DE1568188A1 - Process for the catalytic hydrogenation of diaminodiphenylalkanes or ethers - Google Patents

Description

BADISCHE ANILIN- & SODA-PABRIK AG ι ε ο η 1 ο Ο

I DOO loo

Our reference: O.Z. 24 507 Bk / Hi Iudwigshafen am Rhein, September 29, 1966

Process for the catalytic hydrogenation of diaminodiphenylalkanes or ethers

Addendum to patent (patent application B 86 109 IV "b / 12 o)

and to patent (patent application B 88 573 IV b / i2 o).

Subject of the patent (patent application B 86 109

IV b / 12 o) is a process for the catalytic hydrogenation of Diaminodiphenylalkanes or ethers in the presence of known hydrogenation catalysts, such as copper, chromium, manganese, tungsten, Molybdenum, cobalt or nickel, without the addition of alkaline earth oxides in inert solvents at elevated temperatures and below elevated pressure, the inert solvent being cyclic ethers with an oxygen atom in the ring or cyclohexylamine in Concentrations from 30 to 90 wt. $ Based on the sum of Solvents and compound to be hydrogenated, used *

Subject of the first additional patent. ... ... (patent application B 88 573 IV b / i2 o) is a process for catalytic hydrogenation of diaminodiphenylalkanes or ethers, where one is N-alkylated Cyclohexylamine as a solvent instead of cyclic ethers with an oxygen atom in the ring or cyclohexylamine used,

456/66

00 984 1 / 196-9

- 2 - O.Z. 24 507

It has now been found that the process according to the main patent and, according to the first additional patent, can be further developed when using hydrogenation catalysts containing cobalt and manganese used.

Compared to the main patent, the process has the advantage that the cobalt and manganese-containing catalysts are a special one have prolonged activity. This is particularly advantageous for continuous operation. In addition, one achieves with the Catalysts particularly high yields.

The catalysts used contain cobalt and manganese. The catalysts advantageously contain 1 to 99.5% by weight, preferably 15 to 95% by weight, of cobalt and 0.1 to 50% by weight, preferably 1 to 20% by weight, of manganese, based on the metal content of the catalysts. In addition, the catalysts may also include other metals such as copper, chromium, nickel, tungsten, molybdenum, platinum, palladium or ruthenium in amounts up to 10 wt. Jd contain. It is possible to use the catalysts as so-called unsupported catalysts. In this case, the individual catalyst components are mixed in the form of compounds that can be reduced with hydrogen at elevated temperatures, such as oxides, hydroxides, oxalates, ammoniaates, formates or nitrates, pressed into shaped bodies (e.g. into stretches or pills), then optionally heated to preferably 300 to 1000 ^° C. for some time and then reduced with hydrogen, advantageously at 200 to 400 ^{° C.} To set a certain pore size, the catalyst can again to 400 to 1000 ⁰ C

009841/1959 _8AD

- 3 - O.Z. 24 507

get heated. Bs is also possible to use the metal compounds Carriers such as puller earth, pumice stone, silica strands, silica gel, aluminum oxide or silicates, to be applied and after heating, z. B. in the muffle furnace, to 300 to 1000 ° 0, as described, to reduce with hydrogen, the metal content in the Supported catalysts are generally between 5 and 50% by weight.

With regard to the starting materials, the solvents and the reaction conditions The present process does not differ from those of the main patent and the first additional patent.

The parts given in the following example are parts by weight, they relate to the hem parts like kg: 1.

example

A vertical high pressure pipe is charged with a volume of a catalyst which contains 30% by weight of cobalt and 6% by weight of manganese in the form of oxides on pumice stone. The catalyst is then reduced in the course of 60 hours at 320 to 340 ^° C. without pressure with hydrogen. Then metered in at the head of the high-pressure pipe, hourly 0.150 Eaumteile a mixture of 30 Gewr- <fo ^{4,4-diamino-l-dimethyldiphenylmethane} 3f3' and # tetrahydrofuran 70 wt., And 150 parts by volume of hydrogen to normal. The reaction conditions are 220 to 225 ⁰ O at 300 at total pressure. The reaction mixture and the hydrogen are drained off via a separator at the bottom of the reactor. The one with tetrahydro-

_4_ 009841/1959 BAD ORIGINAL

- 4 - O.Z. 24

hydrogen saturated with furan is combined with fresh hydrogen and returned to the reactor.

After a running time of 10 days , the reaction mixture freed from tetrahydrofuran contains

0.2 io low-boiling first run

95.0 $ 4,4'-diamino-3,3'-dimethyl-dicyclohexylmethane Kp ₀ , = 145 ⁰ C (= 95 ^ of theory)

3.0 io 4,4'-diamino-3,3'-dimethyl-cyclohexylphenylmethane <1.0 # residues

After 3p days of running time you get $ 1 low-boiling forerun

<f ₀ 4,4'-diamino-3,3'-dimethyl-dicyclohexylmethane Kp ₀ ^ ₄ = 145 ⁰ C (= 94 Io of theory)

4 <$> 4,4'-diamino-3,3'-dimethyl-cyclohexylphenylmethane

1 # residues

After a running time of 75 days you will receive

$ 2 low boiling headers

$ 4,4'-diamino-3,3'-dimethyl-dicyclohexylmethane ₄ = 145 ⁰ C (= 92 <$> of theory)

4 io 4,4 'diamino-3,3' dimethyl-cyclohexylphenylmethan

2 # residues

After 90 days of running time you will receive

$ 3> low boiling fore runnings

io 4,4'-diamino-3,3'-dimethyl-dioyclohexylmethane _t4 = 145 ⁰ C (= 91 # of theory)

009841/1959 / UNZ>

⁸ ^ D ORIGINAL

- 5 - 0.Z. 24 507

3 io 4,4'-Mainino-3,3WLimethyl-io cyclQhexylphenylmethan 3 residues.

If the hydrogenation is carried out with a catalyst which contains no manganese in addition to cobalt, the yield of 4->4'-diamino-3,3'-ctimethyl-dicyclohexylmethane drops to 80 % of theory after a running time of 90 days ,

SAD

- 6 009841/1969

Claims (1)

- 6 - O.Z. 24 507 15681S8 Pat entans pruch Further embodiment of the process for the catalytic hydrogenation of diaminodiphenylalkanes or ethers in the presence of known ones Hydrogenation catalysts, such as copper, chromium, manganese, tungsten, molybdenum, cobalt or nickel, without the addition of alkaline earth oxides in inert solvents at elevated temperature and under elevated pressure, being used as an inert solvent cyclic ethers with an oxygen atom in the ring or cyclohexylamine or N-alkylated cyclohexylamines in concentrations From 30 to 90 wt. ^, based on the sum of solvent and compound to be hydrogenated, used, according to patent (Patent application B 86 109 IV b / 12 o) and after the first additional patent. ... ... (Patent Application B 88573 IV b / 12 o), characterized in that cobalt and manganese containing hydrogenation catalysts used. BADISCHE AWILIN- & SODA-FABRIK AG 0098A1 / 1959