A series of ternary crystalline ethylenediammonium compounds and their preparation method and use as energetic materials

Abstract

This application belongs to the field of compounds, and specifically relates to a series of ethylenediamine ternary crystalline compounds, their preparation methods, and their uses as energetic materials. The crystalline compounds of this application include crystalline compounds with the general formula ABX4, and also include crystalline compounds with the general formula B2A′X5, where B can be, for example, a saturated fatty diamine cation, such as an ethylenediamine cation.

Description

Technical Field

[0001] The present invention relates to the field of energetic materials, and in particular to a series of ternary crystalline ethylenediammonium compounds and a preparation method thereof as well as use thereof as energetic materials. Background Art

[0002] Energetic materials are compounds or mixtures that can rapidly undergo redox reactions under external energy stimulation and quickly release large amounts of heat and gas, thereby doing work on the surrounding medium. They are widely used in military (such as weapons and ammunition, propellants, and pyrotechnic flares) and civilian fields (such as fireworks, perforating bullets for oil extraction, civil engineering, and mining blasting), and play an important role in promoting national defense construction and national economic development.

[0003] Newly synthesized energetic materials have increased rapidly in the past few decades, especially in the research of crystalline energetic materials such as organic energetic molecules and their binary salts, all-nitrogen compounds, eutectic compounds, metal complexes and molecular perovskite compounds (Chinese invention patent ZL201610665880.3), which has greatly promoted the development of energetic materials. For energetic materials that use redox reactions as the main mechanism to "rapidly release energy and produce gas", oxygen balance, crystal density and formation enthalpy are some important physical parameters in material design. The oxygen balance parameter reflects the difference between the actual oxygen content in the material and the amount of oxygen required to completely oxidize its carbon and hydrogen. When the oxygen balance is zero, theoretically, its carbon and hydrogen can be fully converted into carbon dioxide and water respectively, that is, complete combustion is achieved to release energy to the maximum extent possible. The density of energetic materials directly affects the detonation velocity and detonation pressure. The higher the density, the higher the theoretical detonation velocity and detonation pressure. However, oxygen balance and crystal density are often interrelated and difficult to improve at the same time, thereby comprehensively improving detonation parameters; in addition, although the increase in formation enthalpy is conducive to improving the energy level of energetic materials, it often leads to lower thermal stability. Therefore, how to reasonably select components based on the principles of crystal engineering to simultaneously optimize the oxygen balance and crystal density of energetic compounds, while taking into account both energy levels and thermal stability, is an important challenge in the design and synthesis of new energetic compounds.

[0004] Ethylenediammonium cation (H2EA 2+) is a divalent positive cation that can exist stably and has a small molecular weight. Therefore, it can form a stable salt with twice the equivalent of a monovalent negative oxidizing anion, which is conducive to obtaining an oxygen balance parameter that is closer to zero. For example, early ethylenediammonium dinitrate and ethylenediammonium diperchlorate all have better detonation performance than TNT. However, both have serious hygroscopicity and have not been further applied (Chemistry and Technology of Explosives (Volume II), (Poland) Urbanski, translated by Niu Bingyi and Chen Shaoliang; National Defense Industry Press, 1976, pages 344 and 356). In 2008, Zhu Shunguan and others from Nanjing University of Science and Technology co-crystallized ethylenediammonium diperchlorate and triethylenediammonium diperchlorate to obtain an energetic compound (C6H 14 N2)(H2EA)(ClO4)4 (named SY, Chinese invention patent ZL200810025381.3), they found that SY has less hygroscopicity and better thermal stability than pure diammonium perchlorate, and shows good performance in detonating explosives. However, the crystallographic density of SY (reported value is 1.834g / cm 3 , the actual value should be 1.867g / cm 3 ) does not reach 1.9g / cm 3 , and its oxygen balance (-27.8%) is also lower than the corresponding values ​​of the currently commonly used RDX and HMX (-21.6%). Considering that the chemical bonds of ethylenediammonium cations are all single bonds, they have a more significant "flexible" structure and contain abundant hydrogen bond donors. Therefore, how to utilize its hydrogen bonding ability and the Coulomb force between anions and cations, based on the principles of crystal engineering, to self-assemble it with suitable anions and cations into a multi-element crystal structure with higher density and / or better oxygen balance parameters, and obtain multi-element energetic crystalline compounds with improved energetic properties, is a challenging topic of great significance. Summary of the invention

[0005] The present application provides crystalline compounds assembled based on ethylenediammonium cations, and their use as energetic materials. It is found that they have excellent energetic properties and practicality when used as energetic materials.

[0006] In some embodiments, the present application provides a compound.

[0007] In some embodiments, the compound is a crystalline compound.

[0008] In some embodiments, the compound has a general formula of ABX4, which consists of an A cation, a B cation and an X anion.

[0009] In some embodiments, the compound has a general formula of B2A′X5, which consists of an A′ cation, a B cation, and an X anion.

[0010] In some embodiments, the A cation is at least one divalent nitrogen-containing heterocyclic cation.

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

[0012] 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.

[0013] In some embodiments, the A cation may be one, two or more selected from the ions of formula (I), and their derivatives, wherein n1 and n2 may each be a positive integer preferably 1, 2, 3, 4 or 5, or preferably 1, 2 or 3, more preferably 2, R1 and R2 may be selected from 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. A derivative refers to a hydrogen atom in the organic cation body that is replaced by a substituent 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.

[0014]

[0015] In some embodiments, the A cation is selected from the ion of formula (I) or a derivative thereof, wherein any one of n1 and n2 is greater than 2, or any one of R1 and R2 includes at least one carbon atom.

[0016] In some embodiments, the A cation is selected from the ion of formula (I) or its derivatives, wherein n1 and n2 are both 2, and 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 (I) or its derivatives, wherein n1 and n2 are 2 and 3 respectively.

[0017] 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. In some embodiments, the A cation is selected from the ion of formula (I) or its derivatives, wherein n1 and n2 are both 2, and any one of R1 and R2 includes a methyl group.

[0018] In some embodiments, the A cation is selected from one, two or more of piperazine-1,4-dionium ion (Formula (II), piperazine-1,4-diium), 1-methylpiperazine-1,4-dionium ion (Formula (III), 1-methylpiperazine-1,4-diium), 1,4-diazepane-1,4-dionium ion (Formula (IV), 1,4-diazepane-1,4-diium), and their derivatives.

[0019]

[0020] 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 and derivatives thereof. In some embodiments, the A cation is selected from one, two or more of piperazine-1,4-dionium ion, 1,4-diazacycloheptane-1,4-dionium ion and derivatives thereof. In some embodiments, the A cation is selected from one, two or more of 1-methylpiperazine-1,4-dionium ion, 1,4-diazacycloheptane-1,4-dionium ion and derivatives thereof.

[0021] 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 1,4-diazacycloheptane-1,4-dionium ions and their derivatives.

[0022] 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 and 1,4-diazacycloheptane-1,4-dionium ion. In some embodiments, the A cation is piperazine-1,4-dionium ion and / or 1-methylpiperazine-1,4-dionium ion. In some embodiments, the A cation is piperazine-1,4-dionium ion and / or 1,4-diazacycloheptane-1,4-dionium ion. In some embodiments, the A cation is 1-methylpiperazine-1,4-dionium ion and / or 1,4-diazacycloheptane-1,4-dionium ion. In some embodiments, the A cation is piperazine-1,4-dionium ion. In some embodiments, the A cation is 1-methylpiperazine-1,4-dionium ion. In some embodiments, the A cation is 1-methylpiperazine-1,4-dionium ion. In some embodiments, the A cation is a 1,4-diazepane-1,4-dionium ion.

[0023] In some embodiments, the A' cation is at least one monovalent cation.

[0024] In some embodiments, the A' cation is an alkali metal ion or a monovalent nitrogen-containing cation.

[0025] In some embodiments, the A' cation is an alkali metal ion or an ammonium ion.

[0026] In some embodiments, the A' cation is a monovalent nitrogen-containing cation. In some embodiments, the A' cation has the general formula NR3R4R5R6 + , wherein R3, R4, R5, and R6 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.

[0027] In some embodiments, the A' cation is an ammonium ion. In some embodiments, the A' cation is a sodium ion. In some embodiments, the A' cation is a potassium ion. In some embodiments, the A' cation is a rubidium ion. In some embodiments, the A' cation is a cesium ion.

[0028] In some embodiments, the B cation is a fatty diammonium cation. In some embodiments, the B cation is a saturated fatty diammonium cation. In some embodiments, the B cation is an alkyl diammonium cation. In some embodiments, the B cation is a linear alkyl diammonium cation. In some embodiments, the general formula of the B cation is wherein n3 is preferably a positive integer of 1, 2, 3, 4 or 5, more preferably 1, 2 or 3, more preferably 2, R7, R8, R9, R 10 , R 11 , R 12 It can be selected from one, two or more of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl. In some embodiments, in the B cation, R7, R8, R9, R 10 , R 11 , R 12 One, two, three, four, five or all of the B cations are hydrogen. In some embodiments, in the B cations, n3 is 1. In some embodiments, in the B cations, n3 is 2. In some embodiments, in the B cations, n3 is 3.

[0029] In some embodiments, the B cation comprises an ethylenediammonium cation. In some embodiments, the B cation is an ethylenediammonium cation.

[0030] In some embodiments, the general formula of the compound is ABX4, the A cation is selected from one, two or more of piperazine-1,4-dionium ion, 1-methylpiperazine-1,4-dionium ion, 1,4-diazacycloheptane-1,4-dionium ion, and their derivatives, and the B cation is an ethylenediammonium cation. 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 and 1,4-diazacycloheptane-1,4-dionium ion, and the B cation is an ethylenediammonium cation. In some embodiments, the A cation is piperazine-1,4-dionium ion and / or 1-methylpiperazine-1,4-dionium ion, and the B cation is an ethylenediammonium cation. In some embodiments, the A cation is a piperazine-1,4-diamium ion and / or a 1,4-diazacycloheptane-1,4-diamium ion, and the B cation is an ethylenediammonium cation. In some embodiments, the A cation is a 1-methylpiperazine-1,4-diamium ion and / or a 1,4-diazacycloheptane-1,4-diamium ion, and the B cation is an ethylenediammonium cation. In some embodiments, the A cation is a piperazine-1,4-diamium ion, and the B cation is an ethylenediammonium cation. In some embodiments, the A cation is a 1-methylpiperazine-1,4-diamium ion, and the B cation is an ethylenediammonium cation. In some embodiments, the A cation is a 1,4-diazacycloheptane-1,4-diamium ion, and the B cation is an ethylenediammonium cation.

[0031] In some embodiments, the compound has a general formula of B2A′X5, the A′ cation is an ammonium ion, and the B cation is an ethylenediammonium cation.

[0032] In some embodiments, the X anion is an anionic energetic group.

[0033] In some embodiments, the X anion is a monovalent anion.

[0034] 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.

[0035] 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.

[0036] In some embodiments, the X anion is a halogen-containing monovalent anion.

[0037] In some embodiments, the X anion is a monovalent oxoacid anion containing a halogen.

[0038] In some embodiments, the X anion is a halide ion or a perhalide ion.

[0039] In some embodiments, the X anion is a perhalate ion or a nitrate ion.

[0040] In some embodiments, the X anion is a perhalate ion.

[0041] 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.

[0042] 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 perchlorate ion and / or perbromate ion. In some embodiments, the X anion is perchlorate ion and / or periodate ion. In some embodiments, the X anion is perbromate ion and / or periodate ion.

[0043] In some embodiments, the X anion is a perchlorate ion. In some embodiments, the X anion is a perbromate ion. In some embodiments, the X anion is a periodate ion.

[0044] In some embodiments, the general formula of the compound is ABX4, the A cation is selected from one, two or more of piperazine-1,4-dionium ion, 1-methylpiperazine-1,4-dionium ion, 1,4-diazacycloheptane-1,4-dionium ion, and their derivatives, the B cation is an ethylenediammonium cation, and the X anion is a perchlorate ion. 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, and 1,4-diazacycloheptane-1,4-dionium ion, the B cation is an ethylenediammonium cation, and the X anion is a perchlorate ion. In some embodiments, the A cation is piperazine-1,4-dionium ion and / or 1-methylpiperazine-1,4-dionium ion, the B cation is an ethylenediammonium cation, and the X anion is a perchlorate ion. In some embodiments, the A cation is a piperazine-1,4-diamium ion and / or a 1,4-diazacycloheptane-1,4-diamium ion, the B cation is an ethylenediammonium cation, and the X anion is a perchlorate ion. In some embodiments, the A cation is a 1-methylpiperazine-1,4-diamium ion and / or a 1,4-diazacycloheptane-1,4-diamium ion, the B cation is an ethylenediammonium cation, and the X anion is a perchlorate ion. In some embodiments, the A cation is a piperazine-1,4-diamium ion, the B cation is an ethylenediammonium cation, and the X anion is a perchlorate ion. In some embodiments, the A cation is a 1-methylpiperazine-1,4-diamium ion, the B cation is an ethylenediammonium cation, and the X anion is a perchlorate ion. In some embodiments, the A cation is a 1,4-diazepane-1,4-diamium ion, the B cation is an ethylenediammonium cation, and the X anion is a perchlorate ion.

[0045] In some embodiments, the compound has a general formula of B2A′X5, the A′ cation is an ammonium ion, the B cation is an ethylenediammonium cation, and the X anion is a perchlorate ion.

[0046] In at least some embodiments of the present application, the compound of the present application can be obtained by adding the corresponding component forming A cation (A component) or the component forming A' cation (A' component), the component forming B cation (B component) and the component forming X anion (X component) to a liquid reaction system in any order, and reacting; the liquid reaction system is preferably a polar solvent that can dissolve component A or component A', component B and component X. Or it 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.

[0047] In some embodiments, the preparation method of the compound of the present application may include the following steps:

[0048] 1) mixing component A or component A', component B and component X in any order in a liquid reaction system; and

[0049] 2) obtaining a solid product produced in the liquid reaction system; and preferably further purifying the solid product.

[0050] The liquid reaction system is preferably a polar solvent that can dissolve component A or 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.

[0051] In some embodiments, component A or 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 perform purification.

[0052] In some embodiments, the preparation method of the compound of the present application may include the following steps:

[0053] 1) synthesizing the A component or A' component solution, i.e., a solution containing the A cation or A' cation in the compound to be synthesized;

[0054] 2) mixing the A component or A' component solution, the B component and the X component in any order in a liquid reaction system; and

[0055] 3) obtaining and purifying the solid product produced in the liquid reaction system.

[0056] 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 the compound of the present application may include the following steps:

[0057] 1) dissolving component A or component A', and component B separately or together in a polar solvent to obtain a solution of component A or component A', and a solution of component B;

[0058] 2) mixing the A component or A' component solution, the B component solution and the X component in any order; and

[0059] 3) obtaining and purifying the solid product produced in the liquid reaction system.

[0060] In some embodiments, the preparation method of the compound of the present application may include the following steps:

[0061] 1) Add component A or component A' into a polar solvent, then add component X, and stir evenly to obtain a solution of component A or A' and component X;

[0062] 2) dissolving component B in a polar solvent to obtain a component B solution; and

[0063] 3) The A or 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.

[0064] In some embodiments, the A component, A' component and / or B component are salts of the A cation, A' cation and / or B cation in the compound to be synthesized, or solutions containing the A cation, A' cation and / or B cation in the compound to be synthesized; or the A component, A' component and / or B component are deprotonated products of the A cation, A' cation and / or B cation, that is, the products of the A component, A' component and / or B component after protonation are the A cation, A' cation and / or B cation, respectively.

[0065] In some embodiments, the A component is selected from a divalent nitrogen-containing monocyclic heterocycle or its salts including its onium salts. 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 their salts including their onium salts.

[0066] In some embodiments, the A component is selected from one, two or more of the compounds of formula (V), salts of organic cations of formula (I) including onium salts thereof, and their derivatives, wherein n1 and n2 are each preferably 1, 2, 3, 4 or 5, or preferably 1, 2 or 3, more preferably a positive integer of 2, R1 and R2 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.

[0067]

[0068] In some embodiments, the A component is selected from the salts of compounds of formula (V) or ions of formula (I) including onium salts or derivatives thereof, wherein either n1 and n2 is greater than 2, or either R1 and R2 includes at least one carbon atom.

[0069] In some embodiments, the A component is selected from the salts of the compounds of formula (V) or the ions of formula (I), including onium salts thereof or derivatives thereof, wherein n1 and n2 are both 2, and any one of R1 and R2 includes at least one carbon atom. In some embodiments, the A component is selected from the salts of the compounds of formula (V) or the ions of formula (I), including onium salts thereof or derivatives thereof, wherein n1 and n2 are 2 and 3, respectively.

[0070] In some embodiments, the A component is selected from the salts of the compounds of formula (V) or the ions of formula (I), including onium salts thereof or derivatives thereof, and any one of R1 and R2 is selected from methyl. In some embodiments, the A component is selected from the salts of the compounds of formula (V) or the ions of formula (I), including onium salts thereof or derivatives thereof, wherein n1 and n2 are both 2, and any one of R1 and R2 includes methyl.

[0071] In some embodiments, the A component is selected from one, two or more of piperazine, piperazine-1,4-dionium salts, 1-methylpiperazine, 1-methylpiperazine-1,4-dionium salts, 1,4-diazacycloheptane (homopiperazine), 1,4-diazacycloheptane-1,4-dionium salts, and their derivatives.

[0072] In some embodiments, the A component is selected from one, two or more of piperazine, piperazine-1,4-dialium salts, 1-methylpiperazine, 1-methylpiperazine-1,4-dialium salts and their derivatives. In some embodiments, the A component is selected from one, two or more of piperazine, piperazine-1,4-dialium salts, 1,4-diazacycloheptane, 1,4-diazacycloheptane-1,4-dialium salts and their derivatives. In some embodiments, the A component is selected from one, two or more of 1-methylpiperazine, 1-methylpiperazine-1,4-dialium salts, 1,4-diazacycloheptane, 1,4-diazacycloheptane-1,4-dialium salts and their derivatives.

[0073] In some embodiments, the A component is selected from one, two or more of piperazine, piperazine-1,4-dionium salts and their derivatives. In some embodiments, the A component is selected from one, two or more of 1-methylpiperazine, 1-methylpiperazine-1,4-dionium salts and their derivatives. In some embodiments, the A component is selected from one, two or more of 1,4-diazacycloheptane, 1,4-diazacycloheptane-1,4-dionium salts and their derivatives.

[0074] In some embodiments, the A component is selected from one, two or more of piperazine, piperazine-1,4-dialium salts, 1-methylpiperazine, 1-methylpiperazine-1,4-dialium salts, 1,4-diazacycloheptane and 1,4-diazacycloheptane-1,4-dialium salts. In some embodiments, the A component is selected from one, two or more of piperazine, piperazine-1,4-dialium salts, 1-methylpiperazine, 1-methylpiperazine-1,4-dialium salts. In some embodiments, the A component is selected from one, two or more of piperazine, piperazine-1,4-dialium salts, 1,4-diazacycloheptane and 1,4-diazacycloheptane-1,4-dialium salts. In some embodiments, the A component is selected from one, two or more of 1-methylpiperazine, 1-methylpiperazine-1,4-diamidium salts, 1,4-diazacycloheptane and 1,4-diazacycloheptane-1,4-diamidium salts. In some embodiments, the A component is piperazine and / or piperazine-1,4-diamidium salts. In some embodiments, the A component is 1-methylpiperazine and / or 1-methylpiperazine-1,4-diamidium salts. In some embodiments, the A component is 1,4-diazacycloheptane and / or 1,4-diazacycloheptane-1,4-diamidium salts.

[0075] In some embodiments, the A' component is a salt or hydroxide of at least one monovalent cation.

[0076] In some embodiments, the A' component is an alkali metal salt or hydroxide, or a monovalent nitrogen-containing cation salt, or a monovalent nitrogen-containing base.

[0077] In some embodiments, the A' component is an alkali metal salt or hydroxide, an ammonium salt, or ammonia.

[0078] In some embodiments, the A' component is a monovalent nitrogen-containing cationic salt or a monovalent nitrogen-containing base. In some embodiments, the A' component is a compound of the general formula NR3R4R5R6 + The invention relates to a salt, alkali or hydroxide of a cation, wherein R3, R4, R5 and R6 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; or it is a compound of the general formula NR3R4R5.

[0079] In some embodiments, the A' component is an ammonium salt or ammonia. In some embodiments, the A' component is a sodium salt or sodium hydroxide. In some embodiments, the A' component is a potassium salt or potassium hydroxide. In some embodiments, the A' component is a rubidium salt or rubidium hydroxide. In some embodiments, the A' component is a cesium salt or cesium hydroxide.

[0080] In some embodiments, the B component is a fatty diamine or a fatty diammonium salt. In some embodiments, the B component is a saturated fatty diamine or a saturated fatty diammonium salt. In some embodiments, the B component is an alkyl diamine or an alkyl diammonium salt. In some embodiments, the B component is a linear alkyl diammonium or a linear alkyl diamine salt. In some embodiments, the B component is a general formula ionic salts or hydroxides, wherein n3 is preferably 1, 2, 3, 4 or 5, more preferably 1, 2 or 3, more preferably 2, R7, R8, R9, R 10 , R 11 , R 12 It can be selected from one, two or more of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl. In some embodiments, the B component is of the general formula wherein n3 is preferably 1, 2, 3, 4 or 5, more preferably 1, 2 or 3, more preferably 2, and R7, R8, R9, R 10 , R 11 , R 12 It can be selected from one, two or more of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl. In some embodiments, in the B component, R7, R8, R9, R 10 , R 11 , R 12 One, two, three, four, five or all of the B components are hydrogen. In some embodiments, in the B component, n3 is 1. In some embodiments, in the B component, n3 is 2. In some embodiments, in the B component, n3 is 3.

[0081] In some embodiments, the B component comprises ethylenediamine and / or ethylenediammonium salt. In some embodiments, the B component comprises ethylenediamine. In some embodiments, the B component comprises ethylenediammonium salt. In some embodiments, the B component is ethylenediamine.

[0082] In some embodiments, the component A is selected from one, two or more of piperazine, piperazine-1,4-diamidium salts, 1-methylpiperazine, 1-methylpiperazine-1,4-diamidium salts and their derivatives, and the component B includes ethylenediamine and / or ethylenediamidium salts. In some embodiments, the component A is selected from one, two or more of piperazine, piperazine-1,4-diamidium salts, 1,4-diazacycloheptane, 1,4-diazacycloheptane-1,4-diamidium salts and their derivatives, and the component B includes ethylenediamine and / or ethylenediamidium salts. In some embodiments, the component A is selected from one, two or more of 1-methylpiperazine, 1-methylpiperazine-1,4-diamidium salts, 1,4-diazacycloheptane, 1,4-diazacycloheptane-1,4-diamidium salts and their derivatives, and the component B includes ethylenediamine and / or ethylenediamidium salts.

[0083] In some embodiments, the component A is selected from one, two or more of piperazine, piperazine-1,4-diamium salts and their derivatives, and the component B includes ethylenediamine and / or ethylenediammonium salts. In some embodiments, the component A is selected from one, two or more of 1-methylpiperazine, 1-methylpiperazine-1,4-diamium salts and their derivatives, and the component B includes ethylenediamine and / or ethylenediammonium salts. In some embodiments, the component A is selected from one, two or more of 1,4-diazacycloheptane, 1,4-diazacycloheptane-1,4-diamium salts and their derivatives, and the component B includes ethylenediamine and / or ethylenediammonium salts.

[0084] In some embodiments, the component A is selected from one, two or more of piperazine, piperazine-1,4-diamidium salts, 1-methylpiperazine, 1-methylpiperazine-1,4-diamidium salts, 1,4-diazacycloheptane and 1,4-diazacycloheptane-1,4-diamidium salts, and the component B includes ethylenediamine and / or ethylenediamidium salts. In some embodiments, the component A is selected from one, two or more of piperazine, piperazine-1,4-diamidium salts, 1-methylpiperazine, 1-methylpiperazine-1,4-diamidium salts, and the component B includes ethylenediamine and / or ethylenediamidium salts. In some embodiments, the component A is selected from one, two or more of piperazine, piperazine-1,4-diamidium salts, 1,4-diazacycloheptane and 1,4-diazacycloheptane-1,4-diamidium salts, and the component B includes ethylenediamine and / or ethylenediamidium salts. In some embodiments, the component A is selected from one, two or more of 1-methylpiperazine, 1-methylpiperazine-1,4-diamidium salts, 1,4-diazacycloheptane and 1,4-diazacycloheptane-1,4-diamidium salts, and the component B includes ethylenediamine and / or ethylenediammonium salts. In some embodiments, the component A includes piperazine and / or piperazine-1,4-diamidium salts, and the component B includes ethylenediamine and / or ethylenediammonium salts. In some embodiments, the component A includes 1-methylpiperazine and / or 1-methylpiperazine-1,4-diamidium salts, and the component B includes ethylenediamine and / or ethylenediammonium salts. In some embodiments, the component A includes 1,4-diazacycloheptane and / or 1,4-diazacycloheptane-1,4-diamidium salts, and the component B includes ethylenediamine and / or ethylenediammonium salts.

[0085] 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.

[0086] In some embodiments, the X component is selected from acids or salts including anionic energetic groups.

[0087] In some embodiments, the X component is selected from acids or salts comprising a monovalent anion.

[0088] 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.

[0089] 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.

[0090] In some embodiments, the X component includes a halogen-containing acid or salt.

[0091] In some embodiments, the X component comprises a halogen-containing oxygen acid or salt thereof, nitric acid or nitrate.

[0092] In some embodiments, the X component comprises a halogen-containing oxygen-containing acid or a salt thereof.

[0093] 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.

[0094] 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.

[0095] 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.

[0096] In some embodiments, the component A is selected from one, two or more of piperazine, piperazine-1,4-diamium salts, 1-methylpiperazine, 1-methylpiperazine-1,4-diamium salts and their derivatives, the component B includes ethylenediamine and / or ethylenediammonium salts, and the component X includes perchloric acid and / or perchlorate. In some embodiments, the component A is selected from one, two or more of piperazine, piperazine-1,4-diamium salts, 1,4-diazacycloheptane, 1,4-diazacycloheptane-1,4-diamium salts and their derivatives, the component B includes ethylenediamine and / or ethylenediammonium salts, and the component X includes perchloric acid and / or perchlorate. In some embodiments, the component A is selected from one, two or more of 1-methylpiperazine, 1-methylpiperazine-1,4-diacium salts, 1,4-diazacycloheptane, 1,4-diazacycloheptane-1,4-diacium salts and derivatives thereof, the component B comprises ethylenediamine and / or ethylenediammonium salt, and the component X comprises perchloric acid and / or perchlorate.

[0097] In some embodiments, the A component is selected from one, two or more of piperazine, piperazine-1,4-diamium salts and their derivatives, the B component includes ethylenediamine and / or ethylenediammonium salts, and the X component includes perchloric acid and / or perchlorate. In some embodiments, the A component is selected from one, two or more of 1-methylpiperazine, 1-methylpiperazine-1,4-diamium salts and their derivatives, the B component includes ethylenediamine and / or ethylenediammonium salts, and the X component includes perchloric acid and / or perchlorate. In some embodiments, the A component is selected from one, two or more of 1,4-diazacycloheptane, 1,4-diazacycloheptane-1,4-diamium salts and their derivatives, the B component includes ethylenediamine and / or ethylenediammonium salts, and the X component includes perchloric acid and / or perchlorate.

[0098] In some embodiments, the A component is selected from one, two or more of piperazine, piperazine-1,4-diamidium salts, 1-methylpiperazine, 1-methylpiperazine-1,4-diamidium salts, 1,4-diazacycloheptane and 1,4-diazacycloheptane-1,4-diamidium salts, the B component includes ethylenediamine and / or ethylenediammonium salts, and the X component includes perchloric acid and / or perchlorate. In some embodiments, the A component is selected from one, two or more of piperazine, piperazine-1,4-diamidium salts, 1-methylpiperazine, 1-methylpiperazine-1,4-diamidium salts, the B component includes ethylenediamine and / or ethylenediammonium salts, and the X component includes perchloric acid and / or perchlorate. In some embodiments, the A component is selected from one, two or more of piperazine, piperazine-1,4-diamidium salts, 1,4-diazacycloheptane and 1,4-diazacycloheptane-1,4-diamidium salts, the B component includes ethylenediamine and / or ethylenediammonium salts, and the X component includes perchloric acid and / or perchlorate. In some embodiments, the A component is selected from one, two or more of 1-methylpiperazine, 1-methylpiperazine-1,4-diamidium salts, 1,4-diazacycloheptane and 1,4-diazacycloheptane-1,4-diamidium salts, the B component includes ethylenediamine and / or ethylenediammonium salts, and the X component includes perchloric acid and / or perchlorate. In some embodiments, the A component includes piperazine and / or piperazine-1,4-diamidium salts, the B component includes ethylenediamine and / or ethylenediammonium salts, and the X component includes perchloric acid and / or perchlorate. In some embodiments, the A component includes 1-methylpiperazine and / or 1-methylpiperazine-1,4-diamium salts, the B component includes ethylenediamine and / or ethylenediammonium salts, and the X component includes perchloric acid and / or perchlorate. In some embodiments, the A component includes 1,4-diazacycloheptane and / or 1,4-diazacycloheptane-1,4-diamium salts, the B component includes ethylenediamine and / or ethylenediammonium salts, and the X component includes perchloric acid and / or perchlorate.

[0099] In some embodiments of the present application, the A component is selected from any one, two or more of the above-mentioned A components, the B component is selected from any one, two or more of the above-mentioned B components, and / or the X component is selected from any one, two or more of the above-mentioned X components.

[0100] In some embodiments, the A component is selected from salts including the A cation in the compound to be synthesized, the B component is selected from salts or hydroxides including the B cation in the compound to be synthesized, and the X component is selected from acids or salts including the X anion in the compound to be synthesized.

[0101] In some embodiments, the polar solvent may be selected from one, two or more of water or alcohols.

[0102] In some embodiments, the polar solvent can be selected from one, two or more of water, ethanol and methanol.

[0103] In some embodiments, the polar solvent may be water.

[0104] 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.

[0105] In some of the above embodiments, the energetic material is a detonator, a secondary explosive, a propellant or a pyrotechnic composition.

[0106] In some embodiments, the energetic material is a high explosive or a propellant, such as a solid propellant.

[0107] In some embodiments, the energetic material is a metal-free energetic material.

[0108] One or more compounds in at least some embodiments of the present application have high theoretical explosion heat and volume energy density, high oxygen balance, high crystallographic density value, excellent detonation performance, are sensitive to friction but insensitive to impact, have good safety performance, low hygroscopicity and good thermal stability, and can be stored for a long time without decomposition; the room temperature crystallinity is single, the raw materials are cheap and easy to obtain, the production process is simple, and it can be safely prepared in large quantities.

[0109] For example, the compounds of the examples of the present application,

[0110] (1) Its theoretical explosion heat can reach up to 1.40 kcal / g, and the room temperature crystal density can reach up to 1.91 g / cm 3 , the oxygen balance parameter value can reach up to 6.25%;

[0111] (2) According to the Kamlet-Jacob formula, its theoretical detonation velocity is up to 9.09 km / s; its theoretical detonation pressure is up to 37.6 GPa;

[0112] (3) Its decomposition peak temperature is as high as 376.0°C;

[0113] (4) Its specific impulse value is up to 264.2s;

[0114] (5) It is sensitive to friction but insensitive to impact. The friction sensitivity (FS) is between 9N and 36N, and the impact sensitivity (IS) is between 9J and 20J. BRIEF DESCRIPTION OF THE DRAWINGS

[0115] Figure 1 Schematic diagram of the structure of the energetic compound EAP of Example 1.

[0116] Figure 2 Schematic diagram of the structure of the energetic compound PEP of Example 2. Wherein (a) shows each H2EA 2+ There are 10 ClO4 around - The ions form an irregular dodecahedron; (b) shows the adjacent H2EA 2+ Ions pass through 4 μ4-ClO4 - ions and 6 μ2-ClO4 - The ions are connected to form a layered structure in the b-axis and c-axis directions; (c) shows that piperazine cations and perchlorate anions are arranged alternately between two adjacent layers.

[0117] Figure 3 This is the powder X-ray diffraction pattern of the energetic compound EAP of Example 1.

[0118] Figure 4 This is the differential thermal analysis spectrum of the energetic compound EAP of Example 1.

[0119] Figure 5 This is the powder X-ray diffraction pattern of the energetic compound PEP of Example 2.

[0120] Figure 6 This is the differential thermal analysis spectrum of the energetic compound PEP of Example 2.

[0121] Figure 7 This is the powder X-ray diffraction pattern of the energetic compound MPEP of Example 3.

[0122] Figure 8 This is the differential thermal analysis spectrum of the energetic compound MPEP of Example 3.

[0123] Fig. 9 This is the powder X-ray diffraction pattern of the energetic compound HPEP of Example 4.

[0124] Fig.10This is the differential thermal analysis spectrum of the energetic compound HPEP of Example 4. DETAILED DESCRIPTION

[0125] The inventors have designed a series of explosive ternary ethylenediammonium crystal energetic compounds, and conducted relevant research on their prospects for use as single-substance crystal explosives in the field of energetic materials.

[0126] In some embodiments, these energetic compounds can be represented by the general formula ABX4. In some embodiments, these energetic compounds can be represented by the general formula B2A′X5. Wherein, X in ABX4 or B2A′X5 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, etc. A and B in ABX4 or B2A′X5 are cations at different sites in the crystalline structure.

[0127] In the compound ABX4 or B2A′X5, for example, X may contain one or more than one ion, 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 ABX4 or B2A′X5 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 ABX4 or B2A′X5 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 ABX4 or B2A′X5 includes more than one X anion, different X anions may be distributed on the X site in an ordered or disordered manner.

[0128] 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, for example, for X, in the three-dimensional framework of ABX4 or B2A'X5, there are many X sites, each X site is composed of one ion, and in the three-dimensional framework, multiple X sites may 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 ABX4 or B2A'X5, 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 minority 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.

[0129] The present invention 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.

[0130] The single crystal structural data of EAP, PEP, MPEP and HPEP were obtained by Rigaku XtaLAB P300DS single crystal diffractometer (Cu-K α , ) at room temperature. 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.

[0131] In a preferred embodiment, the compound used as the energetic material is (H2EA)2(NH4)(ClO4)5 (denoted as EAP), which crystallizes in the I41 / a space group of the tetragonal system at 298K, with a unit cell parameter of α=β=γ=90°, powder X-ray diffraction (Cu-K αThe diffraction angles (2θ) of EAP are about 9.29±0.2°, 14.73±0.2°, 16.30±0.2°, 18.86±0.2°, 21.78±0.2°, 23.25±0.2°, 24.77±0.2°, 25.10±0.2°, 32.11±0.2°, 38.16±0.2°, and 48.28±0.2°. The results of differential thermal analysis show that EAP has two decomposition exothermic peaks, and the peak temperatures are 304.2℃ and 376.0℃ respectively. The friction sensitivity characterization results show that EAP is sensitive to friction (FS=36N), and the impact sensitivity results show that EAP is insensitive to impact (IS=12J). The detonation parameters were calculated by using the method reported in the literature, density functional theory (DFT) and Kamlet-Jacob empirical formula, and the detonation heat, detonation velocity and detonation pressure of the energetic compound were obtained to be 5.07 kJ / g, 8.97 km / s and 37.0 GPa respectively.

[0132] In another preferred embodiment, the compound used as the energetic material is (C4H 12 N2)(H2EA)(ClO4)4 (denoted as PEP), the compound crystallizes in the Pbca space group of the orthorhombic system at 298K, with unit cell parameters α=β=γ=90°, powder X-ray diffraction (Cu-K α The diffraction angle 2θ of the compound (2θ) is about 11.31±0.2°, 11.84±0.2°, 14.78±0.2°, 15.82±0.2°, 18.70±0.2°, 20.56±0.2°, 21.72±0.2°, 22.90±0.2°, 23.44±0.2°, 25.44±0.2°, 26.95±0.2°, 28.76±0.2°, 34.75±0.2°, 41.46±0.2°, 49.69±0.2°. The results of differential thermal analysis show that the peak temperature of thermal decomposition of the compound is 311.6°C. The results of friction sensitivity characterization show that PEP is sensitive to friction (FS=12N), and the results of impact sensitivity characterization show that PEP is insensitive to impact (IS=9J). The detonation parameters were calculated by using the method reported in the literature, density functional theory (DFT) and Kamlet-Jacob empirical formula, and the detonation heat, detonation velocity and detonation pressure of the energetic compound were obtained to be 6.10 kJ / g, 9.09 km / s and 37.6 GPa respectively.

[0133] In another preferred embodiment, the compound used as the energetic material is (C5H 14 N2)(H2EA)(ClO4)4 (denoted as MPEP), the compound crystallizes at 298K in the monoclinic P21 / c space group, with unit cell parameters α=γ=90°,β=99.987(4)°,Powder X-ray diffraction (Cu-K α The diffraction angles (2θ) of the MPEP are about 6.99±0.2°, 14.04±0.2°, 14.94±0.2°, 16.68±0.2°, 18.57±0.2°, 19.53±0.2°, 21.13±0.2°, 22.42±0.2°, 23.88±0.2°, 26.13±0.2°, 26.85±0.2°, 33.33±0.2°, 34.69±0.2°, 47.76±0.2°. The results of differential thermal analysis show that MPEP has three decomposition exothermic peaks, and the peak temperatures are 300.0℃, 323.0℃ and 368.0℃ respectively. The friction sensitivity characterization results show that MPEP is sensitive to friction (FS=9N), and the impact sensitivity characterization results show that MPEP is insensitive to impact (IS=20J). The detonation parameters were calculated by using the method reported in the literature, density functional theory (DFT) and Kamlet-Jacob empirical formula, and the detonation heat, detonation velocity and detonation pressure of the energetic compound were obtained to be 5.86 kJ / g, 8.73 km / s and 34.0 GPa respectively.

[0134] In another preferred embodiment, the compound used as the energetic material is (C5H 14 N2)(H2EA)(ClO4)4 (denoted as HPEP), the compound crystallizes at 298K in the monoclinic P21 / n space group, with unit cell parameters α=γ=90°,β=90.345(2)°,Powder X-ray diffraction (Cu-K α The diffraction angle 2θ of the HPEP is about 7.02±0.2°, 10.98±0.2°, 14.11±0.2°, 15.47±0.2°, 18.35±0.2°, 21.01±0.2°, 22.43±0.2°, 23.54±0.2°, 25.37±0.2°, 26.46±0.2°, 27.50±0.2°, 42.10±0.2°, 48.46±0.2°. The results of differential thermal analysis show that the peak temperature of thermal decomposition of HPEP is 324.6℃. The results of friction sensitivity characterization show that HPEP is sensitive to friction (FS=12N), and the results of impact sensitivity characterization show that MPEP is insensitive to impact (IS=17.5J). The detonation parameters were calculated by using the method reported in the literature, density functional theory (DFT) and Kamlet-Jacob empirical formula, and the detonation heat, detonation velocity and detonation pressure of the energetic compound were obtained to be 5.87 kJ / g, 8.76 km / s and 34.4 GPa respectively.

[0135] Example 1

[0136] Synthesis and Testing of (H2EA)2(NH4)(ClO4)5(EAP)

[0137] (General formula B2A′X5, A is NH4 + , B is ethylenediammonium cation H2EA2 2+ , X is ClO4 - )

[0138] Synthesis method:

[0139] 1) Add 7.14 g of 70%–72% perchloric acid solution to 1 mL of water and stir evenly;

[0140] 2) Add 1.20 g of ethylenediamine to 4 mL of water and stir evenly;

[0141] 3) The solutions of step 1) and step 2) were mixed and stirred for 10 min, and then 1.4 g of 25% aqueous ammonia solution was added while stirring, and stirred for 30 min. The mixture was filtered, and the precipitate was washed with acetone and dried in vacuo to obtain a solid powder, which was identified as pure EAP phase by X-ray powder diffraction, and the yield was 80%.

[0142] Powder X-ray diffraction identification spectrum:

[0143] The powder X-ray diffraction pattern at room temperature is shown in Figure 3 .

[0144] Single crystal structure characterization test:

[0145] See the crystal structure diagram for Figure 1 .like Figure 1 It can be seen that the adjacent NH4 + They are connected to form a The diamond network structure has two perchlorate ions in the independent unit of the structure, one of which has an adjacent Cl1 (from ClO4 - ) are connected to form a Diamond mesh structure, two sets of diamond mesh interlaced, each NH4 + There are 6 ethylenediammonium cations around Cl1 to form an octahedral structure. The three octahedra are connected by a μ3-ethylenediammonium cation, and the other perchlorate (Cl2) is between the three octahedra.

[0146] Detailed crystal determination data are shown in Table 1.

[0147] Table 1 Crystal determination data of EAP

[0148]

[0149]

[0150] [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 ;

[0151] Differential Thermal Analysis (DTA) Characterization of EAP:

[0152] The DTA curve of EAP is as follows Figure 4 As shown. Figure 4 It can be seen that the powdered energetic compound EAP has two decomposition exothermic peaks, and the peak temperatures are 304.2℃ and 376.0℃ respectively.

[0153] Density functional theory (DFT) is used to obtain the detonation heat, detonation pressure and detonation velocity of energetic compounds EAP:

[0154] The decomposition heat of EAP (decomposition enthalpy ΔH det ) Density functional theory (DFT) calculation (J.Am.Chem.Soc.2012,134,1422) is about 1.21 kcal / g. The detonation velocity of EAP is about 8.97 km / s and the detonation pressure is about 37.0 GPa according to the Kamlet-Jacob formula.

[0155] The amount of gas produced per mole of EAP:

[0156] Regarding 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 all gas products: nitrogen, hydrogen halide, water, carbon dioxide and oxygen and other gaseous substances. Therefore, 1 mole of EAP can produce 22.25 moles of gaseous substances after a complete explosion in an oxygen-free environment.

[0157] Example 2

[0158] (C4H 12 Synthesis and Testing of N2)(H2EA)(ClO4)4(PEP)

[0159] (General formula ABX4, A is piperazine-1,4-diammonium ion, B is ethylenediamine cation H2EA2 2+ , X is ClO4 - )

[0160] Synthesis method:

[0161] 1) Add 11.43 g of 70%–72% perchloric acid solution to 15 mL of water, add 1.20 g of ethylenediamine while stirring, and stir at room temperature for 5 minutes;

[0162] 2) Dissolve 1.72 g of anhydrous piperazine in 5 mL of water;

[0163] 3) The solutions of step 1) and step 2) were mixed, stirred for 10 min, filtered, the precipitate was washed with ethanol, and vacuum dried to obtain a solid powder, which was identified as a pure phase of PEP by X-ray powder diffraction, with a yield of 85%.

[0164] Powder X-ray diffraction identification spectrum:

[0165] The powder X-ray diffraction pattern at room temperature is shown in Figure 5 .

[0166] Single crystal structure characterization test:

[0167] See the crystal structure diagram for Figure 2 , each H2EA 2+ There are 10 ClO4 around - The ions form an irregular dodecahedron (see Figure 2 (a)), adjacent H2EA 2+ Ions pass through 4 μ4-ClO4 - ions and 6 μ2-ClO4 - The ions are connected to form a layered structure in the b-axis and c-axis directions (see Figure 2 (b)), piperazine cations and perchlorate anions are arranged alternately between adjacent layers (see Figure 2 (c)).

[0168] Detailed crystal determination data are shown in Table 2.

[0169] Table 2 Crystal determination data of PEP

[0170]

[0171] [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 ;

[0172] Differential Thermal Analysis (DTA) Characterization of PEP:

[0173] The DTA curve of PEP is as follows Figure 6 As shown. Figure 6 It can be seen that the powdered energetic compound PEP decomposes at a decomposition peak temperature of 311.6°C and the decomposition peak is sharp and rapid, followed by two continuous slow decompositions with peak temperatures of 336.1°C and 391.7°C respectively.

[0174] Density functional theory (DFT) is used to obtain the detonation heat, detonation pressure and detonation velocity of energetic compounds EAP:

[0175] The decomposition heat of PEP (decomposition enthalpy ΔH det ) is about 1.46 kcal / g using density functional theory (DFT) calculation (J.Am.Chem.Soc.2012,134,1422). The detonation velocity of PEP is about 9.09 km / s and the detonation pressure is about 37.6 GPa according to the Kamlet-Jacob formula.

[0176] The amount of gas produced per mole of PEP:

[0177] Regarding 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 PEP can produce 18.5 moles of gaseous substances and 2.5 moles of elemental carbon after a complete explosion in an oxygen-free environment. When enough oxidant is mixed in, there is no solid residue after the complete explosion of PEP.

[0178] Example 3

[0179] (C5H 14 Synthesis and Testing of N2)(H2EA)(ClO4)4(MPEP)

[0180] (General formula ABX4, A is 1-methylpiperazine-1,4-diammonium ion, B is ethylenediammonium cation H2EA2 2+, X is ClO4 - )

[0181] Synthesis method:

[0182] 1) Add 11.43 g of 70%–72% perchloric acid solution to 15 mL of water, add 1.20 g of ethylenediamine while stirring, and stir at room temperature for 5 minutes;

[0183] 2) Add 2.00 g of 1-methylpiperazine to 5 mL of water and dissolve;

[0184] 3) The solutions of step 1) and step 2) were mixed, stirred for 10 min, filtered, the precipitate was washed with ethanol, and vacuum dried to obtain a solid powder, which was identified as pure MPEP phase by X-ray powder diffraction, and the yield was 80%.

[0185] Powder X-ray diffraction identification spectrum:

[0186] The powder X-ray diffraction pattern at room temperature is shown in Figure 7 .

[0187] Single crystal structure characterization test:

[0188] Detailed crystal determination data are shown in Table 3.

[0189] Table 3 Crystal measurement data of MPEP

[0190]

[0191]

[0192] [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 ;

[0193] Differential Thermal Analysis (DTA) Characterization of MPEP:

[0194] The DTA curve of MPEP is as follows Figure 8 As shown. Figure 8It can be seen that the powdered energetic compound MPEP has a multi-step decomposition process. It decomposes rapidly at a peak temperature of 299.2°C, followed by two continuous slow decompositions with peak temperatures of 322.0°C and 366.1°C respectively.

[0195] Density functional theory (DFT) is used to obtain the values ​​of detonation heat, detonation pressure and detonation velocity of energetic compound MEAP:

[0196] The decomposition heat of MPEP (decomposition enthalpy ΔH det ) is about 1.40 kcal / g according to density functional theory (DFT) (J.Am.Chem.Soc.2012,134,1422). The detonation velocity of MPEP is about 8.73 km / s and the detonation pressure is about 34.0 GPa according to the Kamlet-Jacob formula.

[0197] The amount of gas produced per unit mole of MPEP:

[0198] Regarding 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: 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, after a complete explosion of 1 mole of MPEP in an oxygen-free environment, 19 moles of gaseous substances can be produced, and 4 moles of elemental carbon will remain. When sufficient oxidants are mixed in, there is no solid residue after the complete explosion of MPEP.

[0199] Example 4

[0200] (C5H 14 Synthesis and Testing of N2)(H2EA)(ClO4)4(HPEP)

[0201] (General formula ABX4, A is 1,4-diazacycloheptane-1,4-diammonium ion, B is ethylenediamine cation H2EA2 2+ , X is ClO4 - )

[0202] Synthesis method:

[0203] 1) Add 11.43 g of 70%–72% perchloric acid solution to 15 mL of water, add 1.20 g of ethylenediamine while stirring, and stir at room temperature for 5 minutes;

[0204] 2) Add 2.00 g of homopiperazine to 5 mL of water and dissolve;

[0205] 3) The solutions of step 1) and step 2) were mixed, stirred for 10 min, filtered, the precipitate was washed with ethanol, and vacuum dried to obtain a solid powder, which was identified as HPEP pure phase by X-ray powder diffraction, and the yield was 75%.

[0206] Powder X-ray diffraction identification spectrum:

[0207] The powder X-ray diffraction pattern at room temperature is shown in Fig. 9 .

[0208] Single crystal structure characterization test:

[0209] Detailed crystal determination data are shown in Table 4.

[0210] Table 4 Crystal measurement data of HPEP

[0211]

[0212]

[0213] [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 ;

[0214] Differential Thermal Analysis (DTA) Characterization of HPEP:

[0215] The DTA curve of HPEP is as follows Fig.10 As shown. Fig.10 It can be seen that the powdered energetic compound HPEP decomposes rapidly at a peak decomposition temperature of 324.6°C.

[0216] Density functional theory (DFT) obtains the values ​​of explosion heat, explosion pressure and explosion velocity of energetic compound HEAP:

[0217] The decomposition heat of HPEP (decomposition enthalpy ΔH det ) is about 1.40 kcal / g according to density functional theory (DFT) calculation (J.Am.Chem.Soc.2012,134,1422). The MPEP detonation velocity is about 8.76 km / s and the detonation pressure is about 34.4 GPa according to the Kamlet-Jacob formula.

[0218] The amount of gas produced per unit mole of HPEP:

[0219] Regarding 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.A2014,118,4575; Chem.Eur.J.2016,22,1141), the decomposition products are: 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 HPEP can produce 19 moles of gaseous substances and 4 moles of elemental carbon after a complete explosion in an oxygen-free environment. When enough oxidant is mixed in, there is no solid residue after the complete explosion of HPEP.

[0220] Comparison of Examples and Comparative Examples

[0221] As shown in Table 5, the compounds of Examples 1-4 and the comparative examples (whose chemical formula is ABX4, A is 1,4-diazabicyclo[2.2.2]octane-1,4-diammonium ion, B is ethylenediammonium cation H2EA2 2+ , X is ClO4 - ) performance comparison.

[0222] Where: ρ is specific gravity, Q is explosion heat, D is explosion velocity, P is explosion pressure, ΔH f is 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.

[0223] Table 5 Performance comparison of examples and comparative examples

[0224]

[0225]

[0226] From the above embodiments, we can see that:

[0227] 1) Compared with the comparative example, the oxygen balance of Examples 1, 2, 3 and 4 of the present application is closer to zero oxygen balance; in particular, the oxygen balance parameter of Example 1 is a positive value, which means that it can be used as an oxidant component in various formulation designs.

[0228] 2) Compared with the comparative example, Example 2 has a similar (slightly higher) density, but has higher explosion heat, explosion velocity, explosion pressure and better specific impulse performance.

[0229] 3) Compared with the comparative example, the oxygen balance and density of Example 1 are significantly higher, and better technical effects are reflected in performance indicators such as detonation velocity and detonation pressure.

[0230] The above-mentioned implementation modes are only preferred implementation modes of the present application and cannot be used to limit the scope of protection of the present application. Any non-substantial changes and substitutions made by technicians in this field on the basis of the present application shall fall within the scope of protection required by the present application.

Claims

1. A compound, characterized in that The compound is: The compound ABX4 composed of A cation, B cation and X anion, where The A cation is selected from piperazine-1,4-dionium ion, 1-methylpiperazine-1,4-dionium ion, 1,4-diazepane-1,4-dionium ion; The B cation is an ethylenediammonium cation; and The X anion is selected from perchlorate ion and nitrate ion; or A compound B2A'X5 composed of an A' cation, a B cation and an X anion, wherein The A′ cation is an ammonium ion; The B cation is an ethylenediammonium cation; and The X anion is selected from the group consisting of perchlorate ions and nitrate ions.

2. The compound according to claim 1, characterized in that The compound is the compound ABX4, and the A cation is a piperazine-1,4-dionium ion.

3. The compound according to claim 2, characterized in that The compound is the compound ABX4, and the A cation is a 1-methylpiperazine-1,4-dionium ion.

4. The compound according to claim 1, characterized in that The compound is the compound ABX4, and the A cation is a 1,4-diazepane-1,4-dionium ion.

5. The compound according to claim 1, characterized in that The compound is the compound B2A'X5.

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, or 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 piperazine, piperazine-1,4-dionium salt, 1-methylpiperazine, 1-methylpiperazine-1,4-dionium salt, 1,4-diazacycloheptane and 1,4-diazacycloheptane-1,4-dionium salt; The A' component is selected from ammonia or an ammonium salt; The B component is selected from ethylenediamine or ethylenediammonium salt; 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 or 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 method comprises mixing component A, component B and component X in a liquid reaction system in any order, and the component A is selected from piperazine and piperazine-1,4-dionium salt.

11. The method for preparing the compound according to claim 8, characterized in that: The method comprises mixing component A, component B and component X in a liquid reaction system in any order, and the component A is selected from 1-methylpiperazine and 1-methylpiperazine-1,4-dionium salt.

12. The method for preparing the compound according to claim 8, characterized in that: The method comprises mixing component A, component B and component X in a liquid reaction system in any order, and the component A is selected from 1,4-diazacycloheptane and 1,4-diazacycloheptane-1,4-dialium salt.

13. The method for preparing the compound according to claim 8, characterized in that: The method comprises mixing the A' component, the B component and the X component in any order in a liquid reaction system.

14. The method for preparing the compound according to claim 8, characterized in that: The X component is selected from nitric acid and / or nitrates.

15. The method for preparing the compound according to claim 8, 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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