CS213509B1 - Process for preparing a mixture of cyclic nltramines and the predominant content of 1,3,5,7-tetranitro-1,3,5,7-tetraazacycloctane - Google Patents

Abstract

The invention relates to a method for producing a mixture of cyclic nitramines with a predominant content of 1, 3, 5, 7 -tetranitro- 1, 3, 5, 7 -tetraazacyclooctane by nitrolysis of hexamethylenetetramine in an environment of acetic acid and acetic anhydride in the presence of urea. This mixture is in technical practice a desired source of octagane designated by the code HMZ, or is applicable for special purposes

Description

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2X3 SOB

SUMMARY OF THE INVENTION The present invention relates to a process for the preparation of a mixture of cyclic nitramines with the prevailing content of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane, by the nitration cleavage of hexamethylentetramine in an acetic acid / acetic anhydride medium, the conditions selected so as to favor nutrition reactions.

For the formation of cyclic nitramines in the nitrolysis of hexamethylentetramic, the beneficial effect of some compounds in the reaction mixture is favorable. The action of formaldehyde, parafonaldehyde and / or ammonium nitrate is known to be beneficial, i.e. the nitration cleavage of hexamethylentetramine under the so-called Beckmann conditions. According to the latest knowledge of the formation of cyclic nitramines in the nitrolysis mixture, the presence of urea or urea-formaldehyde condensates, respectively, also has a beneficial effect. also other acid amides and their derivatives (Czechoslovak author certificate no. ...... = PV 7398-79, ... ... = PV 8034-79, no ... ... = PV 3304-80, No. ... ... = PV3632-80 and no ....... = PV 59Ο5-8Ο), The mechanism of action of these aditives in the process of nitration cleavage of hexamethylentetramine was a form of hypothesis suggested in two works (MS). copyright certificate No. ... ... = PV 7398-79 or ... ... = PV 3304-80) In the cited works urea and / or urea-formaldehyde condensates, respectively acid amides and their derivatives, were applied in the synthesis of pure pure cyclic nitramines, namely 1, 3,5, -trinitro-1,3,5, -triazacyclohexane, termed the same hexogen, 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane, called the same octogen, and / or 1,5-endomethylene-3,7 "dinitro-1,3,5,7-tetraazacycloctene, designated DPT.

The present invention relates to a process for the preparation of a mixture of cyclic nitramines with a predominant content of 1,3,5,7-tetranitro-1,3,5,7 "tetraazacycloctane by nitration cleavage of hexamethylenetetramine in an acetic acid / acetic anhydride medium in the presence of urea added to the reaction system in a single or sequential manner, in an amount of 0.05 to 12.00% by weight, preferably 0.49 to 9.90% by weight, by weight of the hexamethylentetraml reaction. An advantage of the process of the present invention is to increase the yield of the process, thus increasing the use of the methylene base of the starting hexamethylentetramine. In the case of the production of the title-type mixtures of titramines, which is the most preferred octogen source in practice, this higher effect in the literature has not been described and is illustrated by the following example. Example 1

As the nitrator, a cylindrical reactor having an internal diameter of 71 microns, a total height of 172 millimeters and a bottom with a sphere height of 29 millimeters is applied. The reactor is equipped with a propeller mixer, a thermometer, three burettes and a honeycomb cooling or heating.

To the present 75 ml of acetic acid was 97.9%. 1.5 ml of acetic anhydride 96.8% and 1.7 g of paraphthaldehyde of melting point 178 and 181 ° C are stirred at 44 to 46 ° C with stirring at three to four minutes. a solution of 10.1 g of hexamethylentetramine (moisture content 0.217% by weight) in acetic acid, a solution of 8.7 g of ammonium nitrate (moisture content 0.31% by weight) in 99.15% nitric acid and 24 ml of acetic anhydride. After delivery! acetone-2 (6 ml) was added to the reaction mixture once

213 SOS hydride and a 15 minute recovery at 45-47 ° C. After this operation, 44 ml of ethanolic anhydride and a solution of 13.2 g of ammonium nitrate in 9.5 ml of acid are added proportionally over a period of 13 minutes, at 44 to 47 ° C. After feeding and reacting for 60 minutes at 45 to 47 ° C, 35 ml of water at 82 ° C are added to the reaction mixture. The reaction mixture is diluted with water for 30 minutes, diluted with 100 ml of water and cooled to 18 ° C. The product isolated by filtration is washed with 50 ml of water, then with 50 ml of about 5% of ammonia water and finally with 50 ml of 70-80 ° C twice. 13.96 g of a mixture of nitramines containing 73.06% of octogen are obtained, yield 47.87% of octogen and 23.54% of hexogen versus theory, which represents 43.68% utilization of methylene base of hexamethylenetetramine. Example 2

The procedure is as in Example 1, except that the hexamethylenetetramine solution in acetic acid contains 0.05 g of urea and the first and second dosages of the solutions into the triple lysis mixture last for 15 minutes. 15.34 g of a mixture of nitramines containing 80.22 wt. Yield 57.75% of octogen and 18.99% of hexogen versus theory, which represents a 47.99% utilization of methylene base. Example 3

The procedure is as in Example 1, except that acetic acid, distilled acetic anhydride (fraction boiling 137.5 to 139.0 ° C) is applied, the first dosing of the solutions takes 14 and the second 10 minutes, at 43 to 46 ° C. From the urea-free phenolysis, 14.52 g of a mixture of nitramines containing 81.18 wt. octogen. The yield was 55.55% of octogen and 17.09% of hexogen, representing 45.43% utilization of the methylene base of hexamethylenetetramine. Example 4

The procedure is as in Example 1, with acetic acid and acetic anhydride as in Example 3, with the first dosing of the solutions in the nitrosation mixture for 11 minutes at 43-45 ° C with a second dosing for 10 minutes at 44-46 ° C. C. Before the second dosing of the solutions, 0.05 g of urea is added to the reaction mixture once. 15.86 g of a mixture of nitramines containing 85.21% by weight of octogen are obtained. The yield is 63.42% octogen and 14.68% hexogen versus theory, representing a 49.62% utilization of methylene base hexamethylenetetramine. Example 5

The procedure is as in Example 1, but the dosage of 24 ml of acetic anhydride (first dosing of solutions) is omitted. The quality of the raw materials is, as in Example 1, only acetic acid applied at a concentration of 99.1% by weight. From urea-free nitrolysis, 10.5 g of mixtures of nitrites containing 75.62 wt. octogen. The yield is 37.28% octogen and 16.02% hexagon versus theory, which represents a 32.85% utilization of the methylene base of hexamethylenetetramine.

Claims (1)

A process for the preparation of a mixture of cyclic nitramines with a predominant 1,3,5,7-tetranitro-1,3,5,7-tetrazazycyclooctane content by nitrating cleavage of hexamathylenetetramine in an acetic acid / acetic anhydride medium characterized in that the nitrolysis process is carried out in the presence of urea %, added to the reaction system at once or sequentially, in an amount of 0.05 12.00% by weight, preferably in an amount of 0.49 to 9.90% by weight, based on the weight of the reaction to be played by hexamethylenetetramine.