Energetic composite material containing multi-component energetic crystal and preparation method of energetic composite material

Abstract

The invention provides a preparation method of an energetic composite material comprising a multi-component energetic crystal, which comprises the following steps: mixing a first reagent comprising a first solvent and a first component with a second reagent comprising a second solvent to obtain a first emulsion; and mixing a third reagent comprising a second component with the first emulsion wherein the multi-component energetic crystal consists of a first cation, a second cation, and an anion; the multi-component energetic crystal component consists of a first component and a second component, and comprises or consists of a first cationic component, a second cationic component and an anionic component; the first reagent further comprises a coating agent, and / or the second reagent further comprises a coating agent. The invention provides an energetic composite material prepared by the preparation method of the energetic composite material comprising multi-component energetic crystals. The invention provides an energetic composite material which comprises a multi-component energetic crystal and a coating agent, and the coating agent coats or partially coats the multi-component energetic crystal.

Description

Technical Field

[0001] The present application relates to the field of energetic materials, and in particular to an energetic composite material comprising a multi-component energetic crystal and a preparation method thereof. Background Art

[0002] Multi-component energetic crystals are different from traditional organic molecular energetic compounds. They are a new type of multi-component energetic crystals formed by alternating and tightly stacking ionic oxidizing components and organic fuel components in a perovskite structure. As a newly emerging new system of domestic single-element explosives, multi-component energetic crystals have the unique advantages of simple preparation process, low cost, high energy output and high thermal stability, providing a new opportunity for the systematic development of high-performance practical energetic materials.

[0003] Among them, many multi-component energetic crystals (such as DAP-4) not only have excellent explosive performance comparable to current military benchmark high-energy explosives such as RDX and HMX, but also have higher thermal stability, and their thermal decomposition temperature is significantly higher than that of classic energetic materials such as HMX, CL-20, and RDX.

[0004] Based on the principle of supramolecular self-assembly in solution, multi-component energetic crystals can be prepared by using low-cost raw materials, at room temperature and pressure, and through a simple one-pot reaction, which has a great synthetic cost advantage. In addition, most multi-component energetic crystals have the advantages of non-hygroscopicity, non-volatility, and weathering resistance, which are conducive to daily storage and transportation. Therefore, as a new type of energetic material with the advantages of high explosive performance, high stability, and low cost, multi-component energetic crystals are expected to be used in mixed explosives, detonators, solid propellants, and propellants, and have good practical prospects.

[0005] However, probably due to the ionic crystal characteristics of this type of energetic material, most perchlorate-based multi-component energetic crystals (such as DAP-4) have high friction sensitivity, which brings potential dangers to sample processing and subsequent formulation synthesis. This danger is particularly prominent when the particle size of the multi-component energetic crystal is small (large surface area, high reaction rate). In addition, these multi-component energetic crystals cannot be well combined with many commonly used binders, so it is difficult to evenly mix and press with a small amount of binder or sensitivity reducing agent. Summary of the invention

[0006] In one aspect, a method for preparing an energetic composite material comprising multi-component energetic crystals is provided, comprising:

[0007] mixing a first reagent including a first solvent and a first component with a second reagent including a second solvent to obtain a first emulsion; and

[0008] mixing a third agent including the second component with the first emulsion,

[0009] in,

[0010] The multi-component energetic crystal is composed of a first cation, a second cation, and an anion;

[0011] The multi-component energetic crystal component consists of a first component and a second component and includes or consists of a first cationic component, a second cationic component, and an anionic component; and

[0012] The first reagent further includes a coating agent, and / or the second reagent further includes a coating agent.

[0013] In one aspect, an energetic composite material prepared by a method for preparing an energetic composite material including multi-component energetic crystals is provided.

[0014] In one aspect, there is provided an energetic composite material comprising:

[0015] Multi-component energetic crystals; and

[0016] Coating agent,

[0017] The coating agent coats or partially coats the multi-component energetic crystal. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 This is a flow chart for preparing the energetic composite material of Example 1.

[0019] Figure 2 A is a scanning electron microscope photograph of the energetic composite material of Example 1. Figure 2 B is Figure 2 A magnified photograph of A.

[0020] Figure 3 Powder X-ray diffraction characterization of the energetic composite material of Example 1 and the multi-component energetic crystal DAP-4.

[0021] Figure 4 Differential thermal analysis (DTA) characterization of the energetic composite material of Example 1 and DAP-4.

[0022] Figure 5 Thermogravimetric characterization of the energetic composite material of Example 1.

[0023] Figure 6 FIG. 4 is a scanning electron microscope photograph showing the surface of a copper wire treated with DAP-4.

[0024] Figure 7 : is a scanning electron microscope picture showing the surface of the copper wire treated with the energetic composite material of Example 1.

[0025] Figure 8 Scanning electron microscope images of the energetic composite material of Example 2 at different magnifications.

[0026] Fig. 9 This is a scanning electron microscope photograph of the energetic composite material of Example 3.

[0027] Fig.10 This is a scanning electron microscope photograph of the energetic composite material of Example 4.

[0028] Fig.11 This is a scanning electron microscope photograph of the energetic composite material of Comparative Example 1.

[0029] Fig.12 This is a scanning electron microscope photograph of the energetic composite material of Comparative Example 2. DETAILED DESCRIPTION

[0030] In order to further explain the technical means and effects adopted by the present application to achieve the predetermined purpose, the specific implementation methods, structures, features and effects of the present application are described in detail below in combination with the accompanying drawings and preferred embodiments.

[0031] Terms and Definitions

[0032] As used herein, singular terms refer to one or more than one. For example, "element" or "an element" refers to one element or more than one element. As used herein, the term "plurality" refers to at least two.

[0033] As used herein, the term "about" refers to approximation, in the range of about or near. When the term "about" is used in conjunction with a numerical range, it modifies the range by expanding the limit above or below the provided numerical value. In general, the term "about" is used herein to make the numerical value change 10% above and below the provided value. On the one hand, the term "about" refers to adding or subtracting 20% ​​of the numerical value of the number modified by it. For example, "about 50%" refers to within the range of 45%-55%. The numerical ranges mentioned herein by endpoints include all integers and fractions contained in the range (e.g., "1 to 5" includes 1, 1.5, 2, 2.75, 3, 3.90, 4 and 5). It should also be understood that all integers and fractions thereof are considered to be modified by the term "about".

[0034] As used herein, the terms "comprising", "including", or "containing", as non-exclusive or open terms, are intended to indicate that a combination (e.g., a device, a composition, a method, etc.) includes the listed elements (e.g., each unit of a device, each component of a composition, a substantial step of a method, etc.), but does not exclude other elements. As used herein, the term "substantially consisting of..." when used to define compositions and methods means excluding other elements that have any substantial impact on the combination of the stated purpose, but does not exclude other elements that do not substantially affect the basic and novel features of the present invention. As used herein, the term "consisting of..." refers to a combination (units, components, substantial steps, etc.) excluding other elements, but unless otherwise specified, it is not intended to exclude trace amounts of unavoidable impurities. The embodiments defined by each of these connecting terms are within the scope of the present invention. As a specific embodiment thereof, the technical solution disclosed including the terms "comprising", "including", or "containing" should also be deemed to simultaneously disclose the corresponding technical solutions including the terms "substantially consisting of..." and "consisting of...".

[0035] As used herein, the term "and / or" refers to and encompasses any and all possible combinations of one or more associated listed items. When used in a list of two or more items, the term "and / or" means that any one of the listed items may be included alone, or may include any combination of two or more listed items. For example, if a group, combination, or composition, etc., is described as including (or containing) components A, B, C, and / or D, the composition may include A alone; B alone; C alone; D alone; a combination of A and B; a combination of A and C; a combination of A and D; a combination of B and C; a combination of B and D; a combination of C and D; a combination of A, B and C; a combination of A, B and D; a combination of A, C and D; a combination of B, C and D; or a combination of A, B, C and D.

[0036] As used herein, the terms "first", "second", "third", etc., unless otherwise specified or further limitations are provided, are only used to distinguish objects with the same attributes in name, and are not used to describe a specific order or sequence, nor are they used to further limit these objects through these ordinal numbers themselves. It should be understood that these ordinal numbers can be interchanged under appropriate circumstances without affecting the understanding of this application. In addition, it should be understood that the disclosure of any further limited implementation methods without ordinal numbers in this application should also be regarded as the disclosure of any further limited implementation methods with these ordinal numbers. It should also be understood that the objects defined by the later ordinal numbers in this application do not mean that the same objects defined by the earlier ordinal numbers must also be included in the same implementation method.

[0037] As used herein, the compounds or ions of the present application include a plurality of variable groups. One of ordinary skill in the art will recognize that the combinations of groups contemplated by the present application are chemically permitted combinations of compounds or ions.

[0038] As used herein, the term "multi-component energetic crystal", specifically as described in Wei-Xiong Zhang et al., "Molecular perovskites as a new platform for designing advanced multi-component energetic crystals", Energ.Mater.Front.2020, Vol.1, Issue 3-4, pp.123-135 (hereinafter referred to as "Zhang et al.", the entire contents of which are incorporated herein by reference), is an energetic crystal that is self-assembled into a specific ternary crystal structure (in some cases, for example, a "perovskite-type" crystal structure similar to perovskite) by different molecular components. Specific examples of multi-component energetic crystals include, but are not limited to, the multi-component energetic crystals mentioned in Zhang et al., such as the compound "ABX3", compound "ABX4", compound "AB2X4", compound "AB2X5", or compound "A2B′B″X6" mentioned therein. Specific examples of multi-component energetic crystals also include, but are not limited to, the compounds disclosed in WO 2018 / 028685 A1 (the entire contents of which are incorporated herein by reference) and WO 2021 / 147960 A1 (the entire contents of which are incorporated herein by reference), specifically, for example, the compound "ABX3" (for example, the perovskite-type compound ABX3), compound "AB′X4", or compound "B′2A′X5" recorded therein.

[0039] As used herein, the term "multi-component energetic crystal ABX3" is intended to mean a multi-component energetic crystal composed of one or more divalent cations ("A"), one or more monovalent cations ("B"), and one or more monovalent anions ("X"), in a molar ratio of 1:1:3; it can be prepared in a liquid reaction system by one or more divalent cation components ("A component"), one or more monovalent cation components ("B component"), and one or more monovalent anion components ("X component"). As used herein, the term "multi-component energetic crystal ABX3" should be understood to include at least the compounds "ABX3" and "A2B′B″X6" in Zhang et al., the compound "ABX3" in WO 2018 / 028685 A1, and the compound "ABX3" in WO2021 / 147960A1, and is not limited to the embodiments specifically disclosed in these public documents.

[0040] As used herein, the term "multi-component energetic crystal AB2X4" is intended to mean a multi-component energetic crystal composed of one or more divalent cations ("A"), one or more monovalent cations ("B"), and one or more monovalent anions ("X"), in a molar ratio of 1:2:4; which can be prepared in a liquid reaction system by one or more divalent cation components ("A component"), one or more monovalent cation components ("B component"), and one or more monovalent anion components ("X component"). As used herein, the term "multi-component energetic crystal AB2X4" should be understood to include at least the compound "AB2X4" in Zhang et al., and is not limited to the embodiments specifically disclosed in these public documents.

[0041] As used herein, the term "multi-component energetic crystal ABX4" is intended to mean a multi-component energetic crystal composed of one or more divalent cations ("A"), another one or more divalent cations ("B"), and one or more monovalent anions ("X"), in a molar ratio of 1:1:4; it can be prepared in a liquid reaction system by one or more divalent cation components ("A component"), another one or more divalent cation components ("B component"), and one or more monovalent anion components ("X component"). As used herein, the term "multi-component energetic crystal ABX4" should be understood to include at least the compound "ABX4" in Zhang et al. and the compound "AB'X4" of WO 2021 / 147960 A1, and is not limited to the embodiments specifically disclosed in these public documents.

[0042] As used herein, the term "multi-component energetic crystals AB2X5" is intended to mean a multi-component energetic crystal composed of one or more monovalent cations ("A"), one or more divalent cations ("B"), and one or more monovalent anions ("X"), in a molar ratio of 1:2:5; which can in particular be prepared by one or more monovalent cation components ("A component"), one or more divalent cation components ("B component"), and one or more monovalent anion components ("X component") in a liquid reaction system. As used herein, the term "multi-component energetic crystals AB2X5" should be understood to include at least compound AB2X5 in Zhang et al. and compound B'2A'X5 of WO 2021 / 147960 A1, and is not limited to the embodiments specifically disclosed in these public documents.

[0043] As used herein, the term "cation", when used to refer to the cations in multi-component energetic crystals, should be deemed to include cations A and cations B in multi-component energetic crystals ABX3, multi-component energetic crystals AB2X4, multi-component energetic crystals ABX4, and multi-component energetic crystals AB2X5, as well as "cation A", "cation A'", "cation B", and "cation B'" mentioned in WO 2021 / 147960A1.

[0044] As used herein, the term "monovalent cation", when used to refer to cations in multi-component energetic crystals, should be deemed to include cations A and cations B in multi-component energetic crystals ABX3, multi-component energetic crystals AB2X4, multi-component energetic crystals ABX4, and multi-component energetic crystals AB2X5, as well as "cation A", "cation A'", "cation B", and "cation B'" mentioned in WO 2021 / 147960 A1, those that are monovalent (i.e., having a positive charge).

[0045] As used herein, the term "divalent cation", when used to refer to cations in multi-component energetic crystals, should be deemed to include cations A and cations B in multi-component energetic crystals ABX3, multi-component energetic crystals AB2X4, multi-component energetic crystals ABX4, and multi-component energetic crystals AB2X5, as well as "cation A", "cation A'", "cation B", and "cation B'" mentioned in WO 2021 / 147960 A1, among which are divalent (i.e., having two positive charges).

[0046] As a specific example of the definition of the above terms, any disclosure of further defined embodiments of the "cation" of the multi-component energetic crystal mentioned in the present application should also be deemed as disclosure of any further defined embodiments of the "first cation" or the "second cation"; any disclosure of further defined embodiments of the "monovalent cation" mentioned in the present application should also be deemed as disclosure of any further defined embodiments of the "first monovalent cation" or the "second monovalent cation"; any disclosure of further defined embodiments of the "divalent cation" mentioned in the present application should also be deemed as disclosure of any further defined embodiments of the "first divalent cation" or the "second divalent cation". For example, when the present application discloses an embodiment in which “the divalent cation comprises 1,4-diazabicyclo[2.2.2]octane-1,4-dionium ion”, it should be understood that the present application also discloses an embodiment in which “the first divalent cation comprises 1,4-diazabicyclo[2.2.2]octane-1,4-dionium ion” and an embodiment in which “the second divalent cation comprises 1,4-diazabicyclo[2.2.2]octane-1,4-dionium ion”.

[0047] As used herein, the term "cation component" may be understood to mean that it includes cations in a multi-component energetic crystal, or its conjugate acid or base, such as its electrically neutral Brunstier-Lowry conjugate base, or cations in a multi-component energetic crystal obtained by dissolving it in a solvent. The cation component may be a compound, a complex, a salt, a solution, a composition, or a mixture, but is not limited thereto.

[0048] As used herein, the term "anion component" may be understood to mean an anion in a multi-component energetic crystal, or its conjugate acid or base, such as its electrically neutral Brunstier-Lowry conjugate acid, or an anion in a multi-component energetic crystal obtained by dissolving it in a solvent. The anion component may be a compound, a complex, a salt, a solution, a composition, or a mixture, but is not limited thereto.

[0049] As a specific example of the above definition, when the first cation in the multi-component energetic crystal includes 1,4-diazabicyclo[2.2.2]octane-1,4-dionium ion, the corresponding "first cation component" can be any compound, complex, salt, composition, solution, or mixture that includes 1,4-diazabicyclo[2.2.2]octane-1,4-dionium ion (whether it is an ion in the solution or as one of the constituent ions in the salt), or 1,4-diazabicyclo[2.2.2]octane (i.e., triethylenediamine), or a 1,4-diazabicyclo[2.2.2]octane-1,4-dionium ion that can be obtained when dissolved in a solvent.

[0050] As another specific example of the above definition, when the second cation in the multi-component energetic crystal includes an ammonium ion and the anion includes a perchlorate ion, ammonia water can be used as the "second cation component" corresponding thereto, perchloric acid can be used as the "anion component" corresponding thereto, and ammonium perchlorate can be used as both the "second cation component" and the "anion component" corresponding thereto. In such a case, in some embodiments, when a component is defined as "including a second cation component and an anion component", an embodiment in which the component only includes ammonium perchlorate is included.

[0051] As used herein, the term "energetic group" refers to a group that has oxidizing properties, such as a group that is commonly considered to be explosive, or a group that can produce an internal redox reaction. Common energetic groups include ClO3 - 、ClO4 - IO4 - 、NO3 - 、ONC - , azo group, azide ion, nitro group and other groups.

[0052] As used herein, the term "derivative" is intended to mean that the hydrogen atoms in the chemical structure are replaced by substituents simultaneously or not. Common substituents include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, hydroxyl, carbonyl, carboxyl, amine, halogen, thiol, peroxy, azo, and nitro.

[0053] As used herein, the term "amine" is intended to mean ammonia or a derivative thereof in which one, two or three hydrogen atoms are replaced by one, two or three substituents, or a compound having an amino group; amines have a nitrogen atom having a lone pair of electrons thereon, and include organic amines (such as primary amines, secondary amines, tertiary amines, etc.) and inorganic amines (such as hydrazine, hydroxylamine, etc.).

[0054] As used herein, the terms "aqueous phase" and "oil phase" should be understood as merely customary terms used based on the relative magnitude of the polarity of these solvents, and are not intended to limit the types of solvents of these solutions. Specifically, it is generally believed that the solution referred to as the "aqueous phase" has a higher solvent polarity than the solution of the "oil phase" in the same embodiment or the same reaction system. The term "oil phase" can be used interchangeably with the term "organic phase" herein.

[0055] As used herein, the term "miscible" is intended to mean that the miscibility of two or more substances or systems with each other at 25° C. and atmospheric pressure is greater than 50% by mass, particularly greater than or equal to 75%, particularly greater than or equal to 90%, more particularly greater than or equal to 95%, and more particularly greater than or equal to 99%.

[0056] As used herein, the term "immiscible" is intended to mean that the miscibility of two or more substances or systems with each other at 25° C. and atmospheric pressure is less than 50% by mass, particularly less than or equal to 25%, particularly less than or equal to 10%, more particularly less than or equal to 5%, more particularly less than or equal to 1%.

[0057] As used herein, the term "coating agent" can be understood as a material used to bond or attach to the surface of a multi-component energetic crystal in the method for preparing an energetic composite material including a multi-component energetic crystal of the present application, or a material bonded or attached to the surface of a multi-component energetic crystal in the energetic composite material including a multi-component energetic crystal of the present application. For the energetic composite material of the present application, the term "coating agent" can be used interchangeably with the term "coating"; and, in some cases, it can be referred to by the term "coating layer". As used herein, the terms "coating agent", "coating", or "coating layer" should be understood as, unless otherwise specified, not intended to limit the surface area of ​​at least a specific proportion of the multi-component energetic crystals coated thereon. In the energetic composite material of the present application, the "coating agent", "coating", or "coating layer" may cover at least 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 100% of the surface area of ​​the multi-component energetic crystals. As used herein, the term "coating agent" may be used interchangeably with the term "binder"; however, it should be understood that, unless otherwise specified, it is not intended to limit how many multi-component energetic crystals are bonded together by the binder. As used herein, the term "coating agent" may be used interchangeably with the term "surface modifier".

[0058] As used herein, the term "coating", as a verb or its variation, can be understood as, for example, a material (such as a "coating", "coating agent" or "coating layer") for coating, coating at least 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 100% of the surface area of ​​the coated object. The term "partial coating" or "coating or partial coating" should be understood in the same manner.

[0059] As used herein, the term "emulsion" can be understood as a discontinuous phase dispersed in a continuous phase in the form of a dispersion or droplets, particularly a liquid (whether a pure substance or a solution) dispersed in another liquid immiscible therewith in the form of a dispersion or droplets. In some cases, the emulsion can be a "multiple emulsion", in which the dispersion or droplets can consist of one phase and another phase coated therewith. Examples of emulsions include water-in-oil emulsions, oil-in-water emulsions, water-in-oil-in-water emulsions, and oil-in-water-in-oil emulsions, but are not limited thereto. As used herein, the term "emulsion" can be used interchangeably with the terms "microemulsion" and "nanoemulsion".

[0060] Implementation

[0061] In some embodiments, an energetic composite material is provided, comprising:

[0062] Multi-component energetic crystals; and

[0063] Coating agent,

[0064] The capping agent caps or partially caps the multi-component energetic crystal.

[0065] In some embodiments, a method for preparing an energetic composite material including multi-component energetic crystals is provided, comprising:

[0066] mixing a first reagent including a first solvent and a first component with a second reagent including a second solvent to obtain a first emulsion; and

[0067] mixing a third agent including the second component with the first emulsion,

[0068] in,

[0069] The multi-component energetic crystal is composed of a first cation, a second cation, and an anion;

[0070] The multi-component energetic crystal component consists of a first component and a second component and includes or consists of a first cationic component, a second cationic component, and an anionic component; and

[0071] The first reagent further includes a coating agent, and / or the second reagent further includes a coating agent.

[0072] In some embodiments, the first solvent and the second solvent are immiscible.

[0073] In some embodiments, the third reagent further includes a third solvent, the third solvent is miscible with the first solvent, and the third solvent is immiscible with the second solvent.

[0074] In some embodiments, the mixing of the first reagent and the second reagent to obtain the first emulsion comprises:

[0075] mixing the first agent and the second agent to obtain a second emulsion; and

[0076] mixing the second emulsion and the fourth solvent to obtain a first emulsion;

[0077] The fourth solvent is miscible with the first solvent, and the fourth solvent is immiscible with the second solvent.

[0078] In some embodiments, the third reagent is mixed with the first emulsion to obtain a first reaction system. In some embodiments, the third reagent is mixed with the first emulsion to obtain a first reaction system, and a first precipitate is generated from the first reaction system.

[0079] In some embodiments, in the preparation method of the present application:

[0080] - through an emulsion-assisted liquid phase self-assembly reaction, the multi-component energetic crystal is synthesized and composited with a capping agent to form an energetic composite material including the multi-component energetic crystal;

[0081] - The mixing of the first agent and the second agent forms a metastable emulsion system (colostrum), especially a uniformly dispersed emulsion under stirring driving force;

[0082] - Adding a fourth solvent to form a double emulsion improves the stability of the emulsion; and / or

[0083] - The addition of the third agent destroys the emulsion system and causes demulsification, so that the multi-component energetic crystals and the coating agent precipitate simultaneously. The coating agent gradually approaches the multi-component energetic crystals under the intermolecular force and hydrophobic effect, thereby obtaining the energetic composite material of the present application.

[0084] In some embodiments, an energetic composite material prepared by the method for preparing an energetic composite material including multi-component energetic crystals of the present application is provided.

[0085] In some embodiments, the energetic composite material of the present application, or the energetic composite material including multi-component energetic crystals prepared by the preparation method of the present application, can achieve uniform molding preparation of multi-component energetic crystals and coating agents, and the energetic composite material has a composite structure with multi-component energetic crystals as the main body and the coating agent uniformly coating its surface.

[0086] In some embodiments, the energetic composite material of the present application, or the energetic composite material comprising multi-component energetic crystals prepared by the preparation method of the present application, has significantly reduced friction sensitivity (manifested as an increase in test values) compared to multi-component energetic crystals.

[0087] In some embodiments, the energetic composite material of the present application, or the energetic composite material including multi-component energetic crystals prepared by the preparation method of the present application, has a lower content of coating agent than the multi-component energetic crystals, but has significantly lower friction sensitivity (manifested as higher test values).

[0088] In some embodiments, the energetic composite material of the present application, or the energetic composite material including multi-component energetic crystals prepared by the preparation method of the present application, when used to process a material (such as a metal material), has better compatibility with the material and can be more evenly attached to the material compared to the multi-component energetic crystals.

[0089] In some embodiments, the preparation method of the present application is simple to operate and requires low operating equipment. The preparation method of the present application can simply adjust the friction sensitivity of the energetic composite material of the present application by adding the coating agent. In particular, the preparation method of the present application can achieve graded adjustable friction sensitivity of the energetic composite material.

[0090] In some embodiments, the preparation method of the present application can allow small-sized multi-component energetic crystals to be coated during their generation, thereby avoiding the generation of multi-component energetic crystals with exposed surfaces having higher friction sensitivity, making the preparation of energetic composite materials safer.

[0091] In some embodiments, the multi-component energetic crystals include at least one selected from the group consisting of multi-component energetic crystals ABX2, multi-component energetic crystals AB2X4, multi-component energetic crystals ABX4, and multi-component energetic crystals AB2X5.

[0092] In some embodiments, the multi-component energetic crystal:

[0093] A first divalent cation, a second monovalent cation, and a monovalent anion in a molar ratio of 1:1:3; or

[0094] A first divalent cation, a second monovalent cation, and a monovalent anion in a molar ratio of 1:2:4; or

[0095] A first divalent cation, a second divalent cation, and a monovalent anion in a molar ratio of 1:1:4; or

[0096] The composition is composed of a first monovalent cation, a second divalent cation, and a monovalent anion in a molar ratio of 1:2:5.

[0097] In some embodiments:

[0098] The first cation is a divalent cation, the second cation is a monovalent cation, and the anion is a monovalent anion, in particular the molar ratio of the first cation, the second cation, and the anion is 1:1:3; or

[0099] The first cation is a divalent cation, the second cation is a monovalent cation, and the anion is a monovalent anion, in particular the molar ratio of the first cation, the second cation, and the anion is 1:2:4; or

[0100] The first cation is a divalent cation, the second cation is a divalent cation, and the anion is a monovalent anion, in particular, the molar ratio of the first cation, the second cation, and the anion is 1:1:4; or

[0101] The first cation is a monovalent cation, the second cation is a divalent cation, and the anion is a monovalent anion, and in particular, the molar ratio of the first cation, the second cation, and the anion is 1:2:5.

[0102] In some embodiments, the multi-component energetic crystal composition comprises or consists of:

[0103] a first divalent cation component, a second monovalent cation component, and a monovalent anion component; or

[0104] a first divalent cation component, a second divalent cation component, and a monovalent anion component; or

[0105] A first monovalent cation component, a second divalent cation component, and a monovalent anion component.

[0106] In some embodiments:

[0107] The first cationic component is a divalent cationic component, the second cationic component is a monovalent cationic component, and the anionic component is a monovalent anionic component;

[0108] The first cationic component is a divalent cationic component, the second cationic component is a divalent cationic component, and the anionic component is a monovalent anionic component; or

[0109] The first cationic component is a monovalent cationic component, the second cationic component is a divalent cationic component, and the anionic component is a monovalent anionic component.

[0110] In some embodiments, the multi-component energetic crystal is a multi-component energetic crystal ABX3. In some embodiments, the multi-component energetic crystal is composed of a first divalent cation, a second monovalent cation, and a monovalent anion in a molar ratio of 1:1:3. In some embodiments, the first cation is a divalent cation, the second cation is a monovalent cation, the anion is a monovalent anion, and the molar ratio of the first cation, the second cation, and the anion is 1:1:3. In some embodiments, the multi-component energetic crystal component includes or consists of a first divalent cation component, a second monovalent cation component, and a monovalent anion component. In some embodiments, the first cation component is a divalent cation component, the second cation is a monovalent cation component, and the anion component is a monovalent anion component.

[0111] In some embodiments, the multi-component energetic crystal is a multi-component energetic crystal AB2X4. In some embodiments, the multi-component energetic crystal is composed of a first divalent cation, a second monovalent cation, and a monovalent anion in a molar ratio of 1:2:4. In some embodiments, the first cation is a divalent cation, the second cation is a monovalent cation, the anion is a monovalent anion, and the molar ratio of the first cation, the second cation, and the anion is 1:2:4. In some embodiments, the multi-component energetic crystal components include or consist of a first divalent cation component, a second monovalent cation component, and a monovalent anion component. In some embodiments, the first cation component is a divalent cation component, the second cation component is a monovalent cation component, and the anion component is a monovalent anion component.

[0112] In some embodiments, the multi-component energetic crystal is a multi-component energetic crystal ABX4. In some embodiments, the multi-component energetic crystal is composed of a first divalent cation, a second divalent cation, and a monovalent anion in a molar ratio of 1:1:4. In some embodiments, the first cation is a divalent cation, the second cation is a divalent cation, the anion is a monovalent anion, and the molar ratio of the first cation, the second cation, and the anion is 1:1:4. In some embodiments, the multi-component energetic crystal components include or consist of a first divalent cation component, a second divalent cation component, and a monovalent anion component. In some embodiments, the first cation component is a divalent cation component, the second cation component is a divalent cation component, and the anion component is a monovalent anion component.

[0113] In some embodiments, the multi-component energetic crystal is a multi-component energetic crystal AB2X5. In some embodiments, the multi-component energetic crystal is composed of a first monovalent cation, a second divalent cation, and a monovalent anion in a molar ratio of 1:2:5. In some embodiments, the first cation is a monovalent cation, the second cation is a divalent cation, the anion is a monovalent anion, and the molar ratio of the first cation, the second cation, and the anion is 1:2:5. In some embodiments, the multi-component energetic crystal component includes or consists of a first monovalent cation component, a second divalent cation component, and a monovalent anion component. In some embodiments, the first cation component is a monovalent cation component, the second cation component is a divalent cation component, and the anion component is a monovalent anion component.

[0114] In some embodiments, the first component includes or consists of one or two selected from the group consisting of a first cationic component, a second cationic component, and an anionic component, and the second component includes or consists of one or two selected from the group consisting of a first cationic component, a second cationic component, and an anionic component.

[0115] In some embodiments, the first component includes or consists of one selected from the group consisting of the first cationic component, the second cationic component, and the anionic component, and the second component includes or consists of the other two. In some embodiments, the first component includes or consists of two selected from the group consisting of the first cationic component, the second cationic component, and the anionic component, and the second component includes or consists of the other one. In some embodiments, the first component includes or consists of the first cationic component, and the second component includes or consists of the second cationic component and the anionic component. In some embodiments, the first component includes or consists of the second cationic component, and the second component includes or consists of the first cationic component and the anionic component. In some embodiments, the first component includes or consists of the anionic component, and the second component includes or consists of the first cationic component and the second cationic component. In some embodiments, the first component includes or consists of the first cationic component and the second cationic component, and the second component includes or consists of the anionic component. In some embodiments, the first component includes or consists of the first cationic component and the anionic component, and the second component includes or consists of the second cationic component. In some embodiments, the first component includes or consists of a second cationic component and an anionic component, and the second component includes or consists of a first cationic component. In some embodiments, the first component includes or consists of a first cationic component and a second cationic component, and the second component includes or consists of a first cationic component and an anionic component. In some embodiments, the first component includes or consists of a first cationic component and a second cationic component, and the second component includes or consists of a second cationic component and an anionic component. In some embodiments, the first component includes or consists of a first cationic component and an anionic component, and the second component includes or consists of a first cationic component and a second cationic component. In some embodiments, the first component includes or consists of a first cationic component and an anionic component, and the second component includes or consists of a second cationic component and an anionic component. In some embodiments, the first component includes or consists of a second cationic component and an anionic component, and the second component includes or consists of a first cationic component and a second cationic component. In some embodiments, the first component includes or consists of a second cationic component and an anionic component, and the second component includes or consists of a first cationic component and an anionic component. In some embodiments, the first component includes or consists of a second cationic component and an anionic component, and the second component includes or consists of a first cationic component and an anionic component.

[0116] In some embodiments, the first component comprises or consists of a first cationic component and an optional second cationic component, and the second component comprises or consists of an anionic component and an optional second cationic component. In some embodiments: the first component comprises or consists of a first cationic component, and the second component comprises or consists of a second cationic component and an anionic component; or the first component comprises or consists of a first cationic component and a second cationic component, and the second component comprises or consists of an anionic component.

[0117] In some embodiments, the divalent cation is a divalent organic cation. In some embodiments, the divalent cation is an organic diammonium ion. In some embodiments, the divalent cation is a cyclic diammonium ion. In some embodiments, the divalent cation is a fatty diammonium ion. In some embodiments, the divalent cation is a saturated fatty diammonium ion. In some embodiments, the divalent cation is a chain diammonium ion. In some embodiments, the divalent cation is a cyclic diammonium ion or a fatty diammonium ion. In some embodiments, the divalent cation is a cyclic diammonium ion or a saturated fatty diammonium ion. In some embodiments, the divalent cation is a cyclic diammonium ion or a chain diammonium ion. In some embodiments, the first divalent cation is a cyclic diammonium ion. In some embodiments, the second divalent cation is a fatty diammonium ion. In some embodiments, the second divalent cation is a saturated fatty diammonium ion. In some embodiments, the second divalent cation is a chain diammonium ion.

[0118] In some embodiments, the cyclic diammonium ion is a five-membered ring diammonium ion, a six-membered ring diammonium ion, or a seven-membered ring diammonium ion. In some embodiments, the cyclic diammonium ion is a bicyclic diammonium ion.

[0119] In some embodiments, the cyclic diammonium ion is selected from the group consisting of ions of formula (I), and ions of formula (II), and optionally derivatives thereof, wherein n1, n2, n3, n4 and n5 are each a positive integer of, in particular, 1, 2, 3, 4 or 5, more in particular, 1, 2 or 3, and R1, R2, R3 and R4 are selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, hydroxyl, carbonyl, carboxyl, amine, halogen, thiol, peroxide, azo, and nitro.

[0120]

[0121] In some embodiments,

[0122] The cyclic diammonium ion is an ion of formula (I), or optionally a derivative thereof, and

[0123] Either n1 or n2 is greater than 2, or either R1 or R2 includes at least one carbon atom;

[0124] or

[0125] The cyclic diammonium ion is an ion of formula (II), or optionally a derivative thereof, and

[0126] Any one of n3, n4 and n5 is greater than 2, or any one of R3 and R4 includes at least one carbon atom.

[0127] In some embodiments, the cyclic diammonium ion is an ion of formula (I) or optionally a derivative thereof; and any one of n1 and n2 is greater than 2, or any one of R1 and R2 includes at least one carbon atom. In some embodiments, the cyclic diammonium ion is an ion of formula (II) or optionally a derivative thereof; and any one of n3, n4 and n5 is greater than 2, or any one of R3 and R4 includes at least one carbon atom. In some embodiments, the cyclic diammonium ion is an ion of formula (I) or optionally a derivative thereof, and any one of n1 and n2 is greater than 2; or the cyclic diammonium ion is an ion of formula (II) or optionally a derivative thereof, and any one of n3, n4 and n5 is greater than 2. In some embodiments, the cyclic diammonium ion is an ion of formula (I) or optionally a derivative thereof, and any one of R1 and R2 includes at least one carbon atom; or the cyclic diammonium ion is an ion of formula (II) or optionally a derivative thereof, and any one of R3 and R4 includes at least one carbon atom.

[0128] In some embodiments, the cyclic diammonium ion is an ion of formula (I) or optionally a derivative thereof, and any one of R1 and R2 is a methyl group; or the cyclic diammonium ion is an ion of formula (II) or optionally a derivative thereof, and any one of R3 and R4 is a methyl group.

[0129] In some embodiments, the cyclic diammonium ion is an ion of formula (I) or optionally a derivative thereof, and any one of n1 and n2 is 2. In some embodiments, the cyclic diammonium ion is an ion of formula (I) or optionally a derivative thereof, and n1 and n2 are both 2. In some embodiments, the cyclic diammonium ion is an ion of formula (I) or optionally a derivative thereof, and n1 is 2, and n2 is greater than or equal to 2. In some embodiments, the cyclic diammonium ion is an ion of formula (I) or optionally a derivative thereof, and any one of n1 and n2 is 3. In some embodiments, the cyclic diammonium ion is an ion of formula (II) or optionally a derivative thereof, and any one of n3, n4 and n5 is 2. In some embodiments, the cyclic diammonium ion is an ion of formula (II) or optionally a derivative thereof, and n3, n4 and n5 are all 2.

[0130] In some embodiments, the cyclic diammonium ion is selected from the group consisting of 1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion, 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion, 1,4-dihydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion, pyrazine-1,4-dialium ion, piperazine-1,4-dialium ion, 1-methylpiperazine-1,4-dialium ion, 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion, and 1,4-diazacycloheptane-1,4-dialium ion, and optionally derivatives thereof. In some embodiments, the cyclic diammonium ion is selected from the group consisting of piperazine-1,4-dialium ion, 1-methylpiperazine-1,4-dialium ion, 1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion, 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion, 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion, and 1,4-diazacycloheptane-1,4-dialium ion, and optionally derivatives thereof. In some embodiments, the cyclic diammonium ion is selected from the group consisting of piperazine-1,4-dialium ion, and 1,4-diazacycloheptane-1,4-dialium ion, and optionally derivatives thereof. In some embodiments, the cyclic diammonium ion is selected from the group consisting of piperazine-1,4-dialium ion, 1-methylpiperazine-1,4-dialium ion, 1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion, and 1,4-diazacycloheptane-1,4-dialium ion, and optionally derivatives thereof. In some embodiments, the cyclic diammonium ion is selected from the group consisting of 1-methylpiperazine-1,4-dialium ion, 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion, 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion, and 1,4-diazacycloheptane-1,4-dialium ion, and optionally derivatives thereof. In some embodiments, the cyclic diammonium ion is selected from the group consisting of 1-methylpiperazine-1,4-dialium ion, 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion, and 1,4-diazacycloheptane-1,4-dialium ion, and optionally derivatives thereof. In some embodiments, the cyclic diammonium ion is selected from the group consisting of 1-methylpiperazine-1,4-dialium ion, 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion, and 1,4-diazacycloheptane-1,4-dialium ion, and optionally derivatives thereof. In some embodiments, the cyclic diammonium ion is selected from the group consisting of 1-methylpiperazine-1,4-dionium ion, and 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dionium ion, and optionally derivatives thereof.In some embodiments, the cyclic diammonium ion is selected from the group consisting of 1-methylpiperazine-1,4-dionium ion, and 1,4-diazacycloheptane-1,4-dionium ion, and optionally derivatives thereof. In some embodiments, the cyclic diammonium ion is selected from the group consisting of 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dionium ion, and 1,4-diazacycloheptane-1,4-dionium ion, and optionally derivatives thereof.

[0131] In some embodiments, the cyclic diammonium ion is 1,4-diazabicyclo[2.2.2]octane-1,4-dionium ion or, alternatively, a derivative thereof. In some embodiments, the cyclic diammonium ion is 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dionium ion or, alternatively, a derivative thereof. In some embodiments, the cyclic diammonium ion is 1,4-dihydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dionium ion or, alternatively, a derivative thereof. In some embodiments, the cyclic diammonium ion is pyrazine-1,4-dionium ion or, alternatively, a derivative thereof. In some embodiments, the cyclic diammonium ion is piperazine-1,4-dionium ion or, alternatively, a derivative thereof. In some embodiments, the cyclic diammonium ion is 1-methylpiperazine-1,4-dionium ion or, alternatively, a derivative thereof. In some embodiments, the cyclic diammonium ion is 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dionium ion or alternatively a derivative thereof. In some embodiments, the cyclic diammonium ion is 1,4-diazacycloheptane-1,4-dionium ion or alternatively a derivative thereof.

[0132] In some embodiments, the chain diammonium ion is an alkyl diammonium ion. In some embodiments, the chain diammonium ion is a straight chain alkyl diammonium ion. In some embodiments, the general formula of the chain diammonium ion is wherein n3 is a positive integer which is particularly 1, 2, 3, 4 or 5, more particularly 1, 2 or 3, more particularly 2, R7, R8, R9, R 10 , R 11 , R 12 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl. 10 , R 11 , R 12 One, two, three, four, five or all of are hydrogen. In some embodiments, in the chain diammonium ion, n3 is 1. In some embodiments, in the chain diammonium ion, n3 is 2. In some embodiments, in the chain diammonium ion, n3 is 3. In some embodiments, the chain diammonium ion includes ethylene diammonium ion. In some embodiments, the chain diammonium ion is ethylene diammonium ion.

[0133] In some embodiments, the monovalent cation is an alkali metal ion or a monovalent nitrogen-containing cation. In some embodiments, the monovalent cation is an alkali metal ion, an ammonium ion, or a monovalent organic ammonium ion. In some embodiments, the monovalent cation is an alkali metal ion or an ammonium ion.

[0134] In some embodiments, the monovalent cation is selected from lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions, silver ions, ammonium ions, hydroxylammonium ions, and In some embodiments, the monovalent cation is selected from the group consisting of sodium ions, potassium ions, rubidium ions, cesium ions, silver ions, ammonium ions, hydroxylammonium ions, and ions. In some embodiments, the monovalent cation is selected from the group consisting of lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions, silver ions, and ammonium ions. In some embodiments, the monovalent cation is selected from the group consisting of sodium ions, potassium ions, rubidium ions, cesium ions, silver ions, and ammonium ions. In some embodiments, the monovalent cation is selected from the group consisting of lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions, and ammonium ions. In some embodiments, the monovalent cation is selected from the group consisting of sodium ions, potassium ions, and ammonium ions. In some embodiments, the monovalent cation is selected from the group consisting of sodium ions, potassium ions, and ammonium ions. In some embodiments, the monovalent cation is lithium ion. In some embodiments, the monovalent cation is sodium ion. In some embodiments, the monovalent cation is potassium ion. In some embodiments, the monovalent cation is rubidium ion. In some embodiments, the monovalent cation is cesium ion. In some embodiments, the monovalent cation is silver ion. In some embodiments, the monovalent cation is ammonium ion. In some embodiments, the monovalent cation is hydroxyammonium ion or In some embodiments, the monovalent cation is a hydroxylammonium ion. In some embodiments, the monovalent cation is ion.

[0135] In some embodiments, the monovalent cation is a monovalent nitrogen-containing cation. In some embodiments, the monovalent cation is a monovalent organic ammonium ion. In some embodiments, the general formula of the monovalent cation is NR3R4R5R6 + , wherein R3, R4, R5, and R6 are selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, hydroxyl, carbonyl, carboxyl, amine, halogen, thiol, peroxide, azo, and nitro.

[0136] In some embodiments, the monovalent anion is an anionic energetic group.

[0137] In some embodiments, the monovalent anion is selected from the group consisting of chlorate, bromate, iodate, perchlorate, perbromate, periodate, nitrate, fulminate, azo, and azide. In some embodiments, the monovalent anion is selected from the group consisting of chlorate, perchlorate, nitrate, fulminate, azo, and azide.

[0138] In some embodiments, the monovalent anion is a monovalent halogen-containing anion. In some embodiments, the monovalent anion is a monovalent halogen-containing oxygen-containing acid anion. In some embodiments, the monovalent anion is a halide ion or a perhalide ion. In some embodiments, the monovalent anion is a perhalide ion or a nitrate ion. In some embodiments, the monovalent anion is a perhalide ion. In some embodiments, the monovalent anion is a chlorate ion, a bromate ion, an iodate ion, a perchlorate ion, a perbromate ion, a periodate ion, or a nitrate ion. In some embodiments, the monovalent anion is a perchlorate ion, a perbromate ion, or a nitrate ion. In some embodiments, the monovalent anion is a chlorate ion, a bromate ion, an iodate ion, a perchlorate ion, a perbromate ion, or a periodate ion. In some embodiments, the monovalent anion is a perchlorate ion, a perbromate ion, a periodate ion, or a nitrate ion. In some embodiments, the monovalent anion is a perchlorate ion, a perbromate ion, or a periodate ion. In some embodiments, the monovalent anion is a perchlorate ion or a perbromate ion. In some embodiments, the monovalent anion is a perchlorate ion or a periodate ion. In some embodiments, the monovalent anion is a perbromate ion or a periodate ion. In some embodiments, the monovalent anion is a perchlorate ion. In some embodiments, the monovalent anion is a perbromate ion. In some embodiments, the monovalent anion is a periodate ion.

[0139] In some embodiments, the monovalent anion is selected from the group consisting of perchlorate, perbromate, periodate, or nitrate, and the monovalent cation is selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, ammonium, hydroxylammonium, and In some embodiments, the monovalent anion is a perchlorate ion, and the monovalent cation is selected from the group consisting of lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions, ammonium ions, hydroxylammonium ions, and In some embodiments, the monovalent anion is a perchlorate ion, and the monovalent cation is an ammonium ion, a sodium ion, or a potassium ion. In some embodiments, the monovalent anion is a perchlorate ion, and the monovalent cation is an ammonium ion.

[0140] In some embodiments, the divalent cation component is an organic diamine. In some embodiments, the divalent cation component is a cyclic diamine or its ammonium salt. In some embodiments, the divalent cation component is a fatty diamine or its ammonium salt. In some embodiments, the divalent cation component is a saturated fatty diamine or its ammonium salt. In some embodiments, the divalent cation component is a chain diamine or its ammonium salt. In some embodiments, the divalent cation component is a cyclic diamine or its ammonium salt or a fatty diamine or its ammonium salt. In some embodiments, the divalent cation component is a cyclic diamine or its ammonium salt or a saturated fatty diamine or its ammonium salt. In some embodiments, the divalent cation component is a cyclic diamine or its ammonium salt or a chain diamine or its ammonium salt. In some embodiments, the first divalent cation is a cyclic diamine or its ammonium salt. In some embodiments, the second divalent cation is a fatty diamine or its ammonium salt. In some embodiments, the second divalent cation is a saturated fatty diamine or its ammonium salt. In some embodiments, the second divalent cation is a chain diamine or its ammonium salt.

[0141] In some embodiments, the cyclic diamine or its ammonium salt is a five-membered ring diamine or its ammonium salt, a six-membered ring diamine or its ammonium salt, or a seven-membered ring diamine or its ammonium salt. In some embodiments, the cyclic diamine or its ammonium salt is a bicyclic diamine or its ammonium salt.

[0142] In some embodiments, the cyclic diamine or its ammonium salt is selected from the group consisting of a compound of formula (III), a compound of formula (IV), an ammonium salt of an ion of formula (I), and an ammonium salt of an ion of formula (II), and optionally derivatives thereof, wherein n1, n2, n3, n4 and n5 are each a positive integer of, in particular, 1, 2, 3, 4 or 5, more in particular 1, 2 or 3, and R1, R2, R3 and R4 are selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, hydroxyl, carbonyl, carboxyl, amine, halogen, thiol, peroxide, azo, and nitro.

[0143]

[0144] In some embodiments,

[0145] The cyclic diamine or its ammonium salt is a compound of formula (III) or an ammonium salt of an ion of formula (I), or optionally a derivative thereof, and

[0146] Either n1 or n2 is greater than 2, or either R1 or R2 includes at least one carbon atom;

[0147] or

[0148] The cyclic diamine or its ammonium salt is a compound of formula (IV) or an ammonium salt of an ion of formula (II), or optionally a derivative thereof, and

[0149] Any one of n3, n4 and n5 is greater than 2, or any one of R3 and R4 includes at least one carbon atom.

[0150] In some embodiments, the cyclic diamine or its ammonium salt is an ammonium salt of a compound of formula (III) or an ion of formula (I), or optionally a derivative thereof, and any one of n1 and n2 is greater than 2, or any one of R1 and R2 includes at least one carbon atom. In some embodiments, the cyclic diamine or its ammonium salt is an ammonium salt of a compound of formula (IV) or an ion of formula (II), or optionally a derivative thereof, and any one of n3, n4 and n5 is greater than 2, or any one of R3 and R4 includes at least one carbon atom. In some embodiments, the cyclic diamine or its ammonium salt is an ammonium salt of a compound of formula (III) or an ion of formula (I), or optionally a derivative thereof, and any one of n1 and n2 is greater than 2; or the cyclic diamine or its ammonium salt is an ammonium salt of a compound of formula (IV) or an ion of formula (II), or optionally a derivative thereof, and any one of n3, n4 and n5 is greater than 2. In some embodiments, the cyclic diamine or its ammonium salt is an ammonium salt of a compound of formula (III) or an ion of formula (I), or optionally a derivative thereof, and any one of R1 and R2 includes at least one carbon atom; or the cyclic diamine or its ammonium salt is an ammonium salt of a compound of formula (IV) or an ion of formula (II), or optionally a derivative thereof, and any one of R3 and R4 includes at least one carbon atom. In some embodiments, the cyclic diamine or its ammonium salt is an ammonium salt of a compound of formula (III) or an ion of formula (I), or optionally a derivative thereof, and any one of R1 and R2 is a methyl group; or the cyclic diamine or its ammonium salt is an ammonium salt of a compound of formula (IV) or an ion of formula (II), or optionally a derivative thereof, and any one of R3 and R4 is a methyl group.

[0151] In some embodiments, the cyclic diamine or its ammonium salt is an ammonium salt of a compound of formula (III) or an ion of formula (I), or optionally a derivative thereof, and any one of n1 and n2 is 2. In some embodiments, the cyclic diamine or its ammonium salt is an ammonium salt of a compound of formula (III) or an ion of formula (I), or optionally a derivative thereof, and n1 and n2 are both 2. In some embodiments, the cyclic diamine or its ammonium salt is an ammonium salt of a compound of formula (III) or an ion of formula (I), or optionally a derivative thereof, and n1 is 2, and n2 is greater than or equal to 2. In some embodiments, the cyclic diamine or its ammonium salt is an ammonium salt of a compound of formula (III) or an ion of formula (I), or optionally a derivative thereof, and n1 is 2, and n2 is greater than 2. In some embodiments, the cyclic diamine or its ammonium salt is an ammonium salt of a compound of formula (III) or an ion of formula (I), or optionally a derivative thereof, and any one of n1 and n2 is 3. In some embodiments, the cyclic diamine or its ammonium salt is a compound of formula (IV) or an ammonium salt of an ion of formula (II), or optionally a derivative thereof, and any one of n3, n4, and n5 is 2. In some embodiments, the cyclic diamine or its ammonium salt is a compound of formula (IV) or an ammonium salt of an ion of formula (II), or optionally a derivative thereof, and n3, n4, and n5 are all 2.

[0152] In some embodiments, the cyclic diamine or its ammonium salt is selected from 1,4-diazabicyclo[2.2.2]octane, the reaction product of 1,4-diazabicyclo[2.2.2]octane and hydrogen peroxide, pyrazine, piperazine, 1-methylpiperazine, 1,4-diazacycloheptane, 1,4-diazabicyclo[2.2.2]octane-1,4-dialium salt, 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1, 4-dialium salt, 1,4-dihydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dialium salt, pyrazine-1,4-dialium salt, piperazine-1,4-dialium salt, 1-methylpiperazine-1,4-dialium salt, 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dialium salt, and 1,4-diazacycloheptane-1,4-dialium salt, and optionally derivatives thereof.

[0153] In some embodiments, the cyclic diamine or its ammonium salt is selected from the group consisting of piperazine, 1-methylpiperazine, 1,4-diazabicyclo[2.2.2]octane, the reaction product of 1,4-diazabicyclo[2.2.2]octane and hydrogen peroxide, and 1,4-diazacycloheptane, and optionally derivatives thereof.

[0154] In some embodiments, the cyclic diamine or its ammonium salt is selected from the group consisting of piperazine, 1,4-diazepane, piperazine-1,4-dionium salt, and 1,4-diazepane-1,4-dionium salt, and optionally derivatives thereof.

[0155] In some embodiments, the cyclic diamine or its ammonium salt is selected from the group consisting of piperazine, 1-methylpiperazine, 1,4-diazabicyclo[2.2.2]octane, 1,4-diazacycloheptane, piperazine-1,4-dialium salt, 1-methylpiperazine-1,4-dialium salt, 1,4-diazabicyclo[2.2.2]octane-1,4-dialium salt, and 1,4-diazacycloheptane-1,4-dialium salt, and optionally derivatives thereof.

[0156] In some embodiments, the cyclic diamine or its ammonium salt is selected from the group consisting of 1-methylpiperazine, the reaction product of 1,4-diazabicyclo[2.2.2]octane and hydrogen peroxide, 1,4-diazacycloheptane, 1-methylpiperazine-1,4-dialium salt, 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dialium salt, 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dialium salt, and 1,4-diazacycloheptane-1,4-dialium salt, and optionally derivatives thereof. In some embodiments, the cyclic diamine or its ammonium salt is selected from the group consisting of 1-methylpiperazine, the reaction product of 1,4-diazabicyclo[2.2.2]octane and hydrogen peroxide, 1,4-diazacycloheptane, 1-methylpiperazine-1,4-dialium salt, 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dialium salt, and 1,4-diazacycloheptane-1,4-dialium salt, and optionally derivatives thereof.

[0157] In some embodiments, the cyclic diamine or its ammonium salt is selected from the group consisting of 1-methylpiperazine, 1,4-diazacycloheptane, 1-methylpiperazine-1,4-dialium salt, 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dialium salt, and 1,4-diazacycloheptane-1,4-dialium salt, and optionally derivatives thereof. In some embodiments, the cyclic diamine or its ammonium salt is selected from the group consisting of 1-methylpiperazine, 1-methylpiperazine-1,4-dialium salt, and 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dialium salt, and optionally derivatives thereof. In some embodiments, the cyclic diamine or its ammonium salt is selected from the group consisting of 1-methylpiperazine, 1,4-diazacycloheptane, 1-methylpiperazine-1,4-dialium salt, and 1,4-diazacycloheptane-1,4-dialium salt, and optionally derivatives thereof. In some embodiments, the cyclic diamine or its ammonium salt is selected from the group consisting of 1,4-diazacycloheptane, 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dialium salt, and 1,4-diazacycloheptane-1,4-dialium salt, and optionally derivatives thereof.

[0158] In some embodiments, the cyclic diamine or its ammonium salt is 1,4-diazabicyclo[2.2.2]octane or optionally a derivative thereof. In some embodiments, the cyclic diamine or its ammonium salt is 1-hydroxy-1,4-diazabicyclo[2.2.2]octane or optionally a derivative thereof. In some embodiments, the cyclic diamine or its ammonium salt is 1,4-dihydroxy-1,4-diazabicyclo[2.2.2]octane or optionally a derivative thereof. In some embodiments, the cyclic diamine or its ammonium salt is pyrazine or optionally a derivative thereof. In some embodiments, the cyclic diamine or its ammonium salt is piperazine or optionally a derivative thereof. In some embodiments, the cyclic diamine or its ammonium salt is 1-methylpiperazine or optionally a derivative thereof. In some embodiments, the cyclic diamine or its ammonium salt is 1,4-diazacycloheptane or optionally a derivative thereof. In some embodiments, the cyclic diamine or its ammonium salt is 1,4-diazabicyclo[2.2.2]octane-1,4-dialium salt or alternatively a derivative thereof. In some embodiments, the cyclic diamine or its ammonium salt is 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dialium salt or alternatively a derivative thereof. In some embodiments, the cyclic diamine or its ammonium salt is 1,4-dihydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dialium salt or alternatively a derivative thereof. In some embodiments, the cyclic diamine or its ammonium salt is pyrazine-1,4-dialium salt or alternatively a derivative thereof. In some embodiments, the cyclic diamine or its ammonium salt is piperazine-1,4-dialium salt or alternatively a derivative thereof. In some embodiments, the cyclic diamine or its ammonium salt is 1-methylpiperazine-1,4-dialium salt or alternatively a derivative thereof. In some embodiments, the cyclic diamine or its ammonium salt is 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dionium salt or alternatively a derivative thereof. In some embodiments, the cyclic diamine or its ammonium salt is 1,4-diazacycloheptane-1,4-dionium salt or alternatively a derivative thereof.

[0159] In some embodiments, the chain diamine or its ammonium salt is an alkyl diamine or its ammonium salt. In some embodiments, the chain diamine or its ammonium salt is a linear alkyl diamine or its ammonium salt.

[0160] In some embodiments, the chain diamine or its ammonium salt is of the general formula ionic salts or hydroxides, wherein n3 is a positive integer of, in particular, 1, 2, 3, 4 or 5, more in particular, 1, 2 or 3, more in particular, 2, R7, R8, R9, R 10 , R 11 , R 12 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl. In some embodiments, the chain diamine or its ammonium salt is of the general formula wherein n3 is a positive integer which is particularly 1, 2, 3, 4 or 5, more particularly 1, 2 or 3, more particularly 2, and R7, R8, R9, R 10 , R 11 , R 12 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl. In some embodiments, in the chain diamine or its ammonium salt, R7, R8, R9, R 10 , R 11 , R 12 One, two, three, four, five or all of are hydrogen. In some embodiments, in the chain diamine or its ammonium salt, n3 is 1. In some embodiments, in the chain diamine or its ammonium salt, n3 is 2. In some embodiments, in the chain diamine or its ammonium salt, n3 is 3.

[0161] In some embodiments, the chain diamine or its ammonium salt is ethylenediamine or ethylenediammonium salt. In some embodiments, the chain diamine or its ammonium salt includes ethylenediamine. In some embodiments, the chain diamine or its ammonium salt includes ethylenediammonium salt.

[0162] In some embodiments, the monovalent cation component is an alkali metal salt, an alkali metal hydroxide, a monovalent nitrogen-containing cation salt, or a monovalent nitrogen-containing base. In some embodiments, the monovalent cation component is an alkali metal salt, an alkali metal hydroxide, a monovalent organic ammonium ion salt, a monovalent organic amine, an ammonium salt, or ammonia. In some embodiments, the monovalent cation component is an alkali metal salt, an alkali metal hydroxide, an ammonium salt, or ammonia.

[0163] In some embodiments, the monovalent cationic component is selected from the group consisting of lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions, silver ions, ammonium ions, hydroxylammonium ions, and In some embodiments, the monovalent cation component is selected from the group consisting of sodium ions, potassium ions, rubidium ions, cesium ions, silver ions, ammonium ions, hydroxylammonium ions, and ions, salts, conjugate bases, and hydroxides thereof. In some embodiments, the monovalent cation component is selected from the group consisting of lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions, silver ions, and ammonium ions, salts, conjugate bases, and hydroxides thereof. In some embodiments, the monovalent cation component is selected from the group consisting of sodium ions, potassium ions, rubidium ions, cesium ions, silver ions, and ammonium ions, salts, conjugate bases, and hydroxides thereof.

[0164] In some embodiments, the monovalent cation component is selected from lithium salts, lithium hydroxide, sodium salts, sodium hydroxide, potassium salts, potassium hydroxide, rubidium salts, rubidium hydroxide, cesium salts, cesium hydroxide, silver salts, ammonium salts, ammonia, hydroxylamine, hydroxylammonium salts, hydrazine, and In some embodiments, the monovalent cation component is selected from the group consisting of sodium salts, sodium hydroxide, potassium salts, potassium hydroxide, rubidium salts, rubidium hydroxide, cesium salts, cesium hydroxide, silver salts, ammonium salts, ammonia, hydroxylamine, hydroxylammonium salts, hydrazine, and In some embodiments, the monovalent cation component is selected from the group consisting of lithium salts, lithium hydroxide, sodium salts, sodium hydroxide, potassium salts, potassium hydroxide, rubidium salts, rubidium hydroxide, cesium salts, cesium hydroxide, silver salts, ammonium salts, and ammonia. In some embodiments, the monovalent cation component is selected from the group consisting of sodium salts, sodium hydroxide, potassium salts, potassium hydroxide, rubidium salts, rubidium hydroxide, cesium salts, cesium hydroxide, silver salts, ammonium salts, and ammonia. In some embodiments, the monovalent cation component is selected from the group consisting of lithium salts, lithium hydroxide, sodium salts, sodium hydroxide, potassium salts, potassium hydroxide, rubidium salts, rubidium hydroxide, cesium salts, cesium hydroxide, ammonium salts, and ammonia. In some embodiments, the monovalent cation component is selected from the group consisting of sodium salts, sodium hydroxide, potassium salts, potassium hydroxide, rubidium salts, rubidium hydroxide, cesium salts, cesium hydroxide, ammonium salts, and ammonia. In some embodiments, the monovalent cation component is selected from the group consisting of sodium salts, sodium hydroxide, potassium salts, potassium hydroxide, ammonium salts, and ammonia. In some embodiments, the monovalent cation component is lithium salt or lithium hydroxide. In some embodiments, the monovalent cation component is sodium salt or sodium hydroxide. In some embodiments, the monovalent cation component is a potassium salt or potassium hydroxide. In some embodiments, the monovalent cation component is a rubidium salt or rubidium hydroxide. In some embodiments, the monovalent cation component is a cesium salt or cesium hydroxide. In some embodiments, the monovalent cation component is a silver salt. In some embodiments, the monovalent cation component is an ammonium salt or ammonia, particularly ammonia gas, ammonia water, or ammonia dissolved in other solvents. In some embodiments, the monovalent cation component is hydroxylamine, a salt containing hydroxylamine ions, a base containing hydroxylamine ions, hydrazine, or a salt containing hydroxylamine ions. Ionic salts or In some embodiments, the monovalent cationic component is hydroxylamine, hydroxylammonium salt, hydrazine, or In some embodiments, the monovalent cationic component is hydroxylamine or a hydroxylammonium salt. In some embodiments, the monovalent cationic component is hydrazine or Salt. In some embodiments, the monovalent cationic component is hydroxylamine. In some embodiments, the monovalent cationic component is hydrazine.

[0165] In some embodiments, the monovalent cation component is a monovalent nitrogen-containing cation salt or a monovalent nitrogen-containing base. In some embodiments, the monovalent cation component is a monovalent organic ammonium ion salt or a monovalent organic amine. In some embodiments, the monovalent cation component is selected from the group consisting of + The group consisting of salts, bases, and hydroxides of cations, wherein R3, R4, R5, and R6 can be selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, hydroxyl, carbonyl, carboxyl, amine, halogen, thiol, peroxide, azo, and nitro; or it is a compound of the general formula NR3R4R5.

[0166] In some embodiments, the monovalent anion component is an acid or salt comprising a monovalent anion in a multi-component energetic crystal, and / or the monovalent anion component produces the monovalent anion after being dissolved in a solvent. In some embodiments, the monovalent anion component is an acid or salt comprising an anionic energetic group. In some embodiments, the monovalent anion component is an acid or salt comprising a monovalent anion.

[0167] In some embodiments, the monovalent anion component is selected from the group consisting of chloric acid, chlorate, perchloric acid, perchlorate, bromic acid, bromate, perbromic acid, perbromate, iodic acid, iodate, periodic acid, periodate, nitric acid, nitrate, fulminic acid, fulminate, azo salts, and azide salts. In some embodiments, the monovalent anion component is selected from the group consisting of chloric acid, chlorate, perchloric acid, perchlorate, nitric acid, nitrate, fulminic acid, fulminate, azo salts, and azide salts.

[0168] In some embodiments, the monovalent anion component is a halogen acid or its salt. In some embodiments, the monovalent anion component is selected from the group consisting of halogen-containing oxyacids, halogen-containing oxyacid salts, nitric acid, and nitrates. In some embodiments, the monovalent anion component is a halogen-containing oxyacid or a halogen-containing oxyacid salt. In some embodiments, the monovalent anion component is a halogen acid, a halogenate, a perhalogen acid, a perhalogenate, nitric acid, or a nitrate. In some embodiments, the monovalent anion component is a halogen acid, a halogenate, a perhalogen acid, or a perhalogenate. In some embodiments, the monovalent anion component is a perhalogen acid, a perhalogenate, nitric acid, or a nitrate. In some embodiments, the monovalent anion component is a perhalogen acid or a perhalogenate. In some embodiments, the monovalent anion component is a chloric acid, a chlorate, a bromic acid, a bromate, an iodic acid, an iodate, perchloric acid, perchlorate, perbromic acid, perbromate, periodic acid, periodate, nitric acid, or a nitrate. In some embodiments, the monovalent anion component is chloric acid, chlorate, bromic acid, bromate, iodic acid, iodate, perchloric acid, perchlorate, perbromic acid, perbromate, periodic acid, or periodate. In some embodiments, the monovalent anion component is perchloric acid, perchlorate, perbromic acid, perbromate, periodic acid, periodate, nitric acid, or nitrate. In some embodiments, the monovalent anion component is perchloric acid, perchlorate, perbromic acid, perbromate, periodic acid, or periodate. In some embodiments, the monovalent anion component is perchloric acid, perchlorate, perbromic acid, perbromate, periodic acid, or periodate. In some embodiments, the monovalent anion component is perchloric acid, perchlorate, perbromic acid, or perbromate. In some embodiments, the monovalent anion component is perchloric acid, perchlorate, periodic acid, or periodate. In some embodiments, the monovalent anion component is perbromic acid, perbromate, periodic acid, or periodate. In some embodiments, the monovalent anion component is perchloric acid or perchlorate. In some embodiments, the monovalent anion component is perbromic acid or perbromate. In some embodiments, the monovalent anion component is periodic acid or a periodate salt.

[0169] In some embodiments, the monovalent cation component and / or the monovalent anion component is a monovalent anion selected from the group consisting of perchlorate ion, perbromate ion, periodate ion, or nitrate ion and a monovalent anion selected from the group consisting of lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion, ammonium ion, hydroxylammonium ion, and In some embodiments, the monovalent cation component and / or the monovalent anion component is selected from lithium perchlorate, sodium perchlorate, potassium perchlorate, rubidium perchlorate, cesium perchlorate, silver perchlorate, ammonium perchlorate, hydroxylammonium perchlorate, Lithium perbromate, sodium perbromate, potassium perbromate, rubidium perbromate, cesium perbromate, silver perchlorate, ammonium perbromate, hydroxylammonium perbromate, perbromic acid Lithium periodate, sodium periodate, potassium periodate, rubidium periodate, cesium periodate, silver perchlorate, ammonium periodate, hydroxylammonium periodate, periodic acid Lithium nitrate, sodium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, silver nitrate, ammonium nitrate, hydroxylammonium nitrate, and nitric acid In some embodiments, the monovalent cation component and / or the monovalent anion component is selected from the group consisting of lithium perchlorate, sodium perchlorate, potassium perchlorate, rubidium perchlorate, cesium perchlorate, silver perchlorate, ammonium perchlorate, hydroxylammonium perchlorate, and perchloric acid. In some embodiments, the monovalent cation component and / or the monovalent anion component is ammonium perchlorate, sodium perchlorate, or potassium perchlorate. In some embodiments, the monovalent cation component and / or the monovalent anion component is ammonium perchlorate.

[0170] In some embodiments, for multi-component energetic crystals with perchloric acid as anions, the rate at which the anion component is mixed with the first cationic component and the second cationic component to form the multi-component energetic crystals is moderate. In combination with the method for preparing an energetic composite material including multi-component energetic crystals of the present application, an energetic composite material with a smaller particle size and lower friction sensitivity (larger numerical value) can be formed.

[0171] In some embodiments, the third solvent and the fourth solvent are mutually soluble. In some embodiments, the first solvent, the third solvent, and the fourth solvent are mutually soluble. In some embodiments, the first solvent, the third solvent, and / or the fourth solvent are polar solvents. In some embodiments, the first solvent is a polar solvent, particularly including at least one selected from the group consisting of water, methanol, ethanol, ethylene glycol, propanol, isopropanol, propylene glycol, and glycerol or a mixture thereof, more particularly including at least one selected from the group consisting of water, methanol, ethanol, and isopropanol or a mixture thereof, more particularly water. In some embodiments, the third solvent is a polar solvent, particularly including at least one selected from the group consisting of water, methanol, ethanol, ethylene glycol, propanol, isopropanol, propylene glycol, and glycerol or a mixture thereof, more particularly including at least one selected from the group consisting of water, methanol, ethanol, and isopropanol or a mixture thereof, more particularly water. In some embodiments, the fourth solvent is a polar solvent, in particular, including at least one selected from the group consisting of water, methanol, ethanol, ethylene glycol, propanol, isopropanol, propylene glycol, and glycerol, or a mixture thereof, more particularly including at least one selected from the group consisting of water, methanol, ethanol, and isopropanol, or a mixture thereof, more particularly water. In some embodiments, the first solvent and the third solvent are the same. In some embodiments, the first solvent and the third solvent are both water. In some embodiments, the first solvent, the third solvent, and the fourth solvent are the same. In some embodiments, the first solvent, the third solvent, and the fourth solvent are all water. In some embodiments, by selecting the first solvent, the third solvent, and / or the fourth solvent as a polar solvent, in particular water, the solubility of each component of the multi-component energetic crystal can be made higher, so that each component can be used at a higher concentration, thereby improving the yield of the energetic composite material of the preparation method of the present application.

[0172] In some embodiments, the second solvent is immiscible with the first solvent, the third solvent and / or the fourth solvent, particularly immiscible with the first solvent and / or the third solvent. In some embodiments, the second solvent is a non-polar solvent, particularly an organic solvent immiscible with water, particularly including at least one or a mixture thereof selected from the group consisting of acetone, formic acid, acetic acid, ethyl acetate, dichloromethane, chloroform, toluene, and liquid paraffin, particularly including at least one or a mixture thereof selected from the group consisting of ethyl acetate, dichloromethane, chloroform, toluene, and liquid paraffin, more particularly including or consisting of dichloromethane. In some embodiments, the second solvent is a mixture of acetone, formic acid and dichloromethane, or dichloromethane.

[0173] In some embodiments, the first emulsion is a water-in-oil emulsion, an oil-in-water emulsion, a water-in-oil-in-water emulsion, or an oil-in-water-in-oil emulsion. In some embodiments, the first emulsion is a water-in-oil emulsion or a water-in-oil-in-water emulsion. In some embodiments, the first emulsion is an oil-in-water emulsion or an oil-in-water-in-oil emulsion. In some embodiments, the first emulsion is an oil-in-water-in-oil emulsion or a water-in-oil-in-water emulsion. In some embodiments, the first emulsion is an oil-in-water-in-water emulsion. In some embodiments, the second emulsion is a water-in-oil emulsion or an oil-in-water emulsion. In some embodiments, the second emulsion is a water-in-oil emulsion. In some embodiments, the second emulsion is an oil-in-water emulsion. In some embodiments, the stability of the emulsion can be improved by forming a second emulsion of a water-in-oil emulsion and then adding a fourth solvent to form a first emulsion of a water-in-oil-in-water emulsion. In some embodiments, the first agent and the third agent, one is acidic and the other is alkaline, in particular, the first agent is alkaline and the third agent is acidic; in some embodiments, the alkaline first agent is used to make the coating agent in the first emulsion exist in an alkaline environment to enhance the stability of the coating agent, such as long-chain fatty acid, such as stearic acid, in the first emulsion, for example, to reduce or avoid the precipitation of the coating agent in the first emulsion. In some embodiments: the first agent is alkaline; the third agent is acidic; and the first reaction system is neutral or acidic, in particular acidic. In some embodiments, the pH value of the first agent is above 7, in particular above 8, in particular 8 to 14, in particular 8 to 12, more particularly 8 to 10. In some embodiments, the pH value of the third agent is below 7, in particular below 6, in particular 0 to 6, in particular 0 to 4, more particularly 0 to 2. In some embodiments, the pH value of the first reaction system is below 7, in particular below 6, in particular 0 to 6, in particular 0 to 4, more particularly 0 to 2.

[0174] In some embodiments, the alkalinity is a pH value selected from 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11.0, 11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, 12.0, 12.1, 12.2, 12.3, 12.4, 12.5, 12.6, 12.7, 12.8, 12.9, 13.0, 13.1, 13. .2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, 12.0, 12.1, 12.2, 12.3, 12.4, 12.5, 12.6, 12.7, 12.8, 12.9, 13.0, 13.1, 13.2, 13.3, 13.4, 13.5, 13.6, 13.7, 13.8, 13.9, 14.0, and the range between any two of them. In some embodiments, the acidic pH is selected from the group consisting of 0.0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3. The group consisting of 0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, and the range between any two values ​​therein.

[0175] In some embodiments, the first reagent is acidic and the third reagent is alkaline. In some embodiments: the first reagent is acidic; the third reagent is alkaline; and the first reaction system is neutral or alkaline, especially alkaline. In some embodiments, the pH value of the first reagent is below 7, especially below 6, especially 0 to 6, especially 0 to 4, more especially 0 to 2. In some embodiments, the pH value of the third reagent is above 7, especially above 8, especially 8 to 14, especially 8 to 12, more especially 8 to 10. In some embodiments, the pH value of the first reaction system is above 7, especially above 8, especially 8 to 14, especially 8 to 12, more especially 8 to 10.

[0176] In some embodiments, the concentration of the first component in the first reagent is about 0.1-5000 mg / mL, particularly about 0.5-1000 mg / mL, particularly about 1-1000 mg / mL, particularly about 1-500 mg / mL, or particularly about 10-5000 mg / mL, more particularly about 100-1000 mg / mL, or more particularly about 10-500 mg / mL. In some embodiments, the concentration of the first component in the first reagent is selected from 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, 50, 60 , 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2500, 3000, 3500, 4000, 4500, and 5000, and ranges between any two of the values.

[0177] In some embodiments, the concentration of the second component in the third reagent is about 0.1-5000 mg / mL, particularly about 0.5-1000 mg / mL, particularly about 1-1000 mg / mL, particularly about 1-500 mg / mL, or particularly about 10-5000 mg / mL, more particularly about 100-1000 mg / mL, or more particularly about 10-500 mg / mL. In some embodiments, the concentration of the second component in the third reagent is selected from 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, 50, 60 , 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2500, 3000, 3500, 4000, 4500, and 5000, and ranges between any two of the values.

[0178] In some embodiments, the concentration of any one or more of the first cationic component, the second cationic component, or the anionic component in the first reagent, the concentration in the third reagent, or the sum of the concentration in the first reagent and the concentration in the third reagent is about 0.1-5000 mg / mL, particularly about 0.5-1000 mg / mL, particularly about 1-500 mg / mL, or particularly about 10-5000 mg / mL, particularly about 100-1000 mg / mL. In some embodiments, the concentration of any one or more of the first cationic component, the second cationic component, or the anionic component in the first reagent, the concentration in the third reagent, or the sum of the concentration in the first reagent and the concentration in the third reagent is selected from 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25 1500, 1600, 1700, 1800, 1900, 2000, 2500, 3000, 3500, 4000, 4500, and 5000, as well as ranges between any two of the values.

[0179] In some embodiments, the concentration of the first cationic component in the first agent is about 0.1-5000 mg / mL, in particular about 0.5-1000 mg / mL, in particular about 1-500 mg / mL, or in particular about 10-5000 mg / mL, in particular about 100-1000 mg / mL. In some embodiments, the concentration of the second cationic component in the first agent is about 0.1-5000 mg / mL, in particular about 0.5-1000 mg / mL, in particular about 1-500 mg / mL, or in particular about 10-5000 mg / mL, in particular about 100-1000 mg / mL. In some embodiments, the concentration of the anionic component in the first agent is about 0.1-5000 mg / mL, in particular about 0.5-1000 mg / mL, in particular about 1-500 mg / mL, or in particular about 10-5000 mg / mL, in particular about 100-1000 mg / mL. In some embodiments, the concentration of the first cationic component in the third agent is about 0.1-5000 mg / mL, in particular about 0.5-1000 mg / mL, in particular about 1-500 mg / mL, or in particular about 10-5000 mg / mL, in particular about 100-1000 mg / mL. In some embodiments, the concentration of the second cationic component in the third agent is about 0.1-5000 mg / mL, in particular about 0.5-1000 mg / mL, in particular about 1-500 mg / mL, or in particular about 10-5000 mg / mL, in particular about 100-1000 mg / mL. In some embodiments, the concentration of the anionic component in the third agent is about 0.1-5000 mg / mL, in particular about 0.5-1000 mg / mL, in particular about 1-500 mg / mL, or in particular about 10-5000 mg / mL, in particular about 100-1000 mg / mL.

[0180] In some embodiments, the molar concentration of any one or more of the first cationic component, the second cationic component, or the anionic component in the first reagent, the molar concentration in the third reagent, or the sum of the molar concentration in the first reagent and the molar concentration in the third reagent is about 0.002-100M, particularly about 0.01-20M, particularly about 0.02-10M, or particularly about 0.2-100M, particularly about 2-20M, more particularly about 2-10M, for example 2, 3, 4, 5, 6, 7, 8, 9, or 10M. In some embodiments, the molar concentration of any one or more of the first cationic component, the second cationic component, or the anionic component in the first reagent, the molar concentration in the third reagent, or the sum of the molar concentration in the first reagent and the molar concentration in the third reagent is selected from 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.015, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.1, 1.2 , 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8. 70, 80, 90, and 100 M, and the range between any two of the values.

[0181] In some embodiments, the molar concentration of the first cationic component in the first reagent is about 2mM-100M, in particular about 0.01-20M, in particular about 0.02-10M, or in particular about 0.2-100M, in particular about 2-20M, more in particular about 2-10M. In some embodiments, the molar concentration of the second cationic component in the first reagent is about 2mM-100M, in particular about 0.01-20M, in particular about 0.02-10M, or in particular about 0.2-100M, in particular about 2-20M, more in particular about 2-10M. In some embodiments, the molar concentration of the anionic component in the first reagent is about 2mM-100M, in particular about 0.01-20M, in particular about 0.02-10M, or in particular about 0.2-100M, in particular about 2-20M, more in particular about 2-10M. In some embodiments, the molar concentration of the first cationic component in the third agent is about 2mM-100M, in particular about 0.01-20M, in particular about 0.02-10M, or in particular about 0.2-100M, in particular about 2-20M, more in particular about 2-10M. In some embodiments, the molar concentration of the second cationic component in the third agent is about 2mM-100M, in particular about 0.01-20M, in particular about 0.02-10M, or in particular about 0.2-100M, in particular about 2-20M, more in particular about 2-10M. In some embodiments, the molar concentration of the anionic component in the third agent is about 2mM-100M, in particular about 0.01-20M, in particular about 0.02-10M, or in particular about 0.2-100M, in particular about 2-20M, more in particular about 2-10M.

[0182] In some embodiments, the molar concentration of any one or more of the first cation, the second cation, or the anion in the first reaction system is about 0.2mM-10M, particularly about 1mM-2M, particularly about 2mM-1M, or particularly about 2mM-10M, particularly about 200mM-2M, more particularly about 200mM-1M. In some embodiments, the molar concentration of any one or more of the first cation, the second cation, or the anion in the first reaction system is selected from 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300 , 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 6000, 7000, 8000, 9000, and 10000 mM, and ranges between any two of the values.

[0183] In some embodiments, the molar concentration of the first cation in the first reaction system is 0.2mM-10M, in particular 1mM-2M, in particular 2mM-1M, or in particular 2mM-10M, in particular 200mM-2M, more in particular 200mM-1M. In some embodiments, the molar concentration of the second cation in the first reaction system is 0.2mM-10M, in particular 1mM-2M, in particular 2mM-1M, or in particular 2mM-10M, in particular 200mM-2M, more in particular 200mM-1M. In some embodiments, the molar concentration of the anion in the first reaction system is 0.2mM-10M, in particular 1mM-2M, in particular 2mM-1M, or in particular 2mM-10M, in particular 200mM-2M, more in particular 200mM-1M.

[0184] In some embodiments, the first component includes an amine. In some embodiments, the amine includes or consists of at least one selected from the group consisting of ammonia, hydrazine, and hydroxylamine. In some embodiments, the amine includes or consists of ammonia. In some embodiments, ammonia is aqueous ammonia. In some embodiments, the hydrazine is hydrazine hydrate. In some embodiments, the volume ratio of aqueous ammonia to the first solvent is about 0.1-1000 μL / mL, particularly about 1-500 μL / mL, more particularly about 5-100 μL / mL, and more particularly about 10-50 μL / mL.

[0185] In some embodiments, the first reagent includes a capping agent. In some embodiments, the second reagent includes a capping agent. In some embodiments, the first reagent includes a first capping agent, and the second reagent includes a second capping agent. In some embodiments, the first reagent includes a first capping agent, the second reagent includes a second capping agent, and the first capping agent and the second capping agent are different. In some embodiments, the first reagent includes a capping agent, and the capping agent is soluble in a first solvent. In some embodiments, the second reagent includes a capping agent, and the capping agent is soluble in a second solvent. In some embodiments: the first reagent includes a first capping agent, and the first capping agent is soluble in a first solvent; and the second reagent includes a second capping agent, and the second capping agent is soluble in a second solvent. In some embodiments: the first reagent includes a first capping agent, and the first capping agent is soluble in a first solvent; the second reagent includes a second capping agent, and the second capping agent is soluble in a second solvent; and the first capping agent and the second capping agent are different.

[0186] In some embodiments, the coating agent is an organic acid. In some embodiments, the coating agent is selected from the group consisting of fatty acids, polysaccharides, macromolecular polymers, and optionally derivatives thereof. In some embodiments, the coating agent is fatty acids, polysaccharides or macromolecular polymers. In some embodiments, the coating agent is selected from the group consisting of lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, alginic acid, chitosan, hyaluronic acid and polystyrene. In some embodiments, the coating agent is selected from the group consisting of lauric acid, stearic acid, alginic acid, chitosan, hyaluronic acid and polystyrene.

[0187] In some embodiments, the coating agent is a fatty acid or a macromolecular polymer. In some embodiments, the second reagent includes a coating agent, and the coating agent is a fatty acid or a macromolecular polymer. In some embodiments, the coating agent is a fatty acid. In some embodiments, the second reagent includes a coating agent, and the coating agent is a fatty acid. In some embodiments, the coating agent is a fatty acid, and the first reagent is alkaline.

[0188] In some embodiments, the fatty acid is a saturated or unsaturated fatty acid, especially a saturated or unsaturated fatty acid that is solid at room temperature (25°C). In some embodiments, the fatty acid is a saturated fatty acid, especially a saturated fatty acid with more than 10 carbon atoms. In some embodiments, the fatty acid is an unsaturated fatty acid, especially an unsaturated fatty acid with more than 10 carbon atoms. In some embodiments, the fatty acid is C 10-40 Saturated fatty acids, especially C 12-36 Saturated fatty acids, especially C 12-30 Saturated fatty acids, especially C 12-24 Saturated fatty acids, especially C 12-20 Saturated fatty acids, especially C 12-18 In some embodiments, the fatty acid is C 10-40 Saturated or unsaturated fatty acids, especially C 12-36 Saturated or unsaturated fatty acids, especially C 12-30 Saturated or unsaturated fatty acids, especially C 12-24 Saturated or unsaturated fatty acids, especially C 12-20 Saturated or unsaturated fatty acids, especially C 12-18 Saturated or unsaturated fatty acids. In some embodiments, the fatty acids are C 10-40 Even-numbered saturated fatty acids, especially C 12-36 Even-numbered saturated fatty acids, especially C 12-30 Even-numbered saturated fatty acids, especially C 12-24 Even-numbered saturated fatty acids, especially C 12-18 In some embodiments, the fatty acid is C 10 , C 11 , C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 , C 19 , C 20 , C 21 , C 22 , C 23 , C 24 , C 25 , C 26 , C 27 , C 28 , C 29 , C 30 , C 31 , C 32 , C 33 , C 34 , C35 , C 36 , C 37 , C 38 , C 39 , or C 40 Saturated or unsaturated fatty acids, especially C 10 , C 12 , C 14 , C 16 , C 18 , C 20 , C 22 , C 24 , C 26 , C 28 , C 30 , C 32 , C 34 , C 36 , C 38 , or C 40 In some embodiments, the coating agent is selected from the group consisting of lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid. In some embodiments, the coating agent is lauric acid. In some embodiments, the coating agent is myristic acid. In some embodiments, the coating agent is palmitic acid. In some embodiments, the coating agent is stearic acid.

[0189] In some embodiments, the coating agent is a polysaccharide. In some embodiments, the first agent includes a coating agent, and the coating agent is a polysaccharide. In some embodiments, the polysaccharide is selected from the group consisting of alginic acid, chitosan, and hyaluronic acid, and optionally its salts. In some embodiments, the polysaccharide is selected from the group consisting of alginic acid, chitosan, and hyaluronic acid. In some embodiments, the coating agent is alginic acid or its salts, particularly alginic acid. In some embodiments, the coating agent is chitosan or its salts, particularly chitosan. In some embodiments, the coating agent is hyaluronic acid or its salts, particularly hyaluronic acid.

[0190] In some embodiments, the polymer is a synthetic polymer. In some embodiments, the polymer is selected from the group consisting of polystyrene, polyvinylidene fluoride, nylon 66, and polyvinyl acetate. In some embodiments, the polymer is a polymer soluble in a second solvent. In some embodiments, the polymer is polyvinylidene fluoride, and the second solvent is acetone. In some embodiments, the polymer is nylon 66, and the second solvent is a mixture of formic acid and dichloromethane. In some embodiments, the polymer is polyvinyl acetate, and the second solvent is dichloromethane.

[0191] In some embodiments, the concentration of the coating agent in the first agent or in the second agent is about 0.01-1000 mg / mL, especially 0.1-100 mg / mL, more especially 10-100 mg / mL, more especially 15-100 mg / mL, more especially 25-100 mg / mL. In some embodiments, the concentration of the coating agent in the first agent is about 0.01-1000 mg / mL, especially 0.1-100 mg / mL, more especially 10-100 mg / mL, more especially 15-100 mg / mL, more especially 25-100 mg / mL. In some embodiments, the concentration of the capping agent in the second agent is about 0.01-1000 mg / mL, particularly 0.1-100 mg / mL, more particularly 10-100 mg / mL, more particularly 15-100 mg / mL, and more particularly 25-100 mg / mL.

[0192] In some embodiments, the concentration of the coating agent in the first reagent or in the second reagent is selected from the group consisting of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, and 100 mg / mL, and the range between any two values.

[0193] In some embodiments, the first reagent also includes a surfactant. In some embodiments, the surfactant is selected from the group consisting of polyethylene glycol alkyl ether, polyethylene glycol alkylamine, fatty acid polyethylene glycol and polysorbate (Tween). In some embodiments, the polyethylene glycol alkyl ether is selected from the group consisting of polyethylene glycol dodecyl ether, polyethylene glycol tridecyl ether, polyethylene glycol tetradecyl ether, polyethylene glycol pentadecyl ether, polyethylene glycol hexadecyl ether, polyethylene glycol heptadecanyl ether, polyethylene glycol octadecyl ether, polyethylene glycol nonadecanyl ether, polyethylene glycol eicosyl ether, polyethylene glycol heneicosyl ether, polyethylene glycol behenyl ether, polyethylene glycol tricosyl ether and polyethylene glycol tetracosyl ether. In some embodiments, the polyethylene glycol alkylamine is selected from the group consisting of polyethylene glycol dodecylamine, polyethylene glycol tridecylamine, polyethylene glycol tetradecylamine, polyethylene glycol pentadecylamine, polyethylene glycol hexadecylamine, polyethylene glycol heptadecylamine, polyethylene glycol octadecylamine, polyethylene glycol nonadecylamine, polyethylene glycol eicosylamine, polyethylene glycol heneicosylamine, polyethylene glycol behenic acid alkylamine, polyethylene glycol tricosylamine and polyethylene glycol tetracosylamine. In some embodiments, the polyethylene glycol fatty acid ester is selected from the group consisting of lauric acid polyethylene glycol, myristic acid polyethylene glycol, palmitic acid polyethylene glycol, stearic acid polyethylene glycol, arachidic acid polyethylene glycol, behenic acid polyethylene glycol and wood wax acid polyethylene glycol. In some embodiments, the tween includes or is selected from the group consisting of tween 20, tween 40, tween 60 and tween 80, particularly tween 80. In some embodiments, the surfactant includes or is selected from the group consisting of Tween 20, Tween 40, Tween 60, and Tween 80, in particular Tween 80.

[0194] In some embodiments, the volume ratio of the surfactant to the first solvent is about 0.1-500 μL / mL, particularly about 1-100 μL / mL, and more particularly about 5-20 μL / mL. In some embodiments, the volume ratio of the surfactant to the first solvent is selected from the group consisting of 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, and 100 μL / mL, and ranges between any two values.

[0195] In some embodiments, the volume ratio of the second agent to the first agent is about 0.1-100, particularly about 1-50, more particularly about 1-10, more particularly about 1-5, more particularly about 2.5-3.0. In some embodiments, the volume ratio of the second agent to the first agent is selected from the group consisting of 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10, and ranges between any two values.

[0196] In some embodiments, the volume ratio of the second emulsion to the fourth solvent is about 0.01-1, particularly about 0.02-0.5, and more particularly about 0.05-0.2. In some embodiments, the volume ratio of the second agent to the first agent is selected from 0.010, 0.015, 0.020, 0.025, 0.030, 0.035, 0.040, 0.045, 0.050, 0.055, 0.060, 0.065, 0.070, 0.075, 0.080, 0.085, 0.090, 0.095, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, The group consisting of 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, 1.0, and the range between any two values ​​therein.

[0197] In some embodiments, the volume ratio of the third agent to the first emulsion is about 0.0001-10, particularly about 0.001-5, more particularly about 0.01-1, and more particularly about 0.01-0.1. In some embodiments, the volume ratio of the third agent to the first emulsion is selected from 0.010, 0.015, 0.020, 0.025, 0.030, 0.035, 0.040, 0.045, 0.050, 0.055, 0.060, 0.065, 0.070, 0.075, 0.080, 0.085, 0.090, 0.095, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, The group consisting of 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, 1.0, and the range between any two values ​​therein.

[0198] In some embodiments, the molar ratio of any two of the first cationic component, the second cationic component, and the anionic component is about (1-20): (1-20), particularly about (1-10): (1-10), particularly about (1-5): (1-5), particularly about (1-3): (1-3), more particularly about (1-2): (1-2), more particularly about (1-1.5): (1-1.5). In some embodiments, the molar ratio of the first cationic component to the second cationic component is about (1-20): (1-20), particularly about (1-10): (1-10), particularly about (1-5): (1-5), particularly about (1-3): (1-3), more particularly about (1-2): (1-2), more particularly about (1-1.5): (1-1.5). In some embodiments, the molar ratio of the first cationic component to the anionic component is about (1-20): (1-20), particularly about (1-10): (1-10), particularly about (1-5): (1-5), particularly about (1-3): (1-3), more particularly about (1-2): (1-2), more particularly about (1-1.5): (1-1.5). In some embodiments, the molar ratio of the second cationic component to the anionic component is about (1-20): (1-20), particularly about (1-10): (1-10), particularly about (1-5): (1-5), particularly about (1-3): (1-3), more particularly about (1-2): (1-2), more particularly about (1-1.5): (1-1.5). In some embodiments, the molar ratio of the first cationic component, the second cationic component, and the anionic component is about (1-20):(1-20):(1-20), particularly about (1-10):(1-10):(1-10), particularly about (1-5):(1-5):(1-5), particularly about (1-3):(1-3):(1-3), particularly about (1-2):(1-2):(1-2), and more particularly about (1-1.5):(1-1.5):(1-1.5).In some embodiments, the molar ratio of the first cationic component to the second cationic component, or the molar ratio of the second cationic component to the anionic component, or the molar ratio of the anionic component to the first cationic component, or the molar ratio of the first cationic component to the anionic component, or the molar ratio of the anionic component to the second cationic component, or the molar ratio of the second cationic component to the first cationic component is selected from 0.05, 0.06, 0.07, 0.08, 0.09, 0.1 0、0.15、0.20、0.25、0.30、0.35、0.40、0.45、0.50、0.55、0.60、0.65、0.70、0.75、0.80、0.85、0.90、0.95、1.00、1.05、1.10、1.15、1.20、1.25、1.30、1.35、1.40、1.45、1.50、1.55、1.60、1.65、 1.70, 1.75, 1.85, 1.85, 1.90, 1.95, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.5 , 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5, 15.0, 15.5, 16.0, 16.5, 17.0, 17.5, 18.0, 18.5, 19.0, 19.5, 20.0, and the range between any two of the values.

[0199] In some embodiments, the mixing includes stirring and mixing.

[0200] In some embodiments, mixing the first agent and the second agent comprises a first stirring. In some embodiments, the first stirring time is 10 seconds to 30 minutes, particularly 1 minute to 30 minutes, and more particularly 1 minute to 10 minutes.

[0201] In some embodiments, mixing the second emulsion and the fourth solvent includes a second stirring. In some embodiments, the second stirring time is 1 minute to 30 minutes, more specifically 5 minutes to 15 minutes.

[0202] In some embodiments, mixing the third agent with the first emulsion includes a third stirring. In some embodiments, the third stirring time is 5 minutes to 1 hour, more specifically 15 minutes to 30 minutes.

[0203] In some embodiments, the method further comprises purifying the first precipitate to obtain the energetic composite material.

[0204] In some embodiments, purifying the first precipitate further comprises separating, washing the precipitate with a solvent, and drying.

[0205] In some embodiments, the separation is filtration and / or centrifugation. In some embodiments, the centrifugation speed is 2000-15000 rpm, in particular 5000-12000 rpm. In some embodiments, the centrifugation time is 1-30 minutes, in particular 5-15 minutes.

[0206] In some embodiments, the solvent washing precipitate is washing the first precipitate with a fifth solvent. In some embodiments, the fifth solvent comprises at least one selected from the group consisting of water, methanol, ethanol, ethylene glycol, propanol, isopropanol, propylene glycol, and glycerol, or a mixture thereof, more particularly comprises at least one selected from the group consisting of water, methanol, ethanol, and isopropanol, or a mixture thereof, more particularly water.

[0207] In some embodiments, the energetic composite material of the present application, or the energetic composite material prepared by the preparation method of the present application, has a particle size, especially an average particle size (linear arithmetic average particle size, the same below), of 50 μm or less, especially 40 μm or less, especially 30 μm or less, especially 25 μm or less, especially 20 μm or less, especially 15 μm or less, especially 10 μm or less. In some embodiments, the energetic composite material of the present application, or the energetic composite material prepared by the preparation method of the present application, has a particle size, especially an average particle size, of 1 nm-10 μm, especially 100 nm-10 μm, especially 1 μm-10 μm, especially 3-10 μm, more especially 5-10 μm, or especially 3-7 μm. In some embodiments, the energetic composite material of the present application, or the energetic composite material prepared by the preparation method of the present application, has a particle size, especially an average particle size, of 1 nm–50 μm, especially 100 nm–50 μm, especially 1 μm–50 μm, especially 3–50 μm, especially 5–50 μm, more especially 10–50 μm, or especially 1 μm–30 μm, especially 3–30 μm, especially 5–30 μm, more especially 10–30 μm.

[0208] In some embodiments, the energetic composite material of the present application, or the energetic composite material prepared by the preparation method of the present application, has a friction sensitivity of 5N or more, especially more than 5N, especially more than 6N, especially more than 10N, especially more than 15N, especially more than 20N, especially more than 25N, especially more than 30N, especially more than 35N, more especially more than 40N. In some embodiments, the energetic composite material of the present application, or the energetic composite material prepared by the preparation method of the present application, has a friction sensitivity of 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80N or more. In some embodiments, the energetic composite material of the present application, or the energetic composite material prepared by the preparation method of the present application, has a friction sensitivity of 5–100N, in particular 6–100N, in particular 10–100N, in particular 15–100N, in particular 20–100N, in particular 25–100N, in particular 30–100N, in particular 35–100N, and more in particular 40–100N; or in particular 5–80N, in particular 6–80N, in particular 10–80N, in particular 15–80N, in particular 20–80N, in particular 25–80N, in particular 30–80N, in particular 35–80N, and more in particular 40–80N.

[0209] In some embodiments, the energetic composite material of the present application, or the energetic composite material prepared by the preparation method of the present application, has a coating agent whose mass ratio of the energetic composite material is less than 10%, particularly less than 8%, particularly less than 6%, particularly less than 5%, more particularly less than 3%; or particularly more than 0.1%, particularly more than 0.5%, particularly more than 1%, more particularly more than 1.5%. In some embodiments, the energetic composite material of the present application, or the energetic composite material prepared by the preparation method of the present application, the mass ratio of the coating agent to the energetic composite material is selected from 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5.0%, 5.1%, 5.2%, 5. .1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5.0%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6.0%, 6.5%, 7.0%, 7.5%, 8.0%, 8.5%, 9.0%, 9.5%, 10.0%, and the range between any two of the values.

[0210] Example

[0211] Characterization assays

[0212] X-ray powder diffraction data were acquired on an Advance D8 diffractometer (θ-2θ scanning mode, Cu-K α ) was tested.

[0213] The differential thermal analysis data were tested and measured on a DTA 552-EX explosion-proof differential thermal analyzer (DTA) produced by American Edison Instruments.

[0214] The impact and friction sensitivities were measured on a BFH 10BAM drop weight impact sensitivity meter and a FSKM10 BAM friction sensitivity meter, respectively, according to the United Nations standards for the transport of dangerous goods.

[0215] The electron microscope was an ultra-high resolution field emission scanning electron microscope SU8010.

[0216] Thermogravimetric analysis was performed using a thermogravimetric analyzer TAQ50.

[0217] Example 1

[0218] The energetic composite material prepared in Example 1 has a multi-component energetic crystal of DAP-4 (A is 1,4-diazabicyclo[2.2.2]octane-1,4-diamium ion, B is NH4+, and X is ClO4-), and the coating agent is stearic acid.

[0219] The preparation method of the energetic composite material of Example 1 is as follows, and its flow chart is as follows: Figure 1 shown.

[0220] - 224 mg of triethylenediamine was dissolved in 0.4 mL of deionized water to obtain solution 1 (aqueous phase), whose pH value was about 8-12; 30 mg of stearic acid was ultrasonically dissolved in 1 mL of dichloromethane to obtain solution 2 (oil phase), whose pH value was about 7; and 350 mg of ammonium perchlorate was dissolved in 1 mL of deionized water to obtain solution 3 (demulsifier), whose pH value was about 1;

[0221] - Add solution 1 dropwise to solution 2, the liquid is separated into layers, the upper and lower layers are both colorless and transparent, then stirred vigorously for 2 minutes to form a white emulsion (colostrum). Pour the colostrum into 10 mL of deionized water while stirring, and stir vigorously for 5 minutes to form a white emulsion (double emulsion);

[0222] - Add solution 3 dropwise to the emulsion while stirring to break the emulsion, and stir vigorously for half an hour to evaporate the dichloromethane in the emulsion as completely as possible. At this time, the pH value of the solution is about 1, and a large amount of white precipitate appears at the bottom of the liquid, which is the crude energetic composite material of Example 1; and

[0223] - Filter using a Buchner funnel, wash twice with 10 mL of solvent, dry the sample in an oven at 50°C, collect the sample and store it in a cool and dry place, the yield is 90%.

[0224] Characterization

[0225] Figure 2 A is a scanning electron microscope photograph of the energetic composite material of Example 1, and B is an enlarged photograph thereof. It can be seen that in the energetic composite material of Example 1, stearic acid coats the multi-component energetic crystal DAP-4 to form a granular structure with a particle size of about 3-7 μm. It can be seen that some particles may present a situation where 2 to 3 particles are bonded to each other (similar to the shape of peanuts), but even in this case, the larger particle size of these bonded particles is only about 10-15 μm, and the largest is about 20 μm. Overall, the energetic composite material of Example 1 has an average particle size of about 5-10 μm. Figure 2 It shows that stearic acid uniformly coats DAP-4, and the part of DAP-4 not coated by stearic acid cannot be observed under the electron microscope.

[0226] Thermogravimetric analysis shows that in the energetic composite material of Example 1, the mass proportion of stearic acid is about 3%.

[0227] According to the friction sensitivity test, the friction sensitivity of the energetic composite material of Example 1 is about 40N.

[0228] Figure 3 The figure shows the powder X-ray diffraction characterization of the energetic composite material and the multi-component energetic crystal DAP-4 of Example 1, wherein the X-ray diffraction characterization of DAP-4 adopts powder simulation. It can be seen that the powder X-ray diffraction characterization of the energetic composite material of Example 1 ("stearic acid / DAP-4" in the figure) is basically consistent with the powder simulation X-ray diffraction characterization of DAP-4, which can confirm that the multi-component energetic crystal DAP-4 is effectively prepared by the method of Example 1.

[0229] Figure 4 Characterization of the energetic composite material and DAP-4 by differential thermal analysis of Example 1. It can be seen that the differential thermal analysis of the energetic composite material of Example 1 ("stearic acid / DAP-4" in the figure) is basically consistent with that of DAP-4, both of which decompose at around 364°C and release a large amount of heat (which is consistent with the differential scanning calorimetry analysis results of DAP-4 disclosed in WO 2018 / 028685A1), which can confirm that the multi-component energetic crystalline DAP-4 is effectively prepared by the method of Example 1.

[0230] Figure 5 Thermogravimetric characterization of the energetic composite material of Example 1. It can be seen that the energetic composite material of Example 1 ("stearic acid / DAP-4" in the figure) still has a residual mass of 97% even at a high temperature of about 250°C, that is, its mass loss is only 3%, which reflects the stability of the energetic composite material of Example 1 under high temperature conditions.

[0231] Figure 6 and Figure 7 The expression of DAP-4 ( Figure 6 ) or the energetic composite material of Example 1 ( Figure 7 ) treated copper wire surface. Figure 6 and Figure 7 It can be seen from the comparison that the energetic composite material of Example 1 has significantly better compatibility with the copper wire than the multi-component energetic crystal DAP-4, and can be more evenly coated on the surface of the copper wire.

[0232] Examples 1A-1B

[0233] In Example 1A and Example 1B, the inventors changed the amount of stearic acid added to Solution 2 in Example 1 to study its effect on the prepared energetic composite material.

[0234] The preparation method of the energetic composite material of Example 1A is similar to that of Example 1, except that in Example 1A, 15 mg of stearic acid is added to Solution 2. According to measurement, the mass proportion of stearic acid in the energetic composite material of Example 1A is about 2%. Scanning electron microscopy shows that the particle size of the energetic composite material of Example 1A is about 5-10 μm. According to the friction sensitivity test, the friction sensitivity of the energetic composite material of Example 1A is about 14N.

[0235] The preparation method of the energetic composite material of Example 1B is similar to that of Example 1, except that in Example 1B, 5 mg of stearic acid is added to Solution 2. According to measurement, the mass proportion of stearic acid in the energetic composite material of Example 1B is about 1%. Scanning electron microscopy shows that the particle size of the energetic composite material of Example 1B is about 5-10 μm. According to the friction sensitivity test, the friction sensitivity of the energetic composite material of Example 1B is about 5N.

[0236] It can be seen from Examples 1A and 1B that adjusting the amount of the coating agent used in the preparation method of the present application has no obvious effect on the particle size of the obtained energetic composite material, but the more coating agent is used, the duller the friction sensitivity of the obtained energetic composite material will be (numerically reflected as an increase in the value).

[0237] Example 2

[0238] The energetic composite material prepared in Example 2 has a multi-component energetic crystal of DAP-4 (A is 1,4-diazabicyclo[2.2.2]octane-1,4-diacium ion, B is NH4 + , X is ClO4 - ), the coating agent is alginate.

[0239] The preparation method of the energetic composite material of Example 2 is as follows.

[0240] - 446 mg of triethylenediamine, 0.3 mL of ammonia water, 100 mg of alginic acid and 0.12 mL of Tween 80 were completely dissolved in 10 mL of deionized water under vigorous stirring as solution 1 (aqueous phase), and its pH value was about 8–12.

[0241] -Pour solution 1 into 30 mL of liquid paraffin and stir vigorously to form a white emulsion.

[0242] - Add 2 mL of perchloric acid solution (pH value is about 1) dropwise to the above emulsion to break the emulsion, then a white precipitate appears, and the pH value of the solution is about 1.

[0243] - The solid-liquid mixture was separated by a high-speed centrifuge, the supernatant was poured out, and then washed with a solvent; the sample was dried in an oven at 60°C, collected, and stored in a cool and dry place, with a yield of 90%.

[0244] Figure 8 The scanning electron microscope photos of the energetic composite material of Example 2 at different magnifications are shown. It can be seen that in the energetic composite material of Example 2, alginate coats the multi-component energetic crystal DAP-4 to form a granular structure. The average particle size of the energetic composite material of Example 2 is about 5-20 μm.

[0245] Thermogravimetric analysis shows that in the energetic composite material of Example 2, the mass proportion of alginate is about 6%.

[0246] According to the friction sensitivity test, the friction sensitivity of the energetic composite material of Example 2 is about 80N.

[0247] Examples 2A-2B

[0248] In Example 2A and Example 2B, the inventors changed the amount of alginate added to Solution 1 in Example 2 to study its effect on the prepared energetic composite material.

[0249] The preparation method of the energetic composite material of Example 2A is similar to that of Example 2, except that in Example 2A, 50 mg of alginate is added to Solution 1. According to measurement, the mass proportion of alginate in the energetic composite material of Example 2A is about 3%. Scanning electron microscopy shows that the average particle size of the energetic composite material of Example 2A is about 10-30 μm. According to the friction sensitivity test, the friction sensitivity of the energetic composite material of Example 2A is about 44N.

[0250] The preparation method of the energetic composite material of Example 2B is similar to that of Example 2, except that in Example 2B, 25 mg of alginate is added to Solution 1. According to measurement, the mass proportion of alginate in the energetic composite material of Example 2B is about 1.5%. Scanning electron microscopy shows that the average particle size of the energetic composite material of Example 2B is about 10-30 μm. According to the friction sensitivity test, the friction sensitivity of the energetic composite material of Example 2B is about 20N.

[0251] Examples 2A and 2B also confirm that, regardless of whether the coating agent is added to solution 1 (aqueous phase) or solution 2 (oil phase) in the preparation method of the present application, adjusting the amount of the coating agent used in the preparation method of the present application has no obvious effect on the particle size of the obtained energetic composite material, but the more coating agent is used, the less sensitive the friction sensitivity of the obtained energetic composite material is (numerically reflected as an increase in the value).

[0252] Example 3

[0253] The energetic composite material prepared in Example 3 has a multi-component energetic crystal of DAP-1 (A is 1,4-diazabicyclo[2.2.2]octane-1,4-diacium ion, B is Na + , X is ClO4 - ), the coating agent is stearic acid.

[0254] The preparation method of the energetic composite material of Example 3 is as follows.

[0255] - Weigh 224 mg of triethylenediamine and dissolve it in 0.4 mL of deionized water to obtain solution 1 (aqueous phase); weigh 30 mg of stearic acid and dissolve it in 1 mL of dichloromethane by ultrasonication to obtain solution 2 (oil phase).

[0256] -Solution 1 was added dropwise to solution 2. The liquid was separated into layers, and both the upper and lower layers were colorless and transparent. Then, the mixture was stirred vigorously for 2 minutes to form a white emulsion, which was used as colostrum.

[0257] -In order to maintain the stability of the emulsion, the colostrum was poured into 10 mL of deionized water while stirring, and stirred vigorously for 5 minutes to form a white emulsion as a double emulsion.

[0258] - Weigh 364 mg of sodium perchlorate and dissolve it in 1 mL of deionized water to obtain solution 3 (demulsifier).

[0259] - Add solution 3 dropwise into the emulsion while stirring to break the emulsion. Stir vigorously for half an hour to evaporate the dichloromethane in the emulsion as completely as possible. A large amount of white precipitate will appear at the bottom of the liquid. The white powder is the stearic acid / DAP-1 composite material.

[0260] -Pour the solid-liquid mixture into a Buchner funnel for filtration and wash twice with deionized water (10 mL); dry the sample in an oven at 50°C, collect the sample, and store it in a cool and dry place. The yield is 90%.

[0261] Fig. 9 is a scanning electron microscope photograph of the energetic composite material of Example 3. It can be seen that the average particle size of the energetic composite material of Example 3 is about 3-15 μm.

[0262] Thermogravimetric analysis shows that in the energetic composite material of Example 3, the mass proportion of stearic acid is about 3%.

[0263] According to the friction sensitivity test, the friction sensitivity of the energetic composite material of Example 3 is about 40N.

[0264] Example 4

[0265] The energetic composite material prepared in Example 4 has a multi-component energetic crystal of DAP-2 (A is 1,4-diazabicyclo[2.2.2]octane-1,4-diacium ion, B is K + , X is ClO4 - ), the coating agent is stearic acid.

[0266] - Weigh 224 mg of triethylenediamine and dissolve it in 0.4 mL of deionized water to obtain solution 1 (aqueous phase); weigh 30 mg of stearic acid and dissolve it in 1 mL of dichloromethane by ultrasonication to obtain solution 2 (oil phase).

[0267] -Solution 1 was added dropwise to solution 2. The liquid was separated into layers, and both the upper and lower layers were colorless and transparent. Then, the mixture was stirred vigorously for 2 minutes to form a white emulsion, which was used as colostrum.

[0268] -In order to maintain the stability of the emulsion, the colostrum was poured into 10 mL of deionized water while stirring, and stirred vigorously for 5 minutes to form a white emulsion as a double emulsion.

[0269] - Weigh 412 mg of potassium perchlorate and dissolve it in 10 mL of deionized water to obtain solution 3 (demulsifier).

[0270] - Add solution 3 dropwise into the emulsion while stirring to break the emulsion. Stir vigorously for half an hour to evaporate the dichloromethane in the emulsion as completely as possible. A large amount of white precipitate will appear at the bottom of the liquid. The white powder is the stearic acid / DAP-2 composite material.

[0271] -Pour the solid-liquid mixture into a Buchner funnel for filtration and wash twice with deionized water (10 mL); dry the sample in an oven at 50°C, collect the sample, and store it in a cool and dry place. The yield is 90%.

[0272] Fig.10 is a scanning electron microscope photograph of the energetic composite material of Example 4. It can be seen that the average particle size of the energetic composite material of Example 4 is about 3-15 μm.

[0273] According to measurement, in the energetic composite material of Example 4, the mass proportion of stearic acid is about 3%.

[0274] According to the friction sensitivity test, the friction sensitivity of the energetic composite material of Example 4 is about 40N.

[0275] Comparative Example 1

[0276] The preparation method of the energetic composite material of Comparative Example 1 is as follows: In Comparative Example 1, DAP-4 crystals were first synthesized and then coated with stearic acid.

[0277] -224 mg of triethylenediamine and 0.15 mL of aqueous ammonia were dissolved in 5 mL of deionized water to prepare solution 1.

[0278] - Dissolve 1 mL of perchloric acid in 5 mL of deionized water as solution 2.

[0279] - Add solution 2 to solution 1, stirring as you add.

[0280] -After standing for 5 minutes, a white precipitate appeared.

[0281] - The solid-liquid mixture was filtered, dried, and white powder was collected with a yield of 90%.

[0282] -Take 100 mg of white powder in an agate mortar; take 3 mg of stearic acid and dissolve it in 4 mL of dichloromethane to make solution 3.

[0283] -Pour solution 3 into an agate mortar and grind manually for 2 minutes, wait for the solution to evaporate, and collect the white powder.

[0284] Fig.11 This is a scanning electron microscope photo of the energetic composite material of Comparative Example 1. It can be seen that in Comparative Example 1, the particle size distribution of the obtained energetic composite material is obviously uneven, and there are obvious large-sized particles (particle size is about 50 μm or more), and even the small-sized particles have a particle size of generally 15-20 μm or more, and the average particle size is obviously greater than 20 μm.

[0285] According to the friction sensitivity test, the friction sensitivity of the energetic composite material of Comparative Example 1 is 5N, and compared with the DAP-4 multi-component energetic crystal without the coating agent, the friction sensitivity is not significantly improved.

[0286] Comparative Example 2

[0287] The preparation method of the energetic composite material of Comparative Example 2 is as follows: In Comparative Example 2, DAP-4 crystals were also synthesized first and then coated with stearic acid.

[0288] - Weigh 224 mg of triethylenediamine and dissolve it in 0.4 mL of deionized water to obtain solution 1 (aqueous phase); take 1 mL of dichloromethane as solution 2 (oil phase).

[0289] -Solution 1 was added dropwise to solution 2. The liquid was separated into layers, and both the upper and lower layers were colorless and transparent. Then, the mixture was stirred vigorously for 2 minutes to form a white emulsion, which was used as colostrum.

[0290] -In order to maintain the stability of the emulsion, the colostrum was poured into 10 mL of deionized water while stirring, and stirred vigorously for 5 minutes to form a white emulsion as a double emulsion.

[0291] - Weigh 350 mg of ammonium perchlorate and dissolve it in 1 mL of deionized water to obtain solution 3 (demulsifier).

[0292] - Add solution 3 dropwise into the double emulsion while stirring to break the emulsion. Stir vigorously for half an hour to evaporate the dichloromethane in the emulsion as completely as possible, and a large amount of white precipitate will appear at the bottom of the liquid.

[0293] - The solid-liquid mixture was poured into a Buchner funnel for filtration and washed twice with deionized water (10 mL); the sample was dried in an oven at 50°C, the sample (ie, DAP-4) was collected and stored in a cool and dry place, with a yield of 90%.

[0294] -Take 100 mg of white powder in an agate mortar; take 3 mg of stearic acid and dissolve it in 4 mL of dichloromethane to make solution 4.

[0295] -Pour solution 4 into an agate mortar and grind manually for 2 minutes, wait for the solution to evaporate, and collect the white powder.

[0296] Fig.12 This is a scanning electron microscope photograph of the energetic composite material of Comparative Example 2. It can be seen that the average particle size of the energetic composite material obtained in Comparative Example 2 is close to that of Example 1, but its particle size distribution is obviously uneven.

[0297] According to the friction sensitivity test, the friction sensitivity of the energetic composite material of Comparative Example 2 is 10N. Compared with the DAP-4 multi-component energetic crystal without a coating agent, the friction sensitivity is only slightly improved, but it is still significantly worse than that of Example 1.

[0298] The above-mentioned implementation modes are only preferred implementation modes of the present application and cannot be used to limit the scope of protection of the present application. Any non-substantial changes and substitutions made by technicians in this field on the basis of the present application shall fall within the scope of protection required by the present application.

Claims

1. A method for preparing an energetic composite material comprising multi-component energetic crystals, characterized in that: include: mixing a first reagent including a first solvent and a first component with a second reagent including a second solvent to obtain a first emulsion; as well as mixing a third agent including the second component with the first emulsion, in, The multi-component energetic crystal consists of a first cation, a second cation, and an anion; The multi-component energetic crystal component consists of the first component and the second component and includes or consists of a first cationic component, a second cationic component, and an anionic component; and The first reagent further includes a coating agent, and / or the second reagent further includes a coating agent; Optionally, the first solvent and the second solvent are immiscible; Optionally, the third reagent further includes a third solvent, the third solvent is miscible with the first solvent, and the third solvent is immiscible with the second solvent; or Optionally, the mixing of the first reagent and the second reagent to obtain a first emulsion comprises: mixing the first reagent and the second reagent to obtain a second emulsion; and mixing the second emulsion and a fourth solvent to obtain the first emulsion; The fourth solvent is miscible with the first solvent, and the fourth solvent is immiscible with the second solvent.

2. The preparation method according to claim 1, characterized in that The first cationic component is a divalent cationic component, the second cationic component is a monovalent cationic component, and the anionic component is a monovalent anionic component; The first cationic component is a divalent cationic component, the second cationic component is a divalent cationic component, and the anionic component is a monovalent anionic component; or The first cationic component is a monovalent cationic component, the second cationic component is a divalent cationic component, and the anionic component is a monovalent anionic component. Optionally, the divalent cation is an organic diamine, in particular a cyclic diamine or a chain diamine; Optionally, the cyclic diamine or its ammonium salt is a five-membered ring diamine or its ammonium salt, a six-membered ring diamine or its ammonium salt, or a seven-membered ring diamine or its ammonium salt; Optionally, the cyclic diamine or its ammonium salt is selected from 1,4-diazabicyclo[2.2.2]octane, the reaction product of 1,4-diazabicyclo[2.2.2]octane and hydrogen peroxide, pyrazine, piperazine, 1-methylpiperazine, 1,4-diazacycloheptane, 1,4-diazabicyclo[2.2.2]octane-1,4-dialium salt, 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4- The group consisting of dionium salts, 1,4-dihydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dialium salts, pyrazine-1,4-dialium salts, piperazine-1,4-dialium salts, 1-methylpiperazine-1,4-dialium salts, 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dialium salts, and 1,4-diazacycloheptane-1,4-dialium salts, and optionally derivatives thereof; Optionally, the chain diamine or its ammonium salt is an alkyl diamine or its ammonium salt, in particular a linear alkyl diamine or its ammonium salt, in particular ethylene diamine or ethylene diammonium salt; Optionally, the monovalent cation component is an alkali metal salt, an alkali metal hydroxide, a monovalent nitrogen-containing cation salt, or a monovalent nitrogen-containing base, in particular, the monovalent cation component is an alkali metal salt, an alkali metal hydroxide, a monovalent organic ammonium ion salt, a monovalent organic amine, an ammonium salt, or ammonia, in particular, an alkali metal salt, an alkali metal hydroxide, an ammonium salt, or ammonia; Optionally, the monovalent cation component is selected from lithium salts, lithium hydroxide, sodium salts, sodium hydroxide, potassium salts, potassium hydroxide, rubidium salts, rubidium hydroxide, cesium salts, cesium hydroxide, silver salts, ammonium salts, ammonia, hydroxylamine, hydroxylammonium salts, hydrazine, and The group consisting of salts, in particular selected from the group consisting of sodium salts, sodium hydroxide, potassium salts, potassium hydroxide, ammonium salts, and ammonia; Optionally, the monovalent anion is an acid or salt comprising an anionic energetic group; Optionally, the monovalent anion is selected from the group consisting of chloric acid, chlorate, perchloric acid, perchlorate, bromic acid, bromate, perbromic acid, perbromate, iodic acid, iodate, periodic acid, periodate, nitric acid, nitrate, fulminic acid, fulminate, azo salts, and azide salts; Optionally, the monovalent anion is chloric acid, chlorate, bromic acid, bromate, iodic acid, iodate, perchloric acid, perchlorate, perbromic acid, perbromate, periodic acid, periodate, nitric acid, or nitrate; Optionally, the monovalent anion component is perchloric acid, perchlorate, perbromic acid, perbromate, periodic acid, or periodate, in particular perchloric acid or perchlorate; Optionally, the monovalent cation component and / or the monovalent anion component is a monovalent anion selected from the group consisting of perchlorate ion, perbromate ion, periodate ion, or nitrate ion and a monovalent anion selected from the group consisting of lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion, ammonium ion, hydroxylammonium ion, and Ionic groups consisting of monovalent cations of salts; Optionally, the monovalent cation component and / or the monovalent anion component is selected from lithium perchlorate, sodium perchlorate, potassium perchlorate, rubidium perchlorate, cesium perchlorate, silver perchlorate, ammonium perchlorate, hydroxylammonium perchlorate, and perchloric acid. The group composed of; Optionally, the monovalent cation component and / or the monovalent anion component is ammonium perchlorate, sodium perchlorate, or potassium perchlorate; Optionally, the monovalent cation component and / or the monovalent anion component is ammonium perchlorate.

3. The preparation method according to any one of claims 1 or 2, characterized in that: The first component comprises or consists of one or two selected from the group consisting of a first cationic component, a second cationic component, and an anionic component; and The second component comprises one or two selected from the group consisting of a first cationic component, a second cationic component, and an anionic component, or consists of them, Optionally, the concentration of the first component in the first reagent is 0.1-5000 mg / mL, particularly 0.5-1000 mg / mL, particularly 1-1000 mg / mL, particularly 1-500 mg / mL, or particularly 10-5000 mg / mL, more particularly 100-1000 mg / mL, or more particularly 10-500 mg / mL; Optionally, the concentration of the second component in the third reagent is 0.1-5000 mg / mL, particularly 0.5-1000 mg / mL, particularly 1-1000 mg / mL, particularly 1-500 mg / mL, or particularly 10-5000 mg / mL, more particularly 100-1000 mg / mL, or more particularly 10-500 mg / mL; Optionally, The first component includes a first cationic component; and The second component comprises a second cationic component and an anionic component; or Optionally, The first component includes a first cationic component and a second cationic component; and The second component includes an anionic component; Optionally, the concentration of the first cationic component in the first reagent is 0.1-5000 mg / mL, in particular 0.5-1000 mg / mL, in particular 1-500 mg / mL, or in particular 10-5000 mg / mL, in particular 100-1000 mg / mL; Optionally, the concentration of the second cationic component in the first reagent is 0.1-5000 mg / mL, particularly 0.5-1000 mg / mL, particularly 1-500 mg / mL, or particularly 10-5000 mg / mL, particularly 100-1000 mg / mL; Optionally, the concentration of the second cationic component in the third reagent is 0.1-5000 mg / mL, particularly 0.5-1000 mg / mL, particularly 1-500 mg / mL, or particularly 10-5000 mg / mL, particularly 100-1000 mg / mL; Optionally, the concentration of the anion component in the third reagent is 0.1-5000 mg / mL, particularly 0.5-1000 mg / mL, particularly 1-500 mg / mL, or particularly 10-5000 mg / mL, particularly 100-1000 mg / mL; Optionally, the molar concentration of the first cationic component in the first reagent is about 2mM-100M, particularly about 0.01-20M, particularly about 0.02-10M, or particularly about 0.2-100M, particularly about 2-20M, more particularly about 2-10M; Optionally, the molar concentration of the second cationic component in the first reagent is about 2mM-100M, particularly about 0.01-20M, particularly about 0.02-10M, or particularly about 0.2-100M, particularly about 2-20M, more particularly about 2-10M; Optionally, the molar concentration of the anion component in the first reagent is about 2mM-100M, particularly about 0.01-20M, particularly about 0.02-10M, or particularly about 0.2-100M, particularly about 2-20M, more particularly about 2-10M; Optionally, the molar concentration of the first cationic component in the third agent is about 2mM-100M, particularly about 0.01-20M, particularly about 0.02-10M, or particularly about 0.2-100M, particularly about 2-20M, more particularly about 2-10M; Optionally, the molar concentration of the second cationic component in the third agent is about 2mM-100M, particularly about 0.01-20M, particularly about 0.02-10M, or particularly about 0.2-100M, particularly about 2-20M, more particularly about 2-10M; Optionally, the molar concentration of the anion component in the third reagent is about 2mM-100M, particularly about 0.01-20M, particularly about 0.02-10M, or particularly about 0.2-100M, particularly about 2-20M, more particularly about 2-10M; Optionally, the molar concentration of any one or more of the first cation, the second cation, or the anion in the first reaction system is about 0.2mM-10M, particularly about 1mM-2M, particularly about 2mM-1M, or particularly about 2mM-10M, particularly about 200mM-2M, more particularly about 200mM-1M; Optionally, the molar concentration of the first cation in the first reaction system is 0.2mM-10M, particularly 1mM-2M, particularly 2mM-1M, or particularly 2mM-10M, particularly 200mM-2M, more particularly 200mM-1M; Optionally, the molar concentration of the second cation in the first reaction system is 0.2mM-10M, particularly 1mM-2M, particularly 2mM-1M, or particularly 2mM-10M, particularly 200mM-2M, more particularly 200mM-1M; Optionally, the molar concentration of the anion in the first reaction system is 0.2mM-10M, particularly 1mM-2M, particularly 2mM-1M, or particularly 2mM-10M, particularly 200mM-2M, more particularly 200mM-1M.

4. The preparation method according to any one of claims 1 to 3, characterized in that: The first solvent is a polar solvent, in particular comprising at least one selected from the group consisting of water, methanol, ethanol, ethylene glycol, propanol, isopropanol, propylene glycol, and glycerol, or a mixture thereof, more particularly comprising at least one selected from the group consisting of water, methanol, ethanol, and isopropanol, or a mixture thereof, more particularly water; and / or The second solvent is a non-polar solvent, in particular an organic solvent immiscible with water, in particular comprising at least one selected from the group consisting of ethyl acetate, dichloromethane, chloroform, toluene, and liquid paraffin or a mixture thereof or consisting thereof, more particularly comprising or consisting of dichloromethane; Optionally, the third solvent is a polar solvent, in particular comprising at least one selected from the group consisting of water, methanol, ethanol, ethylene glycol, propanol, isopropanol, propylene glycol, and glycerol, or a mixture thereof, more particularly comprising at least one selected from the group consisting of water, methanol, ethanol, and isopropanol, or a mixture thereof, more particularly water; or Optionally, the fourth solvent is a polar solvent, in particular comprising or consisting of at least one selected from the group consisting of water, methanol, ethanol, ethylene glycol, propanol, isopropanol, propylene glycol, and glycerol, or a mixture thereof, more in particular comprising or consisting of at least one selected from the group consisting of water, methanol, ethanol, and isopropanol, or a mixture thereof, more in particular water.

5. The preparation method according to any one of claims 1 to 4, characterized in that: The first reagent is alkaline; and / or The third reagent is acidic; Optionally, the first reaction system obtained by mixing the third reagent with the first emulsion is neutral or acidic, especially acidic; Optionally, the pH value of the first reagent is above 7, particularly above 8, particularly 8 to 14, particularly 8 to 12, more particularly 8 to 10; Optionally, the pH value of the third agent is below 7, particularly below 6, particularly 0 to 6, particularly 0 to 4, more particularly 0 to 2; Optionally, the pH value of the first reaction system is below 7, particularly below 6, particularly 0 to 6, particularly 0 to 4, and more particularly 0 to 2.

6. The preparation method according to any one of claims 1 to 5, characterized in that: The coating agent is a fatty acid, a polysaccharide, or a high molecular polymer; Optionally, the second reagent includes the coating agent, and the coating agent is a fatty acid or a high molecular polymer; Optionally, the fatty acid is a saturated or unsaturated fatty acid with more than 10 carbon atoms, particularly C 10-40 Saturated or unsaturated fatty acids, especially C 12-36 Saturated or unsaturated fatty acids, especially C 12-30 Saturated or unsaturated fatty acids, especially C 12-24 Saturated or unsaturated fatty acids, especially C 12-20 Saturated or unsaturated fatty acids, more particularly C 12-18 saturated or unsaturated fatty acids; Optionally, the fatty acid is a saturated fatty acid; Optionally, the first reagent includes the coating agent, and the coating agent is a polysaccharide; Optionally, the polysaccharide is selected from the group consisting of alginic acid, chitosan, and hyaluronic acid, and optionally salts thereof; Optionally, the high molecular polymer is selected from the group consisting of polystyrene, polyvinylidene fluoride, nylon 66, and polyvinyl acetate; Optionally, the concentration of the coating agent in the first reagent is 0.01-1000 mg / mL, particularly 0.1-100 mg / mL, more particularly 10-100 mg / mL, more particularly 15-100 mg / mL, more particularly 25-100 mg / mL; Optionally, the concentration of the coating agent in the second reagent is 0.01-1000 mg / mL, particularly 0.1-100 mg / mL, more particularly 10-100 mg / mL, more particularly 15-100 mg / mL, more particularly 25-100 mg / mL.

7. The preparation method according to any one of claims 1 to 6, characterized in that: The first reagent also includes a surfactant; Optionally, the surfactant is selected from the group consisting of polyethylene glycol alkyl ethers, polyethylene glycol alkyl amines, fatty acid polyethylene glycol esters, and polysorbates; Optionally, the surfactant comprises or is selected from the group consisting of Tween 20, Tween 40, Tween 60, and Tween 80, in particular Tween 80; Optionally, the volume ratio of the surfactant to the first solvent is 0.1-500 μL / mL, particularly 1-100 μL / mL, more particularly 5-20 μL / mL.

8. The preparation method according to any one of claims 1 to 7, characterized in that: The volume ratio of the second agent to the first agent is about 0.1-100, particularly about 1-50, more particularly about 1-10, more particularly about 1-5, more particularly about 2.5-3.0; and / or The volume ratio of the second emulsion to the fourth solvent is about 0.01-1, in particular about 0.02-0.5, more in particular about 0.05-0.2; and / or The volume ratio of the third agent to the first emulsion is about 0.0001-10, in particular about 0.001-5, more in particular about 0.01-1, more in particular about 0.01-0.1; and / or The molar ratio of any two of the first cationic component, the second cationic component, and the anionic component is (1-20):(1-20), particularly (1-10):(1-10), particularly (1-5):(1-5), particularly (1-3):(1-3), more particularly (1-2):(1-2), more particularly (1-1.5):(1-1.5); Optionally, the molar ratio of the first cationic component to the second cationic component is (1-20): (1-20), particularly (1-10): (1-10), particularly (1-5): (1-5), particularly (1-3): (1-3), more particularly (1-2): (1-2), more particularly (1-1.5): (1-1.5); Optionally, the molar ratio of the first cationic component to the anionic component is (1-20): (1-20), particularly (1-10): (1-10), particularly (1-5): (1-5), particularly (1-3): (1-3), more particularly (1-2): (1-2), more particularly (1-1.5): (1-1.5); Optionally, the molar ratio of the second cationic component to the anionic component is (1-20): (1-20), particularly (1-10): (1-10), particularly (1-5): (1-5), particularly (1-3): (1-3), more particularly (1-2): (1-2), more particularly (1-1.5): (1-1.5); Optionally, the molar ratio of the first cationic component, the second cationic component, and the anionic component is (1-20):(1-20):(1-20), particularly (1-10):(1-10):(1-10), particularly (1-5):(1-5):(1-5), particularly (1-3):(1-3):(1-3), particularly (1-2):(1-2):(1-2), more particularly (1-1.5):(1-1.5):(1-1.5).

9. An energetic composite material, characterized in that: It is prepared by the preparation method according to any one of claims 1 to 8; and / or It includes: Multi-component energetic crystals; and Coating agent, wherein the coating agent coats or partially coats the multi-component energetic crystal; Optionally, the average particle size of the energetic composite material is 50 μm or less, in particular 40 μm or less, in particular 30 μm or less, in particular 25 μm or less, in particular 20 μm or less, in particular 15 μm or less, in particular 10 μm or less, in particular 1 nm-10 μm, in particular 100 nm-10 μm, in particular 1 μm-10 μm, in particular 3-10 μm, more particularly 5-10 μm, or in particular 3-7 μm; Optionally, the average particle size of the energetic composite material is 1 nm-50 μm, in particular 100 nm-50 μm, in particular 1 μm-50 μm, in particular 3-50 μm, in particular 5-50 μm, more in particular 10-50 μm, or in particular 1 μm-30 μm, in particular 3-30 μm, in particular 5-30 μm, more in particular 10-30 μm; Optionally, the friction sensitivity of the energetic composite material is more than 5N, in particular more than 6N, in particular more than 10N, in particular more than 15N, in particular more than 20N, in particular more than 25N, in particular more than 30N, in particular more than 35N, more particularly more than 40N; Optionally, the friction sensitivity of the energetic composite material is 6–100N, in particular 10–100N, in particular 15–100N, in particular 20–100N, in particular 25–100N, in particular 30–100N, in particular 35–100N, more in particular 40–100N; or in particular 6–80N, in particular 10–80N, in particular 15–80N, in particular 20–80N, in particular 25–80N, in particular 30–80N, in particular 35–80N, more in particular 40–80N.

10. The preparation method according to any one of claims 1 to 8 or the energetic composite material according to claim 9, characterized in that: The first cation is a divalent cation, the second cation is a monovalent cation, and the anion is a monovalent anion, in particular, the molar ratio of the first cation, the second cation, and the anion is 1:1:3; or The first cation is a divalent cation, the second cation is a monovalent cation, and the anion is a monovalent anion, in particular, the molar ratio of the first cation, the second cation, and the anion is 1:2:4; or The first cation is a divalent cation, the second cation is a divalent cation, and the anion is a monovalent anion, in particular, the molar ratio of the first cation, the second cation, and the anion is 1:1:4; or The first cation is a monovalent cation, the second cation is a divalent cation, and the anion is a monovalent anion, and in particular, the molar ratio of the first cation, the second cation, and the anion is 1:2:5; Optionally, the divalent cation is an organic diammonium ion, in particular a cyclic diammonium ion or a chain diammonium ion; Optionally, the cyclic diammonium ion is a five-membered ring diammonium ion, a six-membered ring diammonium ion, or a seven-membered ring diammonium ion; Optionally, the cyclic diammonium ion is selected from the group consisting of 1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion, 1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion, 1,4-dihydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion, pyrazine-1,4-dialium ion, piperazine-1,4-dialium ion, 1-methylpiperazine-1,4-dialium ion, 1-methyl-1,4-diazabicyclo[2.2.2]octane-1,4-dialium ion, and 1,4-diazacycloheptane-1,4-dialium ion, and optionally derivatives thereof; Optionally, the chain diammonium ion is an alkyl diammonium ion, in particular a linear alkyl diammonium ion, in particular an ethylene diammonium ion; Optionally, the monovalent cation is an alkali metal ion or a monovalent nitrogen-containing cation, in particular an alkali metal ion, an ammonium ion or a monovalent organic ammonium ion, in particular an alkali metal ion or an ammonium ion; Optionally, the monovalent cation is selected from lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion, silver ion, ammonium ion, hydroxylammonium ion, and ions, particularly selected from the group consisting of sodium ions, potassium ions, and The groups composed of ions; Optionally, the monovalent anion is an anionic energetic group; Optionally, the monovalent anion is selected from the group consisting of chlorate ion, bromate ion, iodate ion, perchlorate ion, perbromate ion, periodate ion, nitrate ion, fulminate ion, azo group, and azide ion; Optionally, the monovalent anion is a chlorate ion, a bromate ion, an iodate ion, a perchlorate ion, a perbromate ion, a periodate ion, or a nitrate ion, in particular a perchlorate ion, a periodate ion, or a nitrate ion; Optionally, the monovalent anion is selected from the group consisting of perchlorate ion, perbromate ion, and periodate ion, in particular perchlorate ion; Optionally, the monovalent anion is selected from the group consisting of perchlorate ion, perbromate ion, periodate ion, or nitrate ion, and the monovalent cation is selected from the group consisting of lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion, ammonium ion, hydroxylammonium ion, and ions; optionally, the monovalent anion is a perchlorate ion, and the monovalent cation is selected from lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions, ammonium ions, hydroxylammonium ions, and The groups composed of ions; Optionally, the monovalent anion is a perchlorate ion, and the monovalent cation is an ammonium ion, a sodium ion, or a potassium ion; Optionally, the monovalent anion is a perchlorate ion, and the monovalent cation is an ammonium ion.

Images