CS235559B1 - Method of 1,3,5-trinitro-1,3,5-triazacyclohexane production - Google Patents

Abstract

The invention relates to the preparation of 1,3,5-trinitro-1,3,5-triazacyclohexane nitrolysis of hexamethylenetetramine in fuming nitrogen-f in the process of production into the reaction system added incrementally or at once urea nitrate in an amount of 0.01 to 25 wt. weight of hexamethylenetetramine. The process of the invention increases economy and security of home production substance.

Description

The invention relates to a process for the preparation of 1,3,5-trinitro-1,3,5-triazacyclohexane by nitrolysis of hexamethylenetetramine in urea nitrate acid medium in the reaction mixture.

According to the latest knowledge, the yield and safety of the nitrous cleavage process and / or nitration of amines or amides, respectively, to cyclic nitramines is favorably affected by the presence of urea, urea-formaldehyde condensates, aminoguanidine sulphate or tetrahydroimidazo [4,5-djimidazol-2,5] diH, 3H, of the respective reaction mixture (see, for example, the author's certificate no. 206 382, 213 509, 214 311 and others j.) The probable mechanism of impersonation of some of the above mentioned additives was discussed in several works, for example in the author's certificate no. 382, they are essentially third generation catalysts.

According to the present invention, a process for the preparation of 1,3,5-trinitro-1,3,5-triazacyclohexane consists in nitrolysis of hexamethylenetetramine with fuming nitric acid in the presence of 0.01 to 25% by weight. % urea nitrate, preferably in the presence of 0.2 to 20 wt. urea nitrate in the reaction mixture, calculated on the weight of the hexamethylenetetramine portion, wherein urea nitrate is added sequentially or simultaneously to the reaction system.

In particular, the advantage of the present invention is to increase the yield of the nitrolysis process and to increase the stability of the reaction mixture, thus increasing the process safety. In the nitrolysis of hexamethylenetetramine for the purposes of the present invention, 1,3,5-trinitro-1,3,5-triazacyclohexane as a major reaction product by the addition of urea nitrate is more strongly promoted to produce 1,3,5,7-tetranitro-1,3,5, 7-tetraazacyklooktánu; this may be an advantage in some applications of the nitrolysis product and may serve as a starting point in the search for optimal synthesis pathways for the N-nitro derivative of 1,3,5,7-tetraazacycloctoctane.

The higher effect achieved in the sense of the present invention has not been described so far in the literature; is illustrated by the following examples, which in no way exclude the possible variability of the production method according to the invention.

Example 1

Up to 710 parts by volume of nitric acid 96.1% with a content of 0.3% by weight. the analysis of nitric acid, cooled to 9-12 ^C, a good mixing and cooling brought in 100 wt. parts of hexamethylenetetramine so that the temperature of the reaction mixture in this operation was 15-17 ° C. After a 20 minute reaction at 18 to 19 ° C, the reaction mixture is poured into a stirred 3000 vol. the resulting supernatant is filtered after stirring for 30 minutes. Filter cake! is washed 4X to 100 volume with portions of water and then dried for 3 hours. at 90 ° C.

The process is repeated using hexamethylenetetramine to which a certain amount of urea nitrate is always added and thoroughly mixed. The results are summarized in Table no. First

Using a non-isothermal longitudinal thermal analysis (DTA) operating at a temperature rise rate of 5 ° C. min ^-1 , measuring range of 1 mV per scale scale and weighing 80-90 mg of sample, determined the onset of the melting endotherm and the peak melting endotherm (i.e., the onset of exothermic decomposition) by the nitrolysis obtained by 1,3,5-trinitro-1,3, 5-triazacyklohexánu; the results of these measurements are shown in Table no. First

Based on the principle of isothermal differential thermal analysis, for nitrolysis mixtures with a content of zero and a content of 1% by weight. urea nitrate to the hexamethylenetetramine feed, found induction periods of decomposition at 51.2 +0.6 ° C: in the reaction mixture without additive, the exothermic decomposition starts after 2019 s and in the electrolysis mixture with the indicated amount of additive after 2397 s.

Example 2

Proceeding as in Example 1, only nitric acid is taken into the reaction in an amount of 1500 volumes, parts and the reaction mixture, after completion of nitrolysis, is loaded into 6500 volumes of water. This procedure results in 109.2 wt. parts of 1,3,5-trinitro-1,3,5-triazacyclohexane, which is 68.9% yield over theory.

The process is repeated, with 20 wt. parts of urea nitrate. 110.1 wt. parts of 1,3,5-trinitro-1,3,5-triazacyclohexane, which is 69.4% yield over theory.

Using DTA as in Example 1, nitrolysis products are found: the product from the non-additive reaction has an onset of melting endotherm at 189.2 ° C and its peak at 193.1 ° C and the product from the additive reaction has an onset of endotherm at 187.5 ° C and its peak at 192.9 ° C.

Table 1

Overview of the results from Example 1

Amount of urea nitrate dosed Extracts of 1,3,5-trinitro-1,3,5-triazacyclohexane DTA results start of melting endotherm (° C) melting endotherm peak (° C) wt. parts % wt. HMT wt. parts ° / o versus theory 0.0 0.0 111.3 70.20 187.6 193.3 0.2 0.2 115.0 72.54 187.6 193.1 0.7 0.7 117.7 74.24 187.4 192.8 1.0 1.0 118.6 74.81 187.3 192.7 3.0 3.0 116.9 73.74 186.4 191.8 5.0 5.0 112.0 70.64 185.3 191.1

Note: HMT = hexamethylenetetramine;

the trend in DTA results is related to the proportionality between the amount of additive in the reaction mixture and the 1,3,5,7-tetranitro-1,3,5,7-tetraazacycloctane content of the resulting 1,3,5-trinitro-1,3,5 -triazacyklohexáne.

Claims (1)

Process for the preparation of 1,3,5-trinitro-1,3,5-triazacyclohexane by nitrolysis of hexamethylenetetramine in nitric acid, characterized in that urea stearate in an amount of 0.01 to 25% is added gradually or simultaneously to the reaction system in the production process. %, preferably in an amount of 0.2 to 20 wt. to the weight of the hexamethylenetetramine.