COMPOUNDS AND PREPARATION METHOD THEREFOR AND USE THEREOF AS ENERGETIC MATERIALS

TECHNICAL FIELD

The present disclosure relates to the field of energetic materials, and particularly relates to a series of compounds, a preparation method therefor and a use thereof as energetic materials.

BACKGROUND ART

An energetic material is a compound or a mixture which can quickly perform self-oxidation-reduction reaction under the stimulation of external energy and quickly release a large amount of heat and gas so as to apply work to a surrounding medium. The energetic material has very wide use in the military (such as signal bullets of arms and ammunition, propellants and pyrotechnics) and the civil field (such as fireworks and crackers, perforating bullets for oil exploitation, civil engineering and mining blasting), it plays an important role in promoting national defense construction and national economy development, and has the characteristics of high temperature, high pressure and high speed reaction and instant one-time effect.

The energetic material as a special energy source is a power source for various thermal systems to perform projectile launching and rocket missile in military, it is a technical and material basis for national military actual combat power and deterrent power and is widely used in the fields of engineering blasting, machining, geological exploration, ejection devices, fireworks and crackers, safety airbags, etc. in civil. The earliest energetic material is Chinese black powder which appeared in the 9^th Century AD, it is a mixture of sulfur, potassium nitrate and charcoal powder, and has poor effect and unstable performance. An elementary substance energetic material has been on the rise since the mid-19^th Century, and nitroglycerin is the early prominent representation. Nobel used kieselguhr to adsorb nitroglycerin so as to invent the dynamite explosive, thus achieving the industrial use of nitroglycerin. After entering the modern society, elementary substance energetic materials with higher performance than nitroglycerin have been continuously found and put into use, such as famous trinitrotoluene (TNT) and organic energetic materials which are hexogen (RDX) and octogen (HMX) with higher explosion performance than TNT. In the development history of the energetic material, the research of the elementary substance energetic material has always been in a core position. Each great innovation of the elementary substance energetic material (such as invention and application of compounds like TNT, RDX and HMX) brought great changes to the energetic material and even weaponry (Agrawal, J. P. ISBN: 978-3-527-32610-5. Wiley, 2010.).

According to the use occasions and performance characteristics, the energetic material can be mainly divided into four categories, namely primary explosives, high explosives (also called secondary explosives), propellants and pyrotechnics. In order to adapt to different use occasions, the four categories of energetic materials have different emphasis on performance requirements of related elementary substance energetic materials.

The primary explosive is a kind of explosive which deflagrates and can be quickly converted into detonation under the action of initial external weak impact energy (such as friction, impact, needling, electric energy, flame and laser). Such kind of explosive has the characteristics of high sensitivity, quick conversion from deflagrating to detonation, etc., and detonation waves generated by the explosive are used for detonating the high explosive, so the explosive is also called as an initial explosive, an initial charge or a primary explosive. The primary explosive is the initial energy which has the most sensitivity to detonation and ignition, and is widely used to military and civil detonation or ignition devices, such as industrial detonators, igniters of detonating tubes or ignition devices of rockets, satellites, weapons, mining and tunneling. The earliest used primary explosive is mercuric fulminate (MF), which has been an important component of detonator charges and detonating cap percussion powder for more than two hundred years after being discovered in 1628. However, the primary explosive was gradually replaced by lead azide (LA), lead styphnate (LS) and the like from the beginning of 20th Century due to its defects of relatively poor stability, high toxicity, high possibility of corroding bores and cartridges and the like, which opened an era of lead-based primary explosives. At present, the LA and the LS are still the most widely used primary explosives. However, with the improvement of the environmental awareness of people and the increasing attention to lead pollution, the search for a new generation of relatively safe and environment-friendly lead-free primary explosive has become a hot spot in the field of current initiating explosive material research.

The high explosive (also called secondary explosive) has higher stability than the primary explosive, it is generally not detonated by heat or impact in the using process, but is detonated by means of impact waves of the primary explosive to generate detonation, which can generate stronger destructive power. The high explosives in service at present mainly include TNT, RDX, HMX and TATB (Klapötke, T. M., High energy density materials, Springer, 2007). Along with the development of weaponry, there are higher requirements on the safety and detonation performance of the high explosives. TNT and TATB are insensitive, but have low energy level. RDX and HMX have various crystal forms, and have the defects of high mechanical sensitivity, poor safety performance and the like. Therefore, designing a high explosive with high synthesis energy level and good stability is the target pursued in the field of energetic materials all the time.

The propellants and propellant powder belong to gunpowder, both are regularly combusted to release energy and generate gas to push rockets and missiles (the propellants) or to launch bullets in a gun chamber (the propellants). Such kind of gunpowder is usually an energetic compound without metal components. For example, HMX, RDX and the like are usually used as important additives in a propellant formula to increase the specific impulse value of the formula and are used in formulas of some high-energy modified double-base propellants (Tan Huimin, the Chemistry and Technology of Solid Rocket Propellant, Beijing Institute of Technology Press, 2015). A large number of novel modern energetic materials emerging from at present, such as organic energetic materials represented by hexanitrohexaazaisowurtzitane (CL-20) and the like and all-nitrogen compounds which are still in a basic research stage, are good at explosion and specific impulse performance, but are always difficult to be used on a large scale due to their defects of poor structural stability, complex synthesis process, too high price, etc. Therefore, designing and synthesizing a high-energy energetic material with the advantages of low cost, high energy density, high safety and the like is a durable pursuit in the field of energetic materials, particularly in the field of propellants.

The pyrotechnics belong to an important energetic material. Pyrotechnics are a kind of agent which is relatively low in decomposition reaction speed (can be combusted or deflagrated), such agent can generate light, smoke and noise, and can also emit a specific spectral color (Thomas M. Klapötke, Chemistry of High-Energy Materials, De Gruyter, 2012) after adding metal and metal salt and is often used for manufacturing fireworks and making a tracer bullet in military. The field of pyrotechnics is overlapped with the fields of propellants and explosives, and some pyrotechnics can be often used in the field of explosives or propellants. Some modern high-energy explosives can also be applied to a pyrotechnics formula (Conkling, J. A. & Mocella C. J. ISBN: 978-1-4200-1809-7. CRC Press, 2010.) under a low constraint condition. The earliest pyrotechnics are famous black powder, which appeared in the Tang Dynasty at the end of the 9th Century AD and was prepared by mixing potassium nitrate, sulfur and charcoal. The combustion and explosion performance of a black powder mixture is greatly dependent on a preparation process and a using condition. The black powder under an unconstrained condition is just a fuel used by the alchemists in the Middle Ages, and with the improvement of the preparation process, the black powder was gradually used for making performance pyrotechnics, and finally used as explosives, which opened the era of thermal weapons. At present, the black powder is still an important pyrotechnics agent for civil use and military use, but it is easily fired and exploded in the production process of mixed agent, which often causes accidents. Therefore, designing a new generation of elementary-substance pyrotechnics with high invariability, simple process and high stability through theory has become a hot spot in the field of pyrotechnics.

The amount of the newly synthesized energetic material is rapidly increased in the past few decades, and particularly, the development of the energetic material is greatly promoted by the research of crystalline energetic materials such as organic energetic molecules and binary salts thereof, all nitrogen compounds, eutectic compounds, metal complexes and molecular perovskite compounds.

For the energetic material which takes oxidation-reduction reaction as a main mechanism to “quickly release energy and produce gas”, oxygen balance, crystal density and enthalpies of formation are the important physical parameters in material design. The oxygen balance parameter reflects the difference degree between the actual oxygen content in the material and the oxygen content required for complete oxidation of carbon and hydrogen in the material, and when the oxygen balance is zero, the carbon and the hydrogen can be respectively and fully converted into carbon dioxide and water theoretically, namely complete combustion is achieved, so that energy is released to the maximum extent. The density of the energetic material directly influences the detonation velocity and the detonation pressure, and the higher the density is, the higher the theoretical detonation velocity and the detonation pressure are. However, the oxygen balance and the crystal density are often correlated and are difficult to improve at the same time so as to comprehensively improve the detonation parameter; in addition, although the improvement of the enthalpies of formation is favorable for improving the energy level of the energetic material, it often brings lower thermal stability. Therefore, how to reasonably select components based on a crystal engineering principle so as to optimize the oxygen balance and the crystal density of the energetic compound at the same time, and consider the energy level and the thermal stability is an important challenge topic in the process of designing and synthesizing a novel energetic compound.

A metal-free molecular perovskite type energetic material with NH₄⁺ cations as a site B, with the advantages of no metal residue after explosion or decomposition, large gas production rate, high explosion heat or combustion heat value and the like, has a good use prospect in the fields of propellants, high explosive, etc.

However, it is currently found that a metal-free molecular perovskite type energetic compound constructed by adjusting A-site component has encountered a bottleneck in the aspects of improving crystal density and enthalpies of formation at the same time, it is difficult to further break through its energetic characteristic. For example, for the first metal-free molecular perovskite energetic compound (C₆H₁₄N₂)(NH₄)(ClO₄)₃ (DAP-4) and one of its optimized compounds (C₆H₁₄N₂O)(NH₄)(ClO₄)₃ (DAP-04) obtained by adjusting the A-site component, the crystal density is respectively 1.87 g/cm³ and 1.85 g/cm³, the enthalpies of formation are respectively -484.0 kJ/mol and -436.1 kJ/mol, the heat of detonation is respectively 1.40 kcal/g and 1.48 kcal/g, the detonation velocity is respectively 8.806 km/s and 8.900 km/s, and the detonation pressure is respectively 35.2 GPa and 35.7 GPa. The performance of the optimized compound is not significantly improved when compared with that of the first metal-free molecular perovskite energetic compound.

An ethylenediamine cation (H₂EA²⁺) is a positive divalent cation which can exist stably and has a small molecular weight, it can form a stable salt with twice the equivalent of negative monovalent oxidative anions, and thus an oxygen balance parameter close to zero can be obtained. For example, early ethylenediamine dinitrate, ethylenediamine diperchlorate and the like all have better detonation performance than TNT, but both have serious hygroscopicity and are not further applied (The Chemistry and Technology of Propellants and Explosives (Volume II), by Urbanski (Poland), 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 ethylenediamine diperchlorate and triethylene diamine diperchlorate to obtain an energetic compound (C₆H₁₄N₂)(H₂EA)(ClO₄)₄ (named SY, Chinese invention patent ZL200810025381.3), and found that SY has smaller hygroscopicity and better thermal stability than pure ethylenediamine diperchlorate, and shows good performance in the aspect of primary explosives. However, the crystallographic density value (reported value is 1.834 g/cm³, the real value should be 1.867 g/cm³) of SY does not reach 1.9 g/cm³, and the oxygen balance (-27.8%) is also lower than the corresponding values (-21.6%) of the currently commonly used RDX and HMX. In addition, covalent bonds of the ethylenediamine cation are all single bonds, have a significant “flexible” structure, and can be used as hydrogen bond donors.

For the metal-free molecular perovskite type energetic material, how to adjust the components of the energetic material to further improve the crystal density, enthalpy generation and/or oxygen balance parameters at the same time so as to improve the energetic characteristic of the energetic material is a challenging subject with important significance.

The Chinese patent 201610665880.3 discloses an energetic material with a specific structure.

SUMMARY

In some embodiments, a compound is provided. In some embodiments, a crystalline compound is provided. In some embodiments, a metal-free compound, such as a metal-free perovskite-type compound, is provided. In some embodiments, a silver-containing compound, such as a silver-containing perovskite-type compound, is provided. In some embodiments, a potassium-containing compound, such as a potassium-containing perovskite-type compound, is provided. In some embodiments, a hydroxylammonium-containing compound is provided. In some embodiments, a hydrazinium-containing compound is provided.

In some embodiments, an energetic material having good thermal stability, such as a metal-free compound having good thermal stability, such as a metal-free perovskite-type compound, is provided. In some embodiments, an energetic material having good explosive properties, such as a metal-free compound having good explosive properties, such as a metal-free perovskite-type compound, is provided. In some embodiments, a high energy density metal-free compound, such as a high energy density metal-free compound, such as a metal-free perovskite-type compound, is provided. In some embodiments, a metal-free compound having a high theoretical specific impulse, such as a metal-free compound having a high theoretical specific impulse, such as a metal-free perovskite-type compound, is provided. In some embodiments, a more sensitive silver-containing compound, such as a silver-containing perovskite-type compound, is provided. In some embodiments, a silver-containing compound having good explosive properties, such as a silver-containing perovskite-type compound, is provided. In some embodiments, a high energy density silver-containing compound, such as a silver-containing perovskite-type compound, is provided. In some embodiments, a potassium-containing compound having characteristic flame colors, such as potassium-containing perovskite-type compound, is provided. In some embodiments, a potassium-containing compound having good stabilizing properties, such as a potassium-containing perovskite-type compound, is provided. In some embodiments, a crystalline compound assembled based on hydroxylammonium and/or hydrazinium ions, a solid solution therefor, and a use thereof as energetic materials, are provided. In some embodiments, the metal-free compounds of the present application are suitable at least, in particular, as propellants and dynamite. In some embodiments, the silver-containing compounds of the present application are suitable at least, in particular, as a primer. In some embodiments, the potassium-containing compounds of the present application are suitable at least, in particular, as pyrotechnics and dynamite. In some embodiments, the compounds having hydroxylammonium and/or hydrazinium ions of the present application have excellent energetic properties and utility during use.

In some embodiments, the compounds of the present application have energetic ligands. The energetic ligands refer to groups with explosivity, and common groups with explosivity include ClO₃^-, ClO₄^-, NO₃^-, ONC^-, diazenyl groups, and azide ion groups, for example, the ClO₄^- group. Such energetic materials may be used as, but are not limited to, explosives. For example, it may also be used as propellants, rocket fuel or gas generant for airbags.

In some embodiments, the compounds of the present application are perovskite-type compounds. Perovskite-type compounds are a class of solid state compounds with a similar crystal structure to calcium titanate (CaTiO₃), having the same general chemical formula ABX₃, wherein A and B are cations of different sizes and X is an anion. The ideal structure of perovskite-type compounds belongs to the cubic crystal system with high symmetry, and the structural features can be described as: each B cation is connected to six adjacent X anions, and each X anion is connected to two adjacent B cations, thereby forming a three-dimensional anionic backbone consisting of cubic cage-like units; the A cations then fill the pores of the cubic cage-like units. Wherein A is a cation, B is a cation, and X is an anion. However, the perovskite-type compound may also exhibit other structures, such as a hexagonal perovskite structure, and in other embodiments, its structural features may be described as: each B cation is surrounded by six X anions to form a BX₆ octahedral unit, adjacent B cations are connected by three X anions to form a one-dimensional chain, and A cations are filled in the chains. When the perovskite-type 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 perovskite-type 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 perovskite-type compound ABX₃ includes more than one X anion, different X anions may be distributed on the X site in an ordered or disordered manner.

In some embodiments, the compounds of the present application are compounds of a general formula ABX₃, consisting of A cation, B cation, and X anion. In some embodiments, the compounds of the present application are compounds of a general formula AB′X₄, consisting of A cation, B cation, and X anion. In some embodiments, the compounds of the present application are compounds of a general formula B′₂A′X₅, consisting of A′ cation, a B cation, and X anion. In some embodiments, the compounds ABX₃ are perovskite-type compounds ABX₃.

In some embodiments, in the compounds ABX₃, compounds AB′X₄, and/or compounds B′₂A′X₅ of the present application:

In some embodiments, the A cation is an organic cation. In some embodiments, the A cation is a nitrogen-containing heterocyclic organic cation. In some embodiments, the A cation is a divalent nitrogen-containing organic cation. In some embodiments, the A cation is a divalent nitrogen-containing heterocyclic organic cation. In some embodiments, the A cation is selected from at least one 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.

In some embodiments, the A cation may be selected from at least one of ions of Formula (I) and Formula (II), and derivatives thereof, wherein preferably n₁, n₂, n₃, n₄, and n₅ each may be positive integer of 1, 2, 3, 4, or 5, more preferably 1, 2, or 3; R₁, R₂, R₃, and R₄ may be selected from at least one of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, hydroxyl, carbonyl, carboxyl, amino, halogen, mercapto, peroxy, diazenyl, and nitro groups; the derivatives refer to in the organic cationic moiety in which hydrogen atoms are substituted, simultaneously or not, with substituents, and common substituents including methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, hydroxyl, carbonyl, carboxyl, amino, halogen, mercapto, peroxy, diazenyl, nitro, etc.

embedded image - Formula (I)

embedded image - Formula (II)

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

In some embodiments, the A cation is selected from at least one of ions of Formula (I) and derivatives thereof, and any one of R₁ and R₂ is methyl; or the A cation is selected from at least one of ions of Formula (II) and derivatives thereof, and any one of R₃ and R₄ is methyl.

In some embodiments, the A cation is selected from at least one of ions of Formula (I) and derivatives thereof, and any one of n₁ and n₂ is 2. In some embodiments, the A cation is selected from at least one of ions of Formula (I) and derivatives thereof, and both of n₁ and n₂ are 2. In some embodiments, the A cation is selected from at least one of ions of Formula (I) and derivatives thereof, and n₁ is 2, n₂ is greater than or equal to 2. In some embodiments, the A cation is selected from at least one of Formula (I) ions and derivatives thereof, and any one of n₁ and n₂ is 3. In some embodiments, the A cation is selected from at least one of ions of Formula (II) and derivatives thereof, and any one of n₃, n₄, and n₅ is 2. In some embodiments, the A cation is selected from at least one of ions of Formula (II) and derivatives thereof, and n₃, n₄, and n₅ are all 2.

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

embedded image - Formula (III)

embedded image - Formula (IV)

embedded image - Formula (V)

embedded image - Formula (VI)

embedded image - Formula (VII)

embedded image - Formula (VIII)

embedded image - Formula (IX)

embedded image - Formula (X)

In some embodiments, the A cation is selected from at least one of piperazine-1,4-diium, 1-methylpiperazine-1,4-diium, 1,4-diazabicyclo[2.2.2]octane-1,4-diium, 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-diium, 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium, and 1,4-diazepane-1,4-diium, and derivatives thereof.

In some embodiments, the A cation is selected from at least one of piperazine-1,4-diium, and 1,4-diazepane-1,4-diium, and derivatives thereof.

In some embodiments, the A cation is selected from at least one of piperazine-1,4-diium, 1-methylpiperazine-1,4-diium, 1,4-diazabicyclo[2.2.2]octane-1,4-diium, and 1,4-diazepane-1,4-diium, and derivatives thereof.

In some embodiments, the A cation is selected from at least one of 1-methylpiperazine-1,4-diium, 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-diium, 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium, and 1,4-diazepane-1,4-diium, and derivatives thereof. In some embodiments, the A cation is selected from at least one of 1-methylpiperazine-1,4-diium, 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-diium, and 1,4-diazepane-1,4-diium, and derivatives thereof.

In some embodiments, the A cation is selected from at least one of 1-methylpiperazine-1,4-diium, 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium, and 1,4-diazepane-1,4-diium, and derivatives thereof. In some embodiments, the A cation is selected from at least one of 1-methylpiperazine-1,4-diium, and 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium, and derivatives thereof. In some embodiments, the A cation is selected from at least one of 1-methylpiperazine-1,4-diium, and 1,4-diazepane-1,4-diium, and derivatives thereof. In some embodiments, the A cation is selected from at least one of 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium, and 1,4-diazepane-1,4-diium, and derivatives thereof.

In some embodiments, the A cation is selected from at least one of 1,4-diazabicyclo[2.2.2]octane-1,4-diium, and derivatives thereof. In some embodiments, the A cation is selected from at least one of 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-diium, and derivatives thereof. In some embodiments, the A cation is selected from at least one of 1,4-dihydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-diium, and derivatives thereof. In some embodiments, the A cation is selected from at least one of pyrazine-1,4-diium, and derivatives thereof. In some embodiments, the A cation is selected from at least one of piperazine-1,4-diium, and derivatives thereof. In some embodiments, the A cation is selected from at least one of 1-methylpiperazine-1,4-diium, and derivatives thereof. In some embodiments, the A cation is selected from at least one of 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium, and derivatives thereof. In some embodiments, the A cation is selected from at least one of 1,4-diazepane-1,4-diium, and derivatives thereof.

In some embodiments, the B cation and/or A′ cation is monovalent cation.

In some embodiments, the B cation is selected from at least one of sodium ion, potassium ion, rubidium ion, cesium ion, silver ion, ammonium ion, hydroxylammonium ion, and hydrazinium ion. In some embodiments, the B cation is selected from at least one of sodium ion, potassium ion, rubidium ion, cesium ion, silver ion, and ammonium ion. In some embodiments, the B cation is selected from at least one of potassium ion, silver ion, and ammonium ion. In some embodiments, the B cation is selected from at least one of potassium ion and silver ion. In some embodiments, the B cation is selected from at least one of silver ion and ammonium ion. In some embodiments, the B cation is selected from at least one of potassium ion and ammonium ion. In some embodiments, the B cation is sodium ion. In some embodiments, the B cation is potassium ion. In some embodiments, the B cation is rubidium ion. In some embodiments, the B cation is cesium ion. In some embodiments, the B cation is silver ion. In some embodiments, the B cation is ammonium ion. In some embodiments, the B cation is selected from at least one of hydroxylammonium ion and hydrazinium ion. In some embodiments, the B cation is hydroxylammonium ion. In some embodiments, the A cation is hydrazinium ion.

In some embodiments, the B cation is at least one of alkali metal ion and monovalent nitrogen-containing cation. In some embodiments, the B cation is at least one of alkali metal ion and ammonium ion. In some embodiments, the B cation is monovalent nitrogen-containing cation. In some embodiments, the B cation has the general formula NR₃R₄R₅R₆⁺, wherein R₃, R₄, R₅, R₆ may be selected from at least one of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, hydroxyl, carbonyl, carboxyl, amino, halogen, sulfhydryl, peroxy, diazenyl, and nitro groups.

In some embodiments, the A′ cation is selected from at least one of sodium ion, potassium ion, rubidium ion, cesium ion, silver ion, ammonium ion, hydroxylammonium ion, and hydrazinium ion. In some embodiments, the A′ cation is selected from at least one of sodium ion, potassium ion, rubidium ion, cesium ion, silver ion, and ammonium ion. In some embodiments, the A′ cation is selected from at least one of potassium ion, silver ion, and ammonium ion. In some embodiments, the A′ cation is selected from at least one of potassium ion and silver ion. In some embodiments, the A′ cation is selected from at least one of silver ion and ammonium ion. In some embodiments, the A′ cation is selected from at least one of potassium ion and ammonium ion. In some embodiments, the A′ cation is sodium ion. In some embodiments, the A′ cation is potassium ion. In some embodiments, the A′ cation is rubidium ion. In some embodiments, the A′ cation is cesium ion. In some embodiments, the A′ cation is silver ion. In some embodiments, the A′ cation is ammonium ion. In some embodiments, the A′ cation is selected from at least one of hydroxylammonium ion and hydrazinium ion. In some embodiments, the A′ cation is hydroxylammonium ion. In some embodiments, the A′ cation is hydrazinium ion.

In some embodiments, the A′ cation is at least one of alkali metal ion and monovalent nitrogen-containing cation. In some embodiments, the A′ cation is at least one of alkali metal ion and ammonium ion. In some embodiments, the A′ cation is divalent nitrogen-containing organic cation. In some embodiments, the A′ cation has the general formula NR₃R₄R₅R₆⁺, wherein R₃, R₄, R₅, R₆ may be selected from at least one of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, hydroxyl, carbonyl, carboxyl, amino, halogen, sulfhydryl, peroxy, diazenyl, and nitro groups.

In some embodiments, the B′ cation is aliphatic diammonium cation. In some embodiments, the B′ cation is saturated aliphatic diammonium cation. In some embodiments, the B′ cation is alkyldiammonium cation. In some embodiments, the B′ cation is linear alkyl diammonium cation. In some embodiments, the B′ cation has the general formula R₇R₈R₉N⁺-(C_n3H_2n3)-N⁺R₁₀R₁₁R₁₂, where n₃ may be a positive integer preferably 1, 2, 3, 4, or 5, more preferably 1, 2, or 3, more preferably 2, and R₇, R₈, R₉, R₁₀, R₁₁, R₁₂ may be selected from at least one of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl. In some embodiments, one, two, three, four, five, or all of R₇, R₈, R₉, R₁₀, R₁₁, R₁₂ in the B′ cation is hydrogen. In some embodiments, in the B′ cation, n₃ is 1. In some embodiments, in the B′ cation, n₃ is 2. In some embodiments, in the B′ cation, n₃ is 3. In some embodiments, the B′ cation includes ethylene diamine cation. In some embodiments, the B′ cation is ethylenediammonium cation.

In some embodiments, the B cation is selected from potassium ion, and the A cation is selected from at least one of piperazine-1,4-diium, and 1,4-diazepane-1,4-diium, and derivatives thereof. In some embodiments, the B cation is selected from potassium ion and the A cation is selected from at least one of piperazine-1,4-diium, and derivatives thereof.

In some embodiments, the B cation is selected from silver ion and the A cation is selected from at least one of piperazine-1,4-diium, 1-methylpiperazine-1,4-diium, 1,4-diazabicyclo[2.2.2]octane-1,4-diium, and 1,4-diazepane-1,4-diium, and derivatives thereof. In some embodiments, the B cation is selected from silver ion and the A cation is selected from at least one of piperazine-1,4-diium, and 1,4-diazepane-1,4-diium, and derivatives thereof. In some embodiments, the B cation is selected from silver ion, and the A cation is selected from at least one of 1-methylpiperazine-1,4-diium, and 1,4-diazepane-1,4-diium, and derivatives thereof.

In some embodiments, the B cation is selected from ammonium ion and the A cation is selected from at least one of 1-methylpiperazine-1,4-diium, 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-diium, 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium, and 1,4-diazepane-1,4-diium, and derivatives thereof. In some embodiments, the B cation is selected from ammonium ion, and the A cation is selected from at least one of 1-methylpiperazine-1,4-diium, 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-diium, and 1,4-diazepane-1,4-diium, and derivatives thereof. In some embodiments, the B cation is selected from ammonium ion and the A cation is selected from at least one of 1-methylpiperazine-1,4-diium, 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium, and 1,4-diazepane-1,4-diium, and derivatives thereof. In some embodiments, the B cation is selected from ammonium ion, and the A cation is selected from at least one of 1-methylpiperazine-1,4-diium, and 1,4-diazepane-1,4-diium, and derivatives thereof.

In some embodiments, the compound has the formula B′₂A′X₅, the A′ cation is ammonium ion, and the B′ cation is ethylenediamine cation.

In some embodiments, the X anion is an anionic energetic ligand. In some embodiments, the X anion is monovalent anion.

In some embodiments, the X anion is selected from at least one of chlorate ion, bromate ion, iodate ion, perchlorate ion, perbromate ion, periodate ion, nitrate ion, fulminate ion, diazenyl group, and azide ion. In some embodiments, the X anion is selected from at least one of chlorate ion, perchlorate ion, nitrate ion, fulminate ion, diazenyl group, and azide ion.

In some embodiments, the X anion is halogen-containing monovalent anion. In some embodiments, the X anion is halogen-containing monovalent oxyacid anion. In some embodiments, the X anion is at least one of halate ion and perhalate ion. In some embodiments, the X anion is at least one of perhalate ion and nitrate ion. In some embodiments, the X anion is perhalate ion. In some embodiments, the X anion is selected from at least one of chlorate, bromate, iodate, perchlorate, perbromate, periodate, and nitrate. In some embodiments, the X anion is selected from at least one of chlorate ion, bromate ion, iodate ion, perchlorate ion, perbromate ion, and periodate ion. In some embodiments, the X anion is selected from at least one of perchlorate, perbromate and periodate. In some embodiments, the X anion is selected from at least one of perchlorate ion and perbromate ion. In some embodiments, the X anion is selected from at least one of perchlorate ion and periodate ion. In some embodiments, the X anion is selected from at least one of perbromate ion and periodate ion. In some embodiments, the X anion is perchlorate ion. In some embodiments, the X anion is perbromate ion. In some embodiments, the X anion is periodate ion.

In some embodiments, the X anion is perchlorate ion, the B cation is potassium ion, and the A cation are piperazine-1,4-diium, and 1,4-diazepane-1,4-diium. In some of the test examples of these examples, the compound has application advantages as a dynamite or pyrotechnics, the compound having a purple flame reaction; when the A cation is 1,4-dihydro-piperazine ammonium ion, the density of PAP-2 is up to 2.02 g/cm³, the energy density is 3.04 kcal/cm³, the detonation velocity is up to 8.78 km/s, and the detonation pressure is up to 36.6 GPa; when the A cation is 1,4-diazepane-1,4-diium, the density of PAP-H2 is up to 1.96 g/cm³, the energy density is 2.49 kcal/cm³, the detonation velocity is up to 8.17 km/s, and the detonation pressure is up to 31.1 GPa.

In some embodiments, the X anion is perchlorate ion, the B cation is potassium ion, and the A cation is piperazine-1,4-diium.

In some embodiments, the X anion is perchlorate ion, the B cation is silver ion, and the A cation is selected from at least one of piperazine-1,4-diium, 1-methylpiperazine-1,4-diium, 1,4-diazabicyclo[2.2.2]octane-1,4-diium, and 1,4-diazepane-1,4-diium. In some of the test examples of these examples, the compounds have application advantages as dynamites or priming explosives, the energetic compounds of the present invention have a higher crystal density, the crystal density is in the range of 2.35-2.50 g/cm³, and the theoretical heat of detonation can be up to 1.14-1.29 kcal/g; according to the Kamlet-Jacob formula, the theoretical detonation velocity can be up to 8.54-8.96 km/s, and the theoretical detonation pressure can be up to 38.0-42.4 GPa. The thermal decomposition temperatures of the compounds are more than 308.3-341.6° C. The impact sensitivity and friction sensitivity of the compound are more sensitive; when the A cation is piperazine-1,4-diium, the density of PAP-5 is up to 2.50 g/cm³, the energy density is up to 2.91 kcal/cm³, the theoretical detonation velocity is up to 8.96 km/s, and the theoretical detonation pressure is up to 42.4 GPa; when A cation is 1-methylpiperazine-1,4-diium, the density of PAP-M5 is up to 2.35 g/cm³, the energy density is up to 3.05 kcal/cm3, the theoretical detonation velocity is up to 8.73 km/s, and the theoretical detonation pressure is up to 39.2 GPa; where the A cation is 1,4-diazabicyclo[2.2.2]octane-1,4-diium, the impact sensitivity of DAP-5 is 3 J and the friction sensitivity is ≤ 5 N.

In some embodiments, the X anion is perchlorate ion, the B cation is silver ion, and the A cation is selected from at least one of piperazine-1,4-diium, 1-methylpiperazine-1,4-diium, and 1,4-diazepane-1,4-diium. In some embodiments, the X anion is perchlorate ion, the B cation is silver ion, and the A cation is selected from at least one of piperazine-1,4-diium, 1-methylpiperazine-1,4-diium, and 1,4-diazabicyclo[2.2.2]octane-1,4-diium. In some embodiments, the X anion is perchlorate ion, the B cation is silver ion, and the A cation is selected from at least one of 1,4-diium, 1,4-diazabicyclo[2.2.2]octane-1,4-diium, and 1,4-diazepane-1,4-diium. In some embodiments, the X anion is perchlorate ion, the B cation is silver ion, and the A cation is selected from at least one of 1-methylpiperazine-1,4-diium, 1,4-diazabicyclo[2.2.2]octane-1,4-diium, and 1,4-diazepane-1,4-diium. In some embodiments, the X anion is perchlorate ion, the B cation is silver ion, and the A cation is selected from at least one of piperazine-1,4-diium, and 1,4-diazepane-1,4-diium. In some embodiments, the X anion is perchlorate ion, the B cation is silver ion, and the A cation is selected from at least one of 1-methylpiperazine-1,4-diium, and 1,4-diazepane-1,4-diium. In some embodiments, the X anion is perchlorate ion, the B cation is silver ion, and the A cation is selected from at least one of piperazine-1,4-diium, and 1-methylpiperazine-1,4-diium. In some embodiments, the X anion is perchlorate ion, the B cation is silver ion, and the A cation is selected from at least one of piperazine-1,4-diium, and 1,4-diazabicyclo[2.2.2]octane-1,4-diium. In some embodiments, the X anion is perchlorate ion, the B cation is silver ion, and the A cation is selected from at least one of 1,4-diazabicyclo[2.2.2]octane-1,4-diium, and 1,4-diazepane-1,4-diium. In some embodiments, the X anion is perchlorate ion, the B cation is silver ion, and the A cation is selected from at least one of 1-methylpiperazine-1,4-diium, and 1,4-diazabicyclo[2.2.2]octane-1,4-diium.

In some embodiments, the X anion is perchlorate ion, the B cation is ammonium ion, and the A cation is selected from at least one of 1-methylpiperazine-1,4-diium, 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-diium, 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium, and 1,4-diazepane-1,4-diium. Among the test examples of these examples, the compounds have application advantages as dynamites or solid propellants, the energetic compounds of the present invention have a high energy density, a theoretical heat of detonation up to 1.19-1.48 kcal/g, and a crystal density in the range of 1.74-1.85 g/cm³; according to the Kamlet-Jacob formula, the theoretical detonation velocity can be up to 8.08-8.90 km/s, and the theoretical detonation pressure can be up to 28.8-35.7 GPa. The thermal stability is good and the decomposition temperature is more than 288.2-364.0° C. There is a higher theoretical specific impulse, the formation enthalpies of the compounds were deduced according to DFT and the designed explosive decomposition reaction, and the theoretical specific impulse calculated by EXPLO5 can be up to 225.3- 264.2 s. When the A cation is 1-hydroxy-4-hydro-1,4-diazabicyclo[2.2.2]octane ammonium ion, the theoretical heat of detonation of DAP-04 compound is up to 1.48 kcal/g, and the corresponding energy density is up to 2.74 kcal/cm³. When the A cation is 1,4-dihydro-piperazine ammonium ion, the theoretical specific impulse of PAP-4 compound is up to 264.2 s.

In some embodiments, the X anion is perchlorate ion, the B cation is ammonium ion, and the A cation is selected from at least one of 1-methylpiperazine-1,4-diium, 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-diium, and 1,4-diazepane-1,4-diium. In some embodiments, the X anion is perchlorate ion, the B cation is ammonium ion, and the A cation is selected from at least one of 1-methylpiperazine-1,4-diium, 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium, and 1,4-diazepane-1,4-diium. In some embodiments, the X anion is perchlorate ion, the B cation is ammonium ion, and the A cation is selected from at least one of 1-methylpiperazine-1,4-diium, and 1,4-diazepane-1,4-diium.

In some embodiments, A is selected from at least one of 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium, and derivatives thereof; B is selected from at least one of sodium ion, potassium ion, rubidium ion, cesium ion, silver ion, and ammonium ion. X is selected from at least one of chlorate ion, bromate ion, iodate ion, perchlorate ion, perbromate ion, and periodate ion. In some embodiments, A is selected from at least one of 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium, and derivatives thereof; B is selected from at least one of potassium ion, rubidium ion, silver ion, and ammonium ion. X is selected from at least one of chlorate ion, bromate ion, iodate ion, perchlorate ion, perbromate ion, and periodate ion. In some embodiments, A is selected from at least one of 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium, and derivatives thereof; B is selected from at least one of potassium ion, rubidium ion, silver ion, and ammonium ion. X is selected from chlorate ion.

In some embodiments, the A cation is 1,4-diazabicyclo[2.2.2]octane-1,4-diium, the B cation is selected from at least one of hydroxylammonium ion and hydrazinium ion, and the X anion is selected from perchlorate ion. In some embodiments, the A cation is 1,4-diazabicyclo[2.2.2]octane-1,4-diium, the B cation is hydrazinium ion, and the X anion is selected from perchlorate ion. In some embodiments, the A cation is 1,4-diazabicyclo[2.2.2]octane-1,4-diium, the B cation is hydroxylammonium ion, and the X anion is selected from perchlorate ion. In some test examples of these examples, hydroxylammonium ion and hydrazinium ion have higher enthalpies of formation and are expected to form more hydrogen bonding interaction in the crystal, or will contribute to a stronger binding force to increase both enthalpy of formation and crystal density of the compound. In some test examples of these examples, the theoretical heat of detonation is up to 1.52, 1.43 kcal/g, the room temperature densities are up to 1.90, 1.87 g/cm³, respectively, and the corresponding volumetric energy densities are up to 2.89, 2.67 kcal/cm³, respectively; according to the Kamlet-Jacob formula, the theoretical detonation velocities are up to 9.12 km/s and 8.88 km/s, and the theoretical detonation pressures are up to 38.1 GPa and 35.8 GPa. The decomposition peak temperature is 246.1° C. and 376.1° C., and the theoretical specific impulse is 265.3 s and 256.9 s.

In some embodiments, the compound has the general formula AB′X₄, the A cation is selected from at least one of piperazine-1,4-diium, 1-methylpiperazine-1,4-diium, and 1,4-diazepane-1,4-diium, and derivatives thereof, the B′ cation is ethylenediammonium cation, and the X anion is perchlorate ion. In some embodiments, the A cation is selected from at least one of piperazine-1,4-diium, 1-methylpiperazine-1,4-diium, and 1,4-diazepane-1,4-diium, the B′ cation is ethylenediammonium cation, and the X anion is perchlorate ion. In some embodiments, the A cation is at least one of piperazine-1,4-diium, and 1-methylpiperazine-1,4-diium, the B′ cation is ethylenediammonium cation, and the X anion is perchlorate ion. In some embodiments, the A cation is at least one of piperazine-1,4-diium and 1,4-diazepane-1,4-diium, the B′ cation is ethylenediammonium cation, and the X anion is perchlorate ion. In some embodiments, the A cation is at least one of 1-methylpiperazine-1,4-diium, and 1,4-diazepane-1,4-diium, the B′ cation is ethylenediammonium cation, and the X anion is perchlorate ion. In some embodiments, the A cation is piperazine-1,4-diium, the B′ cation is an ethylene diaminium cation, and the X anion is perchlorate ion. In some embodiments, the A cation is 1-methylpiperazine-1,4-diium, the B′ cation is ethylenediammonium cation, and the X anion is perchlorate ion. In some embodiments, the A cation is 1,4-diazepane-1,4-diium, the B′ cation is ethylenediammonium cation, and the X anion is perchlorate ion. In some embodiments, the compound has the general formula B′₂A′X₅, the A′ cation is ammonium ion, the B′ cation is an ethylene diaminium cation, and the X anion is perchlorate ion. In some test examples of these examples, the theoretical heat of detonation and volumetric energy density are high, the oxygen balance is high, the crystallographic density value is high, the detonation performance is superior, it is sensitive to friction but insensitive to impact, the safety performance is good, the moisture absorption is small and the thermal stability is good, it can be stored for a long time without decomposition; the room temperature crystallinity is single, the raw materials are cheap and readily available, the production process is simple, and can be prepared in large quantities safely. Specifically, in some test examples of these examples, the theoretical heat of detonation is up to 1.40 kcal/g, the crystal density at room temperature is up to 1.91 g/cm³, and the oxygen balance parameter value is up to 6.25%; according to Kamlet-Jacob formula, the theoretical detonation velocity is up to 9.09 km/s. The theoretical burst pressure is up to 37.6 GPa. The decomposition peak temperature is up to 376.0° C., and the specific impulse is up to 264.2 s. More sensitive to friction but less sensitive to impact, friction sensitivity (FS) is between 9 N and 36 N and impact sensitivity (IS) is between 9 J and 20 J.

In some embodiments, the compounds of the present application include optionally one, two or more of the A cations described above or optionally one, two or more of the A′ cations described above, optionally one, two or more of the B cations described above or optionally one, two or more of the B′ cations described above, and/or optionally one, two or more of the X anions described above.

In some embodiments, in the compound ABX₃, the sum of the valency of the A cation and the valency of the B cation is three times the valency of the X anion. In some embodiments, the sum of the valency of the A cation and the valency of the B′ cation in the compound AB′X₄ is four times the valency of the X anion. In some embodiments, in the compound B′₂A′X₅, the sum of the valency of the A′ cation and twice the valency of the B′ cation is five times the valency of the X anion.

In some embodiments, a compound of the present application is compound ABX₃, compound AB′X₄, or is compound B′₂A′X₅ consisting of an A cation or A′ cation, a B cation or B′ cation, and an X anion, wherein the A cation is a nitrogen-containing organic cation, the B cation and the A′ cation are cation, the B′ cation is saturated aliphatic diammonium cation, and the X anion is an anionic energetic ligand.

In some embodiments, compound of the present application is compound ABX₃ consisting of A cation, B cation, and X anion, wherein the A cation is nitrogen-containing organic cation, the B cation is cation, and the X anion is anionic energetic ligand; or is compound AB′X₄ consisting of A cation, B′ cation and X anion or is compound B′₂A′X₅ consisting of A′ cation, B′ cation and X anion, wherein the A cation is a divalent nitrogen-containing monocyclic heterocyclic cation, the A′ cation is at least one of alkali metal ion and monovalent nitrogen-containing cation, the B′ cation is saturated aliphatic diammonium cation, and the X anion is an anionic energetic ligand.

In at least some examples of the present application, the compounds of the present application, such as compound ABX₃, compound AB′X₄, or is compound B′₂A′X₅, may be obtained by reacting the corresponding component A or component A′, component B or component B′, and component X in any order in a liquid reaction system; the liquid reaction system is preferably a polar solvent that may dissolve the component A or component A′, the component B or component B′, and the component X. Or obtained by referencing known synthesis methods. The reaction temperature is not particularly limited and may be adjusted within a wide range, for example, from 0 to 100° C.