DE2164169B2 - Process for the production of 13- or M-bis-aminomethyl-cyclohexane - Google Patents

Description

The invention relates to a new process for the production of 1,3- or 1,4-bis-aminomethyl-cyclohexane by catalytic hydrogenation of m- or p-xylylenediamine at 70 to 150 ° C, a pressure of 50 to 500 kg / cm ² in the presence of a solvent and using a ruthenium catalyst, which is characterized in that the hydrogenation is carried out in liquid ammonia as the solvent and a concentration of m- or p-xylylenediamine in the ammonia solution of 5 to 80% by weight is maintained.

It is known that polyamides are made from bis-aminomethylcyclohexanes and an organic dibasic acid such as adipic acid or sebacic acid can be and have good properties. It is also known that using bis-aminomethyl-cyclohexanes Polyurethanes produced as raw materials for the production of elastic fibers, Molded articles or films with extremely high light resistance can be used. Bis-aminomethyl-cyclohexanes have also been used as hardeners for epoxy resins.

The following processes for the production of bis-aminomethyl-cyclohexanes were previously known:

COOH

COOH

COOH

CONH ₂ ^

CN

CH ₂ NH ₂

(Reports of the German Chemical Society, Vol. 71, pp. 759-767 [1938]).

CH

CH ₂

(US-PS 3,012,994)

CN

CN CHO CN

CO H

'H I + I H

CH ₂ NH ₂ CH ₂ NH ₂

CH ₂ NH ₂

CHO

CH ₂ NH ₂

CH ₂ NH
(Japanese Patent 459199)

CH ₂ NHCOR
H ₂ O

CH ₂ NHCOR

CH ₂ NHCOR

CH ₂ NH ₂

CH ₂ NH ₂ CH ₂ NH ₂

(Japanese Patent 517236)

However, these conventional methods have disadvantages. Method 1 is through Hydrogenation of phthalic acid obtained cyclohexanedicarboxylic acid is relatively unstable. It also has the process has many steps and is complicated, so that the yield is low. In method 2, although the condensation reaction of 1,3-butadiene and acrylonitrile proceeds quantitatively, the yield in the stage of the oxo reaction is low. aside from that varies, although 13-bis-aminomethylcyclohexane and 1,4-bis-aminomethylcyclohexane produced together the relationship of one product to another is strong, and accordingly the quality is not uniformly. In method 3, the xylylenediamine used as the starting material is acylated beforehand, then hydrogenated, then hydrolyzed the acyl group with acid or alkali and the reaction product with ether or cyclohexane extracted. The yield of bis-aminomethylcyclohexanes is therefore low. In method 4, water or an organic acid is used as Solvent used Here, too, the yields are low. When using an organic acid are In addition, the materials for the reaction vessel are limited. The amine must also only be added by adding Alkali are released.

In JA-PS 26 783/67 a process for the preparation of cis-cyclohexane-bis-methylamine is carried out catalytic ^ hydrogenation of xylylenediamine using a rhodium oxide catalyst. as Solvents are aqueous solutions of acetic acid or other organic acids, such as Propionic acid, or water is used. The response time in performing this procedure is up between 2 and 4 hours, while the process according to the invention only has a reaction time of 75 minutes or less is required. This considerable reduction in response time enables industrial implementation of the method according to the invention and weighs any due to the use of ammonia related disadvantages.

In "Journal of American Chemical Society", Volume 75, 1953, pages 1156-1159, the preparation of Bis-4-aminocyclohexyl-methane by catalytic hydrogenation of bis-4-aminophenyl-methane in the presence of a ruthenium catalyst using dioxane described as a solvent and ammonia as an adjuvant. The yield achieved is well below that yield achievable according to the invention. An indication of a yield improvement by omitting the Dioxane is not given anywhere.

In all known processes for the hydrogenation of xylylenediamines in the presence of a ruthenium catalyst methylbenzylamine and aminomethyl-methylcyclohexane are formed as by-products. Under mild reaction conditions, part of the xylylenediamine is not converted, so that the yields of bis-aminomethylcyclohexane were unsatisfactory. Because of the impurities that the final Distillation interfered, reached the yield of bis-aminomethylcyclohexanes only values from 60 to 65 mol%.

The inventive use of liquid ammonia as a solvent results in the formation of by-products, such as methylbenzylamine or aminomethyl-methylcyclohexane, are reduced considerably and the yield of bis-aminomethylcyclohexanes by 7 to 20 mol% over usage of a solvent other than liquid ammonia

A rhodium or platinum catalyst is for that

intended hydrogenation not useful, since the activity of such a catalyst by the The catalyst poisoning effect of amines and ammonia is reduced too much.

In the process according to the invention, hardly any impurities are formed, so that a final yield is achieved Bis-aminomethylcyclohexanes from 82 to 89 mol% can be obtained.

According to the invention, m- or p-xylylenediamine is used as the starting material in such an amount that the concentration in the ammonia solution is 5 to 80% by weight, preferably 10 to 60% by weight. The reaction temperature is from 70 to 15O ⁰ C, preferably 90 to 13O ⁰ C, and the reaction pressure is 50 to 500 kg / cm ^2, preferably 100 to 250 kg / cm ^2. Under these conditions, 1,3-bisaminomethylcyclohexane is produced in good yields from m-xylylenediamine and 1,4-bis-aminomethylcyclohexane from p-xylylenediamine.

If the concentration of m- or p-xylylenediamine in an ammonia solution is lower than 5% by weight, the space-time yield drops, while if it is over 80% by weight, the selectivity of the catalyst becomes worse. Even if the reaction temperature rises above 150 ° C, side reactions are liable to occur, while the space-time yield decreases at a work below 70 ^0C. Even if the reaction pressure is below 50 kg / cm ² , the space-time yield drops, while at a pressure above 500 kg / cm ^2, side reactions occur to a large extent.

The ammonia used as a solvent in carrying out the process must be liquid Be ammonia. With ammonia water or ammonia alcohol the effect of the invention cannot be achieved.

The ruthenium catalyst used according to the invention contains ruthenium as an active component, Ruthenium oxide or ruthenium hydroxide. The catalyst can be in the form of a single catalyst component can be used, ruthenium oxide being appropriate and in particular RuC «2 being the most suitable. Farther the active catalyst component can be present on a carrier, for example aluminum oxide, diatomaceous earth or coal. If a carrier is used, the amount of the active catalyst component is 0.1 up to 10% by weight, preferably 0.5 to 5% by weight, based on the total amount of the catalyst.

The amount of catalyst to be used is 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the amount of m- or p-xylylenediamine.

One can either use batchwise using an autoclave or continuously using a fixed bed or fluidized bed reactor work.

In the case of a batch production, the reaction is below the above within 30 minutes to 3 hours specified reaction conditions ended. In a continuous production, the liquid space velocity is the ammonia solution of xylylenediamine below 7 / hour and preferably at 0.5 to 5 / hour.

The starting material can be prepared by hydrogenating isophthalic acid with ammonia as a solvent in Presence of a nickel and / or cobalt catalyst can be produced.

Since both the process according to the invention and the process for the preparation of m- or p-xylylenediamine Ammonia is needed as a solvent, it is

possible, for example!, S-bis-aminomethylcyclohexane continuously produced from isophthalic acid. This continuous manufacturing process is very advantageous.

The invention is illustrated by the following examples. Comparative examples using Solvents other than liquid ammonia also explain the technical aspects that can be achieved progress

| O

example 1

A shaking autoclave with a capacity of 100 ml was charged with 13.6 g of m-xylylenediamine, 3 g of a catalyst composed of 5% by weight of ruthenium on a carbon support and 20 g of liquid ammonia. Then hydrogen was continuously supplied up to a pressure of 200 kg / cm ^2, and the hydrogenation was conducted at a reaction temperature vori ¹ 105 ° C. The absorption of hydrogen was complete in 70 minutes. The resulting reaction solution was applied, filtered and the filtrate analyzed for the products. The yields were 87.3 mol% 1,3-bisaminomethyl-cyclohexane, 3.6 mol% 3-methylbenzylamine, 4.5 mol% 1-aminomethyl-S-methylcyclohexane and a trace of m-xylylenediamine.

The hydrogenation was carried out under the same reaction conditions as before, only was Methanol is used instead of the liquid ammonia. The reaction solution obtained was filtered and the filtrate obtained analyzed for the products. The yields were 71.6 mol% 1,3-bis-aminomethylcyclohexane, 11.2 mol% 3-methylbenzylamine, 10.8 mol% l-aminomethyl-3-methylcyclohexane and 0.3 mol% m-xylylenediamine.

Comparative example

35

Experiment with a solvent mixture of dioxane and ammonia (J. Am. Chem. Soc, 75, 1953, p. 1157).

The procedure described in Example 1 was repeated, with the exception that 10 g of dioxane and 10 g liquid ammonia was used instead of 20 g of liquid ammonia. The yields are 73.9 mol% 1,3-bis-aminomethylcyclohexane, 9.3 mol% 3-methylbenzylamine, 11.9 mole percent 1-aminomethyl-3-methylcyclohexane and a trace amount of m-xylylenediamine.

Example 2

The same autoclave as in Example 1 was charged with 13.6 g of m-xylylenediamine, 0.3 g of ruthen oxide and 30 g of liquid ammonia. Hydrogen was then continuously supplied up to a pressure of 150 kg / cm ² , and hydrogenation was carried out at a reaction temperature of 110 ° C. The absorption of hydrogen was complete in 65 minutes. The reaction solution obtained was discharged, filtered, and the filtrate was analyzed for products. The yields were 87.1 mol% 1,3-bis-aminomethylcyclohexane, 5.0 mol% 3-methylbenzylamine, 4.7 mol% l-aminomethyl-3-methylcyclohexane and 0.1 mol% eo m- Xylylenediamine.

The hydrogenation was carried out under the same reaction conditions as before, except that it was water used instead of liquid ammonia. The reaction solution obtained was used to separate the Catalyst filtered and the filtrate was analyzed. The yields were 73.2 mol% 1,3-bis-aminomethylcyclohexane, 11.3 mole percent 3-methylbenzylamine, 9.7 mole percent 1-aminomethyl-3-methylcyclohexane, and 0.4 Mole percent m-xylylenediamine.

Example 3

The same autoclave as in Example 1 was charged with 13.6 g of m-xylylenediamine, 3 g of a catalyst composed of 5% by weight of ruthenium on a γ-alumina support and 25 g of liquid ammonia. Hydrogen was then continuously introduced up to a pressure of 150 kg / cm ² , and the hydrogenation was carried out at a reaction temperature of 115 ° C. The absorption of hydrogen was complete in 75 minutes. The reaction solution obtained was discharged, filtered to separate the catalyst and examined for products. The yields were 87.1 mol% 1,3-bisaminomethylcyclohexane, 3.8 mol% 3 methylbenzylamine, 2, 9 mole percent 1-aminomethyl-3-methylcyclohexane and 0.2 mole percent m-xylylenediamine.

The hydrogenation was carried out under the same reaction conditions as before, except that 25 g 28% strength by weight ammonia water were used instead of liquid ammonia. The reaction solution obtained was filtered to separate the catalyst and analyzed for products The yields were 76.1 mol% 1,3-bis-aminomethylcyclohexane, 10.6 mole percent 3-methylbenzylamine, 8.6 mole percent 1 aminomethyl-3-methylcyclohexane and a trace of m-xylylenediamine.

Example 4

The same autoclave as in Example 1 was charged with 13.6 p-xylylenediamine, 20 g of a catalyst composed of 5% by weight of ruthenium on a carbon support and 20 g of liquid ammonia. Hydrogen was then continuously supplied up to 200 kg / cm ² and the hydrogenation was carried out at a reaction temperature of 105 ° C. The absorption of the hydrogen was complete in 65 minutes. The reaction solution obtained was discharged, filtered to separate off the catalyst and examined for products. The yields were 88.4 mole percent 1,4-bisaminomethylcyclohexane, 3.2 mole percent 4-methylbenzylamine, 3.4 mole percent 1-aminomethyl-4-methylcyclohexane, and 0.1 mole percent p-xylylenediamine.

The hydrogenation was carried out under the same reaction conditions as before, except that methanol was used instead of the liquid ammonia. The reaction solution obtained was used to separate the Catalyst filtered and examined for products The yields were 71.0 mol% 1,4-bis-aminomethylcyclohexane, 10.8 mol% 4-methylbenzylamine, 1 £ 2 mol% l-aminomethyl-4-methylcyclohexane and 0.4 mol% p-xylylenediamine.

Example 5

Beads of a ruthenium catalyst 3.5 mm in diameter with 0.5% by weight of ruthenium on aluminum oxide were introduced in an amount of 1300 ml into a vertical reaction tube with an inner diameter of 41.5 mm and a height of 1500 mm and activated with hydrogen Then, in this reaction tube, an ammonia solution in which the m-xylylenediamine concentration was 30% by weight was subjected to the hydrogenation reaction at a reaction temperature of 91 to 125 ° C., a reaction pressure of 200 kg / cm ² , a solvent supply rate of 1200 g / Hour and a hydrogen supply rate of 300 l / hour at 0 ° C and atmospheric pressure. Sixty minutes after the start of the reaction, the reactor became a sample

taken and analyzed. A yield of 39.4 mol% of IS-bis-aminomethylcyclohexane was found 2.2 mole percent 3-methylbenzylamine, 2.1 mole percent 1-aminomethyl-3-methylcyclohexane and a trace of m-xylylenediamine was obtained. .

The hydrogenation was carried out under the same reaction conditions as before, except that methanol was used as a solvent. The obtained reaction solution was examined, with the result that that the yields of 81.2 mol% of 1,3-bis-aminomethylcyclohexane, 8.6 mol% 3-methylbenzylamine, 8.1 mol% 1-aminomethyl-3-methylcyclohexane and a trace m-xylylenediamine.

Examples _{] 5}

A vertical reaction tube I with an inner diameter of 41.5 mm and a height of 1500 mm and a vertical reaction tube II with the same inner diameter as before and a height of 3000 mm were connected to one another. The reaction tube I was then filled with 1300 ml of catalyst beads 3.5 mm in diameter made of 45% by weight of nickel, 1.7% by weight of copper and 1.7% by weight of chromium on a diatomaceous earth support, and the reaction tube II was mil 2600 ml of catalyst spheres 3.5 mm in diameter with a content of 0.5% by weight ruthenium were charged on a γ-aluminum oxide support. The two catalysts were activated with hydrogen. A 15% strength by weight ammonia solution of isophthalic acid nitrile was then introduced into reaction tube I and the isophthalic acid nitrile was hydrogenated at a reaction ^{temperature of 70 to 100 °} C. and a reaction pressure of 150 kg / cm ² . This gave m-xylylenediamine, which was then introduced into the reaction tube II and hydrogenated according to the invention ^{at a reaction temperature of 100 to 130 °} C. and a reaction pressure of 150 kg / cm ^2. The yield of xylylenediamine from reaction tube I was 92.3 mol%. The yields of 1,3-bis-aminomethylcyclohexane based on isophthalic acid nitrile were 86.5 mol%, along with 4.6 mol% of 3-methylbenzylamine and 6.8 mol% of l-aminomethyl-3-methylbenzylamine. The yield of 1,3-bis-aminomethylcyclohexane, based on the m-xylylenediamine used, was 93.8 mol%.

Claims (1)

Claim: Process for the production of 13- or 1,4-bisaminomethylcyclohexane by catalytic hydrogenation of m- or p-xylylenediamines at 70 to 150 ° C, a pressure of 50 to 500 kg / cm ² in the presence of a solvent and using a ruthenium catalyst, characterized in that the hydrogenation is carried out in liquid ammonia as solvent and a concentration of m- or p-xylylenediamine in the ammonia solution of 5 to 80% by weight is maintained.