CS227911B1 - Production of monocyclic nitramines - Google Patents

Abstract

The invention relates to the production of a monocyclic mixture nitramines ’content 1,3,5,7-tetranitro-1,3,5,7-tetraazacyklooktánu nltrolysis of hexamethylenetetramine in acetic acid and acetic anhydride in the presence of urea-formaldehyde condensate. This mixture is in practice, a desirable octogen source designated HMX, respectively. is a applicable for special purposes.

Description

The present invention relates to the preparation of a mixture of monocyclic nitramines having a predominant 1,3,5,7-tetranitro-1,3,5,7-tetraazaoyclooctane content by nitrating the cleavage of hexamethylenetetramine in acetic acid and acetic anhydride, the reaction conditions being chosen to positively affect the yield. process.

Nitrile cleavage of hexamethylenetetramine, depending on the conditions of the reaction, yields a binary mixture of monocyclic nitramines in which 1,3,5-trinitro-1,3,5-triazacyclohexane, also known as hexogen and referred to as RDX, or predominates, predominates 1 3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane, called octogen and designated HMX. The second type mixture is a desirable source of HMX in technical practice.

As is known (E. Ju. Orlova et al .: Oktogen - termostojkoje vzryvčatoje veščestvo, Izdat. Nedra, 1978), the synthesis of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane from hexamethylenetetramine proceeds through 1,5-endomethylene-3,7-dinitro-1,3,5,7-tetraazacyclooctene as an intermediate. In order to ensure the maximum yield of octogen, nitrolysis of hexamethylenetetramine should be carried out by first synthesizing 1,5-endomethylene-3,7-dinitro-1,3,5,7-tetraazacyclooctane and then nitrolyzing it to HMX.

This two-step process may be carried out with the isolation of the intermediate, but in technical practice it is carried out without isolation of 1,5-endomethylene-3,7-dinltro-1,3,5,7-tetraazacycloctocane from the reaction mixture. The first variant results in almost pure 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane, the second a mixture of HMX and RDX, in which HMX predominates.

According to the latest knowledge, the presence of urea and / or urea-formaldehyde condensates and / or urea-formaldehyde condensates is beneficial for the formation of cyclic nitramines in the nitrolysis of hexamethylenetetramine. as well as other acid amides and their derivatives (Czech author's certificate no. 227 903, no. 206 J82, no. 227 905 and no. 227 906). Urea was applied in the nitrolysis of 1,5-acetyl-3,7-endomethylene-1,3,5,7-tetraazacyclooctane in sulfuric acid or 1,5-diacetyl-3,7-dinitro-1,3,5,7 -tetraazacyclooctane (U.S. Pat. No. 3,926,953), in the manufacture of 1,5-endomethylene-3,7-dinitro-1,3,5,7-tetraazacyclooctane (U.S. Pat. No. 206,382) and in the manufacture of

1,3,5-trinitro-1,3,5-triazacyclohexane (cf. No. 227 905), other acid amides, resp. derivatives thereof, have been applied in the preparation of 1,3,5-trinitro-1,3,5-triazacyclohexane (U.S. Pat. No. 227 906) by nitrolysis of hexamethylenetetramine.

Swordformaldehyde condensates increase the yield of hexamethylenetetramine to 1,3,5-trinitro-1,3,5-triazecyclohexene (US Patent Nos. 227 903 and 227 905). The mechanism of action of these additives in the nitrous cleavage process has been outlined in the form of a hypothesis in two works (Czechoslovak Authorial Certificate Nos. 227 903 and 227 905). According to published data (US Pat. No. 97 100 and US Pat. No. 227 903), the presence of urea and / or urea-formaldehyde condensates in the nitrolysis mixture increases their stability and hence their safety at work.

According to the invention, a process for the preparation of a mixture of monocyclic nitramines of the general formula

N0 "

N0 _o

X

X represents - CH2 - or - CH2 --N - CH3 - with a predominantly 1,3,5,7-tetrenitro-1,3,5,7-tetraazacycloctocane content by nitration of hexamethylenetetramine in an acetic acid / acetic anhydride medium by the electrolysis process is carried out in the presence of a urea-formaldehyde condensate, preferably of the foam type, such as trimethylene-tetra to hexamethylene-hepta-urea and / or 2-keto-5-carboxamide-1,3,5-perhydro-triazine and / or urone type added to the reaction % of the system in an amount of 0.01 to 15.00% by weight, preferably 0.1 to 10.00% by weight, based on the weight of the reaction of the incoming hexamethylenetetramine.

An advantage of the present invention is, besides the possibility of applying hexamethylenetetramine with an anti-caking agent (cf. author's certificate no. 227 902), to increase the process yield, thus increasing the use of the methylene base of the starting hexamethylenetetramine. In the case of the production of a mixture of nitramines of the title type, this higher effect has not been described in the literature and in the following it is documented depending on the quality of the raw materials applied and to some extent also on the variability of reaction conditions.

The influence of macro-kinetic factors (concrete size and shape, respectively filling of the reactor) is also partially demonstrated. The effect of macrokinetic factors appears here to be the enology of the already described effect of these factors in the case of nitrosative cleavage of hexamethylenetetramine on 1,5-endomethylene-3,7-dinitroso-1,3,5,7-tetraazacycloctane (MS certificate no. 182 625). As is apparent from the example below, nitrolysis in an acetic acid-acetaldehyde medium, for maximum octogen recovery, is most preferred for the application of hexamethylenetetramine containing approximately 0.2 to 0.6% by weight of water-insoluble urea-formaldehyde condensate. . This additive in this amount is a very potent anti-caking additive of hexamethylenetetramine (US Patent No. 227,902).

He did

A three-necked 750-ml sulfonation flask is used for nitration fission, equipped with a propeller stirrer, thermometer, court burettes and jacket cooling, respectively. heating

The raw materials used are of the following quality: acetic acid 97.9%, acetic anhydride 96, **%, ammonium nitrate containing 0.31% moisture, nitric acid 99.15% containing 0.19% by weight. analytical nitric acid, hexamethylenetetramine, technical grade, containing 0.217% by weight of nitric acid; moisture content, hexamethylenetetramine non-caking (prepared according to Czechoslovak author, certificate no. 227 902 with the addition of urea-formaldehyde condensate) containing 0.201 wt. % moisture and a content (tabular overview) of urea-formaldehyde condensate containing 36.7 wt. nitrogen (preparation eg. by the author, certificate, no. 227 901) and paraformaldehyde, melting point 178-183 ° C.

The flask was charged with 75 ml acetic acid, 1.5 ml acetic anhydride and 1.7 g paraformaldehyde. At a temperature between 41 ° C and 44 ° C for 15-17 minutes, two solutions are added concurrently from the burettes, a solution of 10.1 g of hexamethylenetetramine technical grade or hexamethylenetetramine treated with urea-formaldehyde condensate in 16 ml of acetic acid and a solution of 8.7 g- of ammonium nitrate in 6.3 ml of nitric acid.

After the above solutions are added, 6 ml of acetic anhydride is added in one portion to the reaction mixture, followed by a 15-minute reaction at 45-47 ° C. 44.5 ml of acetic anhydride and a solution of 13.2 g of ammonium nitrate in 9.5 ml of nitric acid are then co-fed into the resulting reaction mixture over a period of 15 to 17 min at 45 to 47 ° C. After the addition and 60 minutes of reaction at 45-47 ° C, 35 ml of 75-85 ° C warm water were added to the stirred reaction mixture. The reaction mixture is then reflexed for 30 minutes and, after cooling to 18-22 ° C, diluted with 100 ml of cold water.

The reaction product is isolated by filtration and washed with water, then with 50 ml of about 5% ammonia water and finally twice with 50 ml of water 75-85 ° C warm. The washed product is dried at 80 ° C.

The results from the application of three kinds of hexamethylantetramine are shown in Table 1. The extracts reported in this table relate to the case where one molecule of 1,3,5,7-tetranitro-1,3,5,7-tetraazacycloctoctane and / or 1 molecule

1,3,5-trinitro-1,3,5-triazacyclohexane, in this sense, for the 100% yield of octogen, the utilization of the methylene base of hexamethylanetetramine is 66.66%.

Example 2

A cylindrical reactor with an inside diameter of 71 mm, a height of 172 mm and a bottom with a height of a guT of 29 mm is used for nitration fission. Mixing, cooling, resp. heating and dosing methods of the solutions are carried out as in Example 1.

The raw materials are of the same quality as in Example 1. Similarly, the nitrolysis itself is conducted as in Example 1, except that the first dosing solutions last for 10 min at 4-45 ° C and the second 8-14 min at 45 ° C. to 48 ° C.

The results from the application of the same three kinds of hexamethylantetramine as in Example 1 are shown in Table 2. In this Table, extracts are calculated in the same manner as in Example 1.

Example 3

Nitrolysis of hexamethylantetramine containing 1.23 wt. The urea-formaldehyde condensate obtained by curing at 100 ° C of the precondensate from 2.2 mole of formaldehyde and 1 mole of urea is passed as in Example 2. 10.4 g of treated hexamethylanetetramine are weighed 10.4 g of product containing 67.52 wt. % octogane, the yield being 32.94 wt. % octogane and 21.15 wt. hexogen compared to theory, thus the utilization of the methylene base of hexamethylantetramine is 32.53%. Compared to the nitrolysis of technical hexamethylantetramine, there is a considerably higher octogane yield.

Example 4

The nitrolysis of technical hexamethylantetramine is conducted as in Example 2, except that instead of 1.7 g of paraformaldehyde, 1 g of urea-formaldehyde condensate containing 38.9% by weight is introduced with acetic acid and acetic anhydride. nitrogen (prepared according to the author, certificate no. 227 901). 16.6 g of product with 63.14 wt. octogen, the yield being 49.18 wt. % octogane and 38.30 wt. hexogen compared to theory, thus the utilization of the methylene base of hexamethylantetramine is 51.93%.

Here, there is a markedly increased yield of both octogen and hexogen compared to the nitrolysis of industrial hexamethylenetetramine in the presence of only paraformaldehyde in the reaction mixture.

Example5

The nitrolysis of technical hexamethylantetramine and non-caking hexamethylantetramine (prepared according to the author's name, No. 227 902) is carried out as in Example 2, only the acetic acid applied is 99.1% by weight, and the acetic anhydride is 97.6%. The first dosing solution lasts 10 to 12 minutes at 44 to 46 ° C, the second then 14 to 16 minutes at 43 to 46 ° C.

The results from the application of four kinds of hexamethylenetetramine are shown in Table 3. The yields shown in this Table are calculated in the same way as in Example 1,

Example 6

The nitrolysis of technical hexamethylenetetramine is carried out as in Example 5, except that instead of 1.7 g of paraformaldehyde, only 0.6 g of this raw material is presented with acetic acid, and 0.5 g of urea-formaldehyde condensate, the origin and quality of of urea-formaldehyde condensate in Example 4. 17.4 g of product with a content of 68.70 wt. octogen. The yield was 56.08%. % of octogen and 34.11 wt. hexogen versus theory. Thus, utilization of the methylene base of hexamethylenetetramine is 54.44%.

Example 7

The procedure is as in Example 2 with raw materials of the same quality as in Example 2. The difference is that, together with the first dosing of hexamethylenetetramine and ammonium nitrate solutions, 24 ml of acetic anhydride is metered from the third burette. The first dosing is carried out for 7 to 10 minutes at 44 to 47 ° C and the second for 13 to 14 minutes at 44 to 48 ° C. The results from the application of five species of hexamethylenetetramine are shown in Table 4. The yields in this Table are calculated as in Example 1.

Example 8

Nitrolysis of hexamethylenetetramine containing 0.38 wt. The urea-formaldehyde additive is carried out as in Example 7, but instead of 1.7 g of paraformaldehyde, urea-formaldehyde condensate, of origin and quality identical to urea-formaldehyde condensate in Example 4, is presented in an amount of 0.8 g. containing 81.95 wt. octogen. The yield was 65.75%. % octogen and 19.34 wt. hexogen compared to theory, the utilization of methylene base is therefore 53.50%.

Example 9

Kitrolysis of hexamethylenetetramine is carried out in the reactor as in Example 2. The types of hexamethylenetetramine, nitric acid and ammonium nitrate used are of the same quality as in Example 1. The nitrolysis medium is formed by acetic acid and distilled acetic anhydride (b.p. 137.5-139.0 ° C). The paraformaldehyde applied has a melting point of 171-175 ° C.

To the present 75 ml of glacial acetic acid, 1.5 ml of acetic anhydride and 1.7 g of paraformaldehyde are stirred at 43 to 46 ° C. over a period of 13 to 15 minutes concurrently (proportionally) from three burettes: a solution of 10.1 g of hexamethylenetetramine in 16 ml of acetic acid, a solution of 8.7 g of ammonium nitrate in 6.5 ml of nitric acid and 24 ml of acetic anhydride. After these solutions were added, 6 ml of acetic anhydride was added in one portion to the reaction mixture and then allowed to react at 44-47 ° C for 15 minutes.

In addition, 44 ml of acetic anhydride and a solution of 13.2 g of ammonium nitrate in 9.5 ml of nitric acid are dosed proportionally from two burettes over a period of 8 to 11 minutes at 44 to 48 ° C. After the addition and after 60 minutes of reaction at 44 to 47 ° C, 35 ml of 75 to 85 ° C warm water are added to the reaction mixture. The mixture is further refluxed for 30 min under reflux. Then it is diluted with 100 ml of water and cooled to 15-20 ° C with stirring. The resulting suspension is filtered and the product on the filter is processed as in Example 1. The results of the individual experiments with different types of hexamethylenetetramine are shown in Table 5.

Example 10

The procedure is as in Example 9. Technical hexamethylenetetramine is used. After the first solutions and acetic anhydride are metered in and after 15 minutes of reaction, 0.05 g of urea-formaldehyde condensate with a nitrogen content of 38.9% by weight is added to the reaction mixture. This gives 15.54 g of a mixture of nitramines with a content of 87.12% by weight. octogen. The yield is 63.55% octogen and 12.52% hexogen, compared to theory, the utilization of methylene base is not 48.63%.

Přikladli ‘

The procedure is as in Example 9 except that paraformaldehyde is replaced by 0.75 g of urea-formaldehyde condensate containing 38.9% by weight. nitrogen. Technical hexamethylenetheramine is applied. 15.73 g of a mixture of nitramines, containing 3.11 wt.

% 1,5-endomethylene-3,7-dinitro-1,3,5,7-tetraazacycloctane, 76.28 wt. % of octogen and 20.61 wt. hexogen. Yield 56.32% octogen and 20.28% hexogen over theory. The methylene base utilization of hexemethylenetetramine is 50.30%.

T a b u 1 'k a 1

Additive content in HMT (56 wt.) HMX content of the product (% by weight) Yield in g Yield versus theory in% on pure HMT Utilization of methylene base HMT (%) mixture HMX RDX HMX RDX 0.00 71.90 7.2 5.18 2.02 24.31 12.64 22.53 0.38 72.38 7.6 5.50 2.10 25.91 13.19 23.87 1.06 75.04 8.2 6.15 2.05 29.17 12.97 25.93 Focn .: additive - urea-formaldehyde condensate Hi-fi' = hexamethylenetetramine Table 2 Content of the additive HMX content v Yield in β Yield versus Use of me- in HMT (% by weight, produkte mixture HMX RDX theory in% to tylene bézy (% by weight, pure HMT HMT (%) HMX RDX 0.00 64.66 10.8 6.98 3.82 32.76 23.91. 33.79 0.38 64.95 12.6 8.18 4.42 38.53 27.76 39.56 1.06 66.19 H.1 9.33 4.77 44.25 30.17 44.60

Note: urea-formaldehyde condensate additive HMX> hexamethylenetetremine

Table 3

Additive content in HMT (% by weight) HMX content of the product (% by weight) Yield in g Yield vs.% in pure HMT Utilization of methylene base HMT (%) mixture HMX RDX HMX RDX 0.00 75.62 10.5 7.94 2.56 37.26 16.02 32.85 0.10 69.71 10.7 7.46 3.24 35.04 20.29 33.50 0.38 68.95 11.6 8.00 3.60 37.68 22.61 36.42 1.06 67.04 15.1 10.12 4.97 47.99 31.43 47.71

Note additive = urea-formaldehyde condensate

HMT = hexamethylenetetramine

Table 4

Additive content in HMT (% by weight) HMX content in the product wt.) Extracts in g Extracts vs. theory in% on pure HMT Utilization of methylene base 'HMT% mixture HMX RDX HMX RDX 0.00 80.30 17.10 13.33 3.37 64.44 21, 44 53.50 0.10 80.08 17.15 13.73 3.42 64.49 21, 42 53.70 0.38 79.31 17.20 13.64 3.56 64.25 22.36 54.01 0.50 79.20 17.30 13.70 • 3.60 64.61 22.64 54.39 1, 06 78.76 17.60 13.86 3.74 65.73 23.65 55.64

Note: additive = urea-formaldehyde condensate HMT W hexamethylenetetramine

IN

Τ β b u I k a 5

Additive content in HMT (% wt. HMX content of the product (wt. Yield in g Extracts versus theory in% on pure HMT Utilization of HMT methylene base (%). mixture HMX RDX HMX RDX 0.00 81.18 14.52 11.79 2.73 55.33 17.09 45.43 0.05 81.40 14.81 12.05 2.76 56.57 17.28 46.35 0.10 83.60 15.70 13.12 2.58 61.62 16.16 49, -16 0.38 85.80 15.80 13.55 2.25 63.82 14.13 49.61 0.50 86.24 15.75 13.58 2.17 64.04 13.65 49.52 1.06 89.10 15.00 13.36 1.64 63.36 10.37 47.42

Note: additive = urea-formaldehyde condensate HMT = hexamethylenetetramine

Claims (1)

A process for the preparation of a mixture of monoeylic nitramines of the general formula wherein X represents - ch ₂ NO, I ² or - CH, - N - CHg - and a predominant content of 1,3,5,7-tetranitro-1,3,5,7-tetraazaoyclooctane by nitration of hexamethylenetetramine in acetic acid and acetic anhydride media, characterized in that the process is The nitrolysis is carried out in the presence of a urea-formaldehyde condensate, preferably of the foam type, such as trimethylene tetra to hexamethylanehepta-urea and / or 2-keto-5-carboxamld-1,3,5-perhydrotriazine and / or a urone type added to the reaction system. from 0.01 to 15.00% by weight, preferably from 0.1 to 10.00% by weight, based on the weight of the hexamethylenetetramine entering the reaction.