DE2164169A1 - Process for the production of bis (aminomethyl) cyclohexane - Google Patents

Description

DM. MULLER-BOR £ DJPL.-PHYS. DH. MANITZ dipl.-chem. dr. DEUFEL

DIPL.-lNG. FINSTERWALD DIPI ..- ING. GRAMKOW 0 1 £ / 1 β Q

PATENiAHWALTE * * Ό Η IO vJ

It OEZ. 1171

Ph / th - h 2145

MITSUBISHI GAS CKiTiIGAL CChPAlJY, ine. 1-1, ücJriisaiwai-cho 2 chome, Chiyoda-lcu Tokyo, Japan

V & riahren for the production of bis (aminometiiyi) -cyclohexane

Priority: Japan from December 24, 1970
No. 116805/70

The invention relates to a new method of manufacture of bis (aminometh.yl) -cycloh.exane, in particular a process for the production of bis (aminomethyl) cyclohexane. Hydrogenation of xylylenediamine with liquid ammonia as a solvent in the presence of ruthenium or a Ruthemr bond.

It is known that polyamides made from bis (aminomethyl) cyclohexane and an organic dibasic acid such as adipic acid, sebacic acid or the like and that these polyamides have various superior properties. It is also known that Polyurethane using BisCaminoniethyl.'J-cyclohexane as a raw material, an elastic fiber, a molded article

209829/1103

Dr. MOtlaf-Bor * Dr. Manliz ■ Dr. Booze! - ülpl.-ing. Flnilerw »lrf Oipi.-Ing. arlmkow

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BATH ORIGINAL

or film with extremely superior lightfastness represents. Recently BisCaninonethyl) -cyclohexane also has Attention especially as a Röiuiatarial for hardening agents found for epoxy resin.

So far, the following processes for the production of bis (aminomethjl) -eyelohexane were known:

CGOH

(D

H ₂

COOH

COOH

II COOH

COIiIL

CN

COIiH,

CN

/ -CN

CH

■

■ S CB

CN

(Reports 71, 759-767 (1936)) CHO CN

KO

CH NH
/ -2 2 CH ₀ NH ₂ (US 3 012 + ΓηΊ CH ₂ HH ₂ -PS

CH NH

CH ₂ NH ₂ . H,

CH NH

CH NHCOR CHNHCOR CHJIH

CH NHCOR

CH NH

GK ^ NH

2

^Η 2 °

CH ^ NHCOR

NH

Cöapaniscues Pateat 459 199)

(Japanese pater ,; yi7 236;

209829/1103

BATH ORIGINAL

However, each conventional method has drawbacks as set out below. Namely, in method (1). Cyolcdicarboxylic acid obtained by hydrogenation of phthalic acid is comparatively unstable and, moreover, the statute of limitations has many stages and is; compiled so that the yield is low. In process C-), although the condensation reaction of 1,5-butadiene and acrylonitrile proceeds quantitatively, the yield in the next stage of the Oy.c reaction is low. In addition, there is no evidence that 1,3-bis (aHxinon.etx: yl) -cyclohexane and 1,4-bis (aminomethyl) -cyclohexane are produced together, the ratio of one product to the other is strong and accordingly the quality is not uniformly. In process (3) the raw material xylylenediamine is acylated beforehand, then hydrogenated, then hydrolyzed with an acid or alkali and extracted with ether or cyclohexane, so the yield of bis (aminomethyl) cyclohexane is reduced «And in process (4-) Water or an organic acid is used as a solvent, but in the case of water the yield is low, while in the case of an organic acid the materials for the reaction vessel are limited and, moreover, the air must be added by adding alkali at the time of distillation be released .

Many attempts have been made to hydrogenate the xylylenediamine ring with a ruthenium catalyst c.ur close leads, with the result that in addition to bis (aminomethyl) cyclohexane as K / beiipiOdukte methylbenzylamine and (aminomethyl) methylcyclciiexane formed, and sometimes the starting xylylenediamine continues to exist in the case of milder reaction conditions unur.gese "czt remained so that it was impossible to yield

209829/1 103

BATH ORIGINAL

"■■ τ * ^ ™

of bis (aminomethyl) cyclohexane to over 85 mol% to enhance. In addition, due to many impurities, the distillation yield was reduced to about 85%, so that the yield of bis (aminomethyl) cyclohexane from xylylenediamine was only 60 to 65 mol%.

So it was searched for further improvement and has now found that if liquid ammonia is used as a solvent is used, the formation of by-products such as iiethylbenzylamine, (aminomethyl) methylcyclohexane etc. could be reduced quite considerably and, moreover, the reaction yield of bis (aminomethyl) cyclohexane by 7 "to 20 Mo 1% compared to using one solvent other than liquid ammonia improved could become what the invention represents.

On the other hand, experiments with a rhodium and carried out a platinum catalyst, but their activity is hindered by the catalyst-poisoning effect of amine it was not possible to achieve the desired yield.

In the process of the present invention, the impurities were very little, so the distillation yield of bis (aminomethyl) cyclohexane was improved to more than 95% , and as a result, the final yield of bis (aminomethyl) cyclohexane from xylylenediamine was 82-89 mol%.

A main object of the invention is therefore to provide a process for the production of bis (aminomethyl) cyclohexane in high Yield from hydrogenation of xylylenediamine with liquid ammonia as solvent in the presence of a lithium catalyst to accomplish.

209829/1103

BATH ORIGINAL

2164189

According to the invention, the raw material, xylylenediamine, which is a meta- or para-xylylenediamine, is used in such an amount that its concentration in an 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 150 ^° C., and the reaction pressure is

P P

at 50 to 500 kg / cm, preferably 100 to 250 kg / cm. Under these conditions 1,5-bis (aminomethyl) -oyclohexane becomes from a meta-xylylenediamine and 1,4-bis (aminomethyl) -cyclohexane made from a para-xylylenediamine.

If the concentration of xylylenediamine in an ammonia solution is less than 5% by weight, the space-time yield falls, while above 80% by weight, the selectivity of the catalyst becomes worse. Even if the reaction temperature is above 150 ⁰ C increases tend to occur side reactions, xrährend below 70 ⁰ C, the space-time yield decreases, and when the reaction pressure is below 50 kg / cm, the space-time yield decreases also ,, while at over 500 kg / cm a large number of side reactions occur.

If the process according to the invention is carried out under such desired conditions as mentioned above, is carried out the formation of by-products such as methylbenzylamine, (Aminomethyl) methylcyclohexane, etc. are greatly reduced, so that the reaction yield of bis (aminomethyl) cyclohexane can be improved.

The ammonia solvent used in carrying out the process must be liquid ammonia; with liquid Ammonia water or ammonia alcohol cannot achieve the effect according to the invention.

209829/1103

BATH ORIGINAL

The ruthenium catalyst used according to the invention " contains as a component ruthenium, ruthenoxy or ruthenium hydroxide, etc. The catalyst can be the only one A catalyst component can be used, with ruthenium oxide being desirable and, in particular, RuQ ~ being the best. Furthermore, the catalyst component can be present on a carrier, such as, for example, aluminum oxide, diatomaceous earth or coal. In the case of using a carrier, the amount of catalyst component is 0.1 to 10% by weight, preferably 0.5 to 5 percent 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 percent by weight, based on the amount of Xyly. '. Endiamine.

The division of bis (ami ^ ometh / l) «aylohexane by hydrogenation v _; Xylylenediamine according to the invention can either be carried out batchwise using an autoclave or continuously using a stationary bed reactor or fluidized bed reactors. In the case of batch production, the reaction is complete within 30 minutes to 3 hours under the above-mentioned reaction conditions. In the case of continuous production, the liquid space velocity of the ammonia solution of xylylenediamine is below 7 / h, preferably 0.5 to 5 / h.

The raw material xylylenediamine can be obtained by hydrogenating isophthalonitrile with ammonia as a solvent in the presence a nickel and / or cobalt catalyst.

209829/1103

BAD ORIGIfSSAL

2164163

As mentioned above, the process according to the invention for the production of EIs (aminoffietSi ^ l) »cjcloliexan from Xylylenöiasis linä or the process for the production of Zylylenaiamin from isophthalonitrile are the same, ia with respect to the use of ammonia as" solution silicate, and therefore it is possible , Bi (aminoaetliyl) ~ cycloiie3Dan continuously from isopit-halonitrile to steeper Bisses continuous manufacturing process is very Tortsilliaft _o

Preferred ssispisls des

aung fliissr.gsiL ^ 2ϊ; ώΪ5! ϊ3 dung werdsn In ■ ^ ΐ ,, ^ η-ίΐΘζι under Verwsndrr.g ef.iSD jj- ammonia Ιοί ^ ΐ äü i
five examples _a

Example 1

a ^ -sas aur manufacture of
: "ϊ2.ώ Ji / ljlsndiamin under Tferwen * = iEsi ^ gffiyii ':: ^! gism according to the Srfia = bsj ^ j to 795? (3lsiclxsbeispiel
n Ikc £ ^ 2gsBi-öt®ls as a liquid sispiQl ia any of the first

A shaking autoclave with ICO ml i / ^J a3susg3T © raÖg®n was charged with 13.6 g of seta-xylylenediasine, 5% of catalyst from 5% by weight of a KonSörlger and 20 .g of liquid ammonia. Hydrogen was continuously fed up to a pressure of 200 kg / ca ₅ and the hydrogenation was carried out at a temperature of 105 ° C. The absorption of hydrogen was complete in 70 minutes. The resulting reaction solution was applied, filtered * νή to separate the catalyst, and analyzed for the products. The yields were 87.3 mol% 1,3-bis (amino! Aet] iyl) -cycloliexane, 3.6 mol% 3-methylbenzyl-amine, 4-, 5 mol% -sti-aminomethyl-3-methylcyclohexane and a trace of meta-xylylenediamine.

209829/1103

BAD ORiGINAL

The hydrogenation was carried out under the same reaction conditions as before, with the exception that methanol was used in place of the liquid ammonia. The reaction solution obtained was filtered, to separate the catalyst, and analyzed for the products. The yields were 71.6 mol% 1,3-bis (aminomethyl) cyclohexane, 11.2 mol% 3-methylbenzylamine, 10.8 mol% i-aminomethyl-1-methylcyclohexane and 0.3 col% meta-xylylenediamine.

Example 2

The same autoclave as in Example 1 was 13.6 g meta-xylylenediamine, 0.3 g ruthenoxide and 30 g liquid Loaded with ammonia. Hydrogen then became contingent fed up to a pressure of I50 kg / cm, and the Hydrogenation was carried out at a reaction temperature of 110.degree. In 65 minutes was the absorption of the hydrogen completed. The obtained reaction solution was discharged, filtered to separate the catalyst, and analyzed for products. The yields were 87.1 mol% 1,3-bis (aminomethyl) cyclohexane, 5.0 mol% 3-methylbenzylamine, 4.7 col-% i-aminomethyl-3-methylcyclohexane and 0.1 mol% meta-xylylenediamine.

The hydrogenation was further carried out under the same reaction conditions as before, with the exception that Water was used instead of liquid ammonia. The reaction solution obtained was used to separate the Catalyst * filtered and examined for products. The yields were 73 »2 mol% 1,3-bis (aminomethyl) cyclohexane, 11.3 mole percent 3-methylbenzylamine, 9.7 mole percent 1-aminomethyl-3-methylcyclohexane and 0.4 mole percent meta-xylylenediamine.

209829/1103

BATH ORIGINAL

Example ;?

The same autoclave as in Example 1 was with 13.6 g of meta-xylylenedianine, 3 B of a catalyst composed of 5% by weight of ruthenium on a gamma-aluminum oxide carrier. and charged 25 g of liquid ammonia. Hydrogen was then continuously introduced up to a pressure of 150 kg / cm, and hydrogenation was carried out at a reaction temperature of 115 ° C. The absorption of hydrogen was completed in 75 minutes. The reaction solution obtained was discharged, filtered to separate off the catalyst and examined for products. The yields were 87.1 mol% 1,3-bis (aminomethyl) cyclohexane, 3.8 mol% 3-methylbenzylamine, 2.9 mol% 1-aminomethyl-3-methylcyclohexane and 0.2 mol% meta-xylylenediamine.

The hydrogenation was carried out under the same reaction conditions as before, with the exception that 25 g of 28% strength by weight ammonia water were used instead of liquid ammonia. The reaction solution obtained was filtered to separate off the catalyst and analyzed for products. The yields were 76.1 piston% 1,3-bis (aminomethyl) -cyclohexane, 10.6 mol% of 3T ^{Me 'FCLI} yl ^tl enzylamin, 8.6 mole% I-Aminomethyl-3-iaethylcyclohexan and a trace meta-ylylenediamine.

Example 4

The same autoclave as in Example 1 was charged with 13.6 para-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, and the hydrogenation was carried out ^{at a reaction temperature of 105 ° C.} In 65 minutes

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BATH ORIGINAL

the absorption of hydrogen was complete. The reaction solution obtained was discharged to separate the Filtered catalyst and examined for products. The yields were 88.4 mol% 1,4-bis (aminomethyl) cyclohexane, 3.2 mol% 4-methylbenzylaniine, 3.4 l-iol% i-aminometh.yl-4-methylcyclohexane and 0.1 mole percent para-xylylenediamine.

The hydrogenation was continued under the same reaction conditions carried out as before, with the exception that methanol was used in place of the liquid ammonia. The reaction solution obtained was filtered to separate off the catalyst and examined for products. the Yields were 71 »0 mol% 1,4 ~ bis (aminomethyl) cyclohexane, 10.8 mole percent 4-methylbenzylamine, 12.2 mole percent 1-aminomethyl-4-methylcyclohexane and 0.4 mole percent para-xylylenediamine.

Example 5

Ruthen catalyst pellets ^{with a diameter of 3.5 mm and a height of 3.5 mm} with 0.5% by weight ruthenium on aluminum oxide were placed in an amount of 1,300 ml in a vertical reaction tube with an internal diameter of 41.5 mm and a height of 1,500 mm introduced and activated with hydrogen. An ammonia solution in which the meta-xylylenediamine concentration was 30% by weight was then subjected to the hydrogenation reaction at a reaction temperature of 95 - 125 ° C., a reaction pressure of 200 kg / cm, a solution feed rate of 1,200 g / h and a hydrogen supply rate of 300 l / h at 0 ⁰ C and one atmosphere. Sixty minutes after the reaction became stationary, the reactor was sampled and analyzed, with the result that the yields were 93 »4 mol% 1,3-bis (aminomethyl) cyclohexane, 2.2 mol% 3 -Methylbenzylamine, 2.1 mol%

209829/1103

i-aminomethyl-3-methylcyclohexane and a trace of meta-xylylenediamine cheat.

The hydrogenation was continued under the same reaction "conditions carried out as before, with the exception that methanol was used as the solvent. The received The reaction solution was examined, with the result that the yields were 81.2 mol% of 1,3-bis (aminomethyl) cyclohexane, 8.6 mole percent 3-methylbenzylamine, 8.1 mole percent 1-aminomethyl-3-methylcyclohexane and add a trace of meta-xylylenediamine.

Example 6

A vertical reaction tube (I) having an inner diameter of 41.5 mm and a height of 1,500 mm and a vertical reaction tube (II) having the same inner diameter as before and a height of 3,000 mm were connected to each other. The reaction tube I was then filled with 1,300 ml of catalyst pellets 3 »^ mm in outside diameter and 3» 5 in height made of 45% by weight of nickel, 1.7% by weight of copper and 1.7% by weight of chromium on a diatomaceous earth Carrier and the reaction tube II with 2,600 ml of catalyst pellets 3 »5 mm in diameter and 3.5 mm in height fe * 4 with a content of 0.5 wt .-% ruthenium on a gamma-aluminum oxide carrier. i) he two catalysts were activated with hydrogen, and then a 15 wt .-% of isophthalonitrile was introduced ammonia solution in DBB reaction tube I which isophthalonitrile at a reaction temperature of 70 to 100 ⁰ G

and a reaction pressure of 150 kg / cm neta-xylylenediamine, which is then put into the reaction tube II brought and at a reaction temperature of

9/1103; -, r

BATH ORIGINAL

100 to 130 C and a reaction pressure of 150 kg / cm was hydrogenated to give 1,3-bis (aminometh.yl) -cyclori.exane. The yield of xylylenediamine was 92.5%, but as a result of the analysis of a sample of the reaction product, the yields, based on isophthalonitrile, were 86.5% 1,3-bis (aminomethyl) cyclohexane, 4.6 % 3-methylbenzylamine and 6.8% i-aminomettiyl-3-methylbenzylamine. The reaction yield of 1,3-bis (aminomethyl) -cyclohexane to meta-xylylenediamine was 93-8%.

-Patent claims-

209829/1103

Claims (4)

Claims 1. A process for the preparation of bis (aminomethyl) cyclohexane, characterized in that xylylenediamine is marked is hydrogenated with liquid ammonia as a solvent in the presence of a euthenium catalyst. 2. The method according to claim 1, characterized in that a concentration of xylylenediamine in the ammonia solution of 5 to 80 wt .-%, a reaction ^{temperature of 70 to 150 0} C and a reaction pressure of ο
50 to 500 kg / cm can be applied. 3. The method according to claim 1 or 2, characterized g β k β η η ze.ichnet that meta-xylylenediamine as xylylenediamine with formation of v <m. 1 _i 3-bis (aminomethyl) - »cyclohexaa is used as a product. 4. The method according to claim 1 or 2, characterized in that ale xylylenediamine is para-xylylenediamine for the formation of 1,4-bis (aminomethyl) -cyclohexane is used as a product. 209829/1103 BATH ORIGINAL