DE2164169C3 - Process for the production of 13- or 1,4-bis-aminomethyl-cyclohexane - Google Patents

Description

The invention relates to a new process for the production of 13- or I ^ -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 a solvent and using a Ruthcniunikatalysators, which is 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 wt .-% 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 manufactured as raw materials

2a Po'yurcthanc for the production of elastic fibers, Form articles or films with extremely high lightfastness 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

CONH ₂ J

CN

CH ₂ NH,

(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 \ / \ / A

Ii J • ThJ + [H

'CH ₂ NH ₂

CHO

CH ₂ NH ₂ CH ₂ NH ₂

H | + | H

CH ₂ NH ₂

CH ₂ NH ₂

CH ₂ NH

CU ₂ NHCOR H ₂ O

CH ₂ NHCOR

CH ₂ NHCOR

CH ₂ NH,

CH ₂ NH ₂

(Japanese Patent 459199)

CH ₇ NH,

H,

CH ₂ NII ₂

CH ₂ NH ₂ CH ₂ NLi ₂

1.1 (manic patent specification 51 7 236 »

However, these conventional methods have disadvantages. Method I 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 process 2, although the condensation reaction of 13-butadiene and acrylonitrile proceeds quantitatively, the yield in the stage of the oxo reaction low. In addition, although 1,3-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, this is used as the starting material xylylenediamine used previously acylated, then hydrogenated, then the acyl group with acid or Alkali hydrolyzed and the reaction product extracted with ether or cyclohexane. 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 JP-PS 26 783/67 a process for the preparation of cis-cyclohexane-bis-methylamine is carried out described 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 reaction time when 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-aminocyciohexyI-methane by catalytic hydrogenation of bis-4-aminophenyl-methane in the presence described a ruthenium catalyst using dioxane as a solvent and ammonia as an adjuvant. The yield achieved is significantly below the yield achievable according to the invention. A hint for an improvement in yield by omitting the dioxane is nowhere given.

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. Some of the xylylenediamine is not converted under mild reaction conditions, so that the yields of bis-aminomethylcyclohexane were unsatisfactory. Because of the impurities which disturb the final distillation, the yield of only reached values bis-aminomethylcyclohexanen of 60 to 65 MOI ⁰ Zb.

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 not useful for the intended hydrogenation, since the Activity of such a catalyst due to the catalyst poisoning effect of amines and Ammonia is being reduced too much.

In the process according to the invention, hardly any impurities are formed, so that a final dent occurs 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 70 to 150 ° C, preferably 90 to 130 ° 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 falls, 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 easily occur, while when working below 70 ° C the space-time yield drops. 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, ruthenoxide or ammonium hydroxide as active ingredients. The catalyst can be used in the form of a single catalyst component, ruthen oxide being advantageous and RuO ₂ in particular being the most suitable. Furthermore, the active catalyst component can be present on a carrier, for example aluminum oxide, diatomaceous earth or coal. If a support is used, the amount of active catalyst component is 0.1 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

so 10 wt .-%, preferably 0.5 to 5 wt .-%, 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.

^r > 5 In the case of a batch preparation, the reaction is complete within 30 minutes to 3 hours under the reaction conditions given above. In a continuous production, the liquid space velocity of the ammonia solution of xylylene

bo amin 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

t>'> are produced.

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

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.

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 ruthenium on a carbon support and 20 g of liquid ammonia. Hydrogen was then continuously charged up to a pressure of 200 kg / cm ² fed in, and the hydrogenation was carried out at a reaction ^{temperature of 105 °} C. The absorption of hydrogen was complete in 70 minutes. The resulting reaction solution was poured out, filtered and the filtrate was analyzed for the products. The yields were 873 mol% of 13-bisaminomethyl-cyclohexane, 3.6 mol% of 3-methylbenzylamine, 4.5 mol% of 1-aminomethyl-S-methylcyclohexane and a trace of m-xylylenediamine.

The hydrogenation was carried out under the same reaction conditions as. previously carried out, just was Methanol used instead of the liquid ammonia. The reaction solution obtained was nitrated and the filtrate obtained analyzed for the products. The yields were 71.6 mol% of 13-bis-aminomethylcyclohexane, 11.2 mol% 3-methylbenzylamine, 10.8 mol% l-aminomethyl-S-methylcyclohexane and 03 mol% m-xylylenediamine.

Comparative example

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% 13-bis-aminomethylcyclohexane, 93 mol% 3-methylbenzylamine, 113 mole percent 1-aminomethyl-3-methylcyclohexane and a trace amount of m-xylylenediamine.

Example 2

In the same autoclave as in Example 1 was charged with 13.6 g of m-Xylylendiam'n, 03 g of ruthenium oxide and 30 g of liquid ammonia charged hydrogen was then continuously fed to a pressure of 150 kg / cm ^2, the hydrogenation was conducted at a uno Reaction temperature of 110 ^° C. carried out, the absorption of the hydrogen was complete in 65 minutes. The reaction solution obtained was discharged, filtered and the filtrate analyzed for products. The yields were 87.1 mol% 13-bis-aminomethylcyclohexane , 5.0 mol% 3-methylbenzylamine, 4.7 mol% 1-aminomethyl-S methylcyclohexane and 0.1 mol% 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-S-methylcyclohexane, and 0.4 Mole percent m-xylylenediamine.

Example 3

s The same autoclave as in Example 1 was made with 13.6 g of m-xylylenediamine and 3 g of a catalyst 5% by weight of ruthenium on a γ-alumina support and 25 g of liquid ammonia are charged with hydrogen was then continuous up to a pressure of

ίο 150 kg / cm ² initiated, and the hydrogenation carried out at a reaction temperature of 115 ° C. The absorption of the hydrogen was complete in 75 minutes. % 13-bisaminomethylcyclohexane, 3.8 mol% 3 methylbenzyl

amine, 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 Carried out as before, except that 25 g of 28% strength by weight ammonia water instead of liquid Ammonia were used. The reaction solution obtained was filtered to separate the catalyst and analyzed for products The yields were 76.1 mol% ^ -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 fed in at 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 the catalyst and examined for products were 88.4 mol% 1,4-bisaminomethylcyclohexane, 3.2 mol% 4-methyl-

benzylamine, 3.4 mol% l-aminomethyl-4-methylcyclo-

hexane 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 MoN% 4-methylbenzylamine, 12.2 Mo ', -% l-aminomethyl-4-methylcyclohexane and 0.4 mol% p-xylenediamine.

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 95 to 125 ° C., a reaction pressure of 200 kg / cm ² , a solvent feed 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% l ^ -bis-aminomethylcyclohexane next 2,2MoI- ⁰ Zo 3-methylbenzylamine, 2.1 mol% I-aminomethyl-3-methylcyclohexane, and receive a trace of m-xylylenediamine.

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 the yields of 81.2 mol% of 1,3-bis-aminomethylcyclohexane, 8.6 mole percent 3-methylbenzylamine. 8.1 mole percent 1-aminomethyl-3-methylcyclohexane and a trace m-xylylenediamine.

Example 6

A vertical reaction tube 1 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 and made of 45% by weight nickel. 1.7% by weight copper and 1.7% by weight chromium on a diatomaceous earth support and the reaction tube II is charged with 2600 ml of small catalyst pots 3.5 mm in diameter with a content of 0.5% by weight ruthenium 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%, with 4, b mol% 3-ivieihyibenzylamine and 6.8 mol% i-aminomethyl-3-methylbenzylamine formed. The yield of 1,3-bis-aminomethylcyclohexane, based on the m-xylylenediamine used, was 93.8 mol%.

Claims (1)

Claim: Process for the preparation of 1,3- or 1,4-bisaminomethylcydohexane by catalytic hydrogenation of m- or p-xylylenediamines at 70 to 150 ⁰ C, a pressure of 50 to 500 kg / cm ² in the presence of a solvent and with one 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.