阅读说明：本技术 起爆药[Pb(OH)]4(N5)4及其制备方法 (Initiating explosive [ Pb (OH)]4(N5)4And method for preparing the same ) 是由 许元刚 陆明 王鹏程 林秋汉 袁媛 于 2021-03-24 设计创作，主要内容包括：本发明公开了一种起爆药[Pb(OH)]-(4)(N-(5))-(4)及其制备方法,其化学式为[Pb(OH)]-(4)(N-(5))-(4),具有一维配位聚合物结构。其制备步骤为：制备铅盐溶液；复分解反应；溶剂挥发合成[Pb(OH)]-(4)(N-(5))-(4)。本发明的起爆药具有制备方法简单、稳定性佳、起爆能力高等优点。(The invention discloses a primary explosive [ Pb (OH)] 4 (N 5 ) 4 And a process for preparing the same, which has the chemical formula [ Pb (OH) ]] 4 (N 5 ) 4 Has a one-dimensional coordination polymer structure. The preparation method comprises the following steps: preparing a lead salt solution; carrying out double decomposition reaction; solvent volatilization synthesis [ Pb (OH)] 4 (N 5 ) 4 . The primer has the advantages of simple preparation method, good stability, high priming capability and the like.)

1. An initiating explosive is characterized in that the chemical formula is [ Pb (OH) ]]₄(N₅)₄The structural formula of the crystal structure is as follows:

2. the primary explosive of claim 1, wherein the crystal structure of the primary explosive has the following characteristics:

crystal system: monoclinic system;

point group: p2₁；

Unit cell parameters:α＝γ＝90°，β＝106.440(4)°；

unit cell volume:

Z＝2；

density: 4.537g cm^-3(296K)。

3. The method for preparing the initiating explosive according to claim 1 or 2, comprising the following steps:

the method comprises the following steps: dispersing the silver pentazole solid into a solvent at the temperature of minus 10-30 ℃, adding a lead salt solution into the solvent, stirring the mixture for a period of time at the temperature of minus 10-30 ℃, carrying out ultrasonic treatment for 15min, and then filtering the mixture to obtain a filtrate;

step two: adjusting the pH value of the filtrate to 8 +/-0.1, filtering with a filter membrane, taking clear liquid, placing the clear liquid in a constant-temperature constant-humidity box, setting the temperature to be 40-60 ℃ and the humidity to be 15%, quickly volatilizing the solvent until the solvent is volatilized to 1/2, then setting the temperature to be 15 ℃ and the humidity to be 80%, slowly volatilizing the solvent to obtain the primary explosive [ Pb (OH)]₄(N₅)₄。

4. The method as claimed in claim 3, wherein in the first step, the lead salt solution is prepared by dispersing lead salt into deionized water, adding sodium hydroxide with 5 per mill mass of the lead salt to dissolve the lead salt, wherein the lead salt is lead chloride or lead sulfate, and the ratio of the deionized water to the lead salt is 50 mL/g-80 mL/g.

5. The method of claim 3, wherein in step one, the stirring is carried out at-10 ℃ to 30 ℃ for 0.5h to 24 h.

6. The method according to claim 3, wherein in the first step, the solvent is water, methanol, ethanol or glycerol, and the ratio of the solvent to the silver pentazole is 10mL/g to 50 mL/g.

7. The method of claim 3, wherein in step one, the mass ratio of the pentazole silver to the lead salt is 1:1 to 1.5: 1.

8. The method of claim 3, wherein in the second step, the pH value of the filtrate is adjusted to 8 +/-0.1 by using 0.2mol/L alkali liquor, wherein the alkali liquor is sodium hydroxide, potassium hydroxide, sodium bicarbonate or potassium bicarbonate solution.

Technical Field

The invention relates to a novel primary explosive [ Pb (OH) ]]₄(N₅)₄And a preparation method thereof, belonging to the technical field of energetic materials.

Background

The primary explosive is a simple substance compound or a mixture used for burning or detonating energetic materials in an ignition head or a detonator, and is an important component in initiating explosive devices and weapons. At present, the commercial initiating explosive mainly comprises lead azide, lead stevensonate and the like, and the initiating explosive is simple to synthesize, low in cost and good in relative stability, but the initiating explosive has insufficient explosive performance and needs larger metering during detonation. Therefore, the development of novel high-energy initiating explosive and the reduction of the consumption of the initiating explosive become urgent needs of the current initiating explosive research and development.

Disclosure of Invention

The invention aims to provide the initiating explosive and the preparation method thereof, and compared with the most widely produced initiating explosive, the initiating explosive has the advantages of simple preparation method, better stability, higher initiation capability and the like.

The technical solution for realizing the purpose of the invention is as follows:

an initiating explosive has a one-dimensional coordination polymer structure with a chemical formula of [ Pb (OH) ]]₄(N₅)₄The structural formula of the crystal structure is as follows:

the crystal structure data of the primary explosive is as follows:

crystal system: monoclinic system;

point group: p2₁；

Unit cell parameters:α＝γ＝90°，β＝106.440(4)°；

unit cell volume:

Z＝2；

density: 4.537g cm^-3(296K)。

The invention provides a preparation method of an initiating explosive, which specifically comprises the following steps:

the method comprises the following steps: dispersing the silver pentazole solid into a solvent at the temperature of minus 10-30 ℃, adding a lead salt solution into the solvent, stirring the mixture for a period of time at the temperature of minus 10-30 ℃, carrying out ultrasonic treatment for 15min, and then filtering the mixture to obtain a filtrate;

step two: adjusting the pH of the filtrateFiltering with filter membrane to 8 +/-0.1, placing the clear liquid in a constant temperature and humidity cabinet, setting the temperature at 40-60 ℃ and the humidity at 15%, volatilizing the solvent quickly until the solvent is volatilized to 1/2, setting the temperature at 15 ℃ and the humidity at 80%, volatilizing the solvent slowly to finally obtain the Pb (OH)]₄(N₅)₄。

In the first step, the lead salt solution is prepared by dispersing lead salt into deionized water, and adding sodium hydroxide with the mass of 5 per mill of the lead salt to dissolve the lead salt, wherein the lead salt is lead chloride or lead sulfate, and the mass ratio of the volume of the deionized water to the lead salt is 50 mL/g-80 mL/g.

In the first step, stirring is carried out for 0.5 to 24 hours at a temperature of between 10 ℃ below zero and 30 ℃.

In the first step, the solvent is water, methanol, ethanol or glycerol, and the ratio of the volume consumption of the solvent to the feeding mass of the silver pentazole solid raw material is 10 mL/g-50 mL/g.

In the first step, the ratio of the amounts of the pentazole silver and the lead salt is 1:1 to 1.5: 1.

And in the second step, adjusting the pH value of the filtrate to 8 +/-0.1 by using 0.2mol/L alkali liquor, wherein the alkali liquor is sodium hydroxide, potassium hydroxide, sodium bicarbonate or potassium bicarbonate solution.

Compared with the prior art, the invention has the beneficial effects that:

(1) the novel initiating explosive disclosed by the invention has a one-dimensional coordination polymer structure.

(2) The novel primer has good thermal stability, and the decomposition temperature is 121 ℃ (the heating rate is 5 ℃ for min^-1) The thermal decomposition is direct decomposition, the exothermic peak is sharp, and the exothermic quantity is large (2876J g)^-1) And has remarkable heat release characteristics of the primary explosive.

(3) Novel initiating explosive density is 4.537g cm^-3Has excellent detonation performance, the detonation pressure is 31.5GPa, the detonation velocity is 8156m s^-1Is far higher than lead azide and belongs to high-energy initiating explosive.

(4) The novel initiating explosive is tested to have impact sensitivity of 5J, friction sensitivity of 50N, lower mechanical sensitivity and higher safety than lead azide.

Drawings

FIG. 1 shows the present inventionMing dynamite [ Pb (OH)]₄(N₅)₄Crystal structure of (2).

FIG. 2 shows the primary explosive of the present invention [ Pb (OH) ]]₄(N₅)₄The one-dimensional coordination structure of (1).

FIG. 3 shows the primary explosive of the present invention [ Pb (OH) ]]₄(N₅)₄The unit cell stacking diagram of (a).

FIG. 4 is a diagram of an initiation experimental apparatus.

FIG. 5 shows lead azide and the primary explosive of the present invention [ Pb (OH) ]]₄(N₅)₄Drawing of lead plate through hole.

Detailed Description

The following examples are presented to enable one of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.

The invention provides a primary explosive [ Pb (OH)]₄(N₅)₄Is a white to light yellow powdery solid, and the crystal is white needle-shaped. The crystal density is 4.0-5.0 g cm^-3. It is not sensitive to water, light and steam, can be stored in a constant temperature and humidity box with the temperature of 30 ℃ and the humidity of 90% for three months without deterioration, has the thermal decomposition temperature higher than 120 ℃, does not react with plastic and glass in contact, and does not change the surface color and shape after being exposed to direct sunlight for a long time. The substance has strong initiation capability, 600mg of RDX (cyclotrimethylene trinitroamine) and PETN (pentaerythritol tetranitrate) can be stably initiated when the quantity of the sample is less than 100mg, and a perforation with the diameter of 15mm is formed on a lead plate with the diameter of 5 mm. The detonation capability is about 2-3 times of that of the DDNP.

The preparation method of the initiating explosive provided by the invention has the following reaction formula:

the method specifically comprises the following steps:

the method comprises the following steps: dispersing a certain amount of lead salt into deionized water at room temperature, and adding trace (5 per mill of lead salt by mass) of sodium hydroxide to dissolve the lead salt to obtain a lead salt solution.

Step two: dispersing the silver pentazole solid into a solvent at the temperature of minus 10-30 ℃, adding the lead salt solution prepared in the step one into the solvent, stirring the mixture for a period of time at the temperature of minus 10-30 ℃, carrying out ultrasonic treatment for 15min, and then filtering the mixture to obtain a filtrate.

Step three: adjusting the pH of the filtrate to be about 8 by using 0.2mol/L alkali liquor, filtering by using a filter membrane, taking clear liquid, putting the clear liquid into a constant-temperature and constant-humidity box, setting the temperature to be 40-60 ℃ and the humidity to be 15%, quickly volatilizing the solvent until the solvent is volatilized to 1/2, then setting the temperature to be 15 ℃ and the humidity to be 80%, and slowly volatilizing the solvent to obtain Pb (OH)]₄(N₅)₄。

Example 1: 1.67g of lead chloride was dispersed in 90mL of water at room temperature, and a trace amount of sodium hydroxide was added to dissolve the solid completely, to prepare a lead salt solution. Dispersing 1.60g of pentazol silver solid into 20mL of water at the temperature of 10 ℃, adding the prepared lead salt solution into the water, stirring for 0.5h, carrying out ultrasonic treatment for 15min, then filtering, adjusting the pH of the filtrate to be approximately equal to 8 by using 0.2mol/L sodium hydroxide solution, filtering by using a filter membrane, taking clear liquid, placing the clear liquid into a constant temperature and humidity box, setting the temperature to be 40-60 ℃, setting the humidity to be 15%, quickly volatilizing the solvent until the solvent is volatilized to 1/2, then setting the temperature to be 15 ℃, setting the humidity to be 80%, and slowly volatilizing the solvent to obtain [ Pb (OH) ]]₄(N₅)₄Crystal 1.29 g.

Example 2: 1.67g of lead sulfate was dispersed in 90mL of water at room temperature, and a trace amount of sodium hydroxide was added to dissolve the solid completely, to prepare a lead salt solution. Dispersing 1.60g of pentazol silver solid into 20mL of water at the temperature of 10 ℃, adding the prepared lead salt solution into the water, stirring for 24 hours, carrying out ultrasonic treatment for 15 minutes, then filtering, adjusting the pH of the filtrate to be approximately equal to 8 by using 0.2mol/L sodium bicarbonate solution, filtering by using a filter membrane, taking clear liquid, placing the clear liquid into a constant temperature and humidity box, setting the temperature to be 40-60 ℃, setting the humidity to be 15%, rapidly volatilizing the solvent until the solvent is volatilized to 1/2, then setting the temperature to be 15 ℃, setting the humidity to be 80%, and slowly volatilizing the solvent to obtain [ Pb (OH) ]]₄(N₅)₄Crystal 1.30 g.

Example 3: 1.67g of lead chloride was dispersed in 90mL of water at room temperature, and a trace amount of sodium hydroxide was added to dissolve the solid completely, to prepare a lead salt solution. 1.60g of pentazole are added at 30 DEGDispersing silver solid into 20mL of methanol, adding the prepared lead salt solution into the methanol, stirring for 3h, performing ultrasonic treatment for 15min, filtering, adjusting the pH of the filtrate to be approximately equal to 8 by using 0.2mol/L potassium bicarbonate solution, filtering by using a filter membrane, taking clear liquid, placing the clear liquid into a constant-temperature and constant-humidity box, setting the temperature to be 40-60 ℃ and the humidity to be 15%, quickly volatilizing the solvent until the solvent is volatilized to 1/2, setting the temperature to be 15 ℃ and the humidity to be 80%, and slowly volatilizing the solvent to obtain [ Pb (OH) ]]₄(N₅)₄0.81g of crystals.

Example 4: 2.5g of lead chloride was dispersed in 100mL of water at room temperature, and a trace amount of sodium hydroxide was added to dissolve the solid completely, to prepare a lead salt solution. Dispersing 1.60g of pentazol silver solid into 20mL of ethanol at the temperature of-10 ℃, adding the prepared lead salt solution, stirring for 10h, carrying out ultrasonic treatment for 15min, then filtering, adjusting the pH of the filtrate to be approximately equal to 8 by using 0.2mol/L potassium hydroxide solution, filtering by using a filter membrane, taking clear liquid, putting the clear liquid into a constant temperature and humidity box, setting the temperature to be 40-60 ℃, setting the humidity to be 15%, quickly volatilizing the solvent until the solvent is volatilized to 1/2, then setting the temperature to be 15 ℃, setting the humidity to be 80%, and slowly volatilizing the solvent to obtain [ Pb (OH)]₄(N₅)₄0.87g of crystals.

The crystals obtained in examples 1 to 4 were subjected to single crystal X-ray diffraction measurement, and the crystal structures thereof are shown in FIGS. 1 to 3, and the unit cell parameters thereof are the same as shown in the attached Table below:

attached watch

The crystals obtained in example 1 were characterized and the results of the analysis were as follows:

DSC: 121 ℃ (decomposition); elemental analysis PbHN₅O (%): found (calculated) H0.29 (0.34), N23.77 (23.80); infrared (KBr) light (infrared,)：3347,3258,1655,1250,1233,587,555。

the crystal obtained in example 1 is ground by an agate mortar for 3-5 min, and the test shows that the impact sensitivity is 5J, the friction sensitivity is 50N, the mechanical sensitivity is lower, and the crystal is safer than lead azide.

The crystal obtained in example 1 was ground with an agate mortar for 3-5 min, and an initiation test was performed as shown in fig. 4, wherein the thickness of the lead plate was 5mm, the amount of the initiation explosive was 50mg, and the amount of the explosive RDX was 600 mg. The results of the plate piercing are shown in FIG. 5, where the initiation of lead azide RDX resulted in a plate piercing of 13.5mm, [ Pb (OH) ]]₄(N₅)₄Initiation of RDX resulted in a 15mm lead plate perforation, indicating [ Pb (OH)]₄(N₅)₄The detonating ability of the composite is higher than that of lead azide.