阅读说明：本技术 一种起爆药5-硝基四唑亚铜的制备方法 (Preparation method of initiating explosive 5-nitrotetrazole cuprous ) 是由 刘江 倪德彬 董璐阳 于国强 党鹏阳 朱雅红 于 2021-11-04 设计创作，主要内容包括：本发明公开了一种起爆药5-硝基四唑亚铜的制备方法。采用氯化铜和5-硝基四唑钠为原料,亚硫酸钠为还原剂,糊精为晶型控制剂,在加热条件下反应30-40min后,经过滤、洗涤后得到。该方法合成工艺简单,颗粒均匀,流散性好,后处理容易,易实现工业化生产。(The invention discloses a preparation method of initiating explosive 5-nitrotetrazole cuprous oxide. Copper chloride and 5-nitrotetrazole sodium are used as raw materials, sodium sulfite is used as a reducing agent, dextrin is used as a crystal form control agent, and the copper chloride and the 5-nitrotetrazole sodium are reacted for 30-40min under a heating condition, and then the copper chloride and the 5-nitrotetrazole sodium are filtered and washed to obtain the copper-base alloy. The method has the advantages of simple synthesis process, uniform particles, good free-running property, easy post-treatment and easy realization of industrial production.)

1. A preparation method of cuprous 5-nitrotetrazole as an initiating explosive is characterized by comprising the following steps:

and (2) taking dextrin and 5-nitrotetrazole sodium as base solutions, dripping a copper chloride solution and a part of sodium sulfite solution into the base solutions to react for 60-70min, wherein the dripping time is 20-30min, the reaction temperature is 70-80 ℃, then dripping the rest sodium sulfite solution into the base solutions to react for 30-40min, the dripping time is 5-10min, the reaction temperature is 95-98 ℃, and filtering and washing are carried out to obtain the cuprous 5-nitrotetrazole.

2. The method according to claim 1, wherein the mass concentration of the aqueous dextrin solution is 0.3 to 0.5%.

3. The method according to claim 1, wherein the molar ratio of the sodium 5-nitrotetrazole to the sodium sulfite to the cuprous chloride is 1.2 to 1.5:0.5 to 0.7: 1.

4. The method according to claim 1, wherein the sodium sulfite solution has a mass concentration of 7.4 to 8% and the copper chloride solution has a mass concentration of 10%.

Technical Field

The invention relates to a preparation method of green primary explosive 5-nitrotetrazole cuprous oxide, and belongs to the field of energetic materials.

Background

Cuprous 5-nitrotetrazole is an initiating explosive with excellent performance. Compared with lead azide, lead azide has better initiation capability and is considered to be a candidate for replacing lead azide with high possibility. Researchers have successfully synthesized 5-nitrotetra-n-methyl with cuprous chloride (CuCl) and 5-nitrotetrazole sodium as raw materialsCuprous oxazole (US8071784B 2; US20110108172A 1; initiating explosive devices, 2009(5), 41-45; energetic materials, 2010, 18(6), 654-659). However, CuCl is very easy to be oxidized under high temperature conditions, so that impurities containing Cu (II) salt in the product are not easy to remove. And meanwhile, the CuCl is insoluble in water, the actual reaction process is a solid-liquid reaction, so that the reaction process is difficult to control, and the obtained product has small and uneven particles and cannot meet the practical application. Another investigator used copper chloride (CuCl)₂) And 5-nitrotetrazole sodium as raw materials, and sodium ascorbate as reducing agent to successfully synthesize to obtain 5-nitrotetrazole cuprous (US8440008B 2; propellants, applications, pyrotech, 2011,36, 541-. The method has the defects that the obtained product solution contains a large amount of yellow suspended matters, and the suspended matters are very easy to adsorb on the surface of the cuprous 5-nitrotetrazole and are difficult to treat in the post-treatment process, so that the batch synthesis and application of the cuprous 5-nitrotetrazole are limited.

Disclosure of Invention

Aiming at the problem that 5-nitrotetrazole prepared by the existing synthesis method contains a large amount of impurities and is not easy to remove, the invention provides the preparation method of cuprous 5-nitrotetrazole, and the synthesis method is simple, easy in post-treatment, high in product purity and easy for batch preparation. The technical scheme of the invention is as follows:

a preparation method of green primary explosive 5-nitrotetrazole cuprous oxide comprises the following steps:

dextrin and 5-nitrotetrazole sodium are used as base solutions, copper chloride solution and part of sodium sulfite solution are dripped into the base solutions to react for 60-70min, the dripping time is 20-30min, and the reaction temperature is 70-80 ℃. And then dropwise adding the residual sodium sulfite solution into the base solution for reacting for 30-40min at the reaction temperature of 95-98 ℃ for 5-10min, and filtering and washing to obtain the cuprous 5-nitrotetrazole.

The mass concentration of the dextrin water solution is 0.3-0.5%. The mol ratio of the sodium 5-nitrotetrazole to the sodium sulfite to the cuprous chloride is 1.2-1.5:0.5-0.7: 1. The mass fraction of the sodium sulfite aqueous solution is 7.4-8%, and the mass fraction of the copper chloride aqueous solution is 10%.

Compared with the prior art, the invention has the following remarkable advantages:

(1) the product synthesized by the prior art has small particles and uneven size. Dextrin is added as a crystal form control agent, and the obtained crystal has large particles and good uniformity and free-running property.

(2) In the prior art, a cuprous 5-nitrotetrazole solution synthesized by using sodium ascorbate as a reducing agent contains a large amount of yellow suspended substances, and a large amount of impurities are adsorbed on the surfaces of cuprous 5-nitrotetrazole particles obtained after washing, so that high-purity cuprous 5-nitrotetrazole is difficult to obtain through post-treatment as shown in figure 1. The present invention can obtain bright and pure product on the surface of the particle by using sodium sulfite as a reducing agent to prepare the 5-nitrotetrazole cuprous solution and simply washing the solution (figure 2).

(3) The preparation method is simple in preparation process, and a pure product can be obtained through simple filtration and washing, so that the method is suitable for large-scale industrial production.

Drawings

FIG. 1 is a video microscope photograph of cuprous 5-nitrotetrazole synthesized by sodium ascorbate as a reducing agent in the prior art

FIG. 2 is a video microscope image of cuprous 5-nitrotetrazole produced according to the present invention.

FIG. 3 is a DSC of cuprous 5-nitrotetrazole produced according to the present invention

FIG. 4 is an infrared spectrum of cuprous 5-nitrotetrazole prepared according to the present invention

Detailed Description

The present invention will be described in further detail with reference to examples, which will assist understanding of the present invention, but are not intended to limit the content of the present invention.

Example 1

40ml of dextrin solution with the mass concentration of 0.3 percent and 3.9g of 5-nitrotetrazole sodium are weighed and added into a three-neck flask, the temperature is raised to 80 ℃, and the mixture is stirred to be completely dissolved to obtain transparent solution as base solution. And (3) dropwise adding 10ml of 8% sodium sulfite solution and 20ml of 10% copper chloride solution into the base solution at the same time for 25 min. The reaction was carried out at 80 ℃ for 70 min. 4ml of sodium sulfite solution with the mass concentration of 8 percent is dripped into the base solution, and the dripping time is 10 min. The temperature is increased to 95 ℃ and the reaction is carried out for 30 min. And (3) after suction filtration, washing with water for three times, washing with ethanol for three times, dehydrating, and naturally drying to obtain dark red crystal particles with good free-running property. The yield was 75%, and the average particle diameter was 60 μm.

Example 2

The same as in example 1, except that 3.6g by mass of sodium 5-nitrotetrazole was used. The yield of cuprous 5-nitrotetrazole was 72% and the average particle size was 55 μm.

Example 3

The same as in example 1, except that 3.3g by mass of sodium 5-nitrotetrazole was used. The yield of cuprous 5-nitrotetrazole was 72% and the average particle size was 55 μm.

Example 4

The same as in example 1, except that 3.1g by mass of sodium 5-nitrotetrazole was used. The yield of cuprous 5-nitrotetrazole was 68% and the average particle size was 50 μm.

Example 5

The same procedure as in example 1, except that the copper chloride powder and the dextrin solution were used as the base solution, and the sodium sulfite solution and the sodium 5-nitrotetrazole solution were dropped together into the base solution. The yield of sodium 5-nitrotetrazole was 70% and the average particle size was 25 μm.

Example 6

The same as example 1, except that cuprous chloride solution, dextrin solution, and sodium 5-nitrotetrazole were used as base solutions. The sodium sulfite solution was added dropwise to the base solution. The yield of 5-nitrotetrazolium obtained was 68% and the average particle size was 30 μm.