CS227903B1

CS227903B1 - A method for producing 1,3,5-trinitro-1,3,5-triazacyclohexane

Info

Publication number: CS227903B1
Application number: CS739879A
Authority: CS
Inventors: Svatopluk Ing Zeman; Milan Ing Dimun
Original assignee: ZEMAN Svatopluk; Dimun Milan
Priority date: 1979-10-31
Filing date: 1979-10-31
Publication date: 1984-05-14

Abstract

Vynález sa zaoberá nitrolýzou hexametyléntetramínu vedenej k 1,3,5-trinitro- -1,3,5-triazacyklohexanu v přítomnosti produktu kondenzácie močoviny s formaldehydom v množstve 0,01 až 10 % hmot. počítané na hexametyléntetramín.The invention deals with the nitrolysis of hexamethylenetetramine leading to 1,3,5-trinitro-1,3,5-triazacyclohexane in the presence of the condensation product of urea with formaldehyde in an amount of 0.01 to 10% by mass. calculated on hexamethylenetetramine.

Description

DESCRIPTION OF THE INVENTION

ON THE CERTIFICATE OF CERTIFICATE BY THE CZECHOSLOVAK SOCIALISTICPUBLIC (19)

(22) Registered 31 10 79 (21) (PV 7396-79) 227903 (Π) (BI) (51) Int Cl.3 C 07 D 251 / 04C 07 C 111/00

OFFICE OFFICE

AND DISCOVERIES (40) Published 27 08 81 (45) issued 15 05 66 (75)

The inventor of ZEMAN SVATOPLUK ing., MICHAL0VCE, DIMUN MILAN ing., PRIEVIDZA (54) Method of production of 1,3,5-trinitro-1,3,5-triazacyclohexane

The present invention relates to the nitrolysis of hexamethylenetetramine to 1,3,5-trinitro-1,3,5-triazacyclohexane in the presence of a urea condensation product with formaldehyde in an amount of 0.01 to 10% by weight. to hexamethylenetetramine. 227903 227903 2

The present invention relates to the preparation of 1,3,5-tritonitro-1,3,5-triazacyclohexane by nitrolysis of hexamethylene tetramine.

Mistolysis of hexamethylenetetramine with nitric acid over 80% by weight 56 wt. One of the most extensive methods for the industrial production of 1,3,5-trinol-1,3,5-triaza-cyclohexane. This nitration splitting is a complicated set of subsequent and side reactions of nitro-hydrolysis, hydrolytic, neutralization and oxidation. The relative abundance of exchanged events is determined by the reaction sub-variables.

Reactions nitro-producing produce! from hexamethylenetetramine not only 1,3,5-trinitro-1,3,5-triazacyclohexane and in its small diameter its cyclic homolog 1,3,5,7-tetranitro-1,3,5,7-tetraazaeycoctane and cyclic ether 3, 5-dinltro-1-oxo-3,5-acyclohexane, but also linearnitramines, namely nitroesters of 1,7-dihydroxy-2,4,6-trltro-2,4,6-triaazaheptene 1,9-dihydroxy-2 , 4,6,8-tetranitro-2,4,6,8-tetraazanonane, 5-trimethylolaain and formel-dehyd.

The presence of these products in the reaction mixture depends mainly on the starting molar ratio of nitric acid to hexamethylenetetraamine. the concentration of applied nitric acid and the temperature of the reaction. In New Literature (for example, X. Ju Orlova:

Ghimija i technologi ja brizantny vzryvchych veščestv. Izdat. Chimija, 1973), the starting molar ratio of nitric acid to hexamethylenetetramine is stated to be an increasingly high yield of 1,3,5-trnnotro-1,3,5-triazacyclohexane raatle.

This is not the case, as indicated in the primary work in this field (Chutě JW et al .: Canad. J. Res. 1949, 27 B. 218; Dunning W. et al .: J. Chem. Soc. 1992. 1264) however, there is a certain optimum dissolution of this molar ratio, depending on the concentration of nitric acid and the nitric acid content therein.

For nitric acid, about 96% and more concentrated, the most preferred molar ratio of nitric acid to hexamethylenetetramine is from 21 to 24 in terms of yield. Below this range, the decrease in product yield is due to a decrease in the concentration of nitronic acid. nitroxonium ions in the reaction mixture.

The snake indicated the range of optimal molar ratio, probably due to the cleavage of hexamethylenetetramine to linear nitramines due to the higher concentration of nitroonium, respectively. nitroxonium ions in the mixture, and the process yield decreases. This is exemplified by the exemplary part of the present invention.

If a nitric acid concentration is to be mentioned, it should be noted that the nitrolysis capacity is at least 80% nitric acid. Below this concentration, hydrolytic processes dominate the cleavage of hexamethylenetetramine. For the processes of hydrolytic processes, the presence of water in the applied hexam, ethylene tetrarine is favorable.

The reactions produce neutralizing ammonium compounds in the reaction mixture, and the formation of nitroesters from methylol-containing hexamethylenetetramine fragments or the formation of methylenedinitrate from formaldehyde can also be excluded.

Optimally the nitrousysis temperatures of the hexamethylenetetramine with nitric acid are in the range of 15 to 25 ° C. Conducting the process at very low side temperatures to form 1,3-dinitro-1,3,5-triazapentane nitrate, 3,5-dinitro-1,3,5-triazaeyclohexane nitrate and methylene bis - 1- / 3,5- dinitro-1,3,5-triazacyclohexene / as final products (Dunning KW and DunningW. J .: J. Chem. Soc. 1950. 2920; Vroom AH and Winkler CA: Canada, J. Res. 1950, 28 B. 701; Chutě WJ et al .: Canad. J. Res. 1948, 27 E. 503 /. Conducting the process at temperatures up to 30 ° C, the proportion of hydrolytic-oxidative reactions to the consumption of hexamethylenetetramine decreases, thereby decreasing the yields of 1,3,5-trinitro- 1,3,5-triazacyclohexane and also reduce process safety 3 227903 The presence of nitrous acid or nitrogen oxides in the reaction mixture is favorable for the oxidation reactions. Their suppression, that is to say, stabilization of the hydrolysis mixture, has already been given attention in literature (V. Kadeřábek and J. D enkstein: Goll, Czeoh, Chem Commun, 1960, 25, 1070, Czechoslovakia Patent δ. According to published data, the stability of these mixtures with increasing storage temperature decreases, with the increasing molar ratio of nitric acid to hexamethylenetetramine, with increasing concentration of applied nitric acid and increasing nitrous acid contents of the applied. nitric acid.

Since nitrous acid, respectively. Nitrogen oxides, as an effective oxidizing agent and as a catalyst for nitric acid oxidation reactions with organic compounds, the presence of these substances in the nitric acid used has a substantial negative effect on the stability of the corresponding reaction mixtures. Nitrous acid-reactive substances, respectively. with nitrosonium and that, therefore, stable insoluble mixtures. In this regard, hexamethylene tetramine and / or ammonium nitrate / V. Kadeřábek and J. Denkstein: Coll. Czech. Chem. Commun.1960, 25, 1070, in an amount of 0.1 to 80.0% by weight. for the initial loading of hexamethylenetetraamine (CSK Patent No. 97 100).

An analogous method of stabilizing the reaction mixtures, even during the reaction, is customary in the preparation of n-alkyl nitrates; in this case, urea is added to the nitric acid or nitric acid mixture prior to starting the reaction in an amount of 0.5 to 3.0% by weight. on the weight of the nitrating acid (CSSR author certificate 168 189).

Urea stabilization of the nitrolysis mixture with urea can be documented by the preparation of 1,5-dimethyl-3,7-dinitro-1,3,5,7-tetraazaecyclooctane, whereby urea is added to the starting 5-endomethylene-3,7-diacetyl- 1,3,5-7-tetraazacycloctene (U.S. Pat. No. 3,926,953).

According to the present invention, the process for the preparation of 1,3,5-trinitro-1,3,5-triazacyclohexane non-lysamethylenetetramine at a temperature of -20 to 51.8 [deg.] C. and subsequent product isolation is to add to the reaction system the nitrolysis process 0.01 to 10% by weight, calculated on the hexamethylenetetramine, of a product of condensation of urea with formaldehyde, preferably a pan type, separately and / or in admixture with the reactants involved, preferably in a mixture with hexamethylenetetramine. An advantage of the present invention is to increase the stability of the nitro-dissolving compositions and the resulting process safety, as well as to significantly influence the yield of 1,3,5-tritro-1,3,5-triazacycyclohexane. In the case of the use of a mixture of hexamethylenetetramine with urea-formaldehyde condensate, due to the fluidity of the system, inter alia, uninterrupted trimming is achieved.

Suitable additives during the nitrolysis according to the invention have shown in water and in organic solvents insoluble urea-formaldehyde condensates formed by the urea-formaldehyde reaction, preferably in an acid medium (e.g., U.S. Pat. No. 227,901, U.S. Pat. Nos. 3,981,845 and 4). 081 741). Good results are also obtained by using in water and organic solvents soluble condensates of suitable chemically or thermally modified condensates.

Excellent results give urea-formaldehyde additives with a large reaction surface, which is achieved by using them in foamed form. Relatively wide range of published methods for obtaining of suitable suitable types of foams is the disassembled bibliography, Berlin AAsutov F. A: Penopologists on the warp of reactionary oligomers of Izdat. Moscow, Chimija, 1978; AMM, AM, Salyer I, Polym., Plast. Technol. Eng., 12 (1), 61-88 (1979)]. 227903 4 In the application of urea-formaldehyde condensates for the treatment of hexamethylenetetraamine, author's guideline 8. 227902 is a measure of increasing the stability of the proportions of the condensates contained in hexamethylenetetramine. The presence of urea-formaldehyde condensates in nitrolysis according to the invention affects the yields of 1,3,5-trinitro-1,3,5-triazacyclohexane. There is some optimum content of said condensates in the hexamethylenetetramine used, which increases the yield of the process, calculated on the weight of the treated hexaraethylenetetramine. For a nitric acid of at least 96.6% and an optimum starting molar ratio of nitric acid to hexamethylene tetramine of 21.5 to 24.5, the present invention has the highest yield at 1.2-1.4% by weight of urea-formaldehyde condensate in applied hexamethylenetetramine ,

Exceeding the content of this additive, the 1,3,5-trinitro-1,3,5-triazacyclyclohexane yield begins to decrease and the process yield rate with hexamethylenetetremine without additive at a content of 2.5 to 3.0% by weight of urea-formaldehyde condensate in hexamethylenetetramine. However, in the monitored range of 0.009 to 9.09% by weight of urea-formaldehyde condensate in the applied hexamethylenetetramine, the use of the methylene base of hexamethylene-tetramine and the additive is higher than in the nitrolysis of hexamethylenetetramine without the additive. Taking into account the published data on the mechanism of nitration cleavage of hexamethylene tetramine (GF Wright, published by H. Feuer, edited by The Chemistry of Nitro and Nitroso Groups. Part 1 John Wiley, 1969, pp. 653-654) could be favorable the effects of urea-formaldehyde condensates on yields of 1,3,5-trinitro-1,3,5-triazacyclohexane interpreted as follows: with respect to the presence of electronegative carbonyl groups in the molecule, the urea-formaldehyde condensates in the given reaction medium generate carbammonium ions.

These tones could then participate in equilibria prior to, in particular, cleavage of hexamethylenetetramine to undesirable products and / or combined with the structurally convenient hexamethylenetetramine fragment to the perhydro-1,3,5-triazine cycle. For example, other fission reactions of hexamethylene-tetramine, namely nitroso-cleavage in weakly acidic environments, are indicative of equilibrium recovery: there is a (optimally) amount of free formaldehyde or free ammonia in the applied aqueous solution of hexa-methylenetetramine to increase the yield of the product to which it is 1,5-endomethylene-3,7-dinitroso-1,3,5,7-tetraazacycloctane (CSSR author's certificate S. 191 380).

The process for the nitrolysis of hexamethylenetetramine in the presence of urea-formaldehyde condensates based on the converted literary and patent research is novel, not described in the literature. The method as well as the higher effect of the process according to the invention are illustrated by the following examples. EXAMPLE 1 To 115 parts by volume of 96.9% nitric acid (2.646 moles of nitric acid) containing 0.37% by weight of nitric acid. 15% by weight of analytical acid added in a stirred nitration apparatus under vigorous external cooling for 3 minutes. parts of hexa-methylenetetramine containing 2.83 wt. moisture and in the next two experiments the content of urea-formaldehyde condensate. Cooling of the reaction mixture was large so that its temperature did not exceed 33 ° C and was mostly in the range of 25 to 28 ° C.

After the hexamethylenetetramine was introduced, a 40 minute reaction was carried out at 25-25 ° C. Subsequently, the nitrolysis mixture was poured into 400 parts by volume of water 60-65 ° C and after 10 minutes of stirring the resulting slurry the product was isolated by filtration. After dolconal washing with hot water, 1,3,5-trinitro-1,3,5-triazacyclohexane was dried for 40 hours at 55-60 ° C. 5 227903 The following tabular dams present results:

The content of urea-formaldehyde condensate in hexamethylenetetramine (% w / w) Number of dosed moles of hexamethylene tetramine Yield of product melting point (° C) in weight% in weight per weight of hexamethylene tetramine treated to pure hexamethylenetetramine 0 0.104 17 1 71.94 74.02 205 to 206 3 0.3 00 16.7 70.26 74.54 206 to 207 5 0.098 16.6 69.84 75.66 206 to 207

The amount of raw materials applied corresponds to the mass. the ratio of nitric acid to hexa-methylenetetramine = 11.477. Example 2. Hexamethylenetetramine containing 1.31 56 wt. humidity, resp. the same product treated with 15% by weight of urea-formaldehyde condensate; parts are introduced into the mixed and heavily cooled 96.6 56-nitric acid and containing 0.10 56 wt. Acid. Dosage and early cooling of the nitrating mixture is such that the hexamethylenetetramine recharging does not exceed 3 minutes and the mixture temperature ranges from 24 to 29 ° C. After the introduction of hexamethylenetetramine, the reaction is carried out for 40 minutes at a temperature of 24 to 29 ° C and then the reaction mixture is poured into 100 times the volume of water, warming 60 to 65 ° C, such as the volume of nitric acid applied. After 1 s min treatment of the resulting suspension, the product is isolated by filtration, washed thoroughly with H 2 O (3 x 100 vol, vol) and dried at 55-60 ° C. The dry product was recrystallized from acetone: 10 wt. The product was dissolved in 100 volumes of acetone at boiling and after the solution was filtered, 50 volumes of distilled water was added to the filtrate. After 30 min, the resulting suspension was filtered and the product dried at 55-60 ° C. Crystalline Extracts 8.1 wt. parts up to 8.4 wt. of 1,3,5-trinitro-1,3,5-triazacyclohexane.

Results Overview presents tabular dams on page 31.

Based on a graphical comparison of the yield and the additive content in hexamethylenetetraamine, it was found that the optimum amount from 1.2 to 1.4 56 wt. urea-formaldehyde condensate in hexa-methylenetetramine.

Similarly, based on the graphical confrontation of yield and molar ratio of reactans, it has been found that under the given reaction conditions the molar ratio of nitric acid to hexamethylenetetramine is 21.5 to 24.3. 227903 6

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Remarks: Additive = Moisturomaldehyde CondenserHMT = Hexamethylenetetraiain 7 227903 Example 3 106 Volumetric 99.09% Nitric Acid; (2.520 Nitric Acid Sol); hexa-methylenetetramine in an amount of 15 parts by weight in the nitrous and apparatus cooled to 20 ° C, and the hexa-methylenetetramine was introduced into the cooling and vigorous cooling; hexamethylanetetramine was obtained by drying the hexamethylenetetramine from Example 2 for 48 hours at 50-54 ° C.

The temperature of the mixture while introducing hexamethylanetetramine was kept below + 15 ° C. A 30-ml reaction at 15 to 19 ° C was performed under-dose. Then, the reaction mixture was poured into 400 volumes of hot water parts of 60-65 ° C. After stirring the suspension for 10 minutes, the product was isolated by filtration and washed three times with 100 volumes of diatomaceous water.

The thermal stability of the resulting nitrolysis mixtures was specified by the isothermal differential analysis. The procedure was identical to that of the nitrolysis except that the dilution of the nitrolysis mixture was not carried out; the reaction mixture was placed in a tempered water bath; the isothermal temperature of the nitrolysis mixture was 51.2 * 0.6 ° C.

In thermal exposure! the atmospheric staining of the reaction mixture 6 by Ke-Co terno cells was visually observed; The xenoblastic decomposition of the nitro-lysis mixture always preceded the mist-staining of the atmosphere without the oxide mixture. nitrogen and the time corresponding to this phenomenon was recorded as the induction period of nitrogen oxides. The results obtained in this report are presented in the tabular overview on page 14.

By graphically confronting the additive content and yield, calculated on the weight of the treated hexamethylenetetramine, it has been found that a maximum yield of 1.3% 5-trintrose-1,3,5-triazacyclohexane is achieved by a content of 1.2 to 1.4. & % by weight of urea formaldehyde condensate in applied hexamethylenetetrin. According to the same method, the nitrolysis of hexamethylanetetramine without adulteration is equivalent to nitrolysis of said substance, with the exception of 2.7% by weight. urea-formaldehyde condensate. The result is from the tabular overview on page 14, the extracts of 1,3,5 + trinitro-1,3,5-triazacyclohexane, calculated on the hexamethylanetetramine content in the batch, in the observed range of urea-formaldehyde condensate in the weight higher than the nitrolysis of hexamethylanetetramine without the additive .

Thus, in the observed range of additive content in the hexamethylanetetramine applied, the use of hexamethylanetetramine ethylene base is higher than that of nitrolysis without the presence of urea-formaldehyde condensates. 227903 8 gs co -> 90 «« Or> H * H ti Oo 0 6 £ a >> I 3

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Nitrolysis of hexamethylenetetramine containing 0.21 wt. the moisture was conducted through a non-technological device consisting of a first nitrore, a second nitrator, a crystallizer, an apparatus for cooling the slurry, a continuous J-flare and apparatus on a stabile product.

Nitric acid 99.09% -vA and a content of 0.09% wt. analytical nitrous acid and hexamethylanetetramine containing 0.21% moisture. Feeding of the raw materials was conducted to 1 wt. hexamethylenetetramine adhered to 10.7 wt. nitric acid.

By cooling, the temperature in the first nitrate is maintained between 17 and 22 ° C. The contents of the first controller continuously flow into the second nitrator with a working temperature of max. 24 ° C.

The total retention of both nitrates is 44 minutes. From the second nitrator, it is nitrolyzed and fed to a crystallizer where a temperature of 70 to 80 ° C is maintained and at the same time water (washing water from the continuous filters) is supplied at 4.7 volumes, parts per weight. dieldo reaction of taken hexamethylenetetramine. From the crystallizer, the product slurry in 54.8% nitric acid is passed through a stirred cooling apparatus where it is cooled to 30-40 ° C into continuous filters where nitric acid is separated and the product is washed with water. From the continuous filter, the product filter cake is flushed with water and the resultant suspension is pumped into the stabilizing apparatuses by the steam ejector, where the acidity of the crystals is reduced to below 0.05 wt% by direct vapor heating. nitric acid. 1,3,5-trinitro-1,3,5-triazacyclohexane is obtained after isolation of the filtrate in an amount of 1.177 wt. parts dry on 1 wt. part of the hexamethylenetetramine reaction, 74.3% over theory. Example 5

The nitrolysis of hexamethylenetetramine was conducted as in Example 4. The dosed hexamethylene tetramine of the starting quality as in Example 4 was converted to a treated 1.30% wt content by incorporation into a non-electrolytic mixture. urea-formaldehyde condensate. From 1 wt. 1,248 parts by weight of 1,3,5-trinitro-1,3,5-triazacyclohexane, i.e. 78,76% of the product yield of the treated hexamethylene tetramine and 80,01% of the theory calculated by the to the hexamethylenetetramine content in the feed. The present invention is applicable to all hexamethylene-tetramine nitrolysis processes leading to 1,3,5-trinitro-1,3,5-triazacyclohexane. The importance of the essence of the invention and its unpretentious design gives the possibility of its early use in the production of this highly used explosive in the Czech Republic as well as abroad.

Claims

227903 10 ET DM E DM ET EMBODIMENT OF THE PRODUCTION OF 1,3,5-TRINETRO-1,3,5-TRIAZACYClohexane by Nitrolysis of Hexamethylenetetraamine Pr1 -20 and + + 51,8 ° C and Subsequent Product Isolation In the electrolysis process, 0.01 and 10% by weight are added to the reaction system. counted nahexamethylenetetramine, a urea-formaldehyde condensate product, preferably a foam type, separate and / or mixed with the reactants involved, preferably in a hexamethylenetetramine.