阅读说明：本技术 一种全氘代黑索金的制备方法 (Preparation method of fully deuterated hexogen ) 是由 刘吉平 方祝青 于 2020-05-09 设计创作，主要内容包括：本发明涉及一种全氘代黑索金的制备方法,属于氘代含能材料的合成技术。本发明的制备方法为：<Image he="400" wi="700" file="DDA0002483767720000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>该方法操作相对简单,反应条件温和,产品纯度相对较高,无副产物奥克托今的生成；采用废酸部份循环使用法,使硝化液中始终含有接近饱和或过饱和的ND<Sub>4</Sub>DSO<Sub>4</Sub>,缓和了硝化反应,抑制了副反应,既使反应平稳进行,又提高了得率,实现了对全氘代黑索金的制备,为工业上生产全氘代黑索金提供了参考。(The invention relates to a preparation method of fully-deuterated hexogen, belonging to the synthesis technology of deuterated energetic materials. The preparation method comprises the following steps: the method has the advantages of relatively simple operation, mild reaction conditions, relatively high product purity and no generation of a byproduct, namely HMX; the partial recycling method of waste acid is adopted to lead the nitrifying liquid to always contain nearly saturated or supersaturated ND 4 DSO 4 The method has the advantages of easing nitration reaction, inhibiting side reaction, not only enabling the reaction to be carried out stably, but also improving yield, realizing the preparation of the deuterium-substituted hexogen and providing reference for the industrial production of the deuterium-substituted hexogen.)

1. A preparation method of fully deuterated hexogen is characterized by comprising the following steps: the method comprises the following steps:

slowly pouring deuterated sulfamic acid into a pressure-resistant reaction vessel filled with deionized water, wherein the mass ratio of the deionized water to the deuterated sulfamic acid is (15-20): 1, stirring at the speed of 150-300 rpm, introducing gas into the solution after the deuterated sulfamic acid is completely dissolved, adjusting the pH value of the solution to 7-9, wherein the gas is deuterated ammonia gas and the ventilation rate is 20-40 mL/min; stopping ventilation when the temperature of the solution rises to 40-50 ℃; cooling the system at the speed of 1-5 ℃/min, reducing the temperature to be not higher than 5 ℃, performing suction filtration, and performing vacuum drying on the filter residue at the temperature of 20-40 ℃ for 12-24 hours to obtain a deuterated ammonium sulfamate crystal;

step two, placing a deionized water solution A with the concentration of 35-50% at the temperature of-5-0 ℃, adding the ammonium deuterated sulfamate crystal obtained in the step one into the deionized water solution A, wherein the molar ratio of the ammonium deuterated sulfamate crystal to a solute in the deionized water solution A is (2-4), stirring and dissolving, then dropwise adding deuterated sulfuric acid with the concentration of 70-98% into the solution, keeping the temperature of the system not higher than 5 ℃ in the dropwise adding process, adjusting the pH of the solution to 4-6, then sealing a reaction device, heating the system to 50-70 ℃ at the speed of 1-5 ℃/min, keeping the temperature for 6-10 hours, carrying out suction filtration, carrying out vacuum concentration on the filtrate at the temperature of 30-60 ℃, and concentrating for 12-24 hours to obtain a deuterated cyclotrimethylenetrinosulfonic acid ammonium crystal;

thirdly, placing the deuterated cyclotrimethylenetrinoamino sulfonic acid ammonium crystal obtained in the first step in an environment of-5-0 ℃, dropwise adding 90-98% deuterated nitric acid into the deuterated cyclotrimethylenetrinoamino sulfonic acid ammonium at a dropwise adding rate of 0.3-3 mL/min through a constant-pressure dropping funnel, wherein the mass ratio of the deuterated nitric acid to the deuterated cyclotrimethylenetrinoamino sulfonic acid ammonium is (15-22): 1, keeping the temperature of the system to be not higher than 5 ℃ in the dropwise adding process, adding boron trifluoride into the solution after the dropwise adding is finished, the molar ratio of the deuterated nitric acid to the boron trifluoride is (3-6): 1, sealing the reaction device, stirring at a speed of 400-700 rpm, heating to 15-20 ℃, preserving the temperature for 1-2 hours, pouring the reaction mixed solution into deionized water at a temperature of not higher than 5 ℃, and keeping the volume ratio of the mixed solution to the deionized water to be 1 (1-2), stirring at the speed of 50-100 rpm for 0.5-1 hour, performing suction filtration, collecting filtrate B, washing filter residues with deionized water at the temperature of not higher than 5 ℃ until the pH value of the filtrate is neutral, and performing vacuum drying on the filter residues at the temperature of 20-40 ℃ for 12-24 hours to obtain the fully deuterated hexogen.

2. The method of claim 1, wherein: and in the second step, the solute of the deionized water solution A is one of deuterated formaldehyde, deuterated dicarbaldehyde, deuterated trioxymethylene and deuterated paraformaldehyde.

3. The method of claim 1, wherein: and (3) the treatment method of the filtrate B in the third step is evaporation concentration to obtain the circulating deuterated nitric acid with the required concentration, and then the circulating deuterated nitric acid is mixed with a certain amount of fresh deuterated nitric acid to prepare the deuterated nitric acid used in the third step.

Technical Field

The invention relates to a preparation method of fully-deuterated hexogen, belonging to the synthesis technology of deuterated energetic materials.

Background

Cyclotrimethylenetrinitramine, also known as hexogen, is a very important explosive and has gained widespread attention since its emergence in 1899. The hexogen has good stability which is only slightly lower than that of the aromatic nitro compound explosive, but the explosive property of the hexogen is far higher than that of the aromatic nitro compound explosive, and the explosive strength of the hexogen is 1.5 times that of TNT. The hexogen has wide application range after being subjected to insensitive treatment or being mixed with other explosives with lower melting point, lower sensitivity and good charging performance, such as projectile charging, military engineering blasting, solid rocket propellant and the like.

The mass of deuterium atoms is twice of that of hydrogen atoms, the zero point basic energy of carbon-deuterium bonds is lower than that of carbon-hydrogen bonds, but the transition state activation energy of the carbon-deuterium bonds is similar to that of the carbon-hydrogen bonds, so that the carbon-deuterium bonds are more stable than the carbon-hydrogen bonds. The replacement of hydrogen atoms in hexogen with deuterium atoms can improve the stability of the substance, reduce the sensitivity of the substance and increase the application range of the substance. As the mass difference between deuterium and hydrogen is obvious, the charge density of the deuterated hexogen is higher than that of the hexogen, and the detonation performance is improved. In addition, compared with hexogen, the deuterated hexogen is more beneficial to accurately researching the crystal information in the hexogen by utilizing a neutron diffraction technology. Therefore, the method has important application value in the synthesis research of the deuterium-substituted hexogen.

Chinese patent application publication No. CN108101858A discloses a method for preparing deuterated hexogen, which comprises reacting deuterated formaldehyde and ammonia to obtain intermediate product deuterated urotropin, and further nitrifying the deuterated urotropin to obtain deuterated hexogen. However, the method uses non-deuterated raw materials such as ammonia water and nitric acid in the preparation process, so that the purpose of preparing the fully deuterated hexogen cannot be achieved. In 2018, rhizoma picrorhizae and the like synthesize deuterated urotropine by using deuterated paraformaldehyde as a raw material, and then the deuterated urotropine is directly nitrified in fuming nitric acid to obtain deuterated hexogen; the method has low yield, and the product contains a certain amount of octogen, which affects the mechanical sensitivity of the product (synthesis of the rhizoma imperatae deuterated energetic material and performance research thereof [ D ] southwest science and technology university 2018: 46-62.). The white salt method is a method for producing hexogen, and the method takes ammonia, sulfur trioxide and sylvite as raw materials, an intermediate product of potassium sulfamate is obtained by reaction, the intermediate product of potassium sulfamate is condensed with formaldehyde to obtain cyclotrimethylenetrinate, and the cyclotrimethylenetrinate is further nitrified to obtain hexogen; however, this method produces a large amount of waste water containing potassium salt, increasing the difficulty of post-treatment (Miyaoshao, Huidishu, Chenyi Feng, etc.. Hexogen industrial production technology advances [ J ] chemical intermediates, 2013(8): 26-29.). Since the above method has problems of low yield, low purity, complicated post-treatment, etc., it is required to develop a method for efficiently preparing the deuterated hexogen.

Disclosure of Invention

The invention aims to provide a preparation method of fully deuterated hexogen. The method is relatively simple to operate, mild in reaction conditions and relatively high in product purity, realizes preparation of the deuterium-substituted hexogen, and provides reference for industrial production of the deuterium-substituted hexogen.

The purpose of the invention is realized by the following technical scheme. The specific route is as follows:

a preparation method of the deuterium-substituted hexogen comprises the following steps:

slowly pouring deuterated sulfamic acid into a pressure-resistant reaction vessel filled with deionized water, wherein the mass ratio of the deionized water to the deuterated sulfamic acid is (15-20): 1, stirring at the speed of 150-300 rpm, introducing gas into the solution after the deuterated sulfamic acid is completely dissolved, adjusting the pH value of the solution to 7-9, wherein the gas is deuterated ammonia gas and the ventilation rate is 20-40 mL/min; stopping ventilation when the temperature of the solution rises to 40-50 ℃; cooling the system at the speed of 1-5 ℃/min, reducing the temperature to be not higher than 5 ℃, performing suction filtration, and performing vacuum drying on the filter residue at the temperature of 20-40 ℃ for 12-24 hours to obtain a deuterated ammonium sulfamate crystal;

step two, placing a deionized water solution A with the concentration of 35-50% at the temperature of-5-0 ℃, adding the ammonium deuterated sulfamate crystal obtained in the step one into the deionized water solution A, wherein the molar ratio of the ammonium deuterated sulfamate crystal to a solute in the deionized water solution A is (2-4), stirring and dissolving, then dropwise adding deuterated sulfuric acid with the concentration of 70-98% into the solution, keeping the temperature of the system not higher than 5 ℃ in the dropwise adding process, adjusting the pH of the solution to 4-6, then sealing a reaction device, heating the system to 50-70 ℃ at the speed of 1-5 ℃/min, keeping the temperature for 6-10 hours, carrying out suction filtration, carrying out vacuum concentration on the filtrate at the temperature of 30-60 ℃, and concentrating for 12-24 hours to obtain a deuterated cyclotrimethylenetrinosulfonic acid ammonium crystal;

thirdly, placing the deuterated cyclotrimethylenetrinoamino sulfonic acid ammonium crystal obtained in the first step in an environment of-5-0 ℃, dropwise adding 90-98% deuterated nitric acid into the deuterated cyclotrimethylenetrinoamino sulfonic acid ammonium at a dropwise adding rate of 0.3-3 mL/min through a constant-pressure dropping funnel, wherein the mass ratio of the deuterated nitric acid to the deuterated cyclotrimethylenetrinoamino sulfonic acid ammonium is (15-22): 1, keeping the temperature of the system to be not higher than 5 ℃ in the dropwise adding process, adding boron trifluoride into the solution after the dropwise adding is finished, the molar ratio of the deuterated nitric acid to the boron trifluoride is (3-6): 1, sealing the reaction device, stirring at a speed of 400-700 rpm, heating to 15-20 ℃, preserving the temperature for 1-2 hours, pouring the reaction mixed solution into deionized water at a temperature of not higher than 5 ℃, and keeping the volume ratio of the mixed solution to the deionized water to be 1 (1-2), stirring at the speed of 50-100 rpm for 0.5-1 hour, performing suction filtration, collecting filtrate B, washing filter residues with deionized water at the temperature of not higher than 5 ℃ until the pH value of the filtrate is neutral, and performing vacuum drying on the filter residues at the temperature of 20-40 ℃ for 12-24 hours to obtain the fully deuterated hexogen.

And in the second step, the solute of the deionized water solution A is one of deuterated formaldehyde, deuterated dicarbaldehyde, deuterated trioxymethylene and deuterated paraformaldehyde.

And (3) the treatment method of the filtrate B in the third step is evaporation concentration to obtain the circulating deuterated nitric acid with the required concentration, and then the circulating deuterated nitric acid is mixed with a certain amount of fresh deuterated nitric acid to prepare the deuterated nitric acid used in the third step.

And the pressure-resistant reaction vessels in the first step, the second step and the third step are all provided with a mechanical stirring, a constant-pressure dropping funnel and a condenser.

Advantageous effects

(1) The preparation method of the fully deuterated hexogen is simple, the obtained product has high purity, and no by-product octogen is generated.

(2) The partial recycling method of waste acid is adopted to lead the nitrifying liquid to always contain nearly saturated or supersaturated ND₄DSO₄The nitration reaction is eased, the side reaction is inhibited, the reaction is carried out stably, and the yield is improved; because the nitrifying liquid contains a large amount of inert ND₄DSO₄Therefore, the hexogen particles in the suspension are dispersed and isolated, and the operation safety is higher.

(3) The improved use of boron trifluoride as a catalyst in the nitration process reduces the use amount of deuterated nitric acid and avoids the use of deuterated sulfuric acid; the acid-containing wastewater does not contain potassium ions, so that the complex post-treatment is avoided, and the production cost is reduced.

(4) Compared with the common hexogen, the crystal density of the fully deuterated hexogen is higher, the contained energy is higher, and meanwhile, the 5s delay explosive point of the sample is improved, and the heat sensitivity is reduced.

Detailed Description

The present invention will be further described with reference to the following examples.