] The specific operations are:

[0179] 100g of TNT ground into powder and 100g of bistriazolotriazine fused ring nitrogen-rich compound energetic ion salt 1-1 ground into powder were mixed evenly, heated to 90°C, kept warm for 30 minutes, and then 150g of the paste mixture was carefully injected into a plastic tube. The detonation velocity was measured to be 8090m / s.

[0180] 4) Detonation performance test

[0181] The specific operation steps are: the results of compounds 1, 1-1, 2 and 2-2 are shown in Table 1.

[0182] Table 1 Detonation performance data results

[0183]

[0184] From the analysis in Table 1, it can be seen that compound 2 is better than compound 1 in thermal stability (T d ), density (ρ) and detonation performance. After the introduction of perchlorate ions, the performance of compounds 1-1 and 2-1 were significantly improved, with thermal decomposition temperatures of 325 and 309 °C, respectively, and the density of 2-1 even reaching 1.89 g cm -3 , and their detonation speed and pressure are 8520m s -1 and 32.53GPa, which is superior to TNT and TATB and is a potential energetic material.

[0185] In summary, the bistriazolotriazine fused ring nitrogen-rich skeleton of the present invention has the characteristics of a two-dimensional planar structure, rich nitrogen content and three amino groups, good stability, and can introduce specific functional groups in a targeted manner. The amino groups in the amino-substituted nitrogen-rich fused ring compound can directly form energetic ion salts, and can also be modified to obtain quaternary ammonium salts and substituted amine structures, which has potential application value in constructing new fused ring structures.

[0186] The method for constructing a bistriazolotriazine fused ring nitrogen-rich skeleton of the present invention obtains two mutually isomeric bistriazolotriazine fused ring nitrogen-rich skeletons by molecular rearrangement under acidic conditions, and verifies the rearrangement mechanism by combining experiments with theoretical calculations. The method is simple, has high preparation efficiency, and high product purity, and provides a basis for the subsequent design and synthesis of fused ring energetic molecules, etc., and has the advantages of being environmentally friendly, simple to operate, and excellent product performance. It has broad application prospects in the fields of energy, medicine, materials science, etc., and has promotion and application value in the field of organic compound technology.

[0187] The above embodiments are only preferred embodiments for fully illustrating the present invention, and the protection scope of the present invention is not limited thereto. Any equivalent substitution or change made by a person skilled in the art based on the present invention is within the protection scope of the present invention.

Claims

1. A bistriazolotriazine fused ring nitrogen-rich compound ion salt, characterized in that: The compound having the structural formula as shown in Formula I and its racemate, stereoisomer or tautomer; In Formula I, X - Selected from Cl - 、F - , NO3 - 、ClO4 - 、N(NO2)2 - 、C(NO2)3 - 、1 / 2SO4 - and 1 / 3PO4 - At least one of; and / or, a compound having a structural formula as shown in Formula II and its racemate, stereoisomer or tautomer; In Formula II, X - Selected from Cl - 、F - , NO3 - 、ClO4 - 、N(NO2)2 - 、C(NO2)3 - 、1 / 2SO4 - and 1 / 3PO4 - At least one of . Preferably, said X- is selected from NO3 - 、ClO4 - or N(NO2)2 - .

2. A method for constructing the bistriazolotriazine fused-ring nitrogen-rich compound ion salt as claimed in claim 1, characterized in that: The following steps are involved: Acid is added to the solution and / or suspension of the bistriazolotriazine fused ring nitrogen-rich compound, and the mixture is stirred for reaction to obtain an ionic salt or energetic ionic salt of the bistriazolotriazine fused ring nitrogen-rich compound.

3. The method for constructing the bistriazolotriazine fused-ring nitrogen-rich compound ion salt according to claim 2, characterized in that: The solution is a solution formed by a bistriazolotriazine fused ring nitrogen-rich compound and at least one of water and an alcohol having 1 to 6 carbon atoms; And / or, the suspension is a suspension formed by a bistriazolotriazine fused ring nitrogen-rich compound and at least one of water and an alcohol having 1 to 6 carbon atoms.

4. The method for constructing the bistriazolotriazine fused-ring nitrogen-rich compound ion salt according to claim 2, characterized in that: The bistriazolotriazine fused ring nitrogen-rich compound is selected from 5. The method for constructing the bistriazolotriazine fused-ring nitrogen-rich compound ion salt according to claim 2, characterized in that: The acid is selected from: At least one of HNO3, HClO4, HN(NO2)2, HC(NO2)3, HCl, HF, H2SO4 and H3PO4.

6. The method for constructing the bistriazolotriazine fused-ring nitrogen-rich compound ion salt according to claim 2, characterized in that: The stirring reaction temperature is 0°C to 50°C; And / or, the stirring reaction time is 2.6h to 5h.

7. The method for constructing the bistriazolotriazine fused-ring nitrogen-rich compound ion salt according to claim 2, characterized in that: The following steps are also included: The ion salt of the bistriazolotriazine fused ring nitrogen-rich compound is subjected to double decomposition reaction to obtain an energetic ion salt of the bistriazolotriazine fused ring nitrogen-rich compound; And / or, the ion salt of the bistriazolotriazine fused ring nitrogen-rich compound is subjected to membrane exchange to obtain the energetic ion salt of the bistriazolotriazine fused ring nitrogen-rich compound.

8. The method for constructing the bistriazolotriazine fused-ring nitrogen-rich compound ion salt according to claim 7, characterized in that: The bistriazol-triazine fused ring nitrogen-rich compound ion salt is a compound as shown in Formula I or Formula II, and X - Selected from Cl - 、1 / 2SO4 - and 1 / 3PO4 - At least one of; And / or, the bistriazolotriazine fused ring nitrogen-rich compound ion salt and M + X - Through double decomposition reaction, an energetic ion salt of a bistriazolotriazine fused ring nitrogen-rich compound is obtained; The M + Selected from Ag + 、1 / 2Ca + 、1 / 2Pb + and 1 / 2Cu + At least one of; The X - Selected from F - , NO3 - 、ClO4 - 、N(NO2)2 - and C(NO2)3 - At least one of; And / or, the energetic ion salt of the bistriazolotriazine fused ring nitrogen-rich compound is a compound as shown in Formula I or Formula II, and X - Selected from F - , NO3 - 、ClO4 - 、N(NO2)2 - and C(NO2)3 - At least one of .

9. The method for constructing the bistriazolotriazine fused-ring nitrogen-rich compound ion salt according to claim 7, characterized in that: The membrane is a polymer separation membrane; And / or, the temperature of the metathesis reaction is 0°C to 50°C; And / or, the double decomposition reaction time is 0.5h to 5h.

10. An application of a bistriazolotriazine fused ring nitrogen-rich compound ion salt prepared by the construction method according to any one of claims 2 to 9, characterized in that: Application of the bistriazolotriazine fused ring nitrogen-rich compound ion salt as an energetic material; And / or, the application of the energetic ion salt of the bistriazolotriazine fused ring nitrogen-rich compound as an energetic material.

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