CN116082106A - Copper azide organic compound and preparation method and application thereof - Google Patents
Copper azide organic compound and preparation method and application thereof Download PDFInfo
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- CN116082106A CN116082106A CN202310370866.0A CN202310370866A CN116082106A CN 116082106 A CN116082106 A CN 116082106A CN 202310370866 A CN202310370866 A CN 202310370866A CN 116082106 A CN116082106 A CN 116082106A
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B35/00—Compositions containing a metal azide
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0008—Compounding the ingredient
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0033—Shaping the mixture
- C06B21/0075—Shaping the mixture by extrusion
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
- C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The application discloses copper azide organic compound, a preparation method and application thereof, wherein the preparation method comprises the following steps: preparing organic micromolecular salt solution, sodium hydroxide solution and copper salt solution respectively; adding an organic micromolecular salt solution into a copper salt solution according to a set volume ratio, stirring, adding a proper amount of sodium hydroxide solution while stirring to obtain a mixed solution, and preparing an organic micromolecular intercalated layered copper hydroxide precursor material based on the mixed solution; mixing lamellar copper hydroxide with polyvinyl alcohol in a set mass ratio to prepare a polyvinyl alcohol lamellar copper hydroxide dispersion; obtaining polyvinyl alcohol with corresponding shape and size and layered copper hydroxide by using a die; and (3) preparing a proper amount of sodium azide powder solution into sodium azide solution with a set concentration, placing polyvinyl alcohol with a set mass and layered copper hydroxide into the sodium azide solution, adding hydrochloric acid solution, and standing for reaction to obtain the copper azide organic compound. The composites of the present application are more suitable for use in a micro-initiation device.
Description
Technical Field
The embodiment of the application relates to an initiating explosive and a preparation technology thereof, in particular to a copper azide organic compound, a preparation method thereof and application of the copper azide organic compound.
Background
With the rapid development of miniature initiating explosive devices, miniature detonating devices have been widely studied. Compared with the traditional detonating device, the micro-detonating device has smaller volume and smaller charging cavity. The primary explosive is used as an internal originating energy substance, and the micro-initiating device has higher requirements on the primary explosive in the aspects of charging mode, charging quantity, initiating energy and the like. The conventional detonators such as copper stevenate, copper azide and the like have lower energy, larger size and larger loading capacity, and are difficult to meet the requirements of the micro-detonating device. In addition, the existing primary explosive is mainly made of powdery materials, and for a tiny charging cavity, the traditional prescription pressing mode can not meet the application requirements of the micro-initiation device. Thus, high detonating power and the manner of filling the micro-chambers are the main reasons limiting their application.
Disclosure of Invention
In view of the above, embodiments of the present application provide a copper azide organic compound, a preparation method thereof, and an application of the copper azide organic compound, wherein the volume of the prepared initiating explosive is controllable, and the initiating force is high.
According to a first aspect of the present application, there is provided a method for preparing a copper azide organic compound, comprising the following processing steps:
preparing organic micromolecular salt solution, sodium hydroxide solution and copper salt solution respectively; wherein the concentration of the organic micromolecular salt solution is maintained to be 1.86-2.21 wt%, the concentration of the sodium hydroxide solution is maintained to be 2.46-2.77 wt%, and the concentration of the copper salt solution is maintained to be 2.85-3.34 wt%;
the volume ratio is 1: 0.91-1: 1.08, adding organic micromolecular salt solution into copper salt solution, stirring, and adding a proper amount of sodium hydroxide solution while stirring to obtain mixed solution; maintaining the pH of the mixed solution at 6.4 to 14;
heating the mixed solution to maintain the temperature at 88-97 ℃, continuously introducing nitrogen into the heated mixed solution, reacting for a first set period of time, collecting a product, filtering, washing and drying to obtain a lamellar copper hydroxide precursor material with small organic molecule intercalation;
preparing a polyvinyl alcohol (Polyvinyl Alcohol, PVA) solution with the temperature maintained at 74-85 ℃; wherein, the concentration of the polyvinyl alcohol solution is maintained at 0.11wt% to 0.15wt%;
continuously stirring the polyvinyl alcohol solution, adding the lamellar copper hydroxide precursor material of the organic micromolecule intercalation while stirring, and stirring until the system is uniformly dispersed to obtain a polyvinyl alcohol lamellar copper hydroxide dispersion; in the polyvinyl alcohol lamellar copper hydroxide dispersion liquid, the lamellar copper hydroxide intercalated by polyvinyl alcohol and small organic molecules maintains a set mass ratio;
placing the polyvinyl alcohol layered copper hydroxide dispersion liquid into a mould, and placing the mould into liquid nitrogen to obtain polyvinyl alcohol layered copper hydroxide with a set shape; or rapidly extruding the polyvinyl alcohol layered copper hydroxide dispersion liquid into liquid nitrogen to obtain spherical polyvinyl alcohol layered copper hydroxide;
freeze-drying the polyvinyl alcohol layered copper hydroxide for a second set period of time, and taking out for later use;
dissolving a proper amount of sodium azide in water to prepare a sodium azide solution with a set concentration, and placing the sodium azide solution in an ice bath environment; placing the dried polyvinyl alcohol layered copper hydroxide in a sodium azide solution, adding a proper amount of hydrochloric acid solution with a set concentration, and standing for reaction for a third set period of time to obtain a reactant; wherein, the set molar ratio between the polyvinyl alcohol lamellar copper hydroxide and the sodium azide is maintained;
and washing and drying the reactant to obtain the copper azide organic compound.
In some alternative embodiments, the organic small molecule salt comprises at least one of:
sodium salicylate, potassium salicylate;
the copper salt solution comprises a copper nitrate solution, a copper acetate solution and a copper chloride solution.
In some optional embodiments, the first set duration is 15 hours to 32 hours; the second set time length is 40-62 hours; the third set time is 10-70 min.
In some alternative embodiments, the set mass ratio is 1:7~1:11.
in some alternative embodiments, maintaining a set molar ratio between the polyvinyl alcohol layered copper hydroxide and sodium azide comprises:
the molar ratio of the polyvinyl alcohol layered copper hydroxide to the sodium azide is 0.5-8.3;
the proper amount of hydrochloric acid solution with set concentration is added, and the method comprises the following steps:
the mass ratio between the added hydrochloric acid solution and the sodium azide solution is maintained at 1: 125-1: 90.
in some alternative embodiments, the mold is a cylindrical mold having a barrel inside diameter of: 0.9mm to 40mm.
In some alternative embodiments, the rapid extrusion of the polyvinyl alcohol layered copper hydroxide dispersion into liquid nitrogen comprises:
selecting an injector with the inner diameter of a syringe of 0.3 mm-1.25 mm to extract the polyvinyl alcohol layered copper hydroxide dispersion liquid, and extruding the polyvinyl alcohol layered copper hydroxide dispersion liquid into liquid nitrogen through a liquid outlet of the injector; the caliber of the liquid outlet of the injector is 0.02 mm-0.09 mm.
In some alternative embodiments, the concentration of the sodium azide solution with the set concentration is 0.13mol/L to 0.31 mol/L, and the concentration of the hydrochloric acid solution with the set concentration is 23% -42%.
In some alternative embodiments, the copper azide organic compound has an organic content of 21wt% to 39wt%, and the copper azide has a content of 61wt% to 79wt%.
According to a second aspect of the present application, there is provided a copper azide organic compound prepared by the method for preparing a copper azide organic compound described above.
According to a third aspect of the present application there is provided the use of a copper azide organic complex as an initiating explosive.
In the copper azide organic compound, the lamellar copper hydroxide with the small organic molecule intercalated can be prepared in a large scale, the size range is nanoscale, the powder is extremely fine, the specific surface area is large, and the lamellar copper hydroxide is extremely easy to disperse in a liquid phase environment through stirring. PVA is a hydrophilic compound, and has lower viscosity at higher temperatures and higher viscosity at lower temperatures. PVA is utilized to uniformly disperse the PVA and layered copper hydroxide at high temperature, and then the PVA and layered copper hydroxide can be rapidly placed in a low-temperature environment for shaping. After freeze drying, ice crystals sublimate to form a large number of holes, so that a composite material with developed pore structure and high specific surface area can be obtained, and the subsequent azide reaction can be smoothly carried out. In addition, the polyvinyl alcohol layered copper hydroxide can be prepared into any size such as spherical, cylindrical and the like through a die, and any size can meet the charging mode of the miniature detonating device and the charging of some special-shaped initiating explosive devices. The technical scheme of the embodiment of the application is more suitable for the micro-initiation device with smaller caliber, and the initiation power is larger.
Drawings
Fig. 1 is a schematic flow chart of a preparation method of a copper azide organic compound according to an embodiment of the present application.
Detailed Description
The following details the essence of the technical solutions of the embodiments of the present application.
The main principle of the technical scheme of the embodiment of the application comprises that the lamellar copper hydroxide intercalated by small organic molecules can be simply prepared in a large batch, the size range of the lamellar copper hydroxide is nanoscale, the powder is extremely fine, the specific surface area is large, and the lamellar copper hydroxide is extremely easy to disperse in a liquid phase environment through stirring. PVA is a hydrophilic compound, and has lower viscosity at higher temperatures and higher viscosity at lower temperatures. PVA is utilized to uniformly disperse the PVA and layered copper hydroxide at high temperature, and then the PVA and layered copper hydroxide are rapidly placed in a low-temperature environment for shaping. After the PVA-based organic micromolecular intercalation laminar copper hydroxide precursor material is freeze-dried, ice crystals sublimate to form a large number of holes, so that a composite material with developed pore structure and high specific surface area can be obtained, and the subsequent azide reaction can be smoothly carried out. In addition, the composite material can be prepared into any size, such as spherical shape, cylindrical shape and the like, and any size of the composite material can meet the charging mode of the miniature detonating device and the charging of some special-shaped initiating explosive devices.
Fig. 1 is a schematic flow chart of a preparation method of a graphene-based copper azide composite initiating explosive provided in an embodiment of the present application, and as shown in fig. 1, the preparation method of a graphene-based copper azide composite initiating explosive provided in an embodiment of the present application includes the following processing steps:
and 101, preparing an organic small molecule salt solution, a sodium hydroxide solution and a copper salt solution respectively.
In the embodiment of the application, the organic micromolecular salt solution is maintained at 1.86-2.21 wt%, the concentration of the sodium hydroxide solution is maintained at 2.46-2.77 wt%, and the concentration of the copper salt solution is maintained at 2.85-3.34 wt%.
In an embodiment of the present application, the organic small molecule salt includes at least one of: sodium salicylate, potassium salicylate. The organic small molecule salt solution is maintained at 1.86wt% to 2.21wt%. As one example, the concentration of the small organic molecule salt solution may be 1.87wt%, 1.88wt%, 1.89wt%, 1.90wt%, 1.92wt%, 1.95wt%, 1.98wt%, 2.00wt%, 2.02wt%, 2.05wt%, 2.09wt%, 2.11wt%, 2.14wt%, 2.18wt%, or 2.20wt%, etc.
In the embodiment of the application, the copper salt solution can comprise a copper nitrate solution, a copper acetate solution and a copper chloride solution. The concentration of the copper salt solution is maintained at 2.85wt% to 3.34wt%. As an example, the concentration of the copper salt solution may be 2.86wt%, 2.89wt%, 2.90wt%, 2.93wt%, 295wt%, 2.97wt%, 3.00wt%, 3.03wt%, 3.05wt%, 3.08wt%, 3.10wt%, 3.15wt%, 3.18wt%, 3.20wt%, 3.23wt%, 3.26wt%, 3.29wt%, 3.30wt%, 3.32wt%, or 3.33wt%, etc.
As an example, the concentration of sodium hydroxide solution may be 1.87wt%, 1.89wt%, 1.90wt%, 1.93 wt%, 1.96 wt%, 2.00wt%, 2.04 wt%, 2.08 wt%, 2.10 wt%, 2.14wt%, 2.18wt%, or 2.20wt%, etc.
102, according to the volume ratio of 1: 0.91-1: 1.08, adding organic micromolecular salt solution into copper salt solution, stirring, and adding a proper amount of sodium hydroxide solution while stirring to obtain mixed solution; the pH of the mixed solution is maintained at 6.4 to 14.
As an example, the volume ratio of copper salt solution to organic small molecule salt solution may be 1:1. 1:0.93, 1:0.96, 1:0.98, 1:1.02, 1:1.05, or 1:1.07, etc. And continuously dripping sodium hydroxide solution in the process of mixing and stirring the copper salt solution and the small organic molecule salt solution, so that the pH value of the final mixed solution is maintained to be 6.4-14. As an example, the pH of the mixed solution may be 6.6, 7, 7.2, 7.8, 8, 8.4, 9.2, 9.8, 10, 10.3, 10.8, 11, 11.5, 12, 13, 13.4, 13.6, 13.9, or the like. It will be appreciated by those skilled in the art that testing the pH of the mixed solution is readily accomplished. The pH of the mixed solution may be empirically measured after a certain amount of sodium hydroxide solution has been added.
And step 103, heating the mixed solution to maintain the temperature at 88-97 ℃, continuously introducing nitrogen into the heated mixed solution, reacting for a first set period of time, collecting a product, filtering, washing and drying to obtain the layered copper hydroxide precursor material with the small organic molecule intercalation.
In the embodiment of the application, the mixed solution is heated, the reaction temperature of the mixed solution is kept at about 95 ℃, nitrogen is continuously introduced for reaction for 20 hours, and the product is collected, filtered, washed and dried to obtain the layered copper hydroxide with the organic anion intercalation. The length of the reaction is not limited, and those skilled in the art will appreciate that the longer the length of the reaction, the more complete the reaction. However, in view of the preparation efficiency of the copper azide organic compound according to the embodiment of the present application, the first set period of time is 16 hours to 28 hours, and as an example, the first set period of time may be 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 25 hours, 27 hours, 30 hours, 32 hours, 34 hours, 35 hours, or the like. The reaction temperature of the mixed solution can be kept at 88-97 ℃ by continuously heating the mixed solution. As an example, the reaction temperature of the mixed solution may be 89 ℃, 90 ℃, 92 ℃, 94 ℃, 96 ℃, 97 ℃, or the like.
104, preparing a polyvinyl alcohol solution with the temperature maintained at 74-85 ℃; continuously stirring the polyvinyl alcohol solution, adding the lamellar copper hydroxide precursor material of the organic micromolecule intercalation while stirring, and stirring until the system is uniformly dispersed to obtain a polyvinyl alcohol lamellar copper hydroxide dispersion; in the polyvinyl alcohol lamellar copper hydroxide dispersion liquid, the lamellar copper hydroxide intercalated by polyvinyl alcohol and small organic molecules maintains a set mass ratio.
In the examples herein, PVA of a set quality was dissolved in water at 80℃to give a PVA solution.
The set mass ratio between the polyvinyl alcohol solution and the lamellar copper hydroxide precursor material of the organic micromolecular intercalation is 1:7~1:11. as an example, the mass ratio set may be 1:7.2, 1:7.5, 1:7.7, 1:8. 1:8.2, 1:8.5, 1:8.8, 1:8.9, 1:9. 1:9.1, 1:9.2, 1:9.3, 1:9.5, 1:9.9, 1:10. 1:10.2, 1:10.5, or 1:10.8, etc.
In this embodiment of the application, the mold may be a cylindrical mold, and the inner diameter of the mold is: 0.9mm to 40mm. Here, the inner diameter of the die is selected according to the granularity of the copper azide organic compound to be processed, etc., for example, the inner diameter of the die may be 0.95mm, 1.0mm, 1.2mm, 1.8mm, 2.0mm, 3.0mm, 5.0mm, 8.0mm, 10.0mm, 12.0mm, 18.0mm, 20.0mm, 23.0mm, 25.0mm, 29.0mm, 30.0mm, 34.0mm, 36.0mm, 38.0mm, etc. The mold may be a square mold, a rectangular mold, a truncated cone mold, or the like. The specific shape thereof is not limited in the embodiments of the present application.
As an implementation manner, the polyvinyl alcohol layered copper hydroxide dispersion liquid can be rapidly extruded into liquid nitrogen to obtain spherical polyvinyl alcohol layered copper hydroxide. The method specifically comprises the following steps: selecting an injector with the inner diameter of a syringe of 0.3 mm-1.25 mm to extract the polyvinyl alcohol layered copper hydroxide dispersion liquid, and extruding the polyvinyl alcohol layered copper hydroxide dispersion liquid into liquid nitrogen through a liquid outlet of the injector; the caliber of the liquid outlet of the injector is 0.02 mm-0.09 mm. In this embodiment, the inner diameter of the syringe and the caliber of the liquid outlet of the injector may be determined according to the granularity of the copper azide organic compound to be processed, and the like, which is not limited in this embodiment of the present application. Because the syringes are all standard commercial products, the products with corresponding sizes can be purchased according to the requirements. Of course, custom sized syringes may also be selected. It will be appreciated by those skilled in the art that the extrusion of the polyvinyl alcohol layered copper hydroxide dispersion of the embodiments of the present application may also be accomplished in place of a syringe by a tool similar to a syringe.
And 106, freeze-drying the polyvinyl alcohol layered copper hydroxide for a second set period of time, and taking out for standby.
In this embodiment, the second set period is 40 hours to 62 hours, and as an example, the second set period may be 42 hours, 44 hours, 46 hours, 48 hours, 49 hours, 50 hours, 51 hours, 53 hours, 55 hours, 57 hours, 59 hours, 60 hours, or 61 hours, or the like.
In the embodiment of the application, the molar ratio of the polyvinyl alcohol layered copper hydroxide to the sodium azide is 0.5-8.3. As an example, the molar ratio of the polyvinyl alcohol layered copper hydroxide to the sodium azide is 0.6, 0.8, 1.0, 1.5, 1.8, 2.0, 2.5, 2.8, 3.0, 3.3, 3.8, 4.0, 4.5, 4.8, 5.3, 5.8, 6.0, 6.3, 6.8, 7.0, 7.4, 7.8, 8.0, 8.2, or the like. It will be appreciated by those skilled in the art that in actual reactions, it is necessary to add polyvinyl alcohol layered copper hydroxide or sodium azide, respectively, to the reaction vessel as needed to allow sufficient reaction between the polyvinyl alcohol layered copper hydroxide and sodium azide to produce the copper azide organic complexes of the embodiments of the present application.
In the embodiment of the application, the concentration of the sodium azide solution with the set concentration is 0.13mol/L to 0.31 mol/L. As an example, the concentration of the sodium azide solution may be 0.14mol/L, 0.15mol/L, 0.17mol/L, 0.19mol/L, 0.20mol/L, 0.24mol/L, 0.28mol/L, 0.29mol/L, or 0.30mol/L, etc. The concentration of the hydrochloric acid solution of the set concentration is 23% -42%, and as an example, the concentration of the hydrochloric acid solution may be 25%, 27%, 29%, 30%, 33%, 36%, 38%, 40%, 41%, or the like. The third set time is 10-70 min. As an example, the third set time period may be 11min, 13min, 15min, 18min, 20min, 23min, 25min, 30min, 38min, 45min, 50min, 55min, 60min, 64min, 69min, or the like. An ice bath environment refers to an ice bath environment of about 0 ℃.
In the embodiment of the application, a proper amount of hydrochloric acid solution with a set concentration is added, specifically, the mass ratio between the added hydrochloric acid solution and the sodium azide solution is maintained at 1: 125-1: 90. as an example, the mass ratio between the hydrochloric acid solution and the sodium azide solution may be 1: 92. 1: 95. 1: 97. 1: 100. 1: 102. 1: 105. 1: 108. 1: 110. 1: 112. 1: 115. 1: 117. 1: 120. 1: 122. or 1:124, etc.
And step 108, washing and drying the reactant to obtain the copper azide organic compound.
In the copper azide organic compound, the lamellar copper hydroxide with the small organic molecule intercalated can be prepared in a large scale, the size range is nanoscale, the powder is extremely fine, the specific surface area is large, and the lamellar copper hydroxide is extremely easy to disperse in a liquid phase environment through stirring. PVA is a hydrophilic compound, and has lower viscosity at higher temperatures and higher viscosity at lower temperatures. PVA is utilized to uniformly disperse the PVA and layered copper hydroxide at high temperature, and then the PVA and layered copper hydroxide can be rapidly placed in a low-temperature environment for shaping. After freeze drying, ice crystals sublimate to form a large number of holes, so that a composite material with developed pore structure and high specific surface area can be obtained, and the subsequent azide reaction can be smoothly carried out. In addition, the polyvinyl alcohol layered copper hydroxide can be prepared into any size such as spherical, cylindrical and the like through a die, and any size can meet the charging mode of the miniature detonating device and the charging of some special-shaped initiating explosive devices. The technical scheme of the embodiment of the application is more suitable for the micro-initiation device with smaller caliber, and the initiation power is larger.
The following describes the technical solutions of the embodiments of the present application in conjunction with specific embodiments, but the conditions and results described in the implementation do not limit the scope of protection of the present application. The examples herein illustrate the preparation of copper azide organic complexes at exemplary levels only. For industrial or other preparation quantities, the corresponding equal proportion is used for expanding the dosage. The preparation apparatus used is also only illustrative, and alternative container apparatuses may be used in industrial production or the corresponding container apparatuses may be scaled up in equal proportions.
Example 1: raw materials: concentrated hydrochloric acid (HCl), sodium hydroxide (NaOH), sodium salicylate (C) 7 H 5 O 3 Na), sodium azide (NaN 3 ) Copper nitrate trihydrate [ Cu (NO) 3 ) 2 ×3H 2 O]Polyvinyl alcohol (PVA).
Main instrument and equipment: magnetic stirring machine, beaker, oil bath, three-neck flask, freeze dryer, constant temperature drying oven, measuring cylinder, dropping funnel, injector, mold, super constant temperature water bath.
1.6g of small organic molecule salt, 2.0g of sodium hydroxide and 2.4g of copper nitrate trihydrate are weighed respectively, and dissolved in 75mL of deionized water respectively to obtain respective solutions. Placing all copper nitrate solution into a three-neck flask, adding all small organic molecule salt, and then adding a small amount of sodium hydroxide until the pH value is 8; in a nitrogen atmosphere, 95 o C, reacting for 20 hours under the condition of filtering, washing, and then placing the mixture in a vacuum drying oven for drying for 12 hours to obtain a layered copper hydroxide precursor material with small organic molecule intercalation; dissolving 0.1g of PVA in 75mL of water at 80 ℃ to obtain a PVA solution, adding 0.6g of lamellar copper hydroxide intercalated with small organic molecules into the PVA solution for multiple times, stirring while adding, and stirring until the system is completely and uniformly dispersed to obtain a PVA lamellar copper hydroxide dispersion. Sucking PVA layered copper hydroxide dispersion liquid by a micro injector, rapidly extruding the PVA layered copper hydroxide dispersion liquid into liquid nitrogen, and freezing the PVA layered copper hydroxide dispersion liquid into tiny ballsAnd (5) performing freeze drying on the PVA layered copper hydroxide for 48 hours. Preparing 0.2mol/L sodium azide solution, placing the sodium azide solution in an ice bath environment at 0 ℃, weighing a proper amount of dried spherical PVA layered copper hydroxide, and placing the spherical PVA layered copper hydroxide in the sodium azide solution; preparing 35% hydrochloric acid, adding a proper amount of prepared hydrochloric acid into the solution, reacting for 20min, carefully taking out the product, washing and drying to obtain the copper azide organic compound. In the example, the molar ratio of the polyvinyl alcohol layered copper hydroxide to the sodium azide is 0.5-8.3; the mass ratio between the added hydrochloric acid solution and the sodium azide solution is maintained at 1: 125-1: 90.
example 2: raw materials: concentrated hydrochloric acid (HCl), sodium hydroxide (NaOH), sodium salicylate (C) 7 H 5 O 3 Na), sodium azide (NaN 3 ) Copper nitrate trihydrate [ Cu (NO) 3 ) 2 ×3H 2 O]Polyvinyl alcohol (PVA).
Main instrument and equipment: magnetic stirring machine, beaker, oil bath, three-neck flask, freeze dryer, constant temperature drying oven, measuring cylinder, dropping funnel, injector, mold, super constant temperature water bath.
1.6g of small organic molecule salt, 2.0g of sodium hydroxide and 2.4g of copper nitrate trihydrate are weighed respectively, and dissolved in 75mL of deionized water respectively to obtain respective solutions. Placing all copper nitrate solution into a three-neck flask, adding all small organic molecule salt, and then adding a small amount of sodium hydroxide until the pH value is 8; in a nitrogen atmosphere, 95 o C, reacting for 20 hours under the condition of filtering, washing, and then placing the mixture in a vacuum drying oven for drying for 12 hours to obtain a layered copper hydroxide precursor material with small organic molecule intercalation; dissolving 0.1g of PVA in 75mL of water at 80 ℃ to obtain a PVA solution, adding 0.9g of lamellar copper hydroxide intercalated with small organic molecules into the PVA solution for multiple times, stirring while adding, and stirring until the system is completely and uniformly dispersed to obtain a PVA lamellar copper hydroxide dispersion. The PVA laminar copper hydroxide dispersion was sucked in by a micro-syringe, rapidly squeezed into liquid nitrogen and frozen into tiny spherical PVA laminar copper hydroxide, and freeze-dried for 48 hours. Preparing 0.2mol/L sodium azide solution, placing the sodium azide solution in an ice bath environment at 0 ℃, and weighing a proper amount of sodium azide solutionPlacing the dried spherical PVA layered copper hydroxide in a sodium azide solution; preparing 35% hydrochloric acid, adding a proper amount of prepared hydrochloric acid into the sodium azide solution, reacting for 20min, carefully taking out the product, washing and drying to obtain the copper azide organic compound. In the example, the molar ratio of the polyvinyl alcohol layered copper hydroxide to the sodium azide is 0.5-8.3; the mass ratio between the added hydrochloric acid solution and the sodium azide solution is maintained at 1: 125-1: 90.
example 3: raw materials: concentrated hydrochloric acid (HCl), sodium hydroxide (NaOH), sodium salicylate (C) 7 H 5 O 3 Na), sodium azide (NaN 3 ) Copper nitrate trihydrate [ Cu (NO) 3 ) 2 ×3H 2 O]Polyvinyl alcohol (PVA).
Main instrument and equipment: magnetic stirring machine, beaker, oil bath, three-neck flask, freeze dryer, constant temperature drying oven, measuring cylinder, dropping funnel, injector, mold, super constant temperature water bath.
1.6g of small organic molecule salt, 2.0g of sodium hydroxide and 2.4g of copper nitrate trihydrate are weighed respectively, and dissolved in 75mL of deionized water respectively to obtain respective solutions. Placing all copper nitrate solution into a three-neck flask, adding all small organic molecule salt, and then adding a small amount of sodium hydroxide until the pH value is 8; in a nitrogen atmosphere, 95 o C, reacting for 20 hours under the condition of filtering, washing, and then placing the mixture in a vacuum drying oven for drying for 12 hours to obtain a layered copper hydroxide precursor material with small organic molecule intercalation; dissolving 0.1g of PVA in 75mL of water at 80 ℃ to obtain a PVA solution, adding 0.9g of lamellar copper hydroxide intercalated with small organic molecules into the PVA solution for multiple times, stirring while adding, and stirring until the system is completely and uniformly dispersed to obtain a PVA lamellar copper hydroxide dispersion. Pouring the dispersion into a columnar mould, then placing the mould into liquid nitrogen to obtain columnar PVA layered copper hydroxide, and freeze-drying for 48 hours. Preparing a 0.2M sodium azide solution, placing the sodium azide solution in an ice bath environment at the temperature of 0 ℃, weighing a proper amount of dried columnar PVA layered copper hydroxide, and placing the columnar PVA layered copper hydroxide in the sodium azide solution to maintain the molar ratio of the polyvinyl alcohol layered copper hydroxide to the sodium azide at 0.5-8.3; preparing 35% hydrochloric acid, and adding appropriate amount of hydrochloric acid toReacting the polyvinyl alcohol layered copper hydroxide and sodium azide in the solution for 20min; the product was carefully removed, washed and dried to give copper azide organic complexes. In the example, the molar ratio of the polyvinyl alcohol layered copper hydroxide to the sodium azide is 0.5-8.3; the mass ratio between the added hydrochloric acid solution and the sodium azide solution is maintained at 1: 125-1: 90.
example 4: raw materials: concentrated hydrochloric acid (HCl), sodium hydroxide (NaOH), sodium salicylate (C) 7 H 5 O 3 Na), sodium azide (NaN 3 ) Copper nitrate trihydrate [ Cu (NO) 3 ) 2 ×3H 2 O]Polyvinyl alcohol (PVA).
Main instrument and equipment: magnetic stirring machine, beaker, oil bath, three-neck flask, freeze dryer, constant temperature drying oven, measuring cylinder, dropping funnel, injector, mold, super constant temperature water bath.
1.6g of small organic molecule salt, 2.0g of sodium hydroxide and 2.4g of copper nitrate trihydrate are weighed respectively, and dissolved in 75mL of deionized water respectively to obtain respective solutions. Placing all copper nitrate solution into a three-neck flask, adding all small organic molecule salt, and then adding a small amount of sodium hydroxide until the pH value is 8; in a nitrogen atmosphere, 95 o C, reacting for 20 hours under the condition of filtering, washing, and then placing the mixture in a vacuum drying oven for drying for 12 hours to obtain a layered copper hydroxide precursor material with small organic molecule intercalation; dissolving 0.1g of PVA in 75mL of water at 80 ℃ to obtain a PVA solution, adding 0.7g of lamellar copper hydroxide intercalated with small organic molecules into the PVA solution for multiple times, stirring while adding, and stirring until the system is completely and uniformly dispersed to obtain a PVA lamellar copper hydroxide dispersion. The PVA laminar copper hydroxide dispersion was sucked in by a micro-syringe, rapidly squeezed into liquid nitrogen and frozen into tiny spherical PVA laminar copper hydroxide, and freeze-dried for 48 hours. Preparing a 0.2M sodium azide solution, placing the sodium azide solution in an ice bath environment at 0 ℃, weighing a proper amount of dried spherical PVA layered copper hydroxide, and placing the spherical PVA layered copper hydroxide in the sodium azide solution; preparing 35% hydrochloric acid, adding a proper amount of prepared hydrochloric acid into the sodium azide solution, reacting for 60min, carefully taking out the product, washing and drying to obtain the copper azide organic compound. The book is provided withIn an example, the molar ratio of the polyvinyl alcohol layered copper hydroxide to the sodium azide is 0.5-8.3; the mass ratio between the added hydrochloric acid solution and the sodium azide solution is maintained at 1: 125-1: 90.
in the embodiment of the application, copper acetate or copper chloride can be selected to replace copper nitrate trihydrate, as in the previous example, 2.1 g-2.5 g of copper acetate or copper chloride is selected to replace copper nitrate trihydrate, and the copper azide organic compound of the embodiment of the application can also be prepared. Likewise, the organic small molecule salt is replaced by potassium salicylate (C 7 H 5 O 3 K) Copper azide organic complexes of the embodiments of the present application may also be prepared. It will be appreciated by those skilled in the art that two or more of copper acetate, copper chloride and copper nitrate may be selected as the copper salts described above, provided that the components in the examples described above are matched according to the approximate proportions of the copper salts. Similarly, the small organic molecule salt can be a mixture of potassium salicylate and sodium salicylate.
The embodiment of the application also discloses a copper azide organic compound, which is prepared by adopting the preparation method of the copper azide organic compound described in the previous embodiment.
The application also describes the use of the copper azide organic compound as an initiating explosive. The primer can be used as an initiating explosive in the fields of civil blasting devices, aerospace systems, space initiating explosive devices, military weapon systems and the like.
It should be appreciated that reference throughout this specification to "one embodiment" or "an embodiment" means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment of the present application. Thus, the appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. It should be understood that, in various embodiments of the present application, the sequence numbers of the foregoing processes do not mean the order of execution, and the order of execution of the processes should be determined by the functions and internal logic thereof, and should not constitute any limitation on the implementation process of the embodiments of the present application. The foregoing embodiment numbers of the present application are merely for describing, and do not represent advantages or disadvantages of the embodiments.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The foregoing is merely an embodiment of the present application, but the protection scope of the present application is not limited thereto, and any person skilled in the art can easily think about changes or substitutions within the technical scope of the present application, and the changes and substitutions are intended to be covered in the protection scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (10)
1. A method for preparing a copper azide organic compound, the method comprising the following steps of:
preparing organic micromolecular salt solution, sodium hydroxide solution and copper salt solution respectively; wherein, the organic micromolecular salt solution is maintained at 1.86-2.21 wt%, the concentration of the sodium hydroxide solution is maintained at 2.46-2.77 wt%, and the concentration of the copper salt solution is maintained at 2.85-3.34 wt%;
the volume ratio is 1: 0.91-1: 1.08, adding organic micromolecular salt solution into copper salt solution, stirring, and adding a proper amount of sodium hydroxide solution while stirring to obtain mixed solution; maintaining the pH of the mixed solution at 6.4 to 14;
heating the mixed solution to maintain the temperature at 88-97 ℃, continuously introducing nitrogen into the heated mixed solution, reacting for a first set period of time, collecting a product, filtering, washing and drying to obtain a lamellar copper hydroxide precursor material with small organic molecule intercalation;
preparing a polyvinyl alcohol solution with the temperature maintained at 74-85 ℃; wherein, the concentration of the polyvinyl alcohol solution is maintained at 0.11wt% to 0.15wt%;
continuously stirring the polyvinyl alcohol solution, adding the lamellar copper hydroxide precursor material of the organic micromolecule intercalation while stirring, and stirring until the system is uniformly dispersed to obtain a polyvinyl alcohol lamellar copper hydroxide dispersion; in the polyvinyl alcohol lamellar copper hydroxide dispersion liquid, the lamellar copper hydroxide intercalated by polyvinyl alcohol and small organic molecules maintains a set mass ratio;
placing the polyvinyl alcohol layered copper hydroxide dispersion liquid into a mould, and placing the mould into liquid nitrogen to obtain polyvinyl alcohol layered copper hydroxide with a set shape; or rapidly extruding the polyvinyl alcohol layered copper hydroxide dispersion liquid into liquid nitrogen to obtain spherical polyvinyl alcohol layered copper hydroxide;
freeze-drying the polyvinyl alcohol layered copper hydroxide for a second set period of time, and taking out for later use;
dissolving a proper amount of sodium azide in water to prepare a sodium azide solution with a set concentration, and placing the sodium azide solution in an ice bath environment; placing the dried polyvinyl alcohol layered copper hydroxide in a sodium azide solution, adding a proper amount of hydrochloric acid solution with a set concentration, and standing for reaction for a third set period of time to obtain a reactant; wherein, the set molar ratio between the polyvinyl alcohol lamellar copper hydroxide and the sodium azide is maintained;
and washing and drying the reactant to obtain the copper azide organic compound.
2. The method of preparing copper azide organic compound according to claim 1, wherein the organic small molecule salt includes at least one of:
sodium salicylate, potassium salicylate;
the copper salt solution comprises a copper nitrate solution, a copper acetate solution and a copper chloride solution.
3. The method for preparing a copper azide organic compound according to claim 1, wherein the first set time period is 15 hours to 32 hours; the second set time length is 40-62 hours; the third set time is 10-70 min.
4. The method for producing a copper azide organic compound according to claim 1, wherein the set mass ratio is 1:7~1:11.
5. the method for preparing a copper azide compound according to claim 1, wherein the maintaining of a set molar ratio between the polyvinyl alcohol layered copper hydroxide and the sodium azide comprises:
the molar ratio of the polyvinyl alcohol layered copper hydroxide to the sodium azide is 0.5-8.3;
the proper amount of hydrochloric acid solution with set concentration is added, and the method comprises the following steps:
the mass ratio between the added hydrochloric acid solution and the sodium azide solution is maintained at 1: 125-1: 90.
6. the method for preparing a copper azide organic compound according to claim 1, wherein the mold is a cylindrical mold, and the cylinder of the mold has an inner diameter of: 0.9mm to 40mm.
7. The method of preparing copper azide polymer composition according to claim 1, wherein the rapid extrusion of polyvinyl alcohol layered copper hydroxide dispersion into liquid nitrogen comprises:
selecting an injector with the inner diameter of a syringe of 0.3 mm-1.25 mm to extract the polyvinyl alcohol layered copper hydroxide dispersion liquid, and extruding the polyvinyl alcohol layered copper hydroxide dispersion liquid into liquid nitrogen through a liquid outlet of the injector; the caliber of the liquid outlet of the injector is 0.02 mm-0.09 mm.
8. The method for preparing the copper azide organic compound according to claim 1, wherein the concentration of the sodium azide solution with the set concentration is 0.13mol/L to 0.31 mol/L, and the concentration of the hydrochloric acid solution with the set concentration is 29% -42%;
the content of organic matters in the copper azide organic matter compound is 21-39 wt%, and the content of copper azide is 61-71 wt%.
9. Copper azide organic compound, characterized in that the copper azide organic compound is prepared by the preparation method of the copper azide organic compound according to any one of claims 1 to 8.
10. Use of the copper azide organic compound according to claim 9, wherein the copper azide organic compound is used as an initiating explosive.
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