Hydroxylamine and / or thiophene compounds and methods for their preparation and use as energetic materials

Abstract

The present application belongs to the field of compounds. Specifically, it relates to crystalline compounds and solid solutions assembled based on hydroxylammonium and / or ions, their preparation methods and their uses as energetic materials. It is found that they have excellent energetic properties and practicality when used as energetic materials. Compared with the prior art such as ammonium ions, the compounds of the present application have higher enthalpy of formation of hydroxylammonium and ions, and are expected to form more hydrogen bond interactions in the crystal, which may be conducive to obtaining stronger binding force, so as to simultaneously increase the enthalpy of formation and crystal density of the compound. Therefore, the inventors use this to construct metal-free energetic materials in order to further improve the energetic properties. At least one compound of the present application has high theoretical explosion heat and volume energy density, superior detonation performance, good safety performance, high theoretical specific impulse value, and no volatility, and can be stored for a long time without decomposition; room temperature crystallinity is single, raw materials are cheap and easy to obtain, and the production process is simple, and it can be safely prepared in large quantities.

Description

Technical Field

[0001] The present invention relates to the field of compounds. Specifically, it relates to compounds including hydroxyl ammonium ions (NH3OH + ) and / or Ions (NH2NH3 + ), methods for their preparation and their use as energetic materials. Background Art

[0002] Energetic materials are materials that can undergo violent chemical reactions when subjected to external stimuli (such as mechanical force stimulation, thermal stimulation, etc.), rapidly release a large amount of energy (usually accompanied by a large amount of gas and heat) and produce deflagration / explosion phenomena. The characteristic of energetic materials to rapidly release energy plays an important role in both military and civilian fields. For example, in the modern military field, they can not only be used as a power source for military projection devices such as projectile launch and rocket launch, but also as a material basis for achieving military damage; in the modern civilian field, they are widely used in fireworks, engineering blasting, ejection devices, mechanical processing, geological exploration, airbags, etc.

[0003] In recent decades, the research on energetic materials has experienced a rapid development period, mainly including high nitrogen heterocyclic compounds, energetic ion salts, energetic eutectic compounds, energetic coordination compounds and ABX3 molecular perovskite-type energetic materials (Chinese patent 201610665880.3). 4+ Metal-free molecular perovskite-type energetic materials with cations at the B site have the advantages of no metal residue after explosion or decomposition, large gas production, and high explosion heat or combustion calorific value, which makes them have very good application prospects in the fields of propellants, propellants and as high explosives.

[0004] However, it has been found that the metal-free molecular perovskite energetic compounds constructed by adjusting the A site have encountered bottlenecks in simultaneously improving the crystal density and formation enthalpy, and it is difficult to further break through their energetic properties. For example, the first metal-free molecular perovskite energetic compound (C6H 14 N2)(NH4)(ClO4)3(DAP-4) and its optimal compound (C6H 14 N2O)(NH4)(ClO4)3(DAP-O4), their crystal densities are 1.87 and 1.85 g / cm 3 , their formation enthalpies are -483.96 and -436.08 kJ / mol, their detonation heats are 1.40 and 1.48 kcal / g, their detonation velocities are 8.806 and 8.900 km / s, and their detonation pressures are 35.2 and 35.7 GPa; in comparison, the performance of the latter is not significantly improved over the former.

[0005] In metal-free molecular perovskite energetic materials, how to adjust their components to further increase the crystal density and formation enthalpy at the same time, thereby improving their energetic properties, is a challenging topic of great significance. Summary of the invention

[0006] In one aspect, the present application provides novel compounds, specifically comprising NH3OH + and / or NH2NH3 + In one aspect, the present application provides new energetic compounds. In one aspect, the present application provides energetic materials with good thermal stability. In one aspect, the present application provides energetic materials with good explosion performance. In one aspect, the present application provides energetic materials with high energy density. In one aspect, the present application provides energetic materials with high theoretical specific impulse.

[0007] The present application provides a method based on NH3OH + and / or NH2NH3 + The invention discloses a crystalline compound of cation assembly, a solid solution thereof, and their use as an energetic material. It is found that the crystalline compound has excellent energetic properties and practicality when used as an energetic material.

[0008] In the compound ABX3 of the present application:

[0009] In some embodiments, the compound ABX3 is a perovskite compound ABX3.

[0010] In some embodiments, the A cation is at least one organic cation.

[0011] In some embodiments, the A cation is at least one nitrogen-containing heterocyclic organic cation.

[0012] In some embodiments, the A cation is at least one divalent nitrogen-containing organic cation.

[0013] In some embodiments, the A cation is at least one divalent nitrogen-containing heterocyclic organic cation.

[0014] In some embodiments, the A cation is selected from one, two or more of a divalent nitrogen-containing five-membered ring cation, a divalent nitrogen-containing six-membered ring cation, and a divalent nitrogen-containing seven-membered ring cation.

[0015] In some embodiments, the A cation may be one, two or more selected from the ions of formula (I) and formula (II), and their derivatives, wherein n1, n2, n3, n4 and n5 may each be a positive integer preferably 1, 2, 3, 4 or 5, more preferably 1, 2 or 3, R1, R2, R3 and R4 may be one, two or more selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, hydroxyl, carbonyl, carboxyl, amine, halogen, thiol, peroxide, azo and nitro. The derivative refers to the hydrogen atoms in the organic cation body being replaced by substituents simultaneously or at different times. Common substituents include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, hydroxyl, carbonyl, carboxyl, amine, halogen, thiol, peroxide, azo and nitro.

[0016]

[0017] In some embodiments,

[0018] The A cation is selected from the ion of formula (I) or its derivatives, and

[0019] Either n1 or n2 is greater than 2, or either R1 or R2 includes at least one carbon atom;

[0020] or

[0021] The A cation is selected from the ion of formula (II) or its derivatives, and

[0022] Any one of n3, n4 and n5 is greater than 2, or any one of R3 and R4 includes at least one carbon atom.

[0023] In some embodiments, the A cation is selected from the ion of formula (I) or its derivatives; and any one of n1 and n2 is greater than 2, or any one of R1 and R2 includes at least one carbon atom. In some embodiments, the A cation is selected from the ion of formula (II) or its derivatives; and any one of n3, n4 and n5 is greater than 2, or any one of R3 and R4 includes at least one carbon atom. In some embodiments, the A cation is selected from the ion of formula (I) or its derivatives, and any one of n1 and n2 is greater than 2; or the A cation is selected from the ion of formula (II) or its derivatives, and any one of n3, n4 and n5 is greater than 2. In some embodiments, the A cation is selected from the ion of formula (I) or its derivatives, and any one of R1 and R2 includes at least one carbon atom; or the A cation is selected from the ion of formula (II) or its derivatives, and any one of R3 and R4 includes at least one carbon atom.

[0024] In some embodiments, the A cation is selected from the ion of formula (I) or its derivatives, and any one of R1 and R2 is selected from methyl; or the A cation is selected from the ion of formula (II) or its derivatives, and any one of R3 and R4 is selected from methyl.

[0025] In some embodiments, the A cation is selected from the ion of formula (I) or its derivatives, and any one of n1 and n2 is 2. In some embodiments, the A cation is selected from the ion of formula (I) or its derivatives, and n1 and n2 are both 2. In some embodiments, the A cation is selected from the ion of formula (I) or its derivatives, and n1 is 2, and n2 is greater than or equal to 2. In some embodiments, the A cation is selected from the ion of formula (I) or its derivatives, and any one of n1 and n2 is 3. In some embodiments, the A cation is selected from the ion of formula (II) or its derivatives, and any one of n3, n4 and n5 is 2. In some embodiments, the A cation is selected from the ion of formula (II) or its derivatives, and n3, n4 and n5 are all 2.

[0026] In some embodiments, the A cation is selected from 1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion (Formula (III), 1,4-diazabicyclo[2.2.2]octane-1,4-diium), 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion (Formula (IV), 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-diium), 1,4-dihydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion (Formula (V), 1,4-dihydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion), pyrazine-1,4 -dialium ion (Formula (VI), pyrazine-1,4-diium), piperazine-1,4-dialium ion (Formula (VII), piperazine-1,4-diium), 1-methylpiperazine-1,4-diium ion (Formula (VIII), 1-methylpiperazine-1,4-diium), 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion (Formula (IX), 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium), and 1,4-diazacycloheptane-1,4-dialium ion (Formula (X), 1,4-diazepane-1,4-diium), and their derivatives.

[0027]

[0028] In some embodiments, the A cation is selected from one, two or more of piperazine-1,4-dialium ion, 1-methylpiperazine-1,4-dialium ion, 1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion, 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion, 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion, and 1,4-diazacycloheptane-1,4-dialium ion, and derivatives thereof.

[0029] In some embodiments, the A cation is selected from one, two or more of piperazine-1,4-dionium ion and 1,4-diazepane-1,4-dionium ion, and derivatives thereof.

[0030] In some embodiments, the A cation is selected from one, two or more of piperazine-1,4-dionium ion, 1-methylpiperazine-1,4-dionium ion, 1,4-diazabicyclo[2.2.2]octane-1,4-dionium ion, and 1,4-diazacycloheptane-1,4-dionium ion, and derivatives thereof.

[0031] In some embodiments, the A cation is selected from 1-methylpiperazine-1,4-dialium ion, 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion, 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion, and 1,4-diazacycloheptane-1,4-dialium ion, and one, two or more of their derivatives. In some embodiments, the A cation is selected from 1-methylpiperazine-1,4-dialium ion, 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion, and 1,4-diazacycloheptane-1,4-dialium ion, and one, two or more of their derivatives.

[0032] In some embodiments, the A cation is selected from 1-methylpiperazine-1,4-dialium ion, 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion, and 1,4-diazacycloheptane-1,4-dialium ion, and one, two or more of their derivatives. In some embodiments, the A cation is selected from 1-methylpiperazine-1,4-dialium ion, and 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion, and one, two or more of their derivatives. In some embodiments, the A cation is selected from 1-methylpiperazine-1,4-dialium ion, and 1,4-diazacycloheptane-1,4-dialium ion, and one, two or more of their derivatives. In some embodiments, the A cation is selected from one, two or more of 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dionium ion, 1,4-diazacycloheptane-1,4-dionium ion, and derivatives thereof.

[0033] In some embodiments, the A cation is selected from one, two or more of 1,4-diazabicyclo[2.2.2]octane-1,4-dionium ions and their derivatives. In some embodiments, the A cation is selected from one, two or more of 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dionium ions and their derivatives. In some embodiments, the A cation is selected from one, two or more of 1,4-dihydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dionium ions and their derivatives. In some embodiments, the A cation is selected from one, two or more of pyrazine-1,4-dionium ions and their derivatives. In some embodiments, the A cation is selected from one, two or more of piperazine-1,4-dionium ions and their derivatives. In some embodiments, the A cation is selected from one, two or more of 1-methylpiperazine-1,4-dionium ions and their derivatives. In some embodiments, the A cation is selected from one, two or more of 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dionium ion and its derivatives. In some embodiments, the A cation is selected from one, two or more of 1,4-diazacycloheptane-1,4-dionium ion and its derivatives.

[0034] In some embodiments, the B cation is NH3NH2 + or NH3OH + .

[0035] In some embodiments, the B cation is NH3NH2 + .

[0036] In some embodiments, the B cation is NH3OH+ .

[0037] In some embodiments, the X anion is an anionic energetic group.

[0038] In some embodiments, the X anion is a monovalent anion.

[0039] In some embodiments, the X anion is selected from one, two or more of chlorate ion, bromate ion, iodate ion, perchlorate ion, perbromate ion, periodate ion, nitrate ion, fulminate ion, azo group and azide ion.

[0040] In some embodiments, the X anion is selected from one, two or more of a chlorate ion, a perchlorate ion, a nitrate ion, a fulminate ion, an azo group and an azide ion.

[0041] In some embodiments, the X anion is a halogen-containing monovalent anion.

[0042] In some embodiments, the X anion is a monovalent oxoacid anion containing a halogen.

[0043] In some embodiments, the X anion is a halide ion or a perhalide ion.

[0044] In some embodiments, the X anion is a perhalate ion or a nitrate ion.

[0045] In some embodiments, the X anion is a perhalate ion.

[0046] In some embodiments, the X anion is selected from one, two or more of chlorate ion, bromate ion, iodate ion, perchlorate ion, perbromate ion, periodate ion and nitrate ion. In some embodiments, the X anion is selected from one, two or more of chlorate ion, bromate ion, iodate ion, perchlorate ion, perbromate ion and periodate ion.

[0047] In some embodiments, the X anion is selected from one, two or more of perchlorate ion, perbromate ion and periodate ion. In some embodiments, the X anion is selected from one, two or more of perchlorate ion and perbromate ion. In some embodiments, the X anion is selected from one, two or more of perchlorate ion and periodate ion. In some embodiments, the X anion is selected from one, two or more of perchlorate ion and periodate ion. In some embodiments, the X anion is selected from one, two or more of perbromate ion and periodate ion.

[0048] In some embodiments, the X anion is selected from perchlorate ion. In some embodiments, the X anion is selected from perbromate ion. In some embodiments, the X anion is selected from periodate ion.

[0049] In some embodiments, the A cation is 1,4-diazabicyclo[2.2.2]octane-1,4-diazolium ion, and the B cation is NH3NH2 + or NH3OH + , the X anion is selected from perchlorate ion.

[0050] In some embodiments, the A cation is 1,4-diazabicyclo[2.2.2]octane-1,4-diazolium ion, and the B cation is NH3NH2 + , wherein the X anion is selected from the group consisting of perchlorate ions. The compound is: (C6H 14 N2)(NH3OH)(ClO4)3(DAP-6).

[0051] In some embodiments, the A cation is 1,4-diazabicyclo[2.2.2]octane-1,4-diazolium ion, and the B cation is NH3OH + , wherein the X anion is selected from the group consisting of perchlorate ions. The compound is: (C6H 14 N2)(NH3NH2)(ClO4)3(DAP-7).

[0052] In at least some embodiments of the present application, the ABX3 compound of the present application can be obtained by adding the corresponding organic cation component (component A), the node-building ion component (component B) and the acid radical component (component X) to a liquid reaction system in any order for reaction. For example, two compounds (C6H 14 N2)(NH3OH)(ClO4)3(DAP-6) and (C6H 14 N2)(NH3NH2)(ClO4)3(DAP-7) can be prepared by mixing the organic cation component (component A), NH3OH + and NH2NH3 + The cation (component B) and the perchlorate component (component X) are added to a liquid reaction system in any order and reacted to obtain the product. The liquid reaction system is preferably a polar solvent that can dissolve component A, component B and component X. Alternatively, the product can be obtained by referring to a known synthesis method. The reaction temperature is not particularly limited and can be adjusted in a wide range, for example, 0-100°C.

[0053] In some embodiments, the preparation method of compound ABX3 may include the following steps:

[0054] 1) mixing component A, component B and component X in any order in a liquid reaction system; and

[0055] 2) obtaining a solid product produced in the liquid reaction system; and preferably further purifying the solid product.

[0056] The liquid reaction system is preferably a polar solvent that can dissolve component A, component B and component X. Or it can be obtained by referring to a known synthesis method. The reaction temperature range can be, for example, 0°C to 100°C, for example, room temperature or 25°C, for example, 15°C to 40°C, or 20°C to 30°C, etc.

[0057] In some embodiments, component A, component B and component X can be mixed by sufficient stirring in a liquid reaction system. In some embodiments, the solid product produced in the liquid reaction system is filtered, and the filter residue is washed with ethanol or a similar organic solvent, and vacuum dried to purify.

[0058] In some embodiments, the preparation method of compound ABX3 may include the following steps:

[0059] 1) synthesizing the A component solution, i.e., a solution containing the A cation in the compound ABX3 to be synthesized;

[0060] 2) mixing the A component solution, the B component and the X component in any order in a liquid reaction system; and

[0061] 3) obtaining and purifying the solid product produced in the liquid reaction system.

[0062] In some embodiments, the component A and the component B are solid and can be dissolved in a polar solvent first. Thus, the preparation method of compound ABX3 may include the following steps:

[0063] 1) Dissolving component A and component B separately or together with a polar solvent to obtain a component A solution and a component B solution;

[0064] 2) mixing the A component solution, the B component solution and the X component in any order; and

[0065] 3) obtaining and purifying the solid product produced in the liquid reaction system.

[0066] In some embodiments, the preparation method of compound ABX3 may include the following steps:

[0067] 1) Add component A to a polar solvent, then add component X, and stir evenly to obtain a solution of components A and X;

[0068] 2) dissolving component B in a polar solvent to obtain a component B solution; and

[0069] 3) The A and X component solutions and the B component solution are mixed, fully stirred, filtered, the filter residue is washed with ethanol, and vacuum dried to obtain a white powder compound.

[0070] As an embodiment, the present application provides a preparation method thereof, comprising the following steps:

[0071] 1) Add component A to the polar solvent, then add component X and stir evenly;

[0072] 2) dissolving component B in a polar solvent; and

[0073] 3) The solutions of step 1) and step 2) are mixed, fully stirred, filtered, the filter residue is washed with ethanol, and vacuum dried to obtain a white powdery energetic compound.

[0074] In some embodiments, the A component is a salt including the A cation in the compound ABX3 to be synthesized, or a solution containing the A cation in the compound ABX3 to be synthesized, or the A component is a product after the A cation is deprotonated, that is, the product after the A component is protonated is the A cation;

[0075] In some embodiments, the A component is at least one nitrogen-containing heterocyclic compound.

[0076] In some embodiments, the A component is at least one divalent nitrogen-containing organic compound or a salt thereof.

[0077] In some embodiments, the A component is at least one divalent nitrogen-containing heterocyclic compound or a salt thereof.

[0078] In some embodiments, the A component is selected from one, two or more of a divalent nitrogen-containing five-membered ring, a divalent nitrogen-containing six-membered ring, and a divalent nitrogen-containing seven-membered ring, or salts thereof including onium salts thereof.

[0079] In some embodiments, the A component is selected from one, two or more of the compounds of formula (XI) or formula (XII), salts of organic cations of formula (I) or formula (II), including onium salts thereof, and their derivatives, wherein n1, n2, n3, n4 and n5 can each be a positive integer preferably 1, 2, 3, 4 or 5, more preferably 1, 2 or 3, R1, R2, R3 and R4 can be selected from one, two or more of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, hydroxyl, carbonyl, carboxyl, amine, halogen, thiol, peroxide, azo and nitro. The derivative refers to the hydrogen atoms in the organic cation body being replaced by substituents simultaneously or at different times. Common substituents include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, hydroxyl, carbonyl, carboxyl, amine, halogen, thiol, peroxide, azo and nitro.

[0080]

[0081] In some embodiments,

[0082] The A component is a compound of formula (XI) or a salt of formula (I) including an onium salt thereof or a derivative thereof, and

[0083] Either n1 or n2 is greater than 2, or either R1 or R2 includes at least one carbon atom;

[0084] or

[0085] The component A is a compound of formula (XII) or a salt of formula (II) including an onium salt thereof or a derivative thereof, and

[0086] Any one of n3, n4 and n5 is greater than 2, or any one of R3 and R4 includes at least one carbon atom.

[0087] In some embodiments, the A component is a salt of a compound of formula (XI) or an ion of formula (I) including an onium salt or a derivative thereof; and any one of n1 and n2 is greater than 2, or any one of R1 and R2 includes at least one carbon atom. In some embodiments, the A component is a salt of a compound of formula (XII) or an ion of formula (II) including an onium salt or a derivative thereof; and any one of n3, n4 and n5 is greater than 2, or any one of R3 and R4 includes at least one carbon atom. In some embodiments, the A component is a salt of a compound of formula (XI) or an ion of formula (I) including an onium salt or a derivative thereof, and any one of n1 and n2 is greater than 2; or the A component is a salt of a compound of formula (XII) or an ion of formula (II) including an onium salt or a derivative thereof, and any one of n3, n4 and n5 is greater than 2. In some embodiments, the A component is a compound of formula (XI) or a salt of an ion of formula (I) including an onium salt or a derivative thereof, and any one of R1 and R2 includes at least one carbon atom; or the A component is a compound of formula (XII) or a salt of an ion of formula (II) including an onium salt or a derivative thereof, and any one of R3 and R4 includes at least one carbon atom. In some embodiments, the A component is selected from a compound of formula (XI) or a salt of an ion of formula (I) including an onium salt or a derivative thereof, and any one of R1 and R2 is a methyl group; or the A component is selected from a compound of formula (XII) or a salt of an ion of formula (II) including an onium salt or a derivative thereof, and any one of R3 and R4 is a methyl group.

[0088] In some embodiments, the A component is selected from the compounds of formula (XI) or salts of ions of formula (I) including onium salts or derivatives thereof, and any one of n1 and n2 is 2. In some embodiments, the A component is selected from the compounds of formula (XI) or salts of ions of formula (I) including onium salts or derivatives thereof, and n1 and n2 are both 2. In some embodiments, the A component is selected from the compounds of formula (XI) or salts of ions of formula (I) including onium salts or derivatives thereof, and n1 is 2, and n2 is greater than or equal to. In some embodiments, the A component is selected from the compounds of formula (XI) or salts of ions of formula (I) including onium salts or derivatives thereof, and n1 is 2, and n2 is greater than 2. In some embodiments, the A component is selected from the compounds of formula (XI) or salts of ions of formula (I) including onium salts or derivatives thereof, and any one of n1 and n2 is 3. In some embodiments, the A component is selected from the compounds of formula (XII) or salts of ions of formula (II) including onium salts or derivatives thereof, and any one of n3, n4 and n5 is 2. In some embodiments, the A component is selected from the compounds of formula (XII) or salts of ions of formula (II) including onium salts or derivatives thereof, and n3, n4 and n5 are all 2.

[0089] In some embodiments, the A component is 1,4-diazabicyclo[2.2.2]octane, the reaction product of 1,4-diazabicyclo[2.2.2]octane and hydrogen peroxide, pyrazine, piperazine, 1-methylpiperazine, 1,4-diazacycloheptane, 1,4-diazabicyclo[2.2.2]octane-1,4-dialium salt, 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dialium salt , 1,4-dihydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dialium salt, pyrazine-1,4-dialium salt, piperazine-1,4-dialium salt, 1-methylpiperazine-1,4-dialium salt, 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dialium salt, 1,4-diazacycloheptane-1,4-dialium salt, and their derivatives. One, two or more.

[0090] In some embodiments, the A component is selected from one, two or more of piperazine, 1-methylpiperazine, 1,4-diazabicyclo[2.2.2]octane, the reaction product of 1,4-diazabicyclo[2.2.2]octane and hydrogen peroxide, 1,4-diazacycloheptane and their derivatives.

[0091] In some embodiments, the A component is selected from one, two or more of piperazine, 1,4-diazepane, piperazine-1,4-dionium salt, 1,4-diazepane-1,4-dionium salt, and derivatives thereof.

[0092] In some embodiments, the A component is selected from one, two or more of piperazine, 1-methylpiperazine, 1,4-diazabicyclo[2.2.2]octane, 1,4-diazacycloheptane, piperazine-1,4-dialium salt, 1-methylpiperazine-1,4-dialium salt, 1,4-diazabicyclo[2.2.2]octane-1,4-dialium salt, and 1,4-diazacycloheptane-1,4-dialium salt, and derivatives thereof.

[0093] In some embodiments, the A component is selected from 1-methylpiperazine, the reaction product of 1,4-diazabicyclo[2.2.2]octane and hydrogen peroxide, 1,4-diazacycloheptane, 1-methylpiperazine-1,4-dialium salt, 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dialium salt, 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dialium salt, and 1,4-diazacycloheptane-1,4-dialium salt, and one, two or more of their derivatives. In some embodiments, the A component is selected from one, two or more of 1-methylpiperazine, the reaction product of 1,4-diazabicyclo[2.2.2]octane and hydrogen peroxide, 1,4-diazacycloheptane, 1-methylpiperazine-1,4-dialium salt, 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dialium salt, and 1,4-diazacycloheptane-1,4-dialium salt, and their derivatives.

[0094] In some embodiments, the A component is selected from 1-methylpiperazine, 1,4-diazacycloheptane, 1-methylpiperazine-1,4-dialium salt, 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dialium salt, and 1,4-diazacycloheptane-1,4-dialium salt, and one, two or more of their derivatives. In some embodiments, the A component is selected from 1-methylpiperazine, 1-methylpiperazine-1,4-dialium salt, and 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dialium salt, and one, two or more of their derivatives. In some embodiments, the A component is selected from 1-methylpiperazine, 1,4-diazacycloheptane, 1-methylpiperazine-1,4-dialium salt, and one, two or more of 1,4-diazacycloheptane-1,4-dialium salt, and one, two or more of their derivatives. In some embodiments, the A component is selected from one, two or more of 1,4-diazacycloheptane, 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dionium salt, and 1,4-diazacycloheptane-1,4-dionium salt, and derivatives thereof.

[0095] In some embodiments, the A component is selected from one, two or more of 1,4-diazabicyclo[2.2.2]octane and its derivatives. In some embodiments, the A component is selected from one, two or more of 1-hydroxy-1,4-diazabicyclo[2.2.2]octane and its derivatives. In some embodiments, the A component is selected from one, two or more of 1,4-dihydroxy-1,4-diazabicyclo[2.2.2]octane and its derivatives. In some embodiments, the A component is selected from one, two or more of pyrazine and its derivatives. In some embodiments, the A component is selected from one, two or more of piperazine and its derivatives. In some embodiments, the A component is selected from one, two or more of 1-methylpiperazine and its derivatives. In some embodiments, the A component is selected from one, two or more of 1,4-diazacycloheptane and its derivatives. In some embodiments, the A component is selected from one, two or more of 1,4-diazabicyclo[2.2.2]octane-1,4-dialium salt and its derivatives. In some embodiments, the A component is selected from one, two or more of 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dialium salts and their derivatives. In some embodiments, the A component is selected from one, two or more of 1,4-dihydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dialium salts and their derivatives. In some embodiments, the A component is selected from one, two or more of pyrazine-1,4-dialium salts and their derivatives. In some embodiments, the A component is selected from one, two or more of piperazine-1,4-dialium salts and their derivatives. In some embodiments, the A component is selected from one, two or more of 1-methylpiperazine-1,4-dialium salts and their derivatives. In some embodiments, the A component is selected from one, two or more of 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dialium salts and their derivatives. In some embodiments, the A component is selected from one, two or more of 1,4-diazacycloheptane-1,4-dionium salt and its derivatives.

[0096] In some embodiments, the B component is hydroxylamine, NH3OH + Ionic salt, containing NH3OH + Ionic bases, hydrazine, containing NH3NH2 + Ionic salts, containing NH3NH2 + In some embodiments, the B component is hydroxylamine, hydroxylammonium salt, hydrazine, In some embodiments, the B component is at least one, two or more hydroxylamine or hydroxylammonium salts. In some embodiments, the B component is hydrazine or In some embodiments, the B component is hydroxylamine. In some embodiments, the B component is hydrazine.

[0097] In some embodiments, the X component is selected from acids or salts including the X anion in the compound ABX3 to be synthesized, or the X component will generate the X anion after being dissolved in the liquid reaction system.

[0098] In some embodiments, the X component is selected from acids or salts including anionic energetic groups.

[0099] In some embodiments, the X component is selected from acids or salts comprising a monovalent anion.

[0100] In some embodiments, the X component is selected from one, two or more selected from chloric acid, chlorate, perchloric acid, perchlorate, bromic acid, bromate, perbromic acid, perbromate, iodic acid, iodate, periodic acid, periodate, nitric acid, nitrate, fulminic acid, fulminate, azo salts and azide salts.

[0101] In some embodiments, the X component is selected from one, two or more selected from chloric acid, chlorate, perchloric acid, perchlorate, nitric acid, nitrate, fulminic acid, fulminate, azo salts and azide salts.

[0102] In some embodiments, the X component includes a halogen-containing acid or salt.

[0103] In some embodiments, the X component comprises a halogen-containing oxygen acid or salt thereof, nitric acid or nitrate.

[0104] In some embodiments, the X component comprises a halogen-containing oxygen-containing acid or a salt thereof.

[0105] In some embodiments, the X component comprises a halogen acid, a halogenate, a perhalogen acid, a perhalogenate, nitric acid, or a nitrate. In some embodiments, the X component comprises a halogen acid, a halogenate, a perhalogen acid, or a perhalogenate. In some embodiments, the X component comprises a perhalogen acid, a perhalogenate, nitric acid, or a nitrate. In some embodiments, the X component comprises a perhalogen acid or a perhalogenate.

[0106] In some embodiments, the X component comprises one, two or more of perchloric acid, perchlorate, perbromic acid, perbromate, periodic acid, periodate, nitric acid and nitrate. In some embodiments, the X component comprises one, two or more of perchloric acid, perchlorate, perbromic acid, perbromate, periodic acid and periodate. In some embodiments, the X component comprises perchloric acid, perchlorate, perbromic acid and / or perbromate. In some embodiments, the X component comprises perchloric acid, perchlorate, periodic acid and / or periodate. In some embodiments, the X component comprises perbromic acid, perbromate, periodic acid and / or periodate.

[0107] In some embodiments, the X component comprises perchloric acid and / or a perchlorate. In some embodiments, the X component comprises perbromic acid and / or a perbromate. In some embodiments, the X component comprises periodic acid and / or a periodate.

[0108] In some embodiments, the polar solvent may be selected from one, two or more of water or alcohols.

[0109] In some embodiments, the polar solvent can be selected from one, two or more of water, ethanol and methanol.

[0110] In some embodiments, the polar solvent may be water.

[0111] In some embodiments, the component A is 1,4-diazabicyclo[2.2.2]octane, at least one of the organic salts containing 1,4-diazabicyclo[2.2.2]octane-1,4-diazonium ion; the component B is hydroxylamine, containing NH3OH + Ionic salt, containing NH3OH + Ionic bases, hydrazine, containing NH3NH2 + Ionic salts, containing NH3NH2 + At least one of ionic bases; the X component is at least one of an acid containing a perchlorate group and a salt containing a perchlorate group; the polar solvent is selected from one, two or more of water, ethanol and methanol.

[0112] In some embodiments, the component A is 1,4-diazabicyclo[2.2.2]octane, at least one of the organic salts containing 1,4-diazabicyclo[2.2.2]octane-1,4-diazonium ion; the component B is hydroxylamine, NH3OH + Ionic salts and NH3OH + At least one of ionic bases; the X component is at least one of an acid containing a perchlorate group and a salt containing a perchlorate group.

[0113] In some embodiments, the A component is 1,4-diazabicyclo[2.2.2]octane, at least one of the organic salts containing 1,4-diazabicyclo[2.2.2]octane-1,4-diazonium ion; the B component is hydrazine, NH3NH2 + Ionic salts and NH3NH2 + At least one of ionic bases; the X component is at least one of an acid containing a perchlorate group and a salt containing a perchlorate group.

[0114] In some embodiments of the present application, an energetic material is provided, including any of the above-mentioned embodiments, a combination of the compounds in any two or more of the above-mentioned embodiments, or a compound prepared by the method for preparing the compound in any of the above-mentioned embodiments, or a compound prepared by the combination of the methods for preparing the compound in any two or more of the above-mentioned embodiments. In some embodiments of the present application, a compound in any of the above-mentioned embodiments, a combination of the compounds in any two or more of the above-mentioned embodiments, or a compound prepared by the method for preparing the compound in any of the above-mentioned embodiments, or a compound prepared by the combination of the methods for preparing the compound in any two or more of the above-mentioned embodiments, is provided, and its use as an energetic material. In some embodiments of the present application, a compound in any of the above-mentioned embodiments, a combination of the compounds in any two or more of the above-mentioned embodiments, or a compound prepared by the method for preparing the compound in any of the above-mentioned embodiments, or a compound prepared by the combination of the methods for preparing the compound in any two or more of the above-mentioned embodiments, is provided, and its use in manufacturing energetic materials is provided.

[0115] In some of the above embodiments, the energetic material is a detonator, a secondary explosive, a propellant or a pyrotechnic composition.

[0116] In some embodiments, the energetic material is a high explosive or a propellant, such as a solid propellant.

[0117] In some embodiments, the energetic material is a metal-free energetic material.

[0118] Compared with the NH4 used in the existing technology + ions, the NH3OH used in this application + and NH2NH3 + Ions have a higher enthalpy of formation and are expected to form more hydrogen bonding interactions in the crystal, which may be beneficial to obtain stronger binding forces to simultaneously increase the enthalpy of formation and crystal density of the compound. + and / or NH2NH3 + Ion replacement NH4 + Ions construct metal-free energetic materials in order to further enhance energetic properties.

[0119] One or more compounds in at least some embodiments of the present application have high theoretical explosion heat and volume energy density, superior detonation performance, good safety performance, high theoretical specific impulse value, and are non-volatile and can be stored for a long time without decomposition; they have single crystallinity at room temperature, the raw materials are cheap and easily available, the production process is simple, and they can be safely prepared in large quantities.

[0120] For example, two compounds (C6H 14 N2)(NH3OH)(ClO4)3(DAP-6) and (C6H 14 N2)(NH3NH2)(ClO4)3(DAP-7),

[0121] (1) Their theoretical explosion heats are as high as 1.52 and 1.43 kcal / g, respectively, and their room temperature densities are as high as 1.90 and 1.87 g / cm 3 The corresponding volume energy densities are as high as 2.89 and 2.67 kcal / cm 3 ;

[0122] (2) According to the Kamlet-Jacob formula, the theoretical detonation velocities are 9.12 and 8.88 km / s respectively; the theoretical detonation pressures are 38.1 and 35.8 GPa respectively;

[0123] (3) Its decomposition peak temperatures can reach 246.1 and 376.1 °C respectively;

[0124] (4) The theoretical specific impulse values ​​are as high as 265.3 and 256.9 s respectively. BRIEF DESCRIPTION OF THE DRAWINGS

[0125] Figure 1 This is the powder X-ray diffraction pattern of the compound DAP-6 of Example 1.

[0126] Figure 2 Schematic diagram of the structure of compound DAP-6 in Example 1.

[0127] Figure 3 This is the differential thermal analysis spectrum of the compound DAP-6 in Example 1.

[0128] Figure 4 This is the powder X-ray diffraction pattern of the compound DAP-7 of Example 2.

[0129] Figure 5 Schematic diagram of the structure of compound DAP-7 of Example 2.

[0130] Figure 6 This is the differential thermal analysis spectrum of the compound DAP-7 of Example 2. DETAILED DESCRIPTION

[0131] The inventors have designed a series of ABX3 chemical formulas, based on NH3OH + and NH2NH3 + Crystalline compounds assembled by cations have been studied for their prospects as energetic materials.

[0132] X in ABX3 is at least one anionic energetic group. Energetic groups refer to explosive groups. Common explosive groups include, but are not limited to, ClO3 - 、ClO4 - IO4 - 、NO3 - 、ONC - , azo group, azide ion, nitro group and other groups.

[0133] In the compound ABX3, for example, for X, one or more ions may be included, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10 ... X ions may exist simultaneously. The same is true for A and B. When the crystalline compound ABX3 includes more than one A cation, different A cations may be distributed on the A site in an ordered or disordered manner. When the crystalline compound ABX3 includes more than one B cation, different B cations may be distributed on the B site in an ordered or disordered manner. When the crystalline compound ABX3 includes more than one X anion, different X anions may be distributed on the X site in an ordered or disordered manner.

[0134] Based on such properties, the phrases "X is at least one ... group / ion", "A is at least one ... group / ion", "B is at least one ... group / ion", "X is selected from ...", "A is selected from ...", "B is selected from ...", etc., described herein should be understood as follows: for example, for X, in the three-dimensional framework of ABX3, there are many X sites, each X site is composed of one ion, and in the three-dimensional framework, multiple X sites can be composed of the same ion or of different ions. When composed of different ions, at least some sites (or most sites) are ... groups / ions. At this time, it is not excluded that in the entire three-dimensional framework of ABX3, there are a few sites that may not be the ... groups / ions or some other impurity ions, as long as the number of these sites does not affect the overall performance to a large extent. The few sites may be, for example, less than 50% by mole, such as no more than 40%, 30%, 25%, 20%, 15%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2% or 1%. The same is true for A and B.

[0135] This application carries out a variety of identification and characterization methods including powder X-ray single crystal structure characterization test, X-ray powder diffraction identification, differential thermal analysis (DTA) test characterization, impact and friction sensitivity test characterization, detonation parameter (detonation heat / detonation pressure / detonation velocity value) calculation, etc.

[0136] The single crystal structure data of the compound DAP-6 in Example 1 and the compound DAP-7 in Example 2 were obtained by Agilent SuperNova single crystal diffractometer (CuK α , ) was measured at 223 K. X-ray powder diffraction data were obtained on an Advance D8 diffractometer (θ-2θ scanning mode, Cu-K α ). The differential thermal analysis data were measured on the DTA 552-EX explosion-proof differential thermal analyzer (DTA) of Edison Instruments, USA. The impact and friction sensitivity were measured on the BFH 10BAM drop weight impact sensitivity meter and the FSKM10 BAM friction sensitivity meter respectively according to the United Nations standards for the transportation of dangerous goods.

[0137] In a preferred embodiment, the compound used as the energetic material is (C6H 14 N2)(NH3OH)(ClO4)3 (Example 1, denoted as DAP-6), which crystallizes in the monoclinic P21 space group at 223K, with unit cell parameters β=119.65(1)°, powder X-ray diffraction (Cu-K α The diffraction angles 2θ of DAP-6 are about 9.81±0.2°, 14.56±0.2°, 19.68±0.2°, 21.56±0.2°, 22.46±0.2°, 27.62±0.2°, 29.36±0.2°, 34.12±0.2°, 37.00±0.2°, and 49.34±0.2°. The test results of differential thermal analyzer show that the peak temperature of thermal decomposition of the compound is 246.1°C. The friction sensitivity characterization results show that DAP-6 is sensitive to friction (FS≤5N), and the impact sensitivity results show that DAP-6 is insensitive to impact (IS=15J). The method for calculating detonation parameters reported in the literature was adopted, and the density functional theory (DFT) and KJ empirical formula were used to obtain the detonation heat, detonation velocity and detonation pressure of the energetic compound, which were 1.52 kcal / g, 9.12 km / s and 38.1 GPa, respectively.

[0138] In another preferred embodiment, the compound used as the energetic material is (C6H 14 N2)(NH3NH2)(ClO4)3 (Example 2, denoted as DAP-7), which crystallizes at 223K in the monoclinic P21 / m space group with unit cell parameters β=117.99(2)°, powder X-ray diffraction (Cu-K α The diffraction angles 2θ of DAP-7 were about 14.52±0.2°, 19.36±0.2°, 19.76±0.2°, 21.98±0.2°, 22.30±0.2°, 22.65±0.2°, 29.78±0.2°, 35.74±0.2°, 37.40±0.2°, and 49.68±0.2°. The test results of differential thermal analyzer showed that the peak temperature of thermal decomposition of the compound was 376.1°C. The friction sensitivity characterization results showed that DAP-7 was sensitive to friction (FS≤5N), and the impact sensitivity characterization results showed that DAP-7 was insensitive to impact (IS=27.5J). The method for calculating detonation parameters reported in the literature was adopted, and the density functional theory (DFT) and KJ empirical formula were used to obtain the detonation heat, detonation velocity and detonation pressure of the energetic compound, which were 1.43 kcal / g, 8.89 km / s and 35.80 GPa, respectively.

[0139] Example 1

[0140] (C6H 14 Synthesis and Testing of N2)(NH3OH)(ClO4)3(DAP-6)

[0141] Synthesis method:

[0142] 1) Add 5.74 g of 70% to 72% perchloric acid solution to 5 mL of water, add 1.32 g of 50% hydroxylamine solution while stirring, and stir at room temperature for 5 minutes;

[0143] 2) Add 2.24 g of 1,4-diazabicyclo[2.2.2]octane to 5 mL of water and dissolve;

[0144] 3) The solutions of step 1) and step 2) were mixed, stirred for 10 min, filtered, the precipitate was washed with n-butanol, and vacuum dried to obtain a solid powder, which was identified as pure phase of DAP-6 by X-ray powder diffraction, with a yield of 80%.

[0145] Powder X-ray diffraction identification spectrum:

[0146] The powder X-ray diffraction pattern at room temperature is shown in Figure 1 .

[0147] Single crystal structure characterization test:

[0148] Detailed crystal determination data are shown in Table 1. Schematic diagram of crystal structure is shown in Figure 2 .like Figure 2 It can be seen that NH3OH at site B + There are six ClO4 at X sites around the ion. -The ions form a flattened octahedron, with adjacent NH3OH + Ions pass through three μ2-ClO4 - The ions are connected to form a one-dimensional chain in the b-axis direction. The organic cation 1,4-diazabicyclo[2.2.2]octane-1,4-diacium ion (H2dabco 2+ ) cations fill the spaces between chains.

[0149] Table 1 Crystal determination data of DAP-6

[0150]

[0151]

[0152] [a] R1=Σ||F o |-|F c || / Σ|F o |; [b] wR2={Σw[(F o ) 2 -(F c ) 2 ] 2 / Σw[(F o ) 2 ] 2} 1 / 2 ;

[0153] Differential thermal analysis (DTA) characterization of DAP-6:

[0154] The DTA curve of DAP-6 is as follows Figure 3 As shown. Figure 3 It can be seen that the decomposition peak temperature of the powdered energetic compound DAP-6 is 246.1°C, and the decomposition peak is sharp, indicating that the decomposition process is very rapid.

[0155] Density functional theory (DFT) was used to obtain the detonation heat, detonation pressure, and detonation velocity of the energetic compound DAP-6:

[0156] The decomposition heat of DAP-6 (decomposition enthalpy ΔH det ) Density functional theory (DFT) calculation (J.Am.Chem.Soc.2012,134,1422) is about 1.52 kcal / g. According to the Kamlet-Jacob formula, the detonation velocity of DAP-6 is about 9.12 km / s and the detonation pressure is about 38.1 GPa.

[0157] Theoretical specific impulse of energetic compound DAP-6 calculated by DFT theory and EXPLO5 software:

[0158] The formation enthalpy of DAP-6 is about -373.7 kJ / mol by density functional theory (DFT) calculation (J.Am.Chem.Soc.2012,134,1422). Substituting the formation enthalpy into EXPLO5 v.6.04.02, the theoretical specific impulse of DAP-6 is calculated to be 265.3 s.

[0159] Oxygen balance parameters and the amount of gas produced per mole of DAP-6:

[0160] The oxygen balance calculated based on the CO2 product, that is, for the molecular formula C a H b N c Cl d O e , the oxygen balance parameter is OB[%] = 1600[e-2a-(bd) / 2] / MW, where MW is the relative molecular mass of the molecule; the oxygen balance parameter of DAP-6 is calculated to be -23.3%. Regarding the judgment of the products of the complete explosion of energetic materials in an oxygen-free environment, according to the literature (J.Am.Chem.Soc.2012,134,1422; J.Phys.Chem.A 2014,118,4575; Chem.Eur.J.2016,22,1141), its decomposition products are ultimately: gaseous substances such as nitrogen, hydrogen halides, water and carbon dioxide, and solid substances such as elemental carbon (if the oxygen atoms are not enough to completely convert all carbon atoms into carbon dioxide). Therefore, 1 mole of DAP-6 can produce 14.75 moles of gaseous substances and 3.25 moles of elemental carbon after complete explosion in an oxygen-free environment. When mixed with sufficient oxidant (such as commonly used NH4ClO4), DAP-6 will completely explode without any solid residue.

[0161] Example 2

[0162] (C6H 14 Synthesis and Testing of N2)(NH3NH2)(ClO4)3(DAP-7)

[0163] Synthesis method:

[0164] 1) Dissolve 2.24 g of 1,4-diazabicyclo[2.2.2]octane in 5 mL of water, add 5.74 g of 70% to 72% perchloric acid solution under stirring, and stir at room temperature for 5 min;

[0165] 2) Add 1.02 g of hydrazine hydrate liquid under stirring, stir for 10 min, filter, wash the precipitate with ethanol, and vacuum dry to obtain a solid powder, which is identified as pure phase of DAP-7 by X-ray powder diffraction, with a yield of 90%.

[0166] Powder X-ray diffraction identification spectrum:

[0167] The powder X-ray diffraction pattern at room temperature is shown in Figure 4 .

[0168] Single crystal structure characterization test:

[0169] Detailed crystal determination data are shown in Table 2. Schematic diagram of crystal structure is shown in Figure 5 .like Figure 5 It can be seen that NH2NH3 at the B site + There are six ClO4 at X sites around the ion. - The ions form a flattened octahedron, with adjacent NH2NH3 + Ions pass through three μ2-ClO4 - The ions are connected to form a one-dimensional chain in the b-axis direction. The organic cation 1,4-diazabicyclo[2.2.2]octane-1,4-diacium ion (H2dabco 2+ ) cations fill the spaces between the inter-chains.

[0170] Table 2 Crystal determination data of DAP-7

[0171]

[0172] [a] R1=Σ||F o |-|F c || / Σ|F o |; [b] wR2={Σw[(F o ) 2 -(F c ) 2 ] 2 / Σw[(F o ) 2 ] 2} 1 / 2 ;

[0173] Differential thermal analysis (DTA) characterization of DAP-7:

[0174] The DTA curve of DAP-7 is as follows Figure 6 As shown. Figure 6 It can be seen that the decomposition peak temperature of the powdered energetic compound DAP-7 is 376.1°C, and the decomposition peak is sharp, indicating that the decomposition process is very rapid.

[0175] Density functional theory (DFT) was used to obtain the detonation heat, detonation pressure and detonation velocity of the energetic compound DAP-7:

[0176] The decomposition heat of DAP-7 (decomposition enthalpy ΔH det) Density functional theory (DFT) calculation (J.Am.Chem.Soc.2012,134,1422) is about 1.43 kcal / g. According to the Kamlet-Jacob formula, the detonation velocity of DAP-7 is about 8.88 km / s and the detonation pressure is about 35.8 GPa.

[0177] Theoretical specific impulse of energetic compound DAP-7 calculated by DFT theory and EXPLO5 software:

[0178] The formation enthalpy of DAP-7 was calculated by density functional theory (DFT) (J.Am.Chem.Soc.2012,134,1422) to be approximately -362.1 kJ / mol. Substituting the formation enthalpy into EXPLO5 v.6.04.02, the theoretical specific impulse of DAP-7 was calculated to be 256.9 s.

[0179] Oxygen balance parameters and the amount of gas produced per mole of DAP-7:

[0180] The oxygen balance calculated based on the CO2 product, that is, for the molecular formula C a H b N c Cl d O e , the oxygen balance parameter is OB[%] = 1600[e-2a-(bd) / 2] / MW, where MW is the relative molecular mass of the molecule; the oxygen balance parameter of DAP-7 is calculated to be -28.7%. Regarding the judgment of the products of the complete explosion of energetic materials in an oxygen-free environment, according to the literature (J.Am.Chem.Soc.2012,134,1422; J.Phys.Chem.A 2014,118,4575; Chem.Eur.J.2016,22,1141), the decomposition products are ultimately: gaseous substances such as nitrogen, hydrogen halides, water and carbon dioxide, and solid substances such as elemental carbon (if the oxygen atoms are not enough to completely convert all carbon atoms into carbon dioxide). Therefore, 1 mole of DAP-7 can produce 15 moles of gaseous substances after a complete explosion in an oxygen-free environment, and 4 moles of elemental carbon remain. When sufficient oxidant (such as commonly used NH4ClO4) is mixed in, DAP-7 will completely explode without any solid residue.

[0181] Comparison of Examples and Comparative Examples

[0182] As shown in Table 3, the performance comparison of the compounds of Examples 1 and 2 and several compounds of the prior art as comparative examples is shown.

[0183] Where: ρ is specific gravity, T d is the decomposition temperature, Q is the explosion heat, D is the explosion velocity, P is the explosion pressure, ΔH fis the enthalpy of formation obtained by inverse calculation according to the Hess law based on the assumed explosion reaction, I sp The specific impulse value is calculated by EXPLO5 v6.04.02 software based on the formation enthalpy obtained by reverse calculation. OB is based on the oxygen balance calculated based on CO2. For the molecular formula C a H b N c Cl d O e , OB[%] = 1600[e-2a-(bd) / 2] / MW, where MW is the relative molecular mass of the molecule.

[0184] In the comparative examples, A, B, and X of various compounds represented by ABX3 are as follows:

[0185] Comparative Example 1: A is 1,4-diazabicyclo[2.2.2]octane-1,4-diamium ion, B is CH3NH3 + , X is ClO4 - ;

[0186] Comparative Example 2: A is 1,4-diazabicyclo[2.2.2]octane-1,4-diamium ion, B is NH4 + , X is ClO4 - ;

[0187] Comparative Example 3: A is 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-diamium ion, B is NH4 + , X is ClO4 - ;

[0188] Comparative Example 4: A is piperazine-1,4-diamium ion, B is NH4 + , X is ClO4 - ;

[0189] Comparative Example 5: A is 1-methylpiperazine-1,4-dicarbylium ion, B is NH4 + , X is ClO4 - ;

[0190] Comparative Example 6: A is 1,4-diazacycloheptane-1,4-diazonium ion, B is NH4 + , X is ClO4 - ;

[0191] Comparative Example 7: A is 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-diamium ion, B is NH4 + , X is ClO4 - ;

[0192] Table 3 Performance comparison of examples and comparative examples

[0193] #imgpt13#

[0194] a) Capillary powder refinement data; b) The crystal data at 293(2)K were reported in the literature; c) 5℃ min -1 The starting decomposition temperature of the DTA test at the heating rate; d) The literature reports the decomposition peak temperature of the DSC test.

[0195] From the above embodiments, we can see that:

[0196] 1) The compounds of Examples 1 and 2 have significantly higher formation enthalpy than the compounds of Comparative Examples 1-7;

[0197] 2) For isomers (for example, Example 2 and Comparative Example 3, both are C6H 19 Cl3N4O 12 ), the embodiment of the present application (Example 2) has better properties such as density, explosion heat, detonation velocity, explosion pressure and specific impulse.

[0198] 3) With B as NH4 + For example, when comparing Example 2 with Comparative Example 2, the density is about 1.87 g / cm 3 ), the embodiments of the present application have better performances such as thermal stability, explosion heat, explosion velocity, explosion pressure and specific impulse.

[0199] 4) and B is CH3NH3 + Compared with the embodiments (such as comparative example 1), embodiments 1 and 2 are superior to comparative example 1 in density, formation enthalpy, oxygen balance and all detonation indicators.

Claims

1. A compound, characterized in that The compound is a compound ABX3 composed of A cation, B cation and X anion, wherein The A cation is selected from 1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion, 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion, 1,4-dihydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion, piperazine-1,4-dialium ion, 1-methylpiperazine-1,4-dialium ion, 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion, and 1,4-diazacycloheptane-1,4-dialium ion; The B cation is NH3NH2 + or NH3OH + ;and The X anion is selected from perchlorate ion and nitrate ion.

2. The compound according to claim 1, characterized in that The compound ABX3 is a perovskite compound.

3. The compound according to claim 1, characterized in that The A cation is a 1,4-diazabicyclo[2.2.2]octane-1,4-dionium ion.

4. The compound according to claim 1, characterized in that The B cation is NH3NH2 + .

5. The compound according to claim 1, characterized in that The B cation is NH3OH + .

6. The compound according to any one of claims 1 to 5, characterized in that The X anion is selected from nitrate ions.

7. The compound according to any one of claims 1 to 5, characterized in that The X anion is selected from perchlorate ions.

8. The method for preparing the compound according to any one of claims 1 to 7, characterized in that: The following steps are involved: Mixing component A, component B and component X in any order in a liquid reaction system; as well as Obtaining a solid product produced in the liquid reaction system; in, The component A is selected from 1,4-diazabicyclo[2.2.2]octane, the reaction product of 1,4-diazabicyclo[2.2.2]octane and hydrogen peroxide, piperazine, 1-methylpiperazine, 1,4-diazacycloheptane, 1,4-diazabicyclo[2.2.2]octane-1,4-dialium salt, 1-hydroxy-1,4-diazabicyclo[2.2.2]octane 1,4-dialium salts of 1,4-dihydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dialium salts, 1,4-piperazine-1,4-dialium salts, 1-methylpiperazine-1,4-dialium salts, 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dialium salts, and 1,4-diazacycloheptane-1,4-dialium salts; The B component is selected from NH3NH2 + or NH3OH + Salts or hydroxides of The X component is selected from perchloric acid, perchlorate, nitric acid, and nitrate; and The liquid reaction system is a polar solvent that can dissolve the A component, the B component and the X component.

9. The method for preparing the compound according to claim 8, characterized in that: The steps may also include further purification.

10. The method for preparing the compound according to claim 8, characterized in that: The component A is selected from 1,4-diazabicyclo[2.2.2]octane and / or 1,4-diazabicyclo[2.2.2]octane-1,4-dionium salt.

11. The method for preparing the compound according to claim 8, characterized in that: The B component is selected from NH3OH + Ionic salt, containing NH3OH + Ionic bases, containing NH3NH2 + Ionic salts, containing NH3NH2 + At least one, two or more of the ionic bases.

12. The method for preparing the compound according to claim 8, characterized in that: The B component is selected from NH3OH + Ionic salts and NH3OH + At least one of the ionic bases.

13. The method for preparing the compound according to claim 8, characterized in that: The B component is selected from NH3NH2 + Ionic salts and NH3NH2 + At least one of the ionic bases.

14. A method for preparing a compound according to any one of claims 8 to 13, characterized in that: The X component is selected from nitric acid and / or nitrates.

15. The method for preparing the compound according to any one of claims 8 to 13, characterized in that: The X component is selected from perchloric acid and / or perchlorate.

16. Use of a compound in the preparation of or as an energetic material, the compound being: A compound according to any one of claims 1 to 7, or A compound prepared by the method for preparing a compound according to any one of claims 8 to 15.

17. The use according to claim 16, characterized in that The energetic material is detonator, secondary explosive, propellant or pyrotechnic powder.

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