CN112110859B - Preparation method of sphericized alpha-DATNBI - Google Patents

Abstract

The invention discloses a preparation method of sphericized alpha-DATNBI, which comprises the following steps: (1) dissolving DATNBI in a good solvent at a certain temperature to respectively prepare DATNBI solutions with certain concentrations, filtering the DATNBI solutions to remove impurities, and cooling to room temperature to obtain a first reactant; (2) under the condition of stirring, quickly pouring the first reactant into a poor solvent matched with a good solvent for stirring, and stirring to obtain a second reactant; (3) and (3) filtering and draining the second reactant, fully cleaning by adopting the poor solvent used in the step (2), and drying to obtain a finished product. The preparation of the sphericized alpha-DATNBI obviously improves the blocky or acicular appearance of the DATNBI raw material, customizes the crystal form of the DATNBI, makes the DATNBI into a single stable alpha crystal form, and has considerable prospect in the development and application of the DATNBI.

Description

Preparation method of sphericized alpha-DATNBI

Technical Field

The invention belongs to the field of energetic materials, and particularly relates to a preparation method of a spherical explosive alpha-DATNBI.

Background

The energetic material is a carrier of modern weapon strength, and in order to meet the requirements of modern national defense industry and technological development, the development of a compound with higher energy density, better explosion performance, lower sensitivity and better chemical stability and thermal stability becomes a main target in the field of explosive development. The crystallization operation is an important link for explosive development, the final product morphological characteristics such as crystal morphology, crystal form and the like of the obtained explosive are directly determined, the physical and chemical properties such as different decomposition temperatures, sensitivity, density and the like are given to the explosive, and the feasibility of explosive charging as a weapon is finally determined.

DATNBI (2,2 ', 3, 3' -tetranitro-1, 1 '-diamino-5, 5' -biimidazole) is a novel high-nitrogen diheterocyclic energetic compound developed recently, thermal analysis shows that the compound has good thermal stability, and calculation shows that various explosive properties of the compound are very excellent, so that the compound is a novel explosive compound. The preparation of spheroidized crystals of explosives is an ultimate pursuit of the crystal form of explosives, and the spheroidized explosives are likely to remarkably improve the safety of sensitivity, bulk density, free-flowing property and the like and the physicochemical properties of energy and the like. At present, DATNBI products have two crystal forms of alpha and beta, and earlier researches show that the alpha-DATNBI is a crystal form which is more thermodynamically stable.

Disclosure of Invention

The invention aims to provide a preparation method of spheroidized alpha-DATNBI aiming at the defects in the prior art, and the preparation method has better application prospect in further improving the safety of high-energy low-sensitivity explosive DATNBI such as sensitivity, bulk density and free-running property and the physicochemical properties such as energy.

The technical scheme of the invention is as follows:

a preparation method of a sphericized alpha-DATNBI comprises the following steps:

(1) dissolving DATNBI in a good solvent at a certain temperature to respectively prepare DATNBI solutions with certain concentrations, filtering the DATNBI solutions to remove impurities, and cooling to room temperature to obtain a first reactant;

(2) under the condition of stirring, quickly pouring the first reactant into a poor solvent matched with a good solvent for stirring, and stirring to obtain a second reactant;

(3) and (3) filtering and draining the second reactant, fully cleaning by adopting the poor solvent used in the step (2), and drying to obtain a finished product.

Preferably, the good solvent in step (1) is selected from any one of methanol, ethanol, acetonitrile, NMP, ethyl acetate, tetrahydrofuran, and 2-methyltetrahydrofuran.

Preferably, the poor solvent in step (2) is selected from any one of pure water, dichloromethane, dichloroethane, toluene, xylene, and petroleum ether.

Preferably, the matching relationship between the good solvent and the poor solvent is as follows: when the good solvent is acetonitrile or NMP, the poor solvent cannot be petroleum ether, and when the good solvent is ethyl acetate, the poor solvent cannot be pure water.

Preferably, the concentrations of the solutions prepared by respectively dissolving DATNBI in methanol, ethanol, acetonitrile, NMP, ethyl acetate, tetrahydrofuran and 2-methyltetrahydrofuran are respectively 20-60g/L, 20-60g/L, 80-140g/L, 60-110g/L, 30-80g/L, 80-180g/L and 70-140g/L in sequence.

Preferably, the volume ratio of the first reactant to the poor solvent in the step (2) is 1: 1-1: 5.

preferably, the positive and negative temperature difference between the first reactant and the poor solvent in the step (2) is 0-30 ℃, and the pouring rate of the first reactant is not lower than 2 ml/min.

Preferably, the stirring speed in step (2) is 200-1000rpm, and the stirring time is 5-30 min.

Preferably, the concentration of the poor solvent in the step (3) is 50ml/g, and the drying conditions are as follows: drying in a vacuum oven at 60 deg.C to obtain the final product.

Preferably, in step (1), DATNBI is dissolved in a good solvent at a temperature of 30-50 ℃.

The invention has the following beneficial effects:

1. the prepared sphericized alpha-DATNBI has the advantages of good balling performance, uniform particle size distribution and high purity.

2. The preparation method has the advantages of simple process flow, convenient operation, easy reaction condition achievement, good safety and high product quality.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a diagram of a sphered α -DATNBI product;

FIG. 2 is a PXRD comparison of the sphericized α -DATNBI product with α -DATNBI standards.

Detailed Description

The technical solution of the present invention is further described below with reference to specific examples, but the present invention is not limited to the contents of the examples in any way.

The first embodiment is as follows:

a preparation method of a sphericized alpha-DATNBI comprises the following steps:

(1) weighing 9g of DATNBI, dissolving the DATNBI in 100ml of 2-methyltetrahydrofuran at the temperature of 30 ℃ to form a solution, filtering to remove impurities, and cooling to room temperature to obtain a first reactant;

(2) measuring 200ml of petroleum ether in a jacketed reaction bottle, quickly and completely pouring the first reactant into the petroleum ether at constant temperature of 10 ℃ under the stirring condition of 350rpm, and maintaining the system to stir for 5min to obtain a second reactant;

(3) the second reaction was filtered, drained and washed thoroughly with 450ml of 50ml/g petroleum ether and dried in a vacuum oven at 60 ℃ to give the final product.

The prepared finished product is irradiated by an instrument positive polarizing microscope to obtain a graph 1, as can be seen from the graph 1, the obtained DATNBI product is spherical yellow crystals with uniform shape, the spherical crystals can be preliminarily judged to be compact, the average particle size of the spherical crystals can be seen from a ruler scale to be about 30-40 micrometers, and the DATNBI spheroidized product has good balling property, uniform particle size and good fluidity according to the analysis result of the microscope.

As can be seen from FIG. 2, the PXRD spectrum peak shapes of the sphericized alpha-DATNBI product and the alpha-DATNBI standard sample are consistent, which indicates that the sphericized alpha-DATNBI product and the alpha-DATNBI standard sample are the same crystal material, namely, both are alpha-DATNBI.

Example two:

a preparation method of a sphericized alpha-DATNBI comprises the following steps:

(1) weighing 11g of DATNBI, dissolving the DATNBI in 100ml of 2-methyltetrahydrofuran at 50 ℃ to form a solution, filtering to remove impurities, and cooling to room temperature to obtain a first reactant;

(2) measuring 200ml of petroleum ether in a jacketed reaction bottle, quickly and completely pouring the first reactant into the petroleum ether at constant 10 ℃ under the stirring condition of 350rpm, and maintaining the system to stir for 10min to obtain a second reactant;

(3) the second reaction was filtered, drained and washed thoroughly with 550ml of 50ml/g petroleum ether and dried in a vacuum oven at 60 ℃ to give the final product.

Example three:

a preparation method of a sphericized alpha-DATNBI comprises the following steps:

(1) weighing 10g of DATNBI, dissolving the DATNBI in 100ml of tetrahydrofuran at the temperature of 30 ℃ to form a solution, filtering to remove impurities, and cooling to room temperature to obtain a first reactant;

(2) weighing 200ml of dimethylbenzene in a jacket reaction bottle, quickly and completely pouring the first reactant into the dimethylbenzene under the stirring condition of 500rpm at constant temperature of 10 ℃, and maintaining the stirring of the system for 5min to obtain a second reactant;

(3) the second reaction was filtered and pumped to dryness and washed thoroughly with 450ml of xylene at a concentration of 50ml/g and dried in a vacuum oven at 60 ℃ to give the finished product.

Example four:

a preparation method of a sphericized alpha-DATNBI comprises the following steps:

(1) weighing 6g of DATNBI, dissolving the DATNBI in 100ml of ethyl acetate at 50 ℃ to form a solution, filtering to remove impurities, and cooling to room temperature to obtain a first reactant;

(2) weighing 400ml of dichloromethane in a jacketed reaction bottle, quickly and completely pouring the first reactant into the dichloromethane at constant temperature of 25 ℃ under the stirring condition of 500rpm, and maintaining the system to stir for 15min to obtain a second reactant;

(3) the second reaction was filtered, drained and washed thoroughly with 450ml of 50ml/g dichloromethane and dried in a vacuum oven at 60 ℃ to give the final product.

Although the present invention has been described herein with reference to the illustrated embodiments thereof, which are intended to be preferred embodiments of the present invention, it is to be understood that the invention is not limited thereto, and that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.

Claims (1)

1. A preparation method of a spheroidized alpha-DATNBI is characterized by comprising the following steps:

(1) dissolving DATNBI in a good solvent at the temperature of 30-50 ℃ to respectively prepare DATNBI solutions with certain concentrations; the good solvent is 2-methyltetrahydrofuran, and the concentration of the DATNBI solution is 70-140 g/L;

filtering the DATNBI solution again to remove impurities and cooling to room temperature to obtain a first reactant;

(2) under the condition of stirring, quickly pouring the first reactant into a poor solvent matched with a good solvent for stirring, wherein the stirring speed is 200-1000rpm, and stirring for 5-30min to obtain a second reactant; the pouring speed of the first reactant is not lower than 2 ml/min; the volume ratio of the first reactant to the poor solvent is 1: 1-1: 5; the poor solvent is petroleum ether; the positive and negative temperature difference between the first reactant and the poor solvent is 0-30 ℃;

(3) and (3) filtering and draining the second reactant, fully cleaning by adopting the poor solvent used in the step (2), and drying to obtain a finished product.

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