阅读说明：本技术 一种mtnp/tnaz低共熔物的制备方法 (Preparation method of MTNP/TNAZ eutectic mixture ) 是由 王毅 寇勇 郭凯歌 宋小兰 李凤生 于 2020-07-24 设计创作，主要内容包括：本发明公开了一种MTNP/TNAZ低共熔物的制备方法；包括如下步骤：(1)将MTNP和TNAZ加入到有机溶剂中配制成溶液,其中MTNP和TNAZ的摩尔比为(1-3)：(1-3)；(2)使用注射器控制流速,将配置好的溶液缓慢滴加进反溶剂中,在此过程中需要持续搅拌。本发明采用溶剂反溶剂法,在室温下即可进行实验操作,有效避免了传统熔融法在熔融过程中使用水域或油浴加热升温的环节,极大的提高了实验的安全性与便捷性；使用溶剂反溶剂法制备的共熔物质量更高,混合更加均匀,而且性能非常稳定,完全避免了传统熔融法制备的不同批次共熔物性能有所不同的缺点,使得到的最低共熔物的比例更加准确。(The invention discloses a preparation method of MTNP/TNAZ eutectic mixture; the method comprises the following steps: (1) adding MTNP and TNAZ into an organic solvent to prepare a solution, wherein the molar ratio of MTNP to TNAZ is (1-3): (1-3); (2) the prepared solution was slowly added dropwise into the anti-solvent using a syringe to control the flow rate, during which continuous stirring was required. The method adopts a solvent anti-solvent method, can carry out experimental operation at room temperature, effectively avoids the link of heating and raising temperature by using a water area or an oil bath in the melting process of the traditional melting method, and greatly improves the safety and the convenience of the experiment; the eutectic prepared by the solvent anti-solvent method has higher quality, more uniform mixing and very stable performance, completely avoids the defect of different performances of different batches of eutectic prepared by the traditional melting method, and ensures that the proportion of the obtained lowest eutectic is more accurate.)

1. A method for preparing an MTNP/TNAZ eutectic, comprising the steps of:

step1, preparing a solution: adding 1-methyl-3, 4, 5-trinitropyrazole and 1,3, 3-trinitroazetidine into an organic solvent to prepare a solution;

step2, drug precipitation: and (4) slowly dripping the prepared solution into the anti-solvent by using an injector, and separating out.

2. The method for preparing MTNP/TNAZ eutectic according to claim 1, wherein in step1, the molar ratio of said 1-methyl-3, 4, 5-trinitropyrazole and said 1,3, 3-trinitroazetidine is (1-3): (1-3).

3. The method for preparing MTNP/TNAZ eutectic according to claim 1, wherein in step1, the organic solvent is acetone in an amount of 2 to 4 mL.

4. The method for preparing the MTNP/TNAZ eutectic according to claim 1, wherein the anti-solvent is water in an amount of 200-250mL in step 2.

5. The method for preparing the MTNP/TNAZ eutectic according to claim 1, wherein in step2, said dropping is carried out under conditions of one drop at a time interval of 1-2 s.

6. The method for preparing MTNP/TNAZ eutectic according to claim 1, wherein in step2, the stirring is continued during the dropping process, and the rotation speed is controlled at 350-400 r/min.

Technical Field

The invention belongs to the technical field of explosive improvement; in particular to a preparation method of MTNP/TNAZ eutectic mixture.

Background

The fused cast explosive has low cost, good forming performance and higher automation degree, has no substitutable status in military mixed explosives, wherein the proportion of the TNT-based fused cast explosive in the military mixed explosives is up to more than 90 percent. However, with the progress and development of society, new requirements are provided for charging by the development and use of weapons, and the TNT-based fusion-cast explosive cannot meet the requirements of modern weapons, such as low energy level, low density, unsatisfactory detonation performance, poor mechanical properties, oil leakage, brittleness, high toxicity and the like. There are two solutions today: firstly, a low-melting-point elementary explosive with high comprehensive performance, such as high energy, good mechanical property and the like is continuously searched or synthesized; secondly, two or more than two elementary explosives are mixed to form eutectic, so that the eutectic has the advantages of high energy level, relatively insensitive feeling, low toxicity and the like. In the past decades, however, researchers have explored and improved methods and routes for synthesizing many low-melting-point elementary explosives, but to date, none of the low-melting-point elementary explosives can meet the requirement of TNT replacement, and the large-scale application is limited. Thus, the focal point gradually converges on the eutectic. The eutectic can meet various requirements of modern weaponry, such as:

(1) when eutectic is formed, new performance can be endowed to the eutectic explosive, and the melting point is reduced, so that the problem that the existing single-substance explosive has too high melting point is solved, and the requirement of low melting point for explosive charging of modern weapons is met;

(2) when eutectic is formed, the requirement of weapon for charging and stunning feeling can be met, and by adding explosive with lower sensitivity into eutectic, the mechanical sensitivity and thermal sensitivity of eutectic can be obviously reduced, thereby realizing high-efficiency eutectic sense reduction and improving safety;

(3) when eutectic is formed, the performance of the eutectic explosive can be effectively adjusted, the detonation performance of the eutectic explosive is improved, and the requirement of high energy for charging weapons is met.

However, the traditional eutectic preparation method needs to use a water bath or an oil bath to heat and control the temperature in the preparation process, and has hidden danger in the aspect of safety.

And uneven mixing is easy to occur in the mixing process, so that the stability of the eutectic is poor, namely, the eutectic properties prepared from different batches are different. Especially in the case of small doses, this is more difficult to handle. Therefore, this is a problem to be solved at present.

In Chinese patent CN 105601457A, tetratol tetranitrate (ETN) and Dinitrotoluene (DNT) are prepared into eutectic by a eutectic mixing technology, the friction sensitivity and the impact sensitivity of the obtained eutectic explosive are obviously reduced, the thermal decomposition behavior is obviously regulated and controlled, and the safety performance is improved. However, it is required to mix and grind the raw materials ETN and DNT to a certain fineness, and then mix them in a molten state by heating them in a water bath oven and maintaining the temperature at 80 to 90 ℃. The method still needs heating and temperature range control, so that the safety of the experimental process has certain hidden danger. In addition, the two substances are mixed in a molten state, so that the two substances are easily mixed unevenly, the quality of the eutectic is low, and the performance is unstable.

Disclosure of Invention

The invention aims to provide a preparation method of MTNP/TNAZ eutectic mixture; the invention can avoid the heating step in the experiment, improve the safety performance, can uniformly mix two or more explosives, and can simplify the operation process of the experiment and the lowest eutectic substance prepared by the method.

The invention is realized by the following technical scheme:

the invention relates to a preparation method of MTNP/TNAZ eutectic, which comprises the following steps:

step1, preparing a solution: adding 1-methyl-3, 4, 5-trinitropyrazole and 1,3, 3-trinitroazetidine into an organic solvent to prepare a solution;

step2, drug precipitation: and (4) slowly dripping the prepared solution into the anti-solvent by using an injector, and separating out.

Preferably, in step1, the molar ratio of the 1-methyl-3, 4, 5-trinitropyrazole to the 1,3, 3-trinitroazetidine is (1-3): (1-3).

Preferably, in step1, the organic solvent is acetone, and the dosage of the acetone is 2-4 mL.

Preferably, in step2, the anti-solvent is water, and the dosage of the anti-solvent is 200-250 mL.

Preferably, in step2, the dropping is carried out under the condition of dropping one drop by one drop, and the time interval is about 1-2 s.

Preferably, in step2, the stirring is continued during the dropping process, and the rotation speed is controlled at 350-400 r/min.

The method of the invention has the following advantages:

(1) by using the solvent anti-solvent method, the heating link in the traditional eutectic preparation method can be avoided, the problem of temperature control can be avoided, the safety of the experiment is improved, and the safety of experimenters and laboratories is guaranteed;

(2) compared with the traditional preparation method, the eutectic mixture obtained by using the solvent anti-solvent method has higher quality, more uniform mixing and more stable performance;

(3) compared with the traditional preparation method, the method is more convenient and faster by using the solvent anti-solvent method, and is more suitable for preparing laboratory medicines. And the prepared medicine has lower melting point and mechanical sensitivity and better detonation performance.

Drawings

FIG. 1 is a DSC chart at a molar ratio of MTNP/TNAZ of 1/3 in example 1 of the present invention;

FIG. 2 is a DSC chart at a molar ratio of MTNP/TNAZ of 1/2 in example 2 of the present invention;

FIG. 3 is a DSC chart at a molar ratio of MTNP/TNAZ of 2/3 in example 3 of the present invention;

FIG. 4 is a DSC plot of the molar ratio of MTNP/TNAZ of 46.3/53.7 in example 4 of the present invention;

FIG. 5 is a DSC chart showing the molar ratio of MTNP/TNAZ of 3/1 in example 5 of the present invention.

Detailed Description

The present invention will be described in detail with reference to specific examples. It should be noted that the following examples are only illustrative of the present invention, but the scope of the present invention is not limited to the following examples.

The preparation method of the embodiments 1 to 5 of the present invention is the same as the preparation method of the MTNP/TNAZ eutectic, and the method includes the following steps:

step1, preparing a solution: adding 1-methyl-3, 4, 5-trinitropyrazole and 1,3, 3-trinitroazetidine into an organic solvent to prepare a solution;

step2, drug precipitation: and (4) slowly dripping the prepared solution into the anti-solvent by using an injector, and separating out.