CN115710149A - DAP-4-based composite explosive particles and preparation method thereof - Google Patents
DAP-4-based composite explosive particles and preparation method thereof Download PDFInfo
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- CN115710149A CN115710149A CN202211523113.0A CN202211523113A CN115710149A CN 115710149 A CN115710149 A CN 115710149A CN 202211523113 A CN202211523113 A CN 202211523113A CN 115710149 A CN115710149 A CN 115710149A
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Images
Abstract
The invention discloses DAP-4-based composite explosive particles and a preparation method thereof, wherein the method can be used for reducing the sense of the DAP-4 explosive surface coating and improving the surface interface effect, the DAP-4 is coated by polyacrylic acid and solid-phase polymer, the sensitivity of the DAP-4 is reduced, and the formability of the DAP-4 is improved, wherein 1.1-2.3 parts of polyacrylic acid, 2-3.4 parts of binder, 0.1-0.2 part of ammonium chloride and 0.1-0.3 part of sodium polyacrylate are adopted for every 100 parts of DAP-4. The invention realizes the pressing and molding of DAP-4, can reduce the mechanical sensitivity of DAP-4 and improve the binding effect with the binder.
Description
Technical Field
The invention belongs to the technical field of energetic materials, relates to an energetic material surface coating technology, and particularly relates to a method for reducing the surface sensitivity and improving the surface interface effect of DAP-4 explosive surface coating, which can reduce the mechanical sensitivity of DAP-4 and improve the binding effect between DAP-4 and an adhesive.
Background
(H 2 dabco)[NH 4 (ClO 4 ) 3 ](abbreviated as DAP-4, wherein H 2 dabco 2+ =1, 4-diazabicyclo [2.2.2]Octane-1, 4-diimmonium ion) is an oxidizing component of ClO from an ionic type 4 - With organic fuel component H 2 dabco 2+ The novel metal-free multi-component energetic material formed by alternately and closely accumulating in the perovskite structure is taken as a novel energetic material with the advantages of low cost, high explosion performance, high stability and the like, and the DAP-4 is expected to be taken as an excellent single-component and has good application prospect in military and civil mixed explosives.
However, DAP-4 is sensitive to mechanical stimuli, with a BAM test result of 5N and a military standard test result of 100%, presenting a potential hazard to sample handling and transportation. For safety, the common practice in the industry is to prepare composite materials by using a large amount of high-energy unsafe elementary explosive and safe common explosive or inert bodies, such as CL-20/TATB eutectic, EVA insensitive coating RDX and the like. However, since DAP-4 is a perovskite energetic material, it has a weak interaction force with a conventional binder, and is difficult to be uniformly mixed with the binder and press-molded, and it cannot form an eutectic explosive with explosives such as TATB and RDX to reduce sensitivity.
In order to improve safety, the common practice in the industry is to coat with an inert binder, such as ethylene-vinyl acetate copolymer, paraffin wax, microcrystalline wax, fluororubber, butadiene rubber or polyurethane polymer binder, epoxy resin, etc. However, through materials studio simulation calculation and limited tests, the conventional universal binder suitable for RDX and HMX cannot achieve effective coating. The surfactant and the bonding agent proposed in documents of research progress on surface coating of nitramine explosive particles (Anchong Wei, energetic material, 2007) and research progress on surface coating of explosive particles (Luyue, guangzhou chemical industry, 2011) are modified, and still cannot achieve ideal coating effect.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide DAP-4-based composite explosive particles and a preparation method thereof, and improve the safety and process formability of DAP-4 explosives.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of DAP-4-based composite explosive particles comprises the following raw materials: DAP-4, polyacrylic acid, a binder, ammonium chloride and sodium polyacrylate; the binder comprises solid-phase polymers and a plasticizer, wherein the raw materials of the solid-phase polymers comprise ethylene-vinyl acetate copolymer and paraffin, and the plasticizer is DOA.
The invention also comprises the following technical characteristics:
specifically, the feed comprises the following raw materials in parts by weight: 100 portions of DAP-4, 1.1 to 2.3 portions of polyacrylic acid, 2 to 3.4 portions of binder, 0.1 to 0.2 portion of ammonium chloride and 0.1 to 0.3 portion of sodium polyacrylate.
Specifically, in the binder, the mass ratio of the plasticizer to the solid-phase polymer is 1:10 to 1:20.
specifically, the raw materials of the solid-phase polymer comprise, by weight, 85-90 parts of an ethylene-vinyl acetate copolymer and 10-15 parts of paraffin.
Specifically, the molecular weight of the polyacrylic acid is 500-5000.
Specifically, the method comprises the following steps:
(1) Adding polyacrylic acid powder into chloroform, and stirring at room temperature to dissolve the polyacrylic acid powder to obtain a polyacrylic acid solution;
(2) Sequentially adding DAP-4, ammonium chloride and sodium polyacrylate into a saturated aqueous solution of DAP-4, and stirring to obtain a blending solution;
(3) Adding polyacrylic acid solution into the blending solution at room temperature, sealing, slowly stirring for 1-2 hours, then stirring the solvent to completely volatilize at the temperature of 55-60 ℃ with opening, and obtaining DAP-4@ PAA for later use;
(4) Dissolving ethylene-vinyl acetate copolymer and paraffin by using petroleum ether, adding plasticizer and DAP-4@ PAA, and stirring in a water bath for coating;
(5) And (4) continuing stirring until the solvent is completely volatilized, sieving by using a 20-mesh sieve, and performing vacuum drying to obtain the DAP-4-based composite explosive particles.
DAP-4-based composite explosive particles are prepared by the preparation method of the DAP-4-based composite explosive particles.
Compared with the prior art, the invention has the following technical effects:
(1) After the surface of the DAP-4 explosive is coated, the sense of the explosive is reduced, the effect of improving the combination effect of the DAP-4 and the binding agent is obvious, the DAP-4 explosive is pressed and molded, and the DAP solid content is not lower than 94%.
(2) The invention has high safety and the friction sensitivity is reduced to below 40 percent.
Drawings
FIG. 1 is a schematic diagram of the particle structure of a DAP-4 based composite explosive;
FIG. 2 is a scanning electron micrograph of a DAP-4@ PAA sample;
FIG. 3 is a scanning electron micrograph of a sample of example 1;
FIG. 4 is a photograph showing the pillar of example 1.
Detailed Description
The invention provides a method for surface coating and sense reduction and surface interface effect improvement of a DAP-4 explosive, which adopts a high polymer material with opposite electrostatic potential to coat the DAP-4 explosive, and improves the safety and process formability of the DAP-4 explosive.
The invention has the following conception: EVA, fluororubber, paraffin and the like belong to the common adhesive materials of explosives, have good compatibility with various components of the explosives, and the selection of mature adhesive materials has important significance for the application of the explosives. However, these binder materials do not adhere to the DAP-4 explosive. The invention selects the coating materials with opposite charges by using the principle that electrostatic attraction can be explored and verified by limited experiments in the chemical industry, but the scheme is not reported in the field of explosives, and the electrostatic attraction of coulomb belongs to weak attraction, so that the aim of coating modification cannot be achieved. The DAP-4 material is a spherical particle, small bulges and pits exist on the surface, if the tearing strength is increased by virtue of the structures of the bulges and the pits under the action of the coulomb electrostatic attraction, the adhesive property of the coating material can be improved, and then the adhesive agents such as EVA (ethylene vinyl acetate), fluororubber, paraffin wax and the like are coated on the surface of the coating material, so that the manufacturability of the DAP-4 material is improved during coating.
The design idea of the invention is as follows: based on the conception, the invention is divided into two steps, the first step is to select polyacrylic acid with large contraction elasticity and opposite electric polarity to DAP-4 material as a coating material by using the principle of solidification contraction of a polymer solution while the action of coulombic electrostatic attraction, the polyacrylic acid is infiltrated to the surface of DAP-4 particles under the action of an auxiliary agent, after a solvent is volatilized, the tensile stress among polyacrylic acid contraction molecules is converted into the shear stress of the coating layer, and the tearing strength of the polyacrylic acid is improved by using bulges and pits, so that the DAP-4 is modified. And in the second step, the modified particles are coated by adopting a conventional means, so that the purpose of reducing the feeling is realized, and the manufacturability is improved.
The invention specifically designs: a DAP-4 composite coating bonding structure is designed, wherein the inner layer is uneven polyacrylic acid, and the outer layer is a bonding agent. Polyacrylic acid is uniformly soaked into the surface of DAP-4 in an aqueous solution of sodium polyacrylate and ammonium chloride, and the ammonium chloride improves the surface wettability; in the solvent devolatilization process, the shrinkage speed of the polyacrylic acid is reduced by the sodium polyacrylate, so that the tensile stress between polyacrylic acid shrinkage molecules is converted into the shear stress of the coating layer, and the tearing strength of the polyacrylic acid is improved by utilizing the bulges and the pits.
The following embodiments of the present invention are provided, and it should be noted that the present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention are within the protection scope of the present invention.
Example 1:
the embodiment provides DAP-4-based composite explosive particles and a preparation method thereof, and the preparation method comprises the following steps of:
1.1 raw material components:
the embodiment comprises the following raw materials in parts by weight: 100 parts of DAP-4, 1.5 parts of polyacrylic acid, 3 parts of a binder, 0.2 part of ammonium chloride and 0.1 part of sodium polyacrylate;
the adhesive comprises solid-phase polymers and a plasticizer, wherein the solid-phase polymers comprise the following raw materials in parts by weight: 85 parts of ethylene-vinyl acetate copolymer and 15 parts of paraffin; the plasticizer is DOA, and the mass ratio of the DOA to the solid-phase polymer is 1:10; the molecular weight of polyacrylic acid is 500-5000.
1.2 preparation steps:
(1) Firstly, adding polyacrylic acid powder into chloroform, and dissolving the polyacrylic acid powder under stirring at room temperature to prepare polyacrylic acid solution;
(2) Sequentially adding DAP-4, ammonium chloride and sodium polyacrylate into a saturated aqueous solution of DAP-4, and stirring to prepare a blending solution;
(3) Adding polyacrylic acid solution into the blending solution at room temperature, sealing, slowly stirring for about 1-2 hours, and stirring the solvent to completely volatilize at the temperature of 55-60 ℃ to obtain DAP-4@ PAA for later use;
(4) Dissolving ethylene-vinyl acetate copolymer and paraffin by using proper amount of petroleum ether, adding plasticizer and DAP-4@ PAA, and stirring in water bath for coating;
(5) And (4) continuing stirring until the solvent is completely volatilized, sieving by using a 20-mesh sieve, and performing vacuum drying to obtain the DAP-4-based composite explosive particles.
1.3 testing and performance evaluation:
(1) Testing the impact sensitivity of the particles according to the GJB772A-97 method 601.1;
(2) And pressing DAP-4-based composite explosive particles into explosive columns with different sizes by adopting a die pressing method.
Example 2:
the embodiment provides DAP-4-based composite explosive particles and a preparation method thereof, and the preparation method comprises the following steps of:
2.1 raw material components:
the embodiment comprises the following raw materials in parts by weight: 100 parts of DAP-4, 1.1 parts of polyacrylic acid, 3.4 parts of a binder, 0.1 part of ammonium chloride and 0.3 part of sodium polyacrylate; the adhesive comprises solid-phase polymers and a plasticizer, wherein the solid-phase polymers comprise the following raw materials in parts by mass: 90 parts of ethylene-vinyl acetate copolymer and 10 parts of paraffin; the plasticizer is DOA, and the mass ratio of the DOA to the solid-phase polymer is 1:20.
2.2 the procedure was the same as in example 1.
2.3 testing and performance evaluation are the same as in example 1.
Example 3:
3.1 raw material components:
the embodiment comprises the following raw materials in parts by weight: 100 parts of DAP-4, 2.3 parts of polyacrylic acid, 2 parts of a binder, 0.15 part of ammonium chloride and 0.3 part of sodium polyacrylate; the adhesive comprises solid-phase polymers and a plasticizer, wherein the solid-phase polymers comprise the following raw materials in parts by mass: 90 parts of ethylene-vinyl acetate copolymer and 10 parts of paraffin; the plasticizer is DOA, and the mass ratio of the DOA to the solid-phase polymer is 1:20.
3.2 the procedure was the same as in example 1.
3.3 testing and performance evaluation are the same as in example 1.
Comparative example 1:
referring to the raw material components and preparation steps of example 1, after dissolving ethylene-vinyl acetate copolymer and paraffin wax in petroleum ether, various component materials are directly added, and are stirred in a water bath for coating; and (5) sieving after the solvent is completely volatilized to obtain the DAP-4-based composite explosive particles.
Comparative example 2:
with reference to the raw material components and preparation steps of example 1, sodium polyacrylate was completely replaced with ammonium chloride in the composition.
Comparative example 3:
with reference to the starting material components and preparation steps of example 1, sodium polyacrylate was used in the composition in complete place of ammonium chloride.
The effect of each embodiment of the invention is as follows:
the impact sensitivity of the particles was tested according to GJB772A-97 method 601.1 and the results are shown in the following table:
TABLE 1 sensitivity test results
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | DAP-4 | |
| DAP-4 content | 95％ | 95％ | 95％ | 95％ | 95％ | 95％ | 100％ |
| Sensitivity to impact | 32％ | 36％ | — | 100％ | 80％ | 100％ | 100％ |
The embodiment 1 of the invention is realized by two steps, wherein the first step is that polyacrylic acid forms an uneven coating layer on the surface of DAP-4, and the method is that acrylic acid forms coulomb electrostatic attraction on the surface of DAP to generate weak attraction; the surface wettability is improved under the action of ammonium chloride, and polyacrylic acid is completely soaked on the surface of DAP-4; as shown in figure 1, in the solvent devolatilization process, the shrinkage speed of polyacrylic acid is reduced by sodium polyacrylate, the tensile stress between polyacrylic acid shrinkage molecules is converted into the shear stress F of the coating layer by utilizing the bulges and the pits on the surface, and the shear stress F generates a component force F in the radial direction of particles, so that the tearing strength of the polyacrylic acid and the DAP-4 is improved. The coated particles are shown in figure 2. As can be seen from the figure, polyacrylic acid forms an uneven coating layer on the surface of DAP-4. And the second step is to coat the modified particles by a conventional means, so as to achieve the purpose of reducing the feeling and improve the manufacturability. The solid-phase polymer material commonly used for explosives is selected as the binder, and the plasticizer is selected to reduce the brittleness of the solid-phase polymer and prevent the first-step coating structure from being damaged in the granulation process. The coated particles are shown in figure 3. As can be seen in fig. 3, the adhesive has adhered uniformly to the surface of the DAP-4. As can also be seen from FIG. 4, the invention can realize the forming of DAP-4 explosive and has good stability.
Comparative example 1 shows that the process of the present invention is an inventive process, and the object of the present invention cannot be achieved only by formulation composition, as the binder cannot coat the surface of DAP-4 during the preparation process and the binder is agglomerated during the sieving. Comparative examples 2 and 3 further demonstrate the rationality of the small molecule compositions of the present invention.
Based on the above analysis, compared with the prior art, the invention realizes the following technical advantages: (1) The sense of the coated DAP-4 is reduced, the effect of improving the binding effect of the DAP-4 and the binding agent is obvious, the invention realizes the pressing and molding of the DAP-4, and the solid content of the DAP is not lower than 94 percent. And (2) the safety is improved, and the friction sensitivity is reduced to below 40%.
Claims (7)
1. A preparation method of DAP-4-based composite explosive particles is characterized in that the method comprises the following raw materials: DAP-4, polyacrylic acid, a binder, ammonium chloride and sodium polyacrylate; the binder comprises solid-phase polymers and a plasticizer, wherein the solid-phase polymers comprise ethylene-vinyl acetate copolymer and paraffin, and the plasticizer is DOA.
2. The method for preparing DAP-4 based composite explosive particles of claim 1, comprising the following raw materials in parts by weight: 100 portions of DAP-4, 1.1 to 2.3 portions of polyacrylic acid, 2 to 3.4 portions of binder, 0.1 to 0.2 portion of ammonium chloride and 0.1 to 0.3 portion of sodium polyacrylate.
3. The method of claim 2, wherein the mass ratio of the plasticizer to the solid-phase polymer in the binder is 1:10 to 1:20.
4. the method for preparing DAP-4 based composite explosive particles according to claim 3, wherein the raw materials of the solid phase polymer comprise, by weight, 85-90 parts of ethylene-vinyl acetate copolymer and 10-15 parts of paraffin.
5. The method of making DAP-4 based composite explosive particles of claim 1, wherein the polyacrylic acid has a molecular weight of 500 to 5000.
6. The method of making the DAP-4 based composite explosive particles of claim 4, comprising the steps of:
(1) Adding polyacrylic acid powder into chloroform, and stirring at room temperature to dissolve the polyacrylic acid powder to obtain a polyacrylic acid solution;
(2) Sequentially adding DAP-4, ammonium chloride and sodium polyacrylate into a saturated aqueous solution of DAP-4, and stirring to obtain a blending solution;
(3) Adding polyacrylic acid solution into the blending solution at room temperature, sealing, slowly stirring for 1-2 hours, then stirring the solvent to be completely volatilized at the temperature of 55-60 ℃ to obtain DAP-4@ PAA for later use;
(4) Dissolving ethylene-vinyl acetate copolymer and paraffin by using petroleum ether, adding plasticizer and DAP-4@ PAA, and stirring in a water bath for coating;
(5) And (4) continuing stirring until the solvent is completely volatilized, sieving by using a 20-mesh sieve, and performing vacuum drying to obtain the DAP-4-based composite explosive particles.
7. DAP-4-based composite explosive particles prepared by the preparation method of the DAP-4-based composite explosive particles according to claim 6.
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| CN116283453A (en) * | 2023-03-03 | 2023-06-23 | 湖北航天化学技术研究所 | Heat-resistant mixed explosive and preparation method and application thereof |
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| JP2000143380A (en) * | 1998-11-09 | 2000-05-23 | Nof Corp | Explosive composition and its production |
| WO2014156195A1 (en) * | 2013-03-29 | 2014-10-02 | 日本ゼオン株式会社 | Binder composition for secondary battery electrodes, method for producing same, slurry composition for secondary battery electrodes, electrode for secondary batteries, and secondary battery |
| CN103342619A (en) * | 2013-07-24 | 2013-10-09 | 中国工程物理研究院化工材料研究所 | Surface coating method for explosive particles |
| CN107099290A (en) * | 2017-07-05 | 2017-08-29 | 向爱双 | The method for preparing core shell structure perovskite quantum dot |
| CN107966852A (en) * | 2017-11-09 | 2018-04-27 | 合肥乐凯科技产业有限公司 | A kind of Ca-Ti ore type quantum dot film |
| CN110183290A (en) * | 2019-06-05 | 2019-08-30 | 唐山师范学院 | Application of the polyacrylic acid potassium in emulsified bases, emulsified bases and its preparation method and application, emulsion |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116283453A (en) * | 2023-03-03 | 2023-06-23 | 湖北航天化学技术研究所 | Heat-resistant mixed explosive and preparation method and application thereof |
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