WO2018028685A1 - 一类化合物在作为含能材料方面的用途 - Google Patents

一类化合物在作为含能材料方面的用途 Download PDF

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WO2018028685A1
WO2018028685A1 PCT/CN2017/097136 CN2017097136W WO2018028685A1 WO 2018028685 A1 WO2018028685 A1 WO 2018028685A1 CN 2017097136 W CN2017097136 W CN 2017097136W WO 2018028685 A1 WO2018028685 A1 WO 2018028685A1
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diazabicyclo
energetic
octane
group
clo
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PCT/CN2017/097136
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English (en)
French (fr)
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张伟雄
陈劭力
陈小明
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中山大学
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Priority to KR1020187030235A priority Critical patent/KR102030673B1/ko
Priority to RU2018131394A priority patent/RU2725424C2/ru
Application filed by 中山大学 filed Critical 中山大学
Priority to AU2017311153A priority patent/AU2017311153B2/en
Priority to JP2018546038A priority patent/JP6783868B2/ja
Priority to BR112018075493-5A priority patent/BR112018075493B1/pt
Priority to BR122023024836-8A priority patent/BR122023024836A2/pt
Priority to KR1020197029088A priority patent/KR102159462B1/ko
Priority to EP24155683.6A priority patent/EP4345084A3/en
Priority to CA3027813A priority patent/CA3027813C/en
Priority to US16/099,486 priority patent/US10913693B2/en
Priority to EP17838815.3A priority patent/EP3438076B1/en
Publication of WO2018028685A1 publication Critical patent/WO2018028685A1/zh
Priority to IL262549A priority patent/IL262549B/en
Priority to AU2019232800A priority patent/AU2019232800B2/en
Priority to US17/132,109 priority patent/US20210269375A1/en
Priority to IL288380A priority patent/IL288380B2/en

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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B29/00—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B43/00—Compositions characterised by explosive or thermic constituents not provided for in groups C06B25/00 - C06B41/00
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B29/00—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate
    • C06B29/02—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate of an alkali metal
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
    • C06B31/02—Compositions containing an inorganic nitrogen-oxygen salt the salt being an alkali metal or an alkaline earth metal nitrate
    • C06B31/12—Compositions containing an inorganic nitrogen-oxygen salt the salt being an alkali metal or an alkaline earth metal nitrate with a nitrated organic compound
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B49/00—Use of single substances as explosives
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • C06D5/04—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by auto-decomposition of single substances
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/12—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/08—Bridged systems
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the invention relates to the field of energetic materials.
  • it relates to the use of perovskite-type compounds as energetic materials.
  • Energetic compounds are a class of explosive materials with high energy density.
  • the earliest energetic material was the Chinese black powder that appeared in the ninth century AD. It was made of sulfur, potassium nitrate and charcoal powder. The effect was poor and the performance was unstable.
  • nitroglycerin was first discovered as a pharmaceutical product, and it was found to be a strong explosive in subsequent production. The performance of nitroglycerin is much more advanced than that of black powder, but the sensitivity is high and production and transportation are very dangerous.
  • One of the objects of the present invention is to provide a new class of energetic materials.
  • Another object of the present invention is to provide a class of energetic materials having good safety properties.
  • a third object of the present invention is to provide a class of energetic materials having good explosive properties.
  • a fourth object of the present invention is to provide a class of energetic materials having a high energy density.
  • the present invention is the first to apply a perovskite compound as an energetic material, and has been found to be particularly useful for use as an energetic material.
  • the perovskite compound having a group capable of containing, for example, ClO 4 - Energetic group can be used as, but not limited to, as an explosive.
  • it can also be used as a gas generating agent for propellants, rocket fuels or airbags.
  • the perovskite type compound refers to a type of solid compound having a crystal structure similar to that of calcium titanate (CaTiO 3 ), which have the same chemical formula ABX 3 .
  • a and B are cations of different sizes, and X is an anion; its ideal structure belongs to a highly symmetrical cubic system, and the structural features can be described as: each B-position cation is connected to 6 adjacent X anions, Each X anion is linked to two adjacent B-site cations to form a three-dimensional anion skeleton consisting of cubic cage units; the A-site cations are filled in the pores of these cubic cage units.
  • A is at least one cation
  • B is at least one cation
  • X is at least one anion.
  • the different A cations may be distributed in the ordered or disordered manner at the A site.
  • the different B cations may be distributed in the ordered or disordered manner at the B site.
  • the different X anions may be distributed at the X site in an ordered or disordered manner.
  • perovskite-type compounds are generally studied and applied as ferroelectric materials, photovoltaic materials, electromagnetic materials, and the like.
  • X is an energetic anion group, and the steric structure formed thereby allows the compound to overcome the effects of the energetic material.
  • energetic materials for example, according to the inventors' hypothesis that the structural characteristics of the perovskite type make such compounds have higher stability, overcoming the insecurity of the prior art explosives due to poor stability; At the same time, its structural characteristics give excellent excellent instantaneous energy of such compounds at the time of detonation due to the characteristics of enriched energetic groups and the arrangement of these oxidative energetic anions and reducing organic cations in space.
  • An energetic group refers to an explosive group.
  • an explosive group not all compounds containing explosive groups are explosive. Whether a compound is explosive depends on its entire molecular structure rather than a single group (see “Drug Medicine” on page 3, Zhang Huazhu waits, Beijing: Ordnance Industry Publishing Society, 2004).
  • Common explosive groups are ClO 3 - , ClO 4 - , NO 3 - , ONC - , N(NO 2 ) 2 - , azo groups, azide ions, nitro groups and the like.
  • X of the present invention is at least one anionic energetic group, optionally X is an oxidizing anion energetic group, preferably a monovalent anion energetic group; more preferably a monovalent halogen-containing component Energetic group.
  • the anionic energetic group (X) may be one of: ClO 4 - , BrO 4 - , IO 4 - , ONC - , NO 3 - , N(NO 2 ) 2 - , or both Or a variety.
  • the anionic energetic group (X) may be one, two or more of ClO 4 - , BrO 4 - , IO 4 - ;
  • a of the present invention is at least one organic cation; especially A is a reducing organic cation.
  • A is at least one nitrogen-containing organic cation
  • A is at least one nitrogen-containing heterocyclic organic cation
  • A is at least one six-membered ring nitrogen-containing heterocyclic organic cation
  • the A is one, two or more of the following organic cations formed by protonation and their derivatives: 1,4-diazabicyclo[2.2.2 Octane, pyrazine, piperazine, 3-aminopyrrolidine, imidazoline, aminotriazole, aminotetrazolium, ethylenediamine, dicyandiamide, phenylenediamine, 1,5-diaminopentane , cyclohexanediamine and so on.
  • A is selected from one, two or more of the following organic cationic precursors and derivatives thereof:
  • A is selected from one, two or more of the following organic cationic precursors and derivatives thereof:
  • the derivative of the A component organic cation refers to a hydrogen atom in the bulk of the organic cation which is simultaneously or simultaneously substituted.
  • Substituted, common substituents are methyl, ethyl, isopropyl, t-butyl, hydroxy, carbonyl, carboxyl, halogen, decyl, peroxy, azo and nitro groups.
  • B of the present invention is at least one monovalent cation.
  • B is selected from one, two or more of the following cations:
  • Alkali metal ion NH 4 + .
  • the alkali metal ion is preferably selected from one, two or more of Na + , K + , Rb + , Cs + .
  • A is selected from the group consisting of 1,4-dihydro-1,4-diazabicyclo[2.2.2]octane ammonium ion, 1-hydroxy-4-hydro-1,4-diazabicyclo[ 2.2.2] one, two or more of an octane ammonium ion, a 1,4-dihydroxy-1,4-diazabicyclo[2.2.2]octane ammonium ion, and a derivative thereof; More preferably, A is selected from the group consisting of organic cations 1,4-dihydro-1,4-diazabicyclo[2.2.2]octane ammonium ion, 1,4-dihydroxy-1,4-diaza One or both of the ring [2.2.2] octane ammonium ions;
  • B is selected from one, two or more of Na + , K + , NH 4 + ; more preferably, B is selected from one or both of Na + , NH 4 + ; more preferably , B is selected from NH 4 + ;
  • X is selected from one, two or more of ClO 4 - , NO 3 - , IO 4 - ; more preferably, X is selected from one or both of ClO 4 - , NO 3 - Or one or two selected from the group consisting of ClO 4 - , IO 4 - ; more preferably, X is selected from ClO 4 - .
  • A is selected from the group consisting of organic cations 1,4-dihydro-1,4-diazabicyclo[2.2.2]octane ammonium ion, 1,4-dihydro-pyrazine ammonium ion, 1,4-dihydro- Piperazine ammonium ion, 1-hydroxy-4-hydro-1,4-diazabicyclo[2.2.2]octane ammonium ion, 1,4-dihydroxy-1,4-diazabicyclo[2.2 .2] one, two or more of octane ammonium ions;
  • B is selected from one of Na + , K + , Rb + , NH 4 + , two or more;
  • X is selected from one, two or three of ClO 4 - , NO 3 - , IO 4 - ; more preferably X is selected from one or both of ClO 4 - , IO 4 - or selected from ClO One or two of 4 - , NO 3 - .
  • A is selected from the group consisting of organic cations 1,4-dihydro-1,4-diazabicyclo[2.2.2]octane ammonium ion, 1-hydroxy-4-hydro-1,4-diazabicyclo[2.2 .2] one, two or more of an octane ammonium ion, a 1,4-dihydroxy-1,4-diazabicyclo[2.2.2]octane ammonium ion;
  • B is selected from one of Na + , K + , Rb + , NH 4 + , two or more;
  • X is selected from one or both of ClO 4 - , NO 3 - or one or both selected from ClO 4 - , IO 4 - ; more preferably, X is selected from ClO 4 - .
  • A is selected from the group consisting of organic cations 1,4-dihydro-1,4-diazabicyclo[2.2.2]octane ammonium ion, 1,4-dihydroxy-1,4-diazabicyclo ring [2.2. 2] one or two of octane ammonium ions;
  • B is selected from one of Na + , K + , Rb + , NH 4 + , two or more;
  • X is selected from one or both of ClO 4 - , NO 3 - or one or both selected from ClO 4 - , IO 4 - ; more preferably, X is selected from ClO 4 - .
  • A is selected from the group consisting of organic cations 1,4-dihydro-1,4-diazabicyclo[2.2.2]octane ammonium ion, 1,4-dihydroxy-1,4-diazabicyclo ring [2.2. 2] one or two of octane ammonium ions;
  • B is selected from one, two or more of Na + , K + , NH 4 + ;
  • X is selected from one or both of ClO 4 - , NO 3 - or one or both selected from ClO 4 - , IO 4 - ; more preferably, X is selected from ClO 4 - .
  • A is selected from the group consisting of organic cation 1,4-dihydro-1,4-diazabicyclo[2.2.2]octane ammonium ions;
  • B is selected from one or two of Na + and NH 4 + ;
  • X is selected from one or both of ClO 4 - , NO 3 - or one or both selected from ClO 4 - , IO 4 - ; more preferably, X is selected from ClO 4 - .
  • ABX 3 of the present invention A, X is selected from any of the above-mentioned possible choices, and B is selected from NH 4 + ;
  • A is selected from the group consisting of organic cations 1,4-dihydro-1,4-diazabicyclo[2.2.2]octane ammonium ion, 1,4-dihydro-pyrazine ammonium ion, 1,4-dihydro- Piperazine ammonium ion, 1-hydroxy-4-hydro-1,4-diazabicyclo[2.2.2]octane ammonium ion, 1,4-dihydroxy-1,4-diazabicyclo[2.2 .2] one, two or more of an octane ammonium ion and a derivative thereof;
  • X is selected from one, two or more of ClO 4 - , BrO 4 - , IO 4 - ;
  • B is selected from NH 4 + ;
  • the compound When B selects NH 4 + , the compound does not leave a metal salt solid after the complete explosion, and the amount of gas produced per unit number of moles can be as high as 15.25 moles.
  • This property is more conducive to gas generators for explosives, rocket fuels, propellants and airbags. In particular, it is particularly suitable for applications where high gas production is required, for example as a rocket fuel.
  • ABX 3 of the present invention A, X is selected from any of the above-mentioned possible choices, and B is selected from Na + ;
  • A is selected from the group consisting of organic cations 1,4-dihydro-1,4-diazabicyclo[2.2.2]octane ammonium ion, 1,4-dihydro-pyrazine ammonium ion, 1,4-dihydro- Piperazine ammonium ion, 1-hydroxy-4-hydro-1,4-diazabicyclo[2.2.2]octane ammonium ion, 1,4-dihydroxy-1,4-diazabicyclo[2.2 .2] one, two or more of an octane ammonium ion and a derivative thereof;
  • X is selected from one, two or more of ClO 4 - , BrO 4 - , IO 4 - ;
  • B is selected from Na + ;
  • A is selected from 1,4-dihydro-1,4-diazabicyclo[2.2.2]octane ammonium ion
  • X is selected from ClO 4 -
  • B is selected from Na + .
  • Example 1 the effect of density on the detonation velocity and the detonation pressure is positively correlated, and the effect on the detonation pressure is the square exponential relationship).
  • the present inventors have found (see Example 1) that, when used as an energetic material, it has been straightforward to predict that the use of light sodium ions will reduce the material density, thereby presumably having a negative impact on the detonation rate and detonation pressure of the material.
  • DAP-1 since the raw material sodium perchlorate of DAP-1 is more soluble in the polar solvent than the raw material potassium perchlorate of DAP-2, the solvent required for the synthesis of DAP-1 is much less than that of the synthetic DAP-2, so experimentally And production, DAP-1 synthesis is more convenient. DAP-1 may be more suitable than DAP-2 in high energy explosives and propellant applications.
  • ABX 3 of the present invention A, B is selected from any of the above-mentioned possible choices, and X is selected from NO 3 - ;
  • A is selected from the group consisting of organic cations 1,4-dihydro-1,4-diazabicyclo[2.2.2]octane ammonium ion, 1,4-dihydro-pyrazine ammonium ion, 1,4- Dihydro-piperazinium ion, 1-hydroxy-4-hydro-1,4-diazabicyclo[2.2.2]octane ammonium ion, 1,4-dihydroxy-1,4-diaza One, two or more of cyclo[2.2.2]octane ammonium ions and derivatives thereof;
  • B is selected from one of Na + , K + , Rb + , NH 4 + , two or more;
  • X is selected from NO 3 - ;
  • the compound When X is selected from NO 3 - , the compound does not contain a halogen element at this time, does not generate hydrogen halide gas after the explosion, reduces characteristic signals, and reduces environmental pollution. This property makes it particularly suitable for applications requiring low signature signals, for example as low signature signal propellants or rocket fuels.
  • ABX 3 can be obtained by adding the A component, the B component and the X component to the liquid reaction system in any order; the liquid reaction system preferably dissolves the polar solvent of the A component, the B component and the X component. . Or obtain from known synthetic methods.
  • the reaction temperature is not particularly limited and can be adjusted within an extremely wide range, for example, from 0 to 100 °C.
  • the present invention provides a preparation method thereof, comprising the steps of:
  • the component A is 1,4-diazabicyclo[2.2.2]octane or a derivative thereof, pyrazine or a derivative thereof, piperazine or a derivative thereof, 1-oxidized-1,4-di Azabicyclo[2.2.2]octane or a derivative thereof, 1,4-dioxy-1,4-diazabicyclo[2.2.2]octane or a derivative thereof, containing 1,4-di An organic salt of hydrogen-1,4-diazabicyclo[2.2.2]octane ammonium ion or a derivative thereof, an organic salt containing a 1,4-dihydro-pyrazine ammonium ion or a derivative thereof, and 1 An organic salt of 4-dihydro-piperazinium ion or a derivative thereof, containing 1-hydroxy-4-hydro-1,4-diazabicyclo[2.2.2]octane ammonium ion or a derivative thereof At least one of an organic salt and an organic
  • the cation of the component B is selected from one or two or more of an alkali metal ion, NH 4 + ; the component B is an ammonium ion-containing salt, a sodium-containing ionic salt, a potassium-containing ionic salt, and the like. At least one of a cerium ion salt, a cerium ion salt, an ammonium ion base, a sodium ion base, a potassium ion base, a cerium ion base, and a cerium ion base.
  • the X component is at least one of a halogen-containing energetic group-containing acid and a halogen-containing energetic group-containing salt.
  • the polar solvent is selected from one, two or more of water, ethanol, and methanol.
  • the organic salt containing 1,4-dihydro-1,4-diazabicyclo[2.2.2]octane ammonium ion is 1,4-diazabicyclo[2.2 .2] the hydrochloride salt of octane;
  • the organic salt containing a 1,4-dihydro-1,4-diazabicyclo[2.2.2]octane ammonium ion derivative is 2-hydroxy-1,4-diaza Hydrochloride of bicyclo[2.2.2]octane, hydrochloride of 2-carbonyl-1,4-diazabicyclo[2.2.2]octane, 2-methyl-1,4-diazo At least one of the hydrochloride salts of heterobicyclo[2.2.2]octane;
  • the organic salt containing 1,4-dihydro-pyrazine ammonium ion is the hydrochloride salt of pyrazine;
  • the organic salt containing a 1,4-dihydro-pyrazine ammonium ion derivative is at least one of a hydrochloride of 2-hydroxy-pyrazine and a hydrochloride of 2-methyl-pyrazine;
  • the organic salt containing 1,4-dihydro-piperazinium ion is the hydrochloride salt of piperazine;
  • the organic salt containing a 1,4-dihydro-piperazinium ammonium ion derivative is at least one of a hydrochloride of 2-hydroxy-piperazine and a hydrochloride of 2-methyl-piperazine;
  • the organic salt containing 1-hydroxy-4-hydro-1,4-diazabicyclo[2.2.2]octane ammonium ion is 1-oxidized-1,4-diazabicyclo[2.2.2 Octane hydrochloride;
  • the organic salt containing a 1-hydroxy-4-hydro-1,4-diazabicyclo[2.2.2]octane ammonium ion derivative is 2-hydroxy-1-oxidized-1,4-diaza At least one of the hydrochloride salt of bicyclo [2.2.2] octane and the hydrochloride salt of 2-carbonyl-1-oxo-1,4-diazabicyclo[2.2.2]octane;
  • the organic salt containing 1,4-dihydroxy-1,4-diazabicyclo[2.2.2]octane ammonium ion is 1,4-dioxy-1,4-diazabicyclo[2.2 .2] the hydrochloride salt of octane;
  • the organic salt containing a 1,4-dihydroxy-1,4-diazabicyclo[2.2.2]octane ammonium ion derivative is 2-hydroxy-1,4-dioxy-1,4-di At least one of the hydrochloride salt of azabicyclo[2.2.2]octane and the hydrochloride salt of 2-carbonyl-1,4-dioxy-1,4-diazabicyclo[2.2.2]octane One type;
  • the ammonium ion-containing salt is at least one of ammonium perchlorate, ammonium tetrafluoroborate, ammonium periodate, ammonium perrhenate, ammonium carbonate, ammonium nitrate, ammonium phosphate, ammonium chloride, and ammonium fluoride;
  • the sodium salt is at least one of sodium perchlorate, sodium tetrafluoroborate, sodium periodate, sodium perrhenate, sodium carbonate, sodium nitrate, sodium phosphate, sodium chloride, and sodium fluoride;
  • the potassium salt is at least one of potassium perchlorate, potassium tetrafluoroborate, potassium periodate, potassium perrhenate, potassium carbonate, potassium nitrate, potassium phosphate, potassium chloride, and potassium fluoride;
  • the onium salt is at least one of barium perchlorate, barium tetrafluoroborate, barium periodate, barium perrhenate, barium carbonate, barium nitrate, barium phosphate, barium chloride, barium fluoride;
  • the onium salt is at least one of barium perchlorate, barium tetrafluoroborate, barium periodate, barium perrhenate, barium carbonate, barium nitrate, barium phosphate, barium chloride, and barium fluoride.
  • the ammonium ion-containing base is ammonia water
  • the sodium ion-containing base is sodium hydroxide
  • the potassium ion base is potassium hydroxide
  • the cerium ion-containing base is cerium hydroxide
  • the cerium ion-containing base is cerium hydroxide
  • the X component is a perchlorate-containing material.
  • perchloric acid is preferred.
  • the polar solvent is at least one of water, ethanol, and methanol.
  • ABX 3 perovskite compound containing a perchlorate, a perchlorate its characteristic infrared absorption spectrum peaks at 1070 1100cm 617 ⁇ at the ⁇ 1 and 637cm -1;
  • the powder X-ray diffraction line position 2 ⁇ is about: 12.1 ⁇ 0.70°, 21.1 ⁇ 1.00°, and 24.4 ⁇ 1.20°; further, the powder X-ray diffraction line position 2 ⁇ is about: 12.1 ⁇ 0.70. °, 21.1 ⁇ 1.00 °, 24.4 ⁇ 1.20 °, 27.4 ⁇ 1.30 ° and 36.57 ⁇ 0.88 °;
  • the powder X-ray diffraction line position 2 ⁇ is about: 12.6 ⁇ 0.5°, 21.7 ⁇ 0.5°, 22.4 ⁇ 0.5°, 22.7 ⁇ 0.5°, 25.4 ⁇ 0.5°, and 26.8 ⁇ 0.5°. Further, the powder X-ray diffraction line position 2 ⁇ is approximately: 12.6 ⁇ 0.5°, 21.7 ⁇ 0.5°, 22.4 ⁇ 0.5°, 22.7 ⁇ 0.5°, 25.4 ⁇ 0.5°, 26.8 ⁇ 0.5°, 27.2 ⁇ 0.5°, 37.7 ⁇ 0.5 °, 38.4 ⁇ 0.5 °;
  • the powder X-ray diffraction line position 2 ⁇ is approximately: 17.7 ⁇ 0.5°, 20.4 ⁇ 0.5°, 23.9 ⁇ 0.5°, 24.8 ⁇ 0.5°, 29.7 ⁇ 0.5°, and 30.5 ⁇ 0.5°; Further, the powder X-ray diffraction line position 2 ⁇ is approximately: 10.3 ⁇ 0.5°, 17.7 ⁇ 0.5°, 20.4 ⁇ 0.5°, 23.9 ⁇ 0.5°, 24.8 ⁇ 0.5°, 27.0 ⁇ 0.5°, 29.7 ⁇ 0.5°, 30.5 ⁇ 0.5°, 32.2 ⁇ 0.5°, 37.0 ⁇ 0.5°.
  • the energetic compound of the present invention has high explosive heat and high energy density, the theoretical explosion heat can be as high as 1.53 kcal/g, the crystal density is in the range of 1.8 to 2.3 g/cm 3 , and the corresponding energy density can be as high as 3.11 kcal/ Cm 3 ;
  • the explosive pressure of the energetic compound of the present invention is high, and the theoretical detonation pressure can be as high as 37.3 GPa according to the Kamlet-Jacob formula;
  • the energetic compound of the invention has good safety performance, and the impact sensitivity, friction and electrostatic sensitivity are extremely low, and the thermal sensitivity burst temperature can reach 340 ° C;
  • the energetic compound of the present invention has no volatility, can be stored for a long period of time without decomposition, and is not hygroscopic;
  • the energy-containing compound of the present invention has a single room temperature crystallinity, is inexpensive and easily available, and has a simple production process and can be prepared in a safe and large amount.
  • Figure 1 is a schematic view showing the structure of the energetic compound DAP-1.
  • Figure 8 is a thermogravimetric analysis of the energetic compound DAP-3 of Example 3.
  • Figure 10 is a thermogravimetric analysis of the energetic compound DAP-4 of Example 4.
  • Figure 11 is a differential scanning calorimetry chart of the energetic compound DAP-4 of Example 4.
  • Figure 12 is a thermogravimetric analysis of the energetic compound DAP-O22 of Example 5.
  • Figure 13 is a differential scanning calorimetry chart of the energetic compound DAP-O22 of Example 5.
  • Figure 14 is a differential scanning calorimetry chart of the energetic compound DAP-O24 of Example 7.
  • Figure 15 is a powder X-ray diffraction pattern of the energetic compound PAP-1 of Example 8.
  • Figure 16 is a thermogravimetric analysis of the energetic compound PAP-1 of Example 8.
  • Figure 19 is a powder X-ray diffraction pattern of the energetic compound DAN-2 of Example 10.
  • Figure 20 is an infrared spectrum of the energetic compound DAN-2 of Example 10.
  • Figure 22 is a differential scanning calorimetry chart of the energetic compound DAN-2 of Example 10.
  • Figure 23 is a powder X-ray diffraction pattern of the energetic compound DAN-4 of Example 11.
  • Figure 24 is a thermogravimetric analysis chart of the energetic compound DAN-4 of Example 11.
  • Figure 25 is a differential scanning calorimetry chart of the energetic compound DAN-4 of Example 11.
  • the inventors designed a series of perovskite-type compounds with energetic groups, and for the first time conducted relevant experimental research on their prospects for use in the energetic field as a new type of high-performance explosives.
  • a class of compounds having a perovskite-containing group capable of (ABX 3, corresponding to the embodiment to be respectively abbreviated number and DAP the following embodiment)
  • Energy density and explosive performance can be compared with active high-performance military explosives RDX and HMX, and it has excellent safety performance, no volatility, no moisture absorption, cheap and easy to obtain raw materials, simple synthesis process, and is a kind of practical value in the field of energetic energy.
  • New energetic compounds are examples of energy density and explosive performance.
  • ABX 3 The synthesis of ABX 3 can be carried out according to the synthesis method of the present invention.
  • X in ABX 3 is at least one anionic energetic group.
  • An energetic group refers to an explosive group.
  • Common explosive groups include, but are not limited to, ClO 3 - , ClO 4 - , IO 4 - , NO 3 - , ONC - , azo groups, azide ions, nitro groups and the like.
  • X may contain one or more than one type of ions, for example, two, three, four, five, six, seven, eight, nine may be present simultaneously.
  • a and B When the perovskite comprises more than one A cation, the different A cations may be distributed in the ordered or disordered manner at the A site.
  • the perovskite comprises more than one B cation the different B cations may be distributed in the ordered or disordered manner at the B site.
  • the perovskite comprises more than one X anion, the different X anions may be distributed at the X site in an ordered or disordered manner.
  • X is at least one ... group / ion
  • A is at least one ... group / ion
  • B is at least one ... group / ion
  • X From “"A selected from""B is selected from” and the like, it should be understood that, for example, for X, in the three-dimensional skeleton of ABX 3 , there are many X sites, each X The site is composed of an ion. In the three-dimensional framework, a plurality of X sites may be composed of the same ion or a plurality of different ions. When composed of different ions, at least some sites exist therein (or Most of the sites are... groups/ions.
  • the invention includes powder X-ray diffraction identification, single crystal structure characterization test, infrared spectroscopy characterization, thermal stability characterization, differential scanning calorimetry (DSC), sensitivity characterization, explosion/burst/detonation value calculation A variety of identification and characterization methods.
  • the powder X-ray diffraction data at room temperature was collected on a Bruker D8 Advance diffractometer, using Cu-K ⁇ ray, scanning method: ⁇ : 2 ⁇ linkage, step scan, 2 ⁇ step size was 0.02°.
  • the single crystal X-ray diffraction data was collected on an Oxford Gemini S Ultra CCD diffractometer.
  • the graphite monochromator was collected by ⁇ scanning using Mo-K ⁇ ray.
  • the absorption correction was performed using the SADABS program.
  • the direct method is used for analysis, and then the non-hydrogen atom coordinates are obtained by the difference Fourier function method and the least squares method. Finally, the structure is corrected by the least squares method.
  • the organic hydrogen atom of the compound is obtained by theoretical hydrogenation.
  • the impact sensitivity is determined by the 601.1 explosion probability method; the friction sensitivity is determined by the 602.1 explosion probability method; the thermal sensitivity test is the method 606.1-burst point 5 second lag period method.
  • the electrostatic sensitivity test method is WJ/T 9038.3-2004 industrial pyrotechnics test method Part 3: Static spark sensitivity test.
  • Solution of perchloric acid radicals in the infrared absorption spectrum peaks located at 1070 ⁇ 1100cm -1 (corresponding to the asymmetric stretching vibrations) and 617 ⁇ 637cm -1 (corresponding to the asymmetric bending vibrations); nitric radicals in the infrared absorption spectrum
  • the characteristic peaks are located at 1375 to 1390 cm -1 (corresponding to asymmetric stretching vibration) and 845 to 860 cm -1 (corresponding to asymmetric bending vibration).
  • employed as the compound of energetic material is (C 6 H 14 N 2) [Na (ClO 4) 3] ( referred to as DAP-1), which crystallized in a cubic system at 223K Pa-3 space group, the unit cell length is Its powder X-ray diffraction (Cu-K ⁇ ray) at room temperature occurs at a diffraction angle 2 ⁇ of approximately: 12.3 ⁇ 0.5°, 21.5 ⁇ 0.5°, 24.9 ⁇ 0.5°, 27.9 ⁇ 0.5°, 35.6 ⁇ 0.5°, 37.2 ⁇ 0.5°.
  • the results of thermal stability analysis show that the explosion temperature can be as high as 360 °C; the results of differential scanning calorimetry show that the heat released by 360 °C is 4398J/g; the safety performance characterization results show that DAP-1 is in the impact sensitivity under the national military standard.
  • the friction sensitivity and the static spark sensitivity test are all insensitive. Under the German Federal Institute for Materials Research and Testing (BAM), the impact sensitivity of DAP-1 is about 17J, and the friction sensitivity is about 36N.
  • the burst point of DAP-1 is as high as 340 ° C (5 s lag period method).
  • Density functional DFT theory obtained the calorific value, detonation rate and detonation pressure of energetic compounds were 1.53kcal/g, 8.85km/s and 37.31GPa, respectively.
  • the compound used as the energetic material is (C 6 H 14 N 2 )[K(ClO 4 ) 3 ] (denoted as DAP-2), which crystallizes in the cubic system at 223 K. Pa-3 space group, the unit cell length is Its powder X-ray diffraction (Cu-K ⁇ ray) at room temperature occurs at a diffraction angle 2 ⁇ of approximately 12.15 ⁇ 0.5°, 21.27 ⁇ 0.5°, 24.63 ⁇ 0.5°, 27.64 ⁇ 0.5°, 35.20 ⁇ 0.5°, 36.89 ⁇ 0.5°.
  • the compound used as the energetic material is (C 6 H 14 N 2 )[Rb(ClO 4 ) 3 ] (denoted as DAP-3), which crystallizes in the cubic system at 223 K. Pa-3 space group, the unit cell length is Its powder X-ray diffraction (Cu-K ⁇ ray) at room temperature occurs at a diffraction angle 2 ⁇ of approximately: 12.0 ⁇ 0.5°, 21.0 ⁇ 0.5°, 24.3 ⁇ 0.5°, 27.3 ⁇ 0.5°, 34.7 ⁇ 0.5°, 36.4 ⁇ 0.5°. Thermal stability analysis showed that the explosion temperature can be as high as 343 °C.
  • the compound used as the energetic material is (C 6 H 14 N 2 )[NH 4 (ClO 4 ) 3 ] (denoted as DAP-4), which is crystallized in cubic crystal at 223 K.
  • the Pa-3 space group, the unit cell length is Its powder X-ray diffraction (Cu-K ⁇ ray) at room temperature occurs at a diffraction angle 2 ⁇ of approximately: 12.0 ⁇ 0.5°, 21.0 ⁇ 0.5°, 24.4 ⁇ 0.5°, 27.3 ⁇ 0.5°, 34.8 ⁇ 0.5°, 36.5 ⁇ 0.5°.
  • the compound used as the energetic material is (C 6 H 14 N 2 O 2 )[K(ClO 4 ) 3 ] (denoted as DAP-O22), which is crystallized at 298 K in cubic form.
  • the Fm-3c space group of the crystal system, the unit cell length is Its powder X-ray diffraction (Cu-K ⁇ ray) at room temperature occurs at a diffraction angle 2 ⁇ of approximately: 11.9 ⁇ 0.5°, 20.8 ⁇ 0.5°, 24.1 ⁇ 0.5°, 27.0 ⁇ 0.5°, 34.4 ⁇ 0.5°, 36.1 ⁇ 0.5°.
  • the compound used as the energetic material is (C 6 H 14 N 2 O)[K(ClO 4 ) 3 ] (denoted as DAP-O12). Its powder X-ray diffraction (Cu-K ⁇ ray) at room temperature occurs at a diffraction angle 2 ⁇ of approximately 12.1 ⁇ 0.5°, 21.1 ⁇ 0.5°, 24.4 ⁇ 0.5°, 27.3 ⁇ 0.5°, 34.8 ⁇ 0.5°, 36.5 ⁇ 0.5°.
  • the compound used as the energetic material is (C 6 H 14 N 2 O 2 )[NH 4 (ClO 4 ) 3 ] (denoted as DAP-O24). Its powder X-ray diffraction (Cu-K ⁇ ray) at room temperature occurs at a diffraction angle 2 ⁇ of approximately: 11.9 ⁇ 0.5°, 20.8 ⁇ 0.5°, 24.0 ⁇ 0.5°, 27.0 ⁇ 0.5°, 34.4 ⁇ 0.5°, 36.0 ⁇ 0.5°. The results of differential scanning calorimetry showed that the heat released at 357 °C reached 4632 J/g. The safety performance characterization results showed that the impact sensitivity of DAP-1 was about 4J under the German Federal Institute for Materials Research and Testing (BAM). The sensitivity is about 32N.
  • the compound used as the energetic material is (C 4 H 12 N 2 )[Na(ClO 4 ) 3 ] (denoted as PAP-1). Its powder X-ray diffraction (Cu-K ⁇ ray) at room temperature occurs at a diffraction angle of 2 ⁇ of approximately 12.6 ⁇ 0.5°, 21.7 ⁇ 0.5°, 22.4 ⁇ 0.5°, 22.7 ⁇ 0.5°, 25.4 ⁇ 0.5°, 26.8 ⁇ 0.5°, 27.2 ⁇ 0.5°, 37.7 ⁇ 0.5°, 38.4 ⁇ 0.5°. Differential scanning calorimetry analysis showed that the liberated heat at 375 ° C reached 4685 J/g.
  • the compound used as the energetic material is (C 4 H 12 N 2 )[NH 4 (ClO 4 ) 3 ] (denoted as PAP-4). Differential scanning calorimetry analysis showed that the heat liberated at 356 ° C reached 3780 J / g.
  • the compound used as the energetic material is (C 6 H 14 N 2 )[K(NO 3 ) 3 ] (denoted as DAN-2). Its powder X-ray diffraction (Cu-K ⁇ ray) at room temperature occurs at a diffraction angle 2 ⁇ of approximately: 12.6 ⁇ 0.5°, 17.9 ⁇ 0.5°, 22.0 ⁇ 0.5°, 25.5 ⁇ 0.5°, 28.6 ⁇ 0.5°, 31.3 ⁇ 0.5°, 36.4 ⁇ 0.5°, 38.7 ⁇ 0.5°, 40.9 ⁇ 0.5°, 43.0 ⁇ 0.5°.
  • the compound used as the energetic material is (C 6 H 14 N 2 )[NH 4 (NO 3 ) 3 ] (denoted as DAN-4). Its powder X-ray diffraction (Cu-K ⁇ ray) at room temperature occurs at a diffraction angle 2 ⁇ of approximately 10.3 ⁇ 0.5°, 17.7 ⁇ 0.5°, 20.4 ⁇ 0.5°, 23.9 ⁇ 0.5°, 24.8 ⁇ 0.5°, 27.0 ⁇ 0.5°, 29.7 ⁇ 0.5°, 30.5 ⁇ 0.5°, 32.2 ⁇ 0.5°, 37.0 ⁇ 0.5°. The results of differential scanning calorimetry showed that the heat liberated at 170 ° C reached 1098 J/g.
  • step 1) Mix the solution of step 1) and step 2), stir for 30 minutes, filter, wash the filter residue three times with ethanol, and dry in vacuo to obtain a white powdery solid, which was identified as a perovskite compound (C 6 H 14 N 2 ) [Na(ClO 4 ) 3 ] (numbered DAP-1), the yield is about 80%.
  • Powder X-ray diffraction identification map
  • the powder X-ray diffraction pattern at room temperature is shown in Fig. 2, and the characteristic peaks thereof are shown in Table 1.
  • FIG. 1 A schematic diagram of the three-dimensional crystal structure is shown in Fig. 1.
  • the Na + ion at the B site is connected to 6 adjacent ClO 4 - anions at the X site, and each ClO 4 - anion is connected to two adjacent Na + ions, thereby forming A three-dimensional anion skeleton consisting of a cubic cage unit; an organic cation 1,4-dihydro-1,4-diazabicyclo[2.2.2]octane ammonium ion at the A site (C 6 H 14 N 2 2 + ) Filled in the holes of each cube cage unit.
  • the infrared spectrum of DAP-1 is shown in Figure 3. It can be seen from Fig. 3 that the characteristic peak of the organic component is the stretching vibration peaks 3452, 3188, 3055, 3013, 2924, 2795, 2706 cm -1 of the -CH 2 - group; the stretching vibration peak of NH + is 2606 cm -1 The characteristic peak of perchlorate is its asymmetric stretching vibration of 1078 cm -1 and asymmetric bending vibration of 627 cm -1 .
  • thermogravimetric curve of DAP-1 is shown in Figure 4.
  • the energetic compound DAP-1 of Example 1 exploded at 360 ° C in the case where the loading amount was 3.291 mg and the heating rate was 5 ° C/min.
  • the DSC curve of DAP-1 is shown in Figure 5. As can be seen from Fig. 5, the energetic compound DAP-1 in the non-charged state of Example 1 decomposed at 360 ° C and released a large amount of heat (about 4398 J/g).
  • the impact sensitivity is measured by the 601.1 explosion probability method.
  • the explosion probability of TNT is 9/25, while the DAP-1 explosion probability is 0%;
  • the friction sensitivity is measured by 602.1 explosion probability method. 2.45MPa, 80 ° swing angle), the explosion probability of PETN is 2/25, and the explosion probability of DAP-1 is 0%;
  • the thermal sensitivity test is method 606.1-explosion point 5 seconds lag period method, DAP is measured -1 violent explosion at 340 ° C, indicating that the DAP-1 burst point is 340 ° C.
  • the electrostatic sensitivity test method is WJ/T 9038.3-2004 industrial pyrotechnics test method Part 3: Electrostatic spark sensitivity test, the half-fire voltage V 50 of 25mg sample is 4.77kV (standard deviation 0.21kV), half-fire energy E 50 The electrostatic spark sensitivity of 0.53 J, that is, DAP-1 is 21.2 J.
  • the impact sensitivity of DAP-1 is about 17J, and the friction sensitivity is about 36N.
  • DFT Density functional theory
  • the decomposition calorific value of DAP-1 (decomposition enthalpy ⁇ H det ) is calculated by density functional theory (DFT) theory (J. Am. Chem. Soc. 2012, 134, 1422), which is about 1.53 kcal/g, which is higher than the active duty.
  • DFT density functional theory
  • the detonation velocity of the DAP compound is about 8.85 km/s, and the detonation pressure is about 37.31 GPa.
  • Corresponding values with active energetic materials HMX: detonation speed 9.10km/s, detonation pressure 39.50GPa; RDX: detonation speed 8.80km/s, explosion pressure 33.80GPa).
  • 1 mole of DAP-1 can produce 12 moles of gaseous species after complete explosion in an anaerobic environment, leaving 3 moles of elemental carbon and 1 mole of sodium chloride in a solid state.
  • sufficient oxidant such as the usual NH 4 ClO 4
  • 1 mole of solid residue of sodium chloride is present after 1 mole of DAP-1 is completely exploded.
  • step 1) Mix the solution of step 1) and step 2), stir for 30 minutes, filter, wash the filter residue three times with ethanol, and dry in vacuo to obtain a white powdery solid, which was identified as a perovskite compound (C 6 H 14 N 2 ) [K(ClO 4 ) 3 ] (No. DAP-2), the yield is about 90%.
  • Powder X-ray diffraction identification map
  • the powder X-ray diffraction pattern at room temperature is shown in Fig. 2, and the characteristic peaks thereof are shown in Table 3.
  • thermogravimetric curve of DAP-2 is shown in Figure 6.
  • the energetic compound DAP-2 of Example 2 exploded at 362 ° C in the case where the loading amount was 6.65 mg and the heating rate was 5 ° C/min.
  • the DSC curve of DAP-2 is shown in Figure 7. As is apparent from Fig. 7, the energetic compound DAP-2 in the non-charged state of Example 2 decomposed at 377 ° C and released a large amount of heat (about 4076 J/g).
  • the impact sensitivity of DAP-2 is about 16J, and the friction sensitivity is about 42N.
  • DFT Density functional theory
  • the decomposition calorific value of DAP-2 (decomposition enthalpy ⁇ H det ) is calculated by density functional theory (DFT) theory (J. Am. Chem. Soc. 2012, 134, 1422), which is about 1.46 kcal/g, which is higher than the active duty.
  • DFT density functional theory
  • the detonation velocity of the DAP compound is about 8.64 km/s, and the detonation pressure is about 35.73 GPa.
  • step 1) Mix the solution of step 1) and step 2), stir for 30 minutes, filter, wash the filter residue three times with ethanol, and dry in vacuo to obtain a white powdery solid, which was identified as a perovskite compound (C 6 H 14 N 2 ) [Rb(ClO 4 ) 3 ] (No. DAP-3), the yield is about 85%.
  • Powder X-ray diffraction identification map
  • the powder X-ray diffraction pattern at room temperature is shown in Fig. 2, and the characteristic peaks thereof are shown in Table 5.
  • thermogravimetric curve of DAP-3 is shown in Figure 8. As can be seen from Fig. 8, the energetic compound DAP-3 of Example 3 exploded at 343 ° C in the case where the loading amount was 4.45 mg and the heating rate was 5 ° C / min.
  • the DSC curve of DAP-3 is shown in Figure 9. As is apparent from Fig. 9, the energetic compound DAP-3 in the non-charged state of Example 3 decomposed at 369 ° C and released a large amount of heat (about 3,797 J/g).
  • the impact sensitivity of DAP-3 is about 22J, and the friction sensitivity is about 28N.
  • DFT Density functional theory
  • the decomposition calorific value of DAP-3 (decomposition enthalpy ⁇ H det ) is calculated by density functional theory (DFT) theory (J. Am. Chem. Soc. 2012, 134, 1422), which is about 1.33 kcal/g, which is higher than the active duty.
  • DFT density functional theory
  • the detonation velocity of the DAP compound is about 8.43 km/s, and the detonation pressure is about 35.14 GPa.
  • 1 mole of DAP-3 can produce 12 moles of gaseous species after complete explosion in an anaerobic environment, leaving 3 moles of elemental carbon and 1 mole of ruthenium chloride solid.
  • sufficient oxidant such as the usual NH 4 ClO 4
  • 1 mole of solid residue of ruthenium chloride is present after 1 mole of DAP-3 is completely exploded.
  • step 1) Mix the solution of step 1) and step 2), stir for 10 minutes, filter, wash the filter residue three times with ethanol, and dry in vacuo to obtain a white powdery solid, which was identified as a perovskite compound (C 6 H 14 N 2 [NH 4 (ClO 4 ) 3 ] (DAP-4), the yield is about 90%.
  • Powder X-ray diffraction identification map
  • the powder X-ray diffraction pattern at room temperature is shown in Fig. 2, and the characteristic peaks thereof are shown in Table 7.
  • thermogravimetric curve of DAP-4 is shown in Figure 10. As can be seen from Fig. 10, in the case where the loading amount was 4.825 mg and the heating rate was 5 °C/min, the energetic compound DAP-4 of Example 4 exploded at 370 °C.
  • the DSC curve of DAP-4 is shown in Figure 11. As is apparent from Fig. 11, the energetic compound DAP-4 in the non-charged state of Example 4 decomposed at 364 ° C and released a large amount of heat (about 5177 J/g).
  • the impact sensitivity of DAP-4 is about 23J, and the friction sensitivity is about 36N.
  • step 1) The solution of the step 1) and the step 2) was mixed and stirred for 10 minutes, and the crystal was gradually formed by standing. Filtration, washing the filter residue with ethanol three times, and drying under vacuum to obtain a white powdery solid, which was identified as a perovskite compound (C 6 H 14 N 2 O 2 ) [K(ClO 4 ) 3 ] (DAP-O22). The rate is about 55%.
  • Powder X-ray diffraction identification map
  • the powder X-ray diffraction pattern at room temperature is shown in Fig. 2, and the characteristic peaks thereof are shown in Table 9.
  • thermogravimetric curve of DAP-O22 is shown in Fig. 12. As is clear from Fig. 12, in the case where the loading amount was 4.175 mg and the heating rate was 5 °C/min, the decomposition temperature of the energetic compound DAP-O22 of Example 5 was 354 °C.
  • the DSC curve of DAP-O22 is shown in Figure 13. As is apparent from Fig. 13, the energetic compound DAP-O22 in the non-charged state of Example 5 decomposed at 358 ° C and released a large amount of heat (about 5424 J/g).
  • the impact sensitivity of DAP-O22 is about 11J.
  • the friction sensitivity is about 14N.
  • 1 mole of DAP-O22 can produce 13 moles of gaseous species after complete explosion in an anaerobic environment, leaving 2 moles of elemental carbon and 1 mole of potassium chloride solid.
  • sufficient oxidant such as the usual NH 4 ClO 4
  • 1 mole of potassium chloride solid residue is present after 1 mole of DAP-O22 is completely exploded.
  • step 1) The solution of the step 1) and the step 2) was mixed and stirred for 10 minutes, and the crystal was gradually formed by standing. Filtration, washing the filter residue with ethanol three times, and drying in vacuo to give a white powdery solid, identified as a perovskite compound (C 6 H 14 N 2 O) [K(ClO 4 ) 3 ] (DAP-O12), yield About 30%.
  • Powder X-ray diffraction identification map
  • the powder X-ray diffraction pattern at room temperature is shown in Fig. 2, and the characteristic peaks thereof are shown in Table 11.
  • 1 mole of DAP-O12 can produce 12.5 moles of gaseous species after complete explosion in an oxygen-free environment, leaving 2.5 moles of elemental carbon and 1 mole of potassium chloride in a solid state.
  • sufficient oxidant such as the usual NH 4 ClO 4
  • 1 mole of potassium chloride solid residue is present after 1 mole of DAP-O12 is completely exploded.
  • step 1) The solution of the step 1) and the step 2) was mixed and stirred for 10 minutes, and the crystal was gradually formed by standing. Filtration, washing the filter residue with ethanol three times, and drying in vacuo to give a white powdery solid, identified as a perovskite compound (C 6 H 14 N 2 O 2 ) [NH 4 (ClO 4 ) 3 ] (DAP-O24), The yield is about 30%.
  • Powder X-ray diffraction identification map
  • the powder X-ray diffraction pattern at room temperature is shown in Fig. 2, and the characteristic peaks thereof are shown in Table 12.
  • the DSC curve of DAP-O24 is shown in Figure 14. As is apparent from Fig. 14, the energetic compound DAP-O24 in the non-charged state of Example 7 decomposed at 357 ° C and released a large amount of heat (about 4632 J/g).
  • the impact sensitivity of DAP-O24 is about 4J, and the friction sensitivity is about 32N.
  • step 1) Mix the solution of step 1) and step 2), concentrate by heating, stir for 30 minutes, filter, wash the filter residue three times with ethanol, and dry in vacuo to obtain a white powdery solid, which is identified as a perovskite compound (C 4 H 12 N 2 )[Na(ClO 4 ) 3 ] (numbered PAP-1), the yield was about 50%.
  • a perovskite compound C 4 H 12 N 2 )[Na(ClO 4 ) 3 ] (numbered PAP-1)
  • Powder X-ray diffraction identification map
  • the powder X-ray diffraction pattern at room temperature is shown in Fig. 15, and the characteristic peaks thereof are shown in Table 13.
  • thermogravimetric curve of PAP-1 is shown in Fig. 16. As can be seen from Fig. 16, the energetic compound PAP-1 of Example 8 exploded at 367 ° C in the case where the loading amount was 2.23 mg and the heating rate was 5 ° C / min.
  • the DSC curve of PAP-1 is shown in Figure 17. As is apparent from Fig. 17, the energetic compound PAP-1 in the non-charged state of Example 8 decomposed at 375 ° C and released a large amount of heat (about 4685 J/g).
  • 1 mole of PAP-1 can produce 11.5 moles of gaseous species after complete explosion in an oxygen-free environment, leaving 0.5 moles of elemental carbon and 1 mole of sodium chloride in a solid state.
  • sufficient oxidant such as the usual NH 4 ClO 4
  • 1 mole of sodium chloride solid residue is present after 1 mole of PAP-1 is completely exploded.
  • step 1) Mix the solution of step 1) and step 2), concentrate by heating, stir for 30 minutes, filter, wash the filter residue three times with ethanol, and dry in vacuo to obtain a white powdery solid, which is identified as a perovskite compound (C 4 H 12 N 2 )[NH 4 (ClO 4 ) 3 ] (No. PAP-4), the yield was about 40%.
  • the DSC curve of PAP-4 is shown in Figure 18. As is apparent from Fig. 18, the energetic compound PAP-4 in the non-charged state of Example 9 was decomposed at 356 ° C (exothermic about 3780 J/g).
  • Powder X-ray diffraction identification map
  • the powder X-ray diffraction pattern at room temperature is shown in Fig. 19, and the characteristic peaks thereof are shown in Table 15.
  • the infrared spectrum of DAN-2 is shown in Fig. 20.
  • the characteristic peaks of nitrate are its asymmetric stretching vibration of 1385 cm -1 and asymmetric bending vibration of 852 cm -1 .
  • thermogravimetric curve of DAN-2 is shown in Figure 21. As is clear from Fig. 21, in the case where the loading amount was 3.33 mg and the heating rate was 5 °C/min, the temperature at which the energetic compound DAN-2 of Example 10 started to decompose was 177 °C.
  • the DSC curve of DAN-2 is shown in Figure 22. As is apparent from Fig. 22, the energetic compound DAN-2 in the non-charged state of Example 10 was gradually decomposed at 177 ° C (exothermic about 1222 J/g).
  • the impact sensitivity of DAN-2 is about 29J, and the friction sensitivity is greater than 360N.
  • step 1) Mixing the solutions of step 1) and step 2), stirring and filtering, washing the filter residue three times with ethanol, and drying in vacuo to obtain a white powdery solid, which was identified as a hexagonal perovskite compound (C 6 H 14 N 2 ) [ NH 4 (NO 3 ) 3 ] (No. DAN-4), the yield was about 60%.
  • Powder X-ray diffraction identification map
  • the powder X-ray diffraction pattern at room temperature is shown in Fig. 23, and the characteristic peaks thereof are shown in Table 17.
  • thermogravimetric curve of DAN-4 is shown in Figure 24. As is clear from Fig. 24, in the case where the loading amount was 6.42 mg and the heating rate was 5 °C/min, the temperature at which the energetic compound DAN-4 of Example 11 started to decompose was 167 °C.
  • the DSC curve of DAN-4 is shown in Figure 25. As is apparent from Fig. 25, the energetic compound DAN-4 in the non-charged state of Example 11 started to decompose at 170 ° C (exothermic about 1098 J/g).
  • DAN-4 In the case of mixing sufficient oxidant (such as the usual NH 4 NO 3 ), 1 mole of DAN-4 can be completely free of solid residues after explosion. In particular, DAN-4 does not contain halogen elements and does not generate hydrogen halide gas after explosion, which can reduce characteristic signals and reduce environmental pollution in practical applications.
  • oxidant such as the usual NH 4 NO 3
  • the perovskite-type energetic compound of the invention has high explosive heat, high energy density, high detonation speed, high explosion pressure, good safety performance, low sensitivity to impact, friction and static electricity, no volatility, and long-term storage. Decomposition, non-hygroscopic, cheap and easy to obtain raw materials, simple synthesis process, no by-products, can be prepared in large quantities.
  • perovskite-type energetic compound of the present invention as an energetic material such as an explosive is not expected in the prior art.
  • perchlorate is an energetic group
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Abstract

本发明属于含能化合物领域。具体涉及一类钙钛矿型化合物ABX3在作为含能材料方面的用途。作为本发明的一个发现，钙钛矿型的结构特征使这类化合物具有较高的稳定性，克服现有技术的炸药因稳定性差而带来的不安全性；同时，其结构特点因富含含能基团且这些氧化性含能阴离子与还原性有机阳离子在空间中相间排列的特征而赋予了这类化合物在引爆时的优良的瞬间能量。由此形成的立体结构使得化合物在带来含能材料作用的同时，能克服一些已有含能材料的缺陷。

Description

一类化合物在作为含能材料方面的用途 技术领域
本发明涉及含能材料领域。具体地说，涉及钙钛矿型化合物在作为含能材料方面的用途。
背景技术
含能化合物是一类具有高能量密度的爆炸物质。最早的含能材料是公元九世纪出现的中国黑火药，由硫磺、硝酸钾和木炭粉混合制成，效果差并且性能表现不稳定。到了近代，硝酸甘油最初作为一种医药产品被发现，随后的生产中人们发现它是一种烈性炸药。硝酸甘油的性能比黑火药先进的多，但是感度很高，生产和运输非常危险。阿尔弗雷德·贝恩哈德·诺贝尔在不懈的生产和研究中发现硅藻土可以吸附硝酸甘油，虽然牺牲了一定的爆炸性能，但有效地提高了产品的安全性，由此将硝酸甘油顺利的推向了工业应用。步入现代社会以后，比硝酸甘油更高性能的炸药被不断发现并投入应用。著名的有三硝基甲苯(TNT)以及比TNT爆炸性能更强的有机含能材料黑索金(RDX)和奥托金(HMX)，这三者广泛存在于世界各国的武器弹药之中。近年性能更加优秀但昂贵复杂的有机炸药六硝基六氮杂异伍兹烷(CL-20)的工业化流程被我国科学家探索出来，推动了我国军事弹药更新的前景。近年来，一些带有含能基团的金属有机骨架化合物(如：Angew.Chem.Int.Ed.2013,52,14031；Chem.Eur.J.2013,19,1706)颇受关注，这类化合物具有丰富的基团可调控性以及经由理论计算指出的高爆热性能，被视作下一代炸药开发的重要方向。
现代炸药的开发进展中，不同的炸药除了有各个方面的性能进步也同时不可避免的有各自的缺陷。例如：具有爆炸性的高氯酸钾曾经用作闪光弹助氧剂，但由于撞击感度高，易在运输途中爆炸而被最终弃用(参见《High Energy Materials:Propellants,Explosives and Pyrotechnics》第347页，Jai Prakash Agrawal编著，Wiley-VCH出版社，2010)。现有的有机含能材料以及尚处在基础研究阶段的金属有机骨架含能材料，虽然不乏爆炸性能优异者，但绝大多数存在合成工艺复杂，步骤多，价格较为昂贵，稳定性较差，以及对撞击、摩擦等十分敏感等诸多缺点，因而难以得到实用。因此，如何设计并合成同时具有低成本、高能量密度、低敏感度(高安全性)等优点的钝感高能含能材料，是含能材料领域的一个经久不衰的追求。
发明内容
本发明的目的之一在于提供一类新的含能材料。
本发明的目的之二在于提供一类具有良好安全性能的含能材料。
本发明的目的之三在于提供一类爆炸性能良好的含能材料。
本发明的目的之四在于提供一类能量密度高的含能材料。
在含能材料领域，本发明首次应用了钙钛矿型化合物作为含能材料，并突破性地发现其作为含能材料使用时具有尤其适用的性能。
所述的钙钛矿性化合物具有含能基团，例如，ClO4 -含能基团。该类含能材料可以作为，但不限于作为炸药使用。例如，其还可以作为推进剂、火箭燃料或安全气囊的气体发生剂进行使用。
钙钛矿型化合物是指与钛酸钙(CaTiO3)具有相似晶体结构的一类固态化合物，它们具有相同的化学通式ABX3。其中，A和B是不同尺寸的阳离子，而X是阴离子；其理想的结构属于高对称性的立方晶系，结构特征可以描述为：每个B位阳离子与6个相邻的X阴离子相连，每个X阴离子与两个相邻的B位阳离子相连，进而形成由立方体笼状单元组成的三维阴离子骨架；A位阳离子则填充在这些立方体笼状单元的孔穴中。其中，A是至少一种阳离子，B是至少一种阳离子，而X是至少一种阴离子。当钙钛矿包括多于一种的A阳离子时，不同的A阳离子可以以有序的或无序的方式分布在A位点上。当钙钛矿包括多于一种的B阳离子时，不同的B阳离子可以以有序的或无序的方式分布在B位点上。当钙钛矿包括多于一种X阴离子时，不同的X阴离子可以以有序的或无序的方式分布在X位点上。
目前钙钛矿型化合物一般作为铁电材料、光电材料、电磁材料等而研究和应用。
作为本发明的一个发现，A阳离子比B阳离子大的钙钛矿型化合物中，X为含能阴离子基团，由此形成的立体结构使得化合物在带来含能材料作用的同时，能克服一些已有含能材料的缺陷，例如，根据发明人推测，钙钛矿型的结构特征使这类化合物具有较高的稳定性，克服现有技术的炸药因稳定性差而带来的不安全性；同时，其结构特点因富含含能基团且这些氧化性含能阴离子与还原性有机阳离子在空间中相间排列的特征而赋予了这类化合物在引爆时的优良的瞬间能量。存放时的低感度特点及引爆时的瞬间能量爆发特点，这两个看似矛盾的特点由于钙钛矿型空间立体结构特点而被得以集合于一身，这使得这类化合物尤其适合作为含能材料例如钝感高能炸药而使用。
含能基团是指具有爆炸性的基团。但并非所有含有爆炸性基团的化合物都具有爆炸性，一种化合物是否具有爆炸性取决于其整个分子结构而不是某单个基团(参见《炸药学》第3页，张华祝等著，北京:兵器工业出版社，2004)。常见的具有爆炸性的基团有ClO3 -、ClO4 -、 NO3 -、ONC-、N(NO2)2 -、偶氮基团、叠氮离子、硝基等基团。
本发明的X是至少一种阴离子含能基团，可选地所述的X为氧化性阴离子含能基团，优选一价阴离子含能基团；更优选为一价的含卤组分的含能基团。
在一些实施例中，阴离子含能基团(X)可以是：ClO4 -、BrO4 -、IO4 -、ONC-、NO3 -、N(NO2)2 -中的一种、两种或多种。
在一些优选的实施例中，阴离子含能基团(X)可以是：ClO4 -、BrO4 -、IO4 -中的一种、两种或多种；
本发明的A是至少一种有机阳离子；尤其是A为还原性有机阳离子。
优选地，A是至少一种含氮有机阳离子；
优选地，A是至少一种含氮杂环有机阳离子；
更优选地，A是至少一种含六元环含氮杂环有机阳离子；
作为可选的实施例，所述A是以下有机物在质子化后形成的有机阳离子及它们的衍生物中的一种、两种或多种：1,4-二氮杂二环[2.2.2]辛烷，吡嗪，哌嗪，3-氨基吡咯烷，咪唑啉，氨基三氮唑，氨基四氮唑，乙二胺，二氰二胺，苯二胺，1,5-二氨基戊烷，环己二胺等等。
作为可选的实施方式，A选自以下有机阳离子母体及它们的衍生物中的一种、两种或多种：
Figure PCTCN2017097136-appb-000001
更优选地，A选自以下有机阳离子母体及它们的衍生物中的一种、两种或多种：
Figure PCTCN2017097136-appb-000002
A组分有机阳离子的衍生物指的是有机阳离子本体中的氢原子同时或不同时地被取代基 取代，常见的取代基有甲基、乙基、异丙基、叔丁基、羟基、羰基、羧基、卤素、巯基、过氧基、偶氮基和硝基等。
本发明的B是至少一种一价阳离子。
作为可选的实施方式，B选自以下阳离子的一种、两种或多种：
碱金属离子、NH4 +。
所述的碱金属离子优选地选自Na+、K+、Rb+、Cs+中的一种、两种或多种。
优选地，A选自1,4-二氢-1,4-二氮杂二环[2.2.2]辛烷铵离子、1-羟基-4-氢-1,4-二氮杂二环[2.2.2]辛烷铵离子、1,4-二羟基-1,4-二氮杂二环[2.2.2]辛烷铵离子及它们的衍生物中的一种、两种或多种；更优选地，A选自有机阳离子1,4-二氢-1,4-二氮杂二环[2.2.2]辛烷铵离子、1,4-二羟基-1,4-二氮杂二环[2.2.2]辛烷铵离子中的一种或两种；
优选地，B选自Na+、K+、NH4 +中的一种、两种或多种；更优选地，B选自Na+、NH4 +中的一种或两种；更优选地，B选自NH4 +；
更优选地，X选自ClO4 -、NO3 -、IO4 -中的一种、两种或多种；更优选地，X选自ClO4 -、NO3 -中的一种或两种，或者选自ClO4 -、IO4 -中的一种或两种；更优选地，X选自ClO4 -。
作为进一步优选的实施例，本发明的ABX3中：
A选自有机阳离子1,4-二氢-1,4-二氮杂二环[2.2.2]辛烷铵离子、1,4-二氢-吡嗪铵离子、1,4-二氢-哌嗪铵离子、1-羟基-4-氢-1,4-二氮杂二环[2.2.2]辛烷铵离子、1,4-二羟基-1,4-二氮杂二环[2.2.2]辛烷铵离子中的一种、两种或多种；
B选自Na+、K+、Rb+、NH4 +中的一种、两种或多种；
X选自ClO4 -、NO3 -、IO4 -中的一种、两种或三种；更优选地X选自ClO4 -、IO4 -中的一种或两种，或者选自ClO4 -、NO3 -中的一种或两种。
作为更进一步优选的实施例，本发明的ABX3中：
A选自有机阳离子1,4-二氢-1,4-二氮杂二环[2.2.2]辛烷铵离子、1-羟基-4-氢-1,4-二氮杂二环[2.2.2]辛烷铵离子、1,4-二羟基-1,4-二氮杂二环[2.2.2]辛烷铵离子中的一种、两种或多种；
B选自Na+、K+、Rb+、NH4 +中的一种、两种或多种；
X选自ClO4 -、NO3 -中的一种或两种，或者选自ClO4 -、IO4 -中的一种或两种；更优选地，X选自ClO4 -。
作为更进一步优选的实施例，本发明的ABX3中：
A选自有机阳离子1,4-二氢-1,4-二氮杂二环[2.2.2]辛烷铵离子、1,4-二羟基-1,4-二氮杂二环[2.2.2]辛烷铵离子中的一种或两种；
B选自Na+、K+、Rb+、NH4 +中的一种、两种或多种；
X选自ClO4 -、NO3 -中的一种或两种，或者选自ClO4 -、IO4 -中的一种或两种；更优选地，X选自ClO4 -。
作为更尤其优选的实施例，本发明的ABX3中：
A选自有机阳离子1,4-二氢-1,4-二氮杂二环[2.2.2]辛烷铵离子、1,4-二羟基-1,4-二氮杂二环[2.2.2]辛烷铵离子中的一种或两种；
B选自Na+、K+、NH4 +中的一种、两种或多种；
X选自ClO4 -、NO3 -中的一种或两种，或者选自ClO4 -、IO4 -中的一种或两种；更优选地，X选自ClO4 -。
作为最尤其优选的实施例，本发明的ABX3中：
A选自有机阳离子1,4-二氢-1,4-二氮杂二环[2.2.2]辛烷铵离子；
B选自Na+、NH4 +中的一种或两种；
X选自ClO4 -、NO3 -中的一种或两种，或者选自ClO4 -、IO4 -中的一种或两种；更优选地，X选自ClO4 -。
作为特别的实施例，本发明的ABX3中：A、X选自上述所说的任一种可能的选择，B选自NH4 +；
作为更加具体的特别的实施例，
A选自有机阳离子1,4-二氢-1,4-二氮杂二环[2.2.2]辛烷铵离子、1,4-二氢-吡嗪铵离子、1,4-二氢-哌嗪铵离子、1-羟基-4-氢-1,4-二氮杂二环[2.2.2]辛烷铵离子、1,4-二羟基-1,4-二氮杂二环[2.2.2]辛烷铵离子及它们的衍生物中的一种、两种或多种；
X选自ClO4 -、BrO4 -、IO4 -的一种、两种或多种；
B选自NH4 +；
当B选择NH4 +时，此时化合物在完全爆炸后不残留金属盐固体物质，单位摩尔数所产生的气体量可高达15.25摩尔。这个性质更有利于作为炸药、火箭燃料、推进剂和安全气囊的 气体发生剂等。尤其特别适合于对气体产生量具有高要求的应用领域，例如作为火箭燃料。
作为另一种特别的实施例，本发明的ABX3中：A、X选自上述所说的任一种可能的选择，B选自Na+；
作为更加具体的特别的实施例，
A选自有机阳离子1,4-二氢-1,4-二氮杂二环[2.2.2]辛烷铵离子、1,4-二氢-吡嗪铵离子、1,4-二氢-哌嗪铵离子、1-羟基-4-氢-1,4-二氮杂二环[2.2.2]辛烷铵离子、1,4-二羟基-1,4-二氮杂二环[2.2.2]辛烷铵离子及它们的衍生物中的一种、两种或多种；
X选自ClO4 -、BrO4 -、IO4 -的一种、两种或多种；
B选自Na+；
其中更加优选的是，其中的A选自1,4-二氢-1,4-二氮杂二环[2.2.2]辛烷铵离子，X选自ClO4 -，B选自Na+。
当B选择Na+时，其特别的优势在于：从理论上来讲，对比B选择K+的情况，其密度变低，通常认为变低的密度ρ会降低含能材料的性能(含能材料推算爆速D以及爆压P的Kamlet-Jacob方程：D＝1.01Φ1/2(1+1.30ρ)，P＝1.558Φρ2，其中Φ＝31.68N(MQ)1/2，N是材料单位质量产生的气体摩尔数，M是产物气体平均摩尔质量，Q是材料单位质量放热量。因此密度对爆速和爆压的影响都是正相关的，其中对爆压的影响更是平方指数的关系)。然而，本发明发现(见实施例1)，其作为含能材料时，虽然已经简单明了的预见到使用轻质的钠离子会降低材料密度，由此推测对材料的爆速、爆压产生负面影响，但是实验和理论计算均表明使用钠离子反而在多方面性能上获得更好的效果，例如，DAP-1(见实施例1，该钙钛矿型化合物的B为Na+)与DAP-2(见实施例2，该钙钛矿型化合物的B为K+)相比，单位质量的放热量提高了，单位质量产生的气体摩尔量也提高了，从而使得DAP-1的爆速、爆压的理论预测值均反而比DAP-2更高。此外，由于DAP-1的原料高氯酸钠比DAP-2的原料高氯酸钾更容易在极性溶剂中溶解，合成DAP-1所需溶剂比合成DAP-2的少得多，因此在实验上和生产上，DAP-1的合成更为方便。DAP-1比DAP-2在高能炸药以及推进剂领域应用可能更为适合。
作为另一个特别的实施例，本发明的ABX3中：A、B选自上述所说的任一种可能的选择，X选自NO3 -；
作为更加具体的特别的实施例，
A选自有机阳离子1,4-二氢-1,4-二氮杂二环[2.2.2]辛烷铵离子、1,4-二氢-吡嗪铵离子、1,4- 二氢-哌嗪铵离子、1-羟基-4-氢-1,4-二氮杂二环[2.2.2]辛烷铵离子、1,4-二羟基-1,4-二氮杂二环[2.2.2]辛烷铵离子及它们的衍生物中的一种、两种或多种；
B选自Na+、K+、Rb+、NH4 +中的一种、两种或多种；
X选自NO3 -；
当X选自NO3 -时，此时化合物不含卤族元素，在爆炸后不产生卤化氢气体，降低特征信号，减少环境污染。该性质使其特别适合于要求低特征信号的应用领域，例如作为低特征信号推进剂或火箭燃料。
ABX3可以通过将A组分、B组分和X组分以任意顺序加入到液态反应体系中，反应获得；液态反应体系优选可溶解A组分、B组分和X组分的极性溶剂。或借鉴已知的合成方法获得。反应温度无特别限制，可在极大范围内调节，例如0～100℃。
作为一种实施方案本发明提供了其制备方法，包括以下步骤：
1)将A组分加入到极性溶剂中，再加入X组分，搅拌均匀；
2)将B组分溶于极性溶剂；
3)将步骤1)和步骤2)的溶液混合，充分搅拌，过滤，用乙醇洗涤滤渣，真空干燥，得到白色粉末状含能化合物。
所述A组分为1,4-二氮杂二环[2.2.2]辛烷或其衍生物、吡嗪或其衍生物、哌嗪或其衍生物、1-氧化-1,4-二氮杂二环[2.2.2]辛烷或其衍生物、1,4-二氧化-1,4-二氮杂二环[2.2.2]辛烷或其衍生物、含1,4-二氢-1,4-二氮杂二环[2.2.2]辛烷铵离子或其衍生物的有机盐、含1,4-二氢-吡嗪铵离子或其衍生物的有机盐、含1,4-二氢-哌嗪铵离子或其衍生物的有机盐、含1-羟基-4-氢-1,4-二氮杂二环[2.2.2]辛烷铵离子或其衍生物的有机盐、含1,4-二羟基-1,4-二氮杂二环[2.2.2]辛烷铵离子或其衍生物的有机盐中至少的一种。
优选的，所述B组分的阳离子选自碱金属离子、NH4 +中的一种、两种或多种；B组分为含铵离子盐、含钠离子盐、含钾离子盐、含铷离子盐、含铯离子盐、含铵离子碱、含钠离子碱、含钾离子碱、含铷离子碱、含铯离子碱中的至少一种。
所述X组分为含卤含能基团的酸、含卤含能基团的盐中至少的一种。
所述的极性溶剂选自水、乙醇、甲醇中的一种、两种或多种。
作为非限制性的例子，所述含1,4-二氢-1,4-二氮杂二环[2.2.2]辛烷铵离子的有机盐为1,4-二氮杂二环[2.2.2]辛烷的盐酸盐；
所述含1,4-二氢-1,4-二氮杂二环[2.2.2]辛烷铵离子衍生物的有机盐为2-羟基-1,4-二氮杂 二环[2.2.2]辛烷的盐酸盐、2-羰基-1,4-二氮杂二环[2.2.2]辛烷的盐酸盐、2-甲基-1,4-二氮杂二环[2.2.2]辛烷的盐酸盐中至少的一种；
所述含1,4-二氢-吡嗪铵离子的有机盐为吡嗪的盐酸盐；
所述含1,4-二氢-吡嗪铵离子衍生物的有机盐为2-羟基-吡嗪的盐酸盐、2-甲基-吡嗪的盐酸盐中至少的一种；
所述含1,4-二氢-哌嗪铵离子的有机盐为哌嗪的盐酸盐；
所述含1,4-二氢-哌嗪铵离子衍生物的有机盐为2-羟基-哌嗪的盐酸盐、2-甲基-哌嗪的盐酸盐中至少的一种；
所述含1-羟基-4-氢-1,4-二氮杂二环[2.2.2]辛烷铵离子的有机盐为1-氧化-1,4-二氮杂二环[2.2.2]辛烷的盐酸盐；
所述含1-羟基-4-氢-1,4-二氮杂二环[2.2.2]辛烷铵离子衍生物的有机盐为2-羟基-1-氧化-1,4-二氮杂二环[2.2.2]辛烷的盐酸盐、2-羰基-1-氧化-1,4-二氮杂二环[2.2.2]辛烷的盐酸盐中至少的一种；
所述含1,4-二羟基-1,4-二氮杂二环[2.2.2]辛烷铵离子的有机盐为1,4-二氧化-1,4-二氮杂二环[2.2.2]辛烷的盐酸盐；
所述含1,4-二羟基-1,4-二氮杂二环[2.2.2]辛烷铵离子衍生物的有机盐为2-羟基-1,4-二氧化-1,4-二氮杂二环[2.2.2]辛烷的盐酸盐、2-羰基-1,4-二氧化-1,4-二氮杂二环[2.2.2]辛烷的盐酸盐中至少的一种；
所述含铵离子盐为高氯酸铵、四氟硼酸铵、高碘酸铵、高铼酸铵、碳酸铵、硝酸铵、磷酸铵、氯化铵、氟化铵中至少的一种；
所述钠盐为高氯酸钠、四氟硼酸钠、高碘酸钠、高铼酸钠、碳酸钠、硝酸钠、磷酸钠、氯化钠、氟化钠中的至少一种；
所述钾盐为高氯酸钾、四氟硼酸钾、高碘酸钾、高铼酸钾、碳酸钾、硝酸钾、磷酸钾、氯化钾、氟化钾中的至少一种；
所述铷盐为高氯酸铷、四氟硼酸铷、高碘酸铷、高铼酸铷、碳酸铷、硝酸铷、磷酸铷、氯化铷、氟化铷中的至少一种；
所述铯盐为高氯酸铯、四氟硼酸铯、高碘酸铯、高铼酸铯、碳酸铯、硝酸铯、磷酸铯、氯化铯、氟化铯中的至少一种。
所述含铵离子碱为氨水；
所述含钠离子碱为氢氧化钠；
所述含钾离子碱为氢氧化钾；
所述含铷离子碱为氢氧化铷；
所述含铯离子碱为氢氧化铯；
优选地所述X组分为含高氯酸根的物质。例如优选为高氯酸。
所述极性溶剂为水、乙醇、甲醇中的至少一种。
在一些实施例中，钙钛矿型化合物ABX3含有高氯酸根时，其高氯酸根红外吸收光谱特征峰位于1070～1100cm-1和617～637cm-1之处；
含有硝酸根时，其硝酸根红外吸收光谱特征峰位于1375～1390cm-1和845～860cm-1之处；
处于立方晶系时，粉末X射线衍射线位置2θ约为：12.1±0.70°，21.1±1.00°和24.4±1.20°之处；更进一步地，粉末X射线衍射线位置2θ约为：12.1±0.70°，21.1±1.00°，24.4±1.20°，27.4±1.30°和36.57±0.88°之处；
或，处于单斜晶系时，粉末X射线衍射线位置2θ约为：12.6±0.5°，21.7±0.5°，22.4±0.5°，22.7±0.5°，25.4±0.5°和26.8±0.5°之处；更进一步地，粉末X射线衍射线位置2θ约为：12.6±0.5°，21.7±0.5°，22.4±0.5°，22.7±0.5°，25.4±0.5°，26.8±0.5°，27.2±0.5°，37.7±0.5°，38.4±0.5°之处；
或，处于六方晶系时，粉末X射线衍射线位置2θ约为：17.7±0.5°，20.4±0.5°，23.9±0.5°，24.8±0.5°，29.7±0.5°和30.5±0.5°之处；更进一步地，粉末X射线衍射线位置2θ约为：10.3±0.5°，17.7±0.5°，20.4±0.5°，23.9±0.5°，24.8±0.5°，27.0±0.5°，29.7±0.5°，30.5±0.5°，32.2±0.5°，37.0±0.5°之处。
本发明具有突出的有益效果：
(1)本发明的含能化合物的爆热高，能量密度高，理论爆热可高达1.53kcal/g，晶体密度处于1.8～2.3g/cm3的范围，相应的能量密度可高达3.11kcal/cm3；
(2)本发明的含能化合物的爆速高，根据Kamlet-Jacob公式计算，理论爆速可高达8.85km/s；
(3)本发明的含能化合物的爆压高，根据Kamlet-Jacob公式计算，理论爆压可高达37.3GPa；
(4)本发明的含能化合物的安全性能良好，其撞击感度、摩擦和静电感度极低，热感度爆发点温度可达340℃；
(5)本发明的含能化合物无挥发性，可长期储存不分解，不吸湿；
(6)本发明的含能化合物的室温结晶性单一，原材料便宜易得，生产工艺简单，可以安全大量地制备。
附图说明
图1为含能化合物DAP-1的结构示意图。
图2为实施例1～7的含能化合物的粉末X射线衍射图。
图3为实施例1的含能化合物DAP-1的红外图谱。
图4为实施例1的含能化合物DAP-1的热重分析图谱。
图5为实施例1的含能化合物DAP-1的差示扫描量热分析图谱。
图6为实施例2的含能化合物DAP-2的热重分析图谱。
图7为实施例2的含能化合物DAP-2的差示扫描量热分析图谱。
图8为实施例3的含能化合物DAP-3的热重分析图谱。
图9为实施例3的含能化合物DAP-3的差示扫描量热分析图谱。
图10为实施例4的含能化合物DAP-4的热重分析图谱。
图11为实施例4的含能化合物DAP-4的差示扫描量热分析图谱。
图12为实施例5的含能化合物DAP-O22的热重分析图谱。
图13为实施例5的含能化合物DAP-O22的差示扫描量热分析图谱。
图14为实施例7的含能化合物DAP-O24的差示扫描量热分析图谱。
图15为实施例8的含能化合物PAP-1的粉末X射线衍射图。
图16为实施例8的含能化合物PAP-1的热重分析图谱。
图17为实施例8的含能化合物PAP-1的差示扫描量热分析图谱。
图18为实施例9的含能化合物PAP-4的差示扫描量热分析图谱。
图19为实施例10的含能化合物DAN-2的粉末X射线衍射图。
图20为实施例10的含能化合物DAN-2的红外图谱。
图21为实施例10的含能化合物DAN-2的热重分析图谱。
图22为实施例10的含能化合物DAN-2的差示扫描量热分析图谱。
图23为实施例11的含能化合物DAN-4的粉末X射线衍射图。
图24为实施例11的含能化合物DAN-4的热重分析图谱。
图25为实施例11的含能化合物DAN-4的差示扫描量热分析图谱。
具体实施方式
发明人设计了系列具有含能基团的钙钛矿型化合物，并首次对它们用于含能领域作为一种新型高性能爆炸物的前景进行了相关实验研究。在本发明中我们提出这样一类具有含能基 团的钙钛矿型含能化合物(ABX3，在以下实施例中对应于缩写DAP并予以分别的编号)，通过实验和计算我们指出了其能量密度和爆炸性能可以和现役高性能军用炸药RDX、HMX媲美，并且安全性能优异，不具有挥发性，不吸湿，原材料便宜易得，合成过程简单，是在含能领域具有实用价值的一类新型含能化合物。
ABX3的合成可根据本发明的合成方法进行。也可借鉴Z.M.Jin等公开的一种钙钛矿化合物(C6H14N2)[K(ClO4)3]的合成方法(Z.M.Jin,Y.J.Pan,X.F.Li,M.L.Hu,L.Shen,Journal of Molecular Structure,2003,660,67)。
ABX3中的X是至少一种阴离子含能基团。含能基团是指具有爆炸性的基团。常见的爆炸性基团包括但不限于，ClO3 -、ClO4 -、IO4 -、NO3 -、ONC-、偶氮基团、叠氮离子、硝基等基团。
ABX3中的，例如对于X来说，可以包含一种或多于一种的离子，例如，可以同时存在2种、3种、4种、5种、6种、7种、8种、9种、10种……X离子。对于A、B来说也是同样的道理。当钙钛矿包括多于一种的A阳离子时，不同的A阳离子可以以有序的或无序的方式分布在A位点上。当钙钛矿包括多于一种的B阳离子时，不同的B阳离子可以以有序的或无序的方式分布在B位点上。当钙钛矿包括多于一种X阴离子时，不同的X阴离子可以以有序的或无序的方式分布在X位点上。
基于这样的性质，文中所述的“X是至少一种……基团/离子”“A是至少一种……基团/离子”“B是至少一种……基团/离子”“X选自……”“A选自……”“B选自……”等等，应当理解为，例如对于X来说，在ABX3的三维骨架中，含有很多个X位点，每个X位点由一种离子构成，在三维骨架中，多个X位点可以由同一种离子构成，也可以由不同的多种离子构成，当由不同离子构成时，其中至少存在一些位点(或者大部分位点)是……基团/离子。此时并不排除对于整个ABX3的三维骨架中，存在少数位点可能并非所述的……基团/离子或一些其他的杂质离子，只要这些位点的数量在不会在大的程度上影响整体性能。所述的少数位点可以是，例如是摩尔数在50％以下，例如不超过40％、30％、25％、20％、15％、10％、9％、8％、7％、6％、5％、4％、3％、2％或1％。对于A、B来说，也是同样的道理。
本发明进行了包括粉末X射线衍射鉴定、单晶结构表征测试、红外光谱表征、热稳定性表征、差示扫描量热分析(DSC)、感度表征、爆热/爆压/爆速值计算在内的多种鉴定和表征方法。
其中，室温条件下的粉末X射线衍射数据是在Bruker D8 Advance衍射仪上收集，采用Cu-Kα射线，扫描方式：θ:2θ联动，步进扫描，2θ步长为0.02°。单晶X射线衍射数据是在 Oxford Gemini S Ultra CCD衍射仪上收集，石墨单色器，用Mo-Kα射线，以ω扫描方式收集数据，吸收校正采用SADABS程序。利用直接法进行解析，然后用差值傅立叶函数法和最小二乘法求出全部非氢原子坐标，最后用最小二乘法对结构进行修正。化合物的有机氢原子通过理论加氢法得到。计算工作在PC机上使用Olex2和SHELX程序包完成。红外光谱数据是在IR Tensor27仪器上收集，将干燥样品与KBr压制成透明薄片测试样品。热重分析是在TA Q50仪器上收集，氮气气氛，扫描速度为5℃/min。DSC曲线是在TA DSC Q2000仪器上收集，氮气气氛，扫描速度为5℃/min。
感度表征根据中华人民共和国国家军用标准GJB772A-97标准进行撞击、摩擦、热感度测试。撞击感度用601.1爆炸概率法；摩擦感度用602.1爆炸概率法；热感度测试为方法606.1-爆发点5秒延滞期法。静电感度测试方法为WJ/T 9038.3-2004工业火工药剂试验方法第3部分：静电火花感度测试。
室温下，高氯酸根基团在红外吸收光谱的特征峰位于1070～1100cm-1(对应不对称伸缩振动)以及617～637cm-1(对应不对称弯曲振动)；硝酸根基团在红外吸收光谱的特征峰位于1375～1390cm-1(对应不对称伸缩振动)以及845～860cm-1(对应不对称弯曲振动)。
在一个优选的实施例中，采用作为含能材料的化合物为(C6H14N2)[Na(ClO4)3](记为DAP-1)，其在223K下结晶于立方晶系的Pa-3空间群，晶胞长度为
Figure PCTCN2017097136-appb-000003
其在室温下的粉末X射线衍射(Cu-Kα射线)发生在衍射角度2θ约为：12.3±0.5°，21.5±0.5°，24.9±0.5°，27.9±0.5°，35.6±0.5°，37.2±0.5°之处。热稳定性分析结果显示其爆炸温度可高达360℃；差示扫描量热分析结果显示360℃分解放出的热量达4398J/g；安全性能表征结果显示在国军标标准下DAP-1在撞击感度、摩擦感度以及静电火花感度测试中均表现为钝感，在德国联邦材料研究和检测机构(BAM)的标准下，DAP-1的撞击感度约是17J，摩擦感度约是36N。DAP-1的爆发点高达340℃(5s延滞期法)。密度泛函DFT理论得到含能化合物的爆热、爆速和爆压值分别为1.53kcal/g、8.85km/s和37.31GPa。
在另一个优选的实施例中，采用作为含能材料的化合物为(C6H14N2)[K(ClO4)3](记为DAP-2)，其在223K下结晶于立方晶系的Pa-3空间群，晶胞长度为
Figure PCTCN2017097136-appb-000004
其在室温下的粉末X射线衍射(Cu-Kα射线)发生在衍射角度2θ约为：12.15±0.5°，21.27±0.5°，24.63±0.5°，27.64±0.5°，35.20±0.5°，36.89±0.5°之处。热稳定性分析结果显示其爆炸温度可高达362℃；差示扫描量热分析结果显示377℃分解放出的热量达4076J/g；安全性能表征结果显示在德国联邦材料研究和检测机构(BAM)的标准下，DAP-2的撞击感度约是16J，摩擦感度约是42N。密度泛函DFT理论得到含能化合物的爆热、爆速和爆压值分别为1.46kcal/g、8.64km/s 和35.73GPa。
在另一个优选的实施例中，采用作为含能材料的化合物为(C6H14N2)[Rb(ClO4)3](记为DAP-3)，其在223K下结晶于立方晶系的Pa-3空间群，晶胞长度为
Figure PCTCN2017097136-appb-000005
其在室温下的粉末X射线衍射(Cu-Kα射线)发生在衍射角度2θ约为：12.0±0.5°，21.0±0.5°，24.3±0.5°，27.3±0.5°，34.7±0.5°，36.4±0.5°之处。热稳定性分析结果显示其爆炸温度可高达343℃。差示扫描量热分析结果显示369℃分解放出的热量达3797J/g；安全性能表征结果显示在德国联邦材料研究和检测机构(BAM)的标准下，DAP-3的撞击感度约是22J，摩擦感度约是28N。密度泛函DFT理论得到含能化合物的爆热、爆速和爆压值分别为1.33kcal/g、8.43km/s和35.14GPa。
在另一个优选的实施例中，采用作为含能材料的化合物为(C6H14N2)[NH4(ClO4)3](记为DAP-4)，其在223K下结晶于立方晶系的Pa-3空间群，晶胞长度为
Figure PCTCN2017097136-appb-000006
其在室温下的粉末X射线衍射(Cu-Kα射线)发生在衍射角度2θ约为：12.0±0.5°，21.0±0.5°，24.4±0.5°，27.3±0.5°，34.8±0.5°，36.5±0.5°之处。热稳定性分析结果显示其爆炸温度可高达370℃；差示扫描量热分析结果显示364℃分解放出的热量达5177J/g；安全性能表征结果显示在德国联邦材料研究和检测机构(BAM)的标准下，DAP-4的撞击感度约是23J，摩擦感度约是36N。
在另一个优选的实施例中，采用作为含能材料的化合物为(C6H14N2O2)[K(ClO4)3](记为DAP-O22)，其在298K下结晶于立方晶系的Fm-3c空间群，晶胞长度为
Figure PCTCN2017097136-appb-000007
其在室温下的粉末X射线衍射(Cu-Kα射线)发生在衍射角度2θ约为：11.9±0.5°，20.8±0.5°，24.1±0.5°，27.0±0.5°，34.4±0.5°，36.1±0.5°之处。热稳定性分析结果显示其爆炸温度可高达354℃；差示扫描量热分析结果显示358℃分解放出的热量达5424J/g；安全性能表征结果显示在德国联邦材料研究和检测机构(BAM)的标准下，DAP-1的撞击感度约是11J，摩擦感度约是14N。
在另一个优选的实施例中，采用作为含能材料的化合物为(C6H14N2O)[K(ClO4)3](记为DAP-O12)。其在室温下的粉末X射线衍射(Cu-Kα射线)发生在衍射角度2θ约为：12.1±0.5°，21.1±0.5°，24.4±0.5°，27.3±0.5°，34.8±0.5°，36.5±0.5°之处。
在另一个优选的实施例中，采用作为含能材料的化合物为(C6H14N2O2)[NH4(ClO4)3](记为DAP-O24)。其在室温下的粉末X射线衍射(Cu-Kα射线)发生在衍射角度2θ约为：11.9±0.5°，20.8±0.5°，24.0±0.5°，27.0±0.5°，34.4±0.5°，36.0±0.5°之处。差示扫描量热分析结果显示357℃分解放出的热量达4632J/g；安全性能表征结果显示在德国联邦材料研究和检测机构(BAM) 的标准下，DAP-1的撞击感度约是4J，摩擦感度约是32N。
在另一个优选的实施例中，采用作为含能材料的化合物为(C4H12N2)[Na(ClO4)3](记为PAP-1)。其在室温下的粉末X射线衍射(Cu-Kα射线)发生在衍射角度2θ约为：12.6±0.5°，21.7±0.5°，22.4±0.5°，22.7±0.5°，25.4±0.5°，26.8±0.5°，27.2±0.5°，37.7±0.5°，38.4±0.5°之处。差示扫描量热分析结果显示375℃分解放出的热量达4685J/g。
在另一个优选的实施例中，采用作为含能材料的化合物为(C4H12N2)[NH4(ClO4)3](记为PAP-4)。差示扫描量热分析结果显示356℃分解放出的热量达3780J/g。
在另一个优选的实施例中，采用作为含能材料的化合物为(C6H14N2)[K(NO3)3](记为DAN-2)。其在室温下的粉末X射线衍射(Cu-Kα射线)发生在衍射角度2θ约为：12.6±0.5°，17.9±0.5°，22.0±0.5°，25.5±0.5°，28.6±0.5°，31.3±0.5°，36.4±0.5°，38.7±0.5°，40.9±0.5°，43.0±0.5°之处。差示扫描量热分析结果显示177℃分解放出的热量达1222J/g；安全性能表征结果显示在德国联邦材料研究和检测机构(BAM)的标准下，DAN-2的撞击感度约是29J，摩擦感度大于360N。
在另一个优选的实施例中，采用作为含能材料的化合物为(C6H14N2)[NH4(NO3)3](记为DAN-4)。其在室温下的粉末X射线衍射(Cu-Kα射线)发生在衍射角度2θ约为：10.3±0.5°，17.7±0.5°，20.4±0.5°，23.9±0.5°，24.8±0.5°，27.0±0.5°，29.7±0.5°，30.5±0.5°，32.2±0.5°，37.0±0.5°之处。差示扫描量热分析结果显示170℃分解放出的热量达1098J/g。
实施例1
(C6H14N2)[Na(ClO4)3]的合成及测试
合成方法：
1)将112.88g 1,4-二氮杂二环[2.2.2]辛烷加入100mL水中，再加入360.00g质量分数为70％～72％的高氯酸溶液，常温搅拌5分钟；
2)将140.52g一水合高氯酸钠加入50mL水中，常温搅拌溶解；
3)将步骤1)和步骤2)的溶液混合，搅拌30分钟，过滤，用乙醇洗涤滤渣三次，真空干燥，得白色粉末状固体，经鉴定为钙钛矿型化合物(C6H14N2)[Na(ClO4)3](编号为DAP-1)，产率约为80％。
粉末X射线衍射鉴定图谱：
室温下粉末X射线衍射图见图2，其特征峰值如表1所示。
表1 DAP-1的粉末X射线衍射特征峰值
Figure PCTCN2017097136-appb-000008
单晶结构表征测试：
详细的晶体测定数据见表2。三维晶体结构示意图见图1。如图1可见：处于B位点的Na+离子与6个相邻的处于X位点的ClO4 -阴离子相连，每个ClO4 -阴离子与两个相邻的Na+离子相连，进而形成由立方体笼状单元组成的三维阴离子骨架；处于A位点的有机阳离子1,4-二氢-1,4-二氮杂二环[2.2.2]辛烷铵离子(C6H14N2 2+)填充在每个立方体笼状单元的孔穴中。
表2 DAP-1的单晶结构测定数据
Figure PCTCN2017097136-appb-000009
[a]R1＝Σ||Fo|-|Fc||/Σ|Fo|,[b]wR2＝{Σw[(Fo)2-(Fc)2]2/Σw[(Fo)2]2}1/2
DAP-1的红外光谱表征：
DAP-1的红外光谱图如图3所示。由图3可知：有机组分所具有的特征峰是-CH2-基团的伸缩振动峰3452、3188、3055、3013、2924、2795、2706cm-1；NH+的伸缩振动峰是2606cm-1；高氯酸根所具有的特征峰是其不对称伸缩振动1078cm-1以及不对称弯曲振动627cm-1。
DAP-1的热稳定性表征：
DAP-1的热重曲线如图4所示。由图4可知：在装样量为3.291mg，升温速率为5℃/min的情况下，实施例1的含能化合物DAP-1在360℃处发生爆炸。
DAP-1的差示扫描量热分析：
DAP-1的DSC曲线如图5所示。由图5可知：实施例1的非装药状态粉末态的含能化合物DAP-1在360℃处分解并放出大量的热(约4398J/g)。
DAP-1的撞击、摩擦、热感度、静电感度表征：
根据GJB772A-97标准进行撞击、摩擦、热感度。撞击感度用601.1爆炸概率法，测试中(10kg锤重，500mm落高)，TNT的爆炸概率为9/25，而DAP-1爆炸概率为0％；摩擦感度用602.1爆炸概率法，测试中(2.45MPa、80°摆角)，太恩(PETN)的爆炸概率为2/25，而DAP-1爆炸概率为0％；热感度测试为方法606.1-爆发点5秒延滞期法，测得DAP-1在340℃发生剧烈爆炸，表明DAP-1的爆发点为340℃。静电感度测试方法为WJ/T 9038.3-2004工业火工药剂试验方法第3部分：静电火花感度测试，25mg试样的半发火电压V50为4.77kV(标准偏差0.21kV)，半发火能量E50为0.53J，即DAP-1的静电火花感度为21.2J。
根据德国联邦材料研究和检测机构(BAM)的测试方法，DAP-1的撞击感度约是17J，摩擦感度约是36N。
密度泛函(DFT)理论得到含能化合物DAP-1的爆热、爆压、爆速值：
DAP-1的分解热值(分解焓值⊿Hdet)用密度泛函(DFT)理论计算(J.Am.Chem.Soc.2012,134,1422)约为1.53kcal/g，高于现役含能材料HMX(1.26kcal/g)、RDX(1.27kcal/g)；按照223K时的晶体密度换算得能量密度分别是3.11kcal/cm3，也高于现役含能材料HMX(2.38kcal/cm3)、RDX(2.29kcal/cm3)。根据Kamlet-Jacob公式计算DAP类化合物的爆速约为8.85km/s，爆压约为37.31GPa。与现役含能材料的相应值(HMX：爆速9.10km/s，爆压39.50GPa；RDX：爆速8.80km/s，爆压33.80GPa)相当。
单位摩尔数DAP-1产生的气体量
关于无氧环境中含能材料完全爆炸的产物判断，根据文献(J.Am.Chem.Soc.2012,134,1422；J.Phys.Chem.A.2014,118,4575；Chem.Eur.J.2016,22,1141)，其分解产物最终为：氮气、卤化氢、水和二氧化碳等气态物质，以及金属的氯化盐和单质碳(如果氧原子不足于将所有碳原子完全转化为二氧化碳的话)等固态物质。因此，1摩尔DAP-1无氧环境下完全爆炸之后可产生12摩尔气体物质，并残留3摩尔单质碳和1摩尔氯化钠固态。在混入足够氧化剂(如常用的NH4ClO4)的情况下，1摩尔DAP-1完全爆炸后存在1摩尔氯化钠固体残留物。
实施例2
(C6H14N2)[K(ClO4)3]的合成及测试
合成方法：
1)将2.24g 1,4-二氮杂二环[2.2.2]辛烷加入100mL水中，再加入5.74g质量分数为70％～72％的高氯酸溶液，常温搅拌5分钟；
2)将2.77g高氯酸钾加入100mL水中，加热搅拌溶解；
3)将步骤1)和步骤2)的溶液混合，搅拌30分钟，过滤，用乙醇洗涤滤渣三次，真空干燥，得白色粉末状固体，经鉴定为钙钛矿型化合物(C6H14N2)[K(ClO4)3](编号为DAP-2)，产率约为90％。
粉末X射线衍射鉴定图谱：
室温下粉末X射线衍射图见图2，其特征峰值如表3所示。
表3 DAP-2的粉末X射线衍射特征峰值
Figure PCTCN2017097136-appb-000010
单晶结构表征测试：
详细的晶体测定数据见表4。
表4 DAP-2的单晶结构测定数据
Figure PCTCN2017097136-appb-000011
[a]R1＝Σ||Fo|-|Fc||/Σ|Fo|,[b]wR2＝{Σw[(Fo)2-(Fc)2]2/Σw[(Fo)2]2}1/2
DAP-2的热稳定性表征：
DAP-2的热重曲线如图6所示。由图6可知：在装样量为6.65mg，升温速率为5℃/min的情况下，实施例2的含能化合物DAP-2在362℃处发生爆炸。
DAP-2的差示扫描量热分析：
DAP-2的DSC曲线如图7所示。由图7可知：实施例2的非装药状态粉末态的含能化合物DAP-2在377℃处分解并放出大量的热(约4076J/g)。
DAP-2的撞击、摩擦感度表征：
根据德国联邦材料研究和检测机构(BAM)的测试方法，DAP-2的撞击感度约是16J，摩擦感度约是42N。
密度泛函(DFT)理论得到含能化合物DAP-2的爆热、爆压、爆速值：
DAP-2的分解热值(分解焓值⊿Hdet)用密度泛函(DFT)理论计算(J.Am.Chem.Soc.2012,134,1422)约为1.46kcal/g，高于现役含能材料HMX(1.26kcal/g)、RDX(1.27kcal/g)；按照 223K时的晶体密度换算得能量密度分别是3.01kcal/cm3，也高于现役含能材料HMX(2.38kcal/cm3)、RDX(2.29kcal/cm3)。根据Kamlet-Jacob公式计算DAP类化合物的爆速约为8.64km/s，爆压约为35.73GPa。
单位摩尔数DAP-2产生的气体量
关于无氧环境中含能材料完全爆炸的产物判断，根据文献(J.Am.Chem.Soc.2012,134,1422；J.Phys.Chem.A.2014,118,4575；Chem.Eur.J.2016,22,1141)，其分解产物最终为：氮气、卤化氢、水和二氧化碳等气态物质，以及金属的氯化盐和单质碳(如果氧原子不足于将所有碳原子完全转化为二氧化碳的话)等固态物质。因此，1摩尔DAP-2无氧环境下完全爆炸之后可产生12摩尔气体物质，并残留3摩尔单质碳和1摩尔氯化钾固态。在混入足够氧化剂(如常用的NH4ClO4)的情况下，1摩尔DAP-2完全爆炸后存在1摩尔氯化钾固体残留物。
实施例3
(C6H14N2)[Rb(ClO4)3]的合成及测试
合成方法：
1)将2.24g 1,4-二氮杂二环[2.2.2]辛烷加入100mL水中，再加入5.74g质量分数为70％～72％的高氯酸溶液，常温搅拌5分钟；
2)将3.70g高氯酸铷加入100mL水中，加热搅拌溶解；
3)将步骤1)和步骤2)的溶液混合，搅拌30分钟，过滤，用乙醇洗涤滤渣三次，真空干燥，得白色粉末状固体，经鉴定为钙钛矿型化合物(C6H14N2)[Rb(ClO4)3](编号为DAP-3)，产率约为85％。
粉末X射线衍射鉴定图谱：
室温下粉末X射线衍射图见图2，其特征峰值如表5所示。
表5 DAP-3的粉末X射线衍射特征峰值
Figure PCTCN2017097136-appb-000012
Figure PCTCN2017097136-appb-000013
单晶结构表征测试：
详细的晶体测定数据见表6。
表6 DAP-3的单晶结构测定数据
Figure PCTCN2017097136-appb-000014
[a]R1＝Σ||Fo|-|Fc||/Σ|Fo|,[b]wR2＝{Σw[(Fo)2-(Fc)2]2/Σw[(Fo)2]2}1/2
DAP-3的热稳定性表征：
DAP-3的热重曲线如图8所示。由图8可知：在装样量为4.45mg，升温速率为5℃/min的情况下，实施例3的含能化合物DAP-3在343℃处发生爆炸。
DAP-3的差示扫描量热分析：
DAP-3的DSC曲线如图9所示。由图9可知：实施例3的非装药状态粉末态的含能化合物DAP-3在369℃处分解并放出大量的热(约3797J/g)。
DAP-3的撞击、摩擦感度表征：
根据德国联邦材料研究和检测机构(BAM)的测试方法，DAP-3的撞击感度约是22J，摩擦感度约是28N。
密度泛函(DFT)理论得到含能化合物DAP-3的爆热、爆压、爆速值：
DAP-3的分解热值(分解焓值⊿Hdet)用密度泛函(DFT)理论计算(J.Am.Chem.Soc.2012,134,1422)约为1.33kcal/g，高于现役含能材料HMX(1.26kcal/g)、RDX(1.27kcal/g)；按照223K时的晶体密度换算得能量密度分别是2.92kcal/cm3，也高于现役含能材料HMX(2.38kcal/cm3)、RDX(2.29kcal/cm3)。根据Kamlet-Jacob公式计算DAP类化合物的爆速约为8.43km/s，爆压约为35.14GPa。
单位摩尔数DAP-3产生的气体量
关于无氧环境中含能材料完全爆炸的产物判断，根据文献(J.Am.Chem.Soc.2012,134,1422；J.Phys.Chem.A.2014,118,4575；Chem.Eur.J.2016,22,1141)，其分解产物最终为：氮气、卤化氢、水和二氧化碳等气态物质，以及金属的氯化盐和单质碳(如果氧原子不足于将所有碳原子完全转化为二氧化碳的话)等固态物质。因此，1摩尔DAP-3无氧环境下完全爆炸之后可产生12摩尔气体物质，并残留3摩尔单质碳和1摩尔氯化铷固态。在混入足够氧化剂(如常用的NH4ClO4)的情况下，1摩尔DAP-3完全爆炸后存在1摩尔氯化铷固体残留物。
实施例4：
(C6H14N2)[NH4(ClO4)3]的合成及测试
合成方法：
1)将2.24g 1,4-二氮杂二环[2.2.2]辛烷加入5mL水中，再加入5.74g质量分数为70％～72％的高氯酸溶液，常温搅拌5分钟；
2)将2.35g高氯酸铵加入10mL水中，常温搅拌溶解；
3)将步骤1)和步骤2)的溶液混合，搅拌10分钟，过滤，用乙醇洗涤滤渣三次，真空干燥，得白色粉末状固体，经鉴定为钙钛矿型化合物(C6H14N2)[NH4(ClO4)3](DAP-4)，产率约为90％。
粉末X射线衍射鉴定图谱：
室温下粉末X射线衍射图见图2，其特征峰值如表7所示。
表7 DAP-4的粉末X射线衍射特征峰值
Figure PCTCN2017097136-appb-000015
Figure PCTCN2017097136-appb-000016
单晶结构表征测试：
详细的晶体测定数据见表8。
表8 DAP-4的晶体测定数据
Figure PCTCN2017097136-appb-000017
[a]R1＝Σ||Fo|-|Fc||/Σ|Fo|,[b]wR2＝{Σw[(Fo)2-(Fc)2]2/Σw[(Fo)2]2}1/2
DAP-4的热稳定性表征：
DAP-4的热重曲线如图10所示。由图10可知：在装样量为4.825mg，升温速率为5℃/min的情况下，实施例4的含能化合物DAP-4在370℃处发生爆炸。
DAP-4的差示扫描量热分析：
DAP-4的DSC曲线如图11所示。由图11可知：实施例4的非装药状态粉末态的含能化合物DAP-4在364℃处分解并放出大量的热(约5177J/g)。
DAP-4的撞击、摩擦感度表征：
根据德国联邦材料研究和检测机构(BAM)的测试方法，DAP-4的撞击感度约是23J，摩擦感度约是36N。
单位摩尔数DAP-4产生的气体量
关于无氧环境中含能材料完全爆炸的产物判断，根据文献(J.Am.Chem.Soc.2012,134,1422；J.Phys.Chem.A.2014,118,4575；Chem.Eur.J.2016,22,1141)，其分解产物最终为：氮气、卤化氢、水和二氧化碳等气态物质，以及单质碳(如果氧原子不足于将所有碳原子完全转化为二氧化碳的话)固态物质。因此，1摩尔DAP-4无氧环境下完全爆炸之后可产生14.25摩尔气体物质，并残留3.75摩尔单质碳。在混入足够氧化剂(如常用的NH4ClO4)的情况下，DAP-4完全爆炸后无固体残留物。
实施例5
(C6H14N2O2)[K(ClO4)3]的合成及测试
合成方法：
1)将1.01g 1,4-二氮杂二环[2.2.2]辛烷置于烧杯中，逐渐加入6.0g质量分数为30％的双
氧水，充分反应，得到1,4-二氧化-1,4-二氮杂二环[2.2.2]辛烷的水溶液，再加入2.64g质
量分数为70％～72％的高氯酸溶液，搅拌20分钟；
2)将0.42g高氯酸钾加入20mL水中，加热至沸腾搅拌溶解；
3)将步骤1)和步骤2)的溶液混合搅拌10分钟，静置逐渐产生晶体。过滤，用乙醇洗涤滤渣三次，真空干燥，得白色粉末状固体，经鉴定为钙钛矿型化合物(C6H14N2O2)[K(ClO4)3](DAP-O22)，产率约为55％。
粉末X射线衍射鉴定图谱：
室温下粉末X射线衍射图见图2，其特征峰值如表9所示。
表9 DAP-O22的粉末X射线衍射特征峰值
Figure PCTCN2017097136-appb-000018
Figure PCTCN2017097136-appb-000019
单晶结构表征测试：
详细的晶体测定数据见表10。
表10 DAP-O22的晶体测定数据
Figure PCTCN2017097136-appb-000020
[a]R1＝Σ||Fo|-|Fc||/Σ|Fo|,[b]wR2＝{Σw[(Fo)2-(Fc)2]2/Σw[(Fo)2]2}1/2
DAP-O22的热稳定性表征：
DAP-O22的热重曲线如图12所示。由图12可知：在装样量为4.175mg，升温速率为5℃/min的情况下，实施例5的含能化合物DAP-O22的分解温度是354℃。
DAP-O22的差示扫描量热分析：
DAP-O22的DSC曲线如图13所示。由图13可知：实施例5的非装药状态粉末态的含能化合物DAP-O22在358℃处分解并放出大量的热(约5424J/g)。
DAP-O22的撞击、摩擦感度表征：
根据德国联邦材料研究和检测机构(BAM)的测试方法，DAP-O22的撞击感度约是11J， 摩擦感度约是14N。
单位摩尔数DAP-O22产生的气体量
关于无氧环境中含能材料完全爆炸的产物判断，根据文献(J.Am.Chem.Soc.2012,134,1422；J.Phys.Chem.A.2014,118,4575；Chem.Eur.J.2016,22,1141)，其分解产物最终为：氮气、卤化氢、水和二氧化碳等气态物质，以及金属的氯化盐和单质碳(如果氧原子不足于将所有碳原子完全转化为二氧化碳的话)等固态物质。因此，1摩尔DAP-O22无氧环境下完全爆炸之后可产生13摩尔气体物质，并残留2摩尔单质碳和1摩尔氯化钾固态。在混入足够氧化剂(如常用的NH4ClO4)的情况下，1摩尔DAP-O22完全爆炸后存在1摩尔氯化钾固体残留物。
实施例6：
(C6H14N2O)[K(ClO4)3]的合成及测试
合成方法：
1)将1.01g 1,4-二氮杂二环[2.2.2]辛烷置于烧杯中持续冰浴，缓慢逐渐加入2.0g质量分数为30％的双氧水，得到1-氧化-1,4-二氮杂二环[2.2.2]辛烷的水溶液，再加入2.64g质量分数为70％～72％的高氯酸溶液，搅拌20分钟；
2)将0.42g高氯酸钾加入20mL水中，加热至沸腾搅拌溶解；
3)将步骤1)和步骤2)的溶液混合搅拌10分钟，静置逐渐产生晶体。过滤，用乙醇洗涤滤渣三次，真空干燥，得白色粉末状固体，经鉴定为钙钛矿型化合物(C6H14N2O)[K(ClO4)3](DAP-O12)，产率约为30％。
粉末X射线衍射鉴定图谱：
室温下粉末X射线衍射图见图2，其特征峰值如表11所示。
表11 DAP-O12的粉末X射线衍射特征峰值
Figure PCTCN2017097136-appb-000021
Figure PCTCN2017097136-appb-000022
单位摩尔数DAP-O12产生的气体量
关于无氧环境中含能材料完全爆炸的产物判断，根据文献(J.Am.Chem.Soc.2012,134,1422；J.Phys.Chem.A.2014,118,4575；Chem.Eur.J.2016,22,1141)，其分解产物最终为：氮气、卤化氢、水和二氧化碳等气态物质，以及金属的氯化盐和单质碳(如果氧原子不足于将所有碳原子完全转化为二氧化碳的话)等固态物质。因此，1摩尔DAP-O12无氧环境下完全爆炸之后可产生12.5摩尔气体物质，并残留2.5摩尔单质碳和1摩尔氯化钾固态。在混入足够氧化剂(如常用的NH4ClO4)的情况下，1摩尔DAP-O12完全爆炸后存在1摩尔氯化钾固体残留物。
实施例7：
(C6H14N2O2)[NH4(ClO4)3]的合成及测试
合成方法：
1)将0.34g 1,4-二氮杂二环[2.2.2]辛烷置于烧杯中，常温下缓慢逐渐加入0.69g质量分数为30％的双氧水，得到1，4-二氧化-1,4-二氮杂二环[2.2.2]辛烷的水溶液，再加入0.86g质量分数为70％～72％的高氯酸溶液，搅拌20分钟；
2)将0.41g高氯酸铵加入20mL水中搅拌溶解；
3)将步骤1)和步骤2)的溶液混合搅拌10分钟，静置逐渐产生晶体。过滤，用乙醇洗涤滤渣三次，真空干燥，得白色粉末状固体，经鉴定为钙钛矿型化合物(C6H14N2O2)[NH4(ClO4)3](DAP-O24)，产率约为30％。
粉末X射线衍射鉴定图谱：
室温下粉末X射线衍射图见图2，其特征峰值如表12所示。
表12 DAP-O24的粉末X射线衍射特征峰值
Figure PCTCN2017097136-appb-000023
Figure PCTCN2017097136-appb-000024
DAP-O24的差示扫描量热分析：
DAP-O24的DSC曲线如图14所示。由图14可知：实施例7的非装药状态粉末态的含能化合物DAP-O24在357℃处分解并放出大量的热(约4632J/g)。
DAP-O24的撞击、摩擦感度表征：
根据德国联邦材料研究和检测机构(BAM)的测试方法，DAP-O24的撞击感度约是4J，摩擦感度约是32N。
单位摩尔数DAP-O24产生的气体量
关于无氧环境中含能材料完全爆炸的产物判断，根据文献(J.Am.Chem.Soc.2012,134,1422；J.Phys.Chem.A.2014,118,4575；Chem.Eur.J.2016,22,1141)，其分解产物最终为：氮气、卤化氢、水和二氧化碳等气态物质，以及单质碳(如果氧原子不足于将所有碳原子完全转化为二氧化碳的话)固态物质。因此，1摩尔DAP-O24无氧环境下完全爆炸之后可产生15.25摩尔气体物质，并残留2.75摩尔单质碳。在混入足够氧化剂(如常用的NH4ClO4)的情况下，DAP-O24完全爆炸后无固体残留物。
实施例8
(C4H12N2)[Na(ClO4)3]的合成及测试
合成方法：
1)将0.87g哌嗪加入6mL水中，再加入1.7mL质量分数为70％～72％的高氯酸溶液，
常温搅拌5分钟；
2)将1.24g高氯酸钠加入7mL水中，常温搅拌溶解；
3)将步骤1)和步骤2)的溶液混合，加热浓缩，搅拌30分钟，过滤，用乙醇洗涤滤渣三次，真空干燥，得白色粉末状固体，经鉴定为钙钛矿型化合物(C4H12N2)[Na(ClO4)3](编号为PAP-1)，产率约为50％。
粉末X射线衍射鉴定图谱：
室温下粉末X射线衍射图见图15，其特征峰值如表13所示。
表13 PAP-1的粉末X射线衍射特征峰值
Figure PCTCN2017097136-appb-000025
单晶结构表征测试：
详细的晶体测定数据见表14。
表14 PAP-1的晶体测定数据
Figure PCTCN2017097136-appb-000026
[a]R1＝Σ||Fo|-|Fc||/Σ|Fo|,[b]wR2＝{Σw[(Fo)2-(Fc)2]2/Σw[(Fo)2]2}1/2
PAP-1的热稳定性表征：
PAP-1的热重曲线如图16所示。由图16可知：在装样量为2.23mg，升温速率为5℃/min的情况下，实施例8的含能化合物PAP-1在367℃处发生爆炸。
PAP-1的差示扫描量热分析：
PAP-1的DSC曲线如图17所示。由图17可知：实施例8的非装药状态粉末态的含能化合物PAP-1在375℃处分解并放出大量的热(约4685J/g)。
单位摩尔数PAP-1产生的气体量
关于无氧环境中含能材料完全爆炸的产物判断，根据文献(J.Am.Chem.Soc.2012,134,1422；J.Phys.Chem.A.2014,118,4575；Chem.Eur.J.2016,22,1141)，其分解产物最终为：氮气、卤化氢、水和二氧化碳等气态物质，以及金属的氯化盐和单质碳(如果氧原子不足于将所有碳原子完全转化为二氧化碳的话)等固态物质。因此，1摩尔PAP-1无氧环境下完全爆炸之后可产生11.5摩尔气体物质，并残留0.5摩尔单质碳和1摩尔氯化钠固态。在混入足够氧化剂(如常用的NH4ClO4)的情况下，1摩尔PAP-1完全爆炸后存在1摩尔氯化钠固体残留物。
实施例9
(C4H12N2)[NH4(ClO4)3]的合成及测试
合成方法：
1)将0.8mL氨水加入0.9mL质量分数为70％～72％的高氯酸溶液中，常温搅拌5分钟，
再加入1.6mL质量分数为70％～72％的高氯酸溶液；
2)将0.87g哌嗪加适量水，常温搅拌溶解；
3)将步骤1)和步骤2)的溶液混合，加热浓缩，搅拌30分钟，过滤，用乙醇洗涤滤渣三次，真空干燥，得白色粉末状固体，经鉴定为钙钛矿型化合物(C4H12N2)[NH4(ClO4)3](编号为PAP-4)，产率约为40％。
PAP-4的差示扫描量热分析：
PAP-4的DSC曲线如图18所示。由图18可知：实施例9的非装药状态粉末态的含能化合物PAP-4在356℃处分解(放热约3780J/g)。
单位摩尔数PAP-4产生的气体量
关于无氧环境中含能材料完全爆炸的产物判断，根据文献(J.Am.Chem.Soc.2012,134,1422；J.Phys.Chem.A.2014,118,4575；Chem.Eur.J.2016,22,1141)，其分解产物最终为：氮气、卤化氢、水和二氧化碳等气态物质，以及金属的氯化盐和单质碳(如果氧原子不足于将所有碳原子完全转化为二氧化碳的话)等固态物质。因此，1摩尔PAP-4无氧环境下完全爆炸之后可产生13.75摩尔气体物质，并残留1.25摩尔单质碳。在混入足够氧化剂(如常用的NH4ClO4)的情况下，1摩尔PAP-4完全爆炸后无固体残留物。
实施例10
(C6H14N2)[K(NO3)3]的合成及测试
合成方法：
1)将1.12g 1,4-二氮杂二环[2.2.2]辛烷加入适量水中，再加入1.4mL质量分数为65％的硝酸溶液，常温搅拌5分钟；
2)将1.01g硝酸钾加入适量水中，常温搅拌溶解；
3)将步骤1)和步骤2)的溶液混合，搅拌过滤，用乙醇洗涤滤渣三次，真空干燥，得白色粉末状固体，经鉴定为钙钛矿型化合物(C6H14N2)[K(NO3)3](编号为DAN-2)，产率约为50％。
粉末X射线衍射鉴定图谱：
室温下粉末X射线衍射图见图19，其特征峰值如表15所示。
表15 DAN-2的粉末X射线衍射特征峰值
Figure PCTCN2017097136-appb-000027
单晶结构表征测试：
详细的晶体测定数据见表16。
表16 DAN-2的单晶结构测定数据
Figure PCTCN2017097136-appb-000028
[a]R1＝Σ||Fo|-|Fc||/Σ|Fo|,[b]wR2＝{Σw[(Fo)2-(Fc)2]2/Σw[(Fo)2]2}1/2
DAN-2的红外光谱表征：
DAN-2的红外光谱图如图20所示。由图20可知：硝酸根所具有的特征峰是其不对称伸缩振动1385cm-1以及不对称弯曲振动852cm-1。
DAN-2的热稳定性表征：
DAN-2的热重曲线如图21所示。由图21可知：在装样量为3.33mg，升温速率为5℃/min的情况下，实施例10的含能化合物DAN-2开始分解的温度是177℃。
DAN-2的差示扫描量热分析：
DAN-2的DSC曲线如图22所示。由图22可知：实施例10的非装药状态粉末态的含能化合物DAN-2在177℃处逐步分解(放热约1222J/g)。
DAN-2的撞击、摩擦感度表征：
根据德国联邦材料研究和检测机构(BAM)的测试方法，DAN-2的撞击感度约是29J，摩擦感度大于360N。
实施例11
(C6H14N2)[NH4(NO3)3]的合成及测试
合成方法：
1)在0.78mL质量分数为28％的氨水中加入2.0mL质量分数为65％的硝酸溶液，常温搅拌溶解；
2)将1.14g 1,4-二氮杂二环[2.2.2]辛烷加入适量水中，常温搅拌溶解；
3)将步骤1)和步骤2)的溶液混合，搅拌过滤，用乙醇洗涤滤渣三次，真空干燥，得白色粉末状固体，经鉴定为六方钙钛矿型化合物(C6H14N2)[NH4(NO3)3](编号为DAN-4)，产率约为60％。
粉末X射线衍射鉴定图谱：
室温下粉末X射线衍射图见图23，其特征峰值如表17所示。
表17 DAN-4的粉末X射线衍射特征峰值
Figure PCTCN2017097136-appb-000029
单晶结构表征测试：
详细的晶体测定数据见表18。
表18 DAN-4的单晶结构测定数据
Figure PCTCN2017097136-appb-000030
Figure PCTCN2017097136-appb-000031
[a]R1＝Σ||Fo|-|Fc||/Σ|Fo|,[b]wR2＝{Σw[(Fo)2-(Fc)2]2/Σw[(Fo)2]2}1/2
DAN-4的热稳定性表征：
DAN-4的热重曲线如图24所示。由图24可知：在装样量为6.42mg，升温速率为5℃/min的情况下，实施例11的含能化合物DAN-4开始分解的温度是167℃。
DAN-4的差示扫描量热分析：
DAN-4的DSC曲线如图25所示。由图25可知：实施例11的非装药状态粉末态的含能化合物DAN-4在170℃处开始分解(放热约1098J/g)。
单位摩尔数DAN-4产生的气体量
关于无氧环境中含能材料完全爆炸的产物判断，根据文献(J.Am.Chem.Soc.2012,134,1422；J.Phys.Chem.A.2014,118,4575；Chem.Eur.J.2016,22,1141)，其分解产物最终为：氮气和水等气态物质，以及单质碳(考虑氧原子优先成氢原子结合成水)等固态物质。因此，1摩尔DAN-4无氧环境下完全爆炸之后可产生12摩尔气体物质，并残留6摩尔单质碳。在混入足够氧化剂(如常用的NH4NO3)的情况下，1摩尔DAN-4完全爆炸后可以无固体残留物。特别地，DAN-4不含卤族元素，在爆炸后不产生卤化氢气体，可以在实际应用中降低特征信号，减少环境污染。
本发明的钙钛矿型含能化合物的爆热高，能量密度高，爆速高，爆压高，安全性能良好，对撞击、摩擦和静电等感度极低，不具有挥发性，可长期存放不分解，不吸湿，原材料便宜易得，合成过程简单，无副产物，可以大批量制备。
本发明的钙钛矿型含能化合物用作炸药之类的含能材料其效果是现有技术预期不到的。虽然高氯酸根是含能基团，但目前绝大部分含高氯酸根的化合物由于各种缺点而不能作为实用的含能材料(参见《High Energy Materials:Propellants,Explosives and Pyrotechnics》第28页，Jai Prakash Agrawal编著，Wiley-VCH出版社，2010)，比如高氯酸钠和高氯酸锂等常见的高氯酸盐本身吸湿性极强，而高氯酸钾曾被用于闪光弹氧化剂，但后来发现其撞击感度过 高，易在运输途中爆炸；当前仍被列为爆炸物的高氯酸铵的理论爆热仅1972J/g，远不及本发明的含能化合物的爆热水平。然而本发明的钛矿型化合物即使含有如此的爆炸性基团，却仍能保持很好的热稳定性以及不吸湿的特点，成为安全性极强和易于存放的含能材料。同时，由于其富含含能基团且这些氧化性含能阴离子与还原性有机阳离子在空间上相间排列，晶体密度大，瞬间能量爆发力强，能量密度高，爆热、爆压、爆速水平均高，其作为炸药使用的性能优越性与现有技术相比带来了飞跃性的进步。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 钙钛矿型化合物ABX3在作为含能材料方面的用途，所述的钙钛矿型化合物中X是至少一种阴离子含能基团。
  2. 如权利要求1所述的用途，其特征在于所述的X是至少一种氧化性阴离子含能基团，优选地，所述的X是至少一种一价阴离子含能基团，更优选地是至少一种含卤组分的含能基团。
  3. 如权利要求1所述的用途，其特征在于所述的阴离子含能基团选自ClO4 -、BrO4 -、IO4 -、NO3 -、ONC-和N(NO2)2 -；
    优选地，所述的阴离子含能基团选自ClO4 -、BrO4 -和IO4 -，更优选为ClO4 -。
  4. 如上述任一权利要求所述的用途，其特征在于所述的A是至少一种有机阳离子；
    优选地，A是至少一种还原性有机阳离子；
    优选地，A是至少一种含氮有机阳离子；
    优选地，A是至少一种含氮杂环有机阳离子；
    更优选地，A是至少一种包含六元环含氮杂环有机阳离子。
  5. 如上述任一权利要求所述的用途，其特征在于所述的A是至少一种二价有机阳离子；
    优选地，A是至少一种二价的含氮有机阳离子；
    优选地，A是至少一种二价的含氮杂环有机阳离子；
    更优选地，A是至少一种二价的包含六元环含氮杂环有机阳离子；
    可选地，A选自以下有机阳离子母体及它们的衍生物中的一种、两种或多种：
    Figure PCTCN2017097136-appb-100001
    更优选地，A选自以下有机阳离子母体及它们的衍生物中的一种、两种或多种：
    Figure PCTCN2017097136-appb-100002
    优选地所述的衍生物为有机阳离子母体中的氢原子同时或不同时地被取代基取代；优选地，所述的取代基选自甲基、乙基、异丙基、叔丁基、羟基、羰基、羧基、卤素、巯基、过氧基、偶氮基和硝基。
  6. 如上述任一权利要求所述的用途，其特征在于，所述的B是至少一种以下的离子：碱金属离子、NH4 +；更优选地，所述碱金属选自：Na+、K+、Rb+和Cs+的一种、两种或多种；
    进一步优选选自Na+、K+和Rb+的一种、两种或多种；最优选选自Na+。
  7. 如上述任一权利要求所述的用途，其特征在于，所述的ABX3中，
    A选自有机阳离子1,4-二氢-1,4-二氮杂二环[2.2.2]辛烷铵离子、1,4-二氢-吡嗪铵离子、1,4-二氢-哌嗪铵离子、1-羟基-4-氢-1,4-二氮杂二环[2.2.2]辛烷铵离子、1,4-二羟基-1,4-二氮杂二环[2.2.2]辛烷铵离子及它们的衍生物中的一种、两种或多种；
    B选自Na+、K+、Rb+、NH4 +中的一种、两种或多种；
    X选自ClO4 -、BrO4 -、IO4 -的一种、两种或多种；
    优选地，A选自1,4-二氢-1,4-二氮杂二环[2.2.2]辛烷铵离子、1-羟基-4-氢-1,4-二氮杂二环[2.2.2]辛烷铵离子、1,4-二羟基-1,4-二氮杂二环[2.2.2]辛烷铵离子及它们的衍生物中的一种、两种或多种；
    更优选地，A选自有机阳离子1,4-二氢-1,4-二氮杂二环[2.2.2]辛烷铵离子、1,4-二羟基-1,4-二氮杂二环[2.2.2]辛烷铵离子中的一种或两种；
    更优选地，B选自Na+、K+、NH4 +中的一种、两种或多种；
    更优选地，B选自Na+、NH4 +中的一种或两种；
    更优选地，B选自NH4 +；
    更优选地，X选自ClO4 -、IO4 -、NO3 -中的一种、两种或三种；
    更优选地，X选自ClO4 -、NO3 -中的一种或两种，或者选自ClO4 -、IO4 -中的一种或两种；
    更优选地，X选自ClO4 -。
  8. 如上述任一权利要求所述的用途，其特征在于，所述的钙钛矿型化合物ABX3含有高氯酸根时，其高氯酸根红外吸收光谱特征峰位于1070～1100cm-1和617～637cm-1之处；
    含有硝酸根时，其硝酸根红外吸收光谱特征峰位于1375～1390cm-1和845～860cm-1之处；
    处于立方晶系时，粉末X射线衍射线位置2θ约为：12.1±0.70°，21.1±1.00°和24.4±1.20°之处；更进一步地，粉末X射线衍射线位置2θ约为：12.1±0.70°，21.1±1.00°，24.4±1.20°，27.4±1.30°和36.57±0.88°之处；
    或，处于单斜晶系时，粉末X射线衍射线位置2θ约为：12.6±0.5°，21.7±0.5°，22.4±0.5°，22.7±0.5°，25.4±0.5°和26.8±0.5°之处；更进一步地，粉末X射线衍射线位置2θ约为： 12.6±0.5°，21.7±0.5°，22.4±0.5°，22.7±0.5°，25.4±0.5°，26.8±0.5°，27.2±0.5°，37.7±0.5°，38.4±0.5°之处；
    或，处于六方晶系时，粉末X射线衍射线位置2θ约为：17.7±0.5°，20.4±0.5°，23.9±0.5°，24.8±0.5°，29.7±0.5°和30.5±0.5°之处；更进一步地，粉末X射线衍射线位置2θ约为：10.3±0.5°，17.7±0.5°，20.4±0.5°，23.9±0.5°，24.8±0.5°，27.0±0.5°，29.7±0.5°，30.5±0.5°，32.2±0.5°，37.0±0.5°之处。
  9. 由如下方法获得的化合物在作为含能材料方面的用途：
    将A组分、B组分和X组分以任意顺序加入到液态反应体系中，反应获得；液态反应体系优选可溶解A组分、B组分和X组分的极性溶剂。
    优选地，按下面步骤1-3获得：
    1)将A组分加入到极性溶剂中，再加入X组分，搅拌均匀；
    2)将B组分溶于极性溶剂；
    3)将步骤1)和步骤2)的溶液混合反应获得；
    其中，所述的A组分为1,4-二氮杂二环[2.2.2]辛烷或其衍生物、吡嗪或其衍生物、哌嗪或其衍生物、1-氧化-1,4-二氮杂二环[2.2.2]辛烷或其衍生物、1,4-二氧化-1,4-二氮杂二环[2.2.2]辛烷或其衍生物、含1,4-二氢-1,4-二氮杂二环[2.2.2]辛烷铵离子或其衍生物的有机盐、含1,4-二氢-吡嗪铵离子或其衍生物的有机盐、含1,4-二氢-哌嗪铵离子或其衍生物的有机盐、含1-羟基-4-氢-1,4-二氮杂二环[2.2.2]辛烷铵离子或其衍生物的有机盐、含1,4-二羟基-1,4-二氮杂二环[2.2.2]辛烷铵离子或其衍生物的有机盐中的一种、两种或多种；更优选选自1,4-二氮杂二环[2.2.2]辛烷或其衍生物、1-氧化-1,4-二氮杂二环[2.2.2]辛烷或其衍生物、1,4-二氧化-1,4-二氮杂二环[2.2.2]辛烷或其衍生物的一种、两种或多种；
    B组分中含有阳离子且阳离子选自碱金属离子、NH4 +中的一种、两种或多种；更优选选自Na+、K+、Rb+、NH4 +中的一种、两种或多种；优选地，B组分为含铵离子盐、含钠离子盐、含钾离子盐、含铷离子盐、含铯离子盐、含铵离子碱、含钠离子碱、含钾离子碱、含铷离子碱、含铯离子碱中的至少一种；
    X组分选自含卤含能基团的酸、含卤含能基团的盐中的至少一种，优选选自含卤含能基团ClO4 -、BrO4 -、IO4 -中的一种、两种或多种，更优选ClO4 -；
    优选地，所述的极性溶剂选自水、乙醇、甲醇中的一种、两种或多种。
  10. 如上述任一权利要求所述的用途，其特征在于所述的含能材料用于作为炸药、推进剂、火箭燃料或安全气囊的气体发生剂；尤其地，作为炸药。
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