DE1568188B - Process for the catalytic hydrogenation of diaminodiphenylalkanes or ethers - Google Patents

Description

The invention relates to a method for / \ 7 1

catalytic hydrogenation of diaminodiphenylal-R2
kanen or ethers in the presence of a catalyst. 25th

From U.S. Patent 2,606,927 and

German Patent 894 395 it is known that where R _{1 is} an alkylene residue with 1 to 4 carbon aminodiphenylalkanes in the presence of ethers, atoms such as methylene, ethylene or propylene such as dioxane, and cobalt or nickel catalysts, or an oxygen atom , R ₂ and R ₃ can hydrogenate. The 30 hydrogen atoms or alkyl radicals with 1 to 4 carbon yields obtained by this process are, however, unsatisfactory. According to a substance atom, in particular hydrogen atoms, other processes (German patent specification 888 767) and R ₄ denote a hydrogen atom or an alkyl radical with 1 to 12 carbon atoms such as methyl, ethyl, isophenylmethane, with ruthenium catalysts in the hydrogenation of 4,4-diaminodi- 1 to 12 carbon atoms - propyl, octyl, dodecyl, or a halogen atom, or good yields were obtained from dioxane. Ruthenium catalysts, however, carbonators bound via an ether bridge are less suitable for technical purposes with hydrogen residues with 1 to 4 carbon atoms, since they are very expensive. Further it is known net. For the hydrogenation, for example, are suitable: (German Patent 842 200) that the hydrogenation 4,4'-diaminodiphenylmethane, 4,4'-diamino-2,2'-didof 4,4-diaminodiphenylmethane with cobalt or decyldiphenylmethane, N, N'-dibutyl-4,4'-diaminodi-nickel catalysts in the presence of hydrophobic 4 ° phenylmethane, 4,4'-diaminodiphenylpropane - (1,3), solvents and alkaline earth metal oxides with 4,4'-diaminodiphenylbutane (1,4 ), 4,4'-diaminodiphe in high yields. This process is not suitable for nylpropane- (2,2), 2,2'-diaminodiphenylmethane, 2,4'-dieine continuous operation, since the aminodiphenylmethane, 4,4'-diamino-2,2'-dichlorodi catalyst composition in the continuous operation after phenylpropane- (2,2), 2,2'-diamino-5,5'-dimethoxy cakes together for a short time and thereby loses its effectiveness 45 phenylmethane, N, N'-dimethyl-4,4'-diaminodiphenyl. ether. The procedure is of particular importance for the

The object of the invention is therefore to create a hydrogenation of 4,4'-diamino-diphenylmethane and

new catalyst for the ver 4,4'-diaminodiphenylpropane- (2,2) in question.

drive, which is particularly useful in continuous operation and The hydrogenation catalyst used according to the invention

When used as a fixed bed catalyst, especially 5 ° lysator contains cobalt and manganese, with Mangen in

Has long-lasting reactivity and also has an amount of 1 to 20 percent by weight, based on

there is a high, uniform conversion on the metal content of the catalyst.

possible. Except for cobalt, which is the main metal content of the

There has now been a process for catalytic hy- sators that can make up to 10 percent by weight

dration of diaminodiphenylalkanes or ethers into 55 other metals, such as copper, chromium, nickel, tungsten,

Presence of cobalt containing and present without addition of molybdenum, platinum, palladium or ruthenium

hydrogenation catalysts produced by alkaline earth oxide.

It is possible to use the catalysts as so-called

To use pressure in a cyclic ether with an all-oxygen catalyst without a carrier. In this

atom and 4 to 8 carbon atoms in the ring or 60 case, the individual catalyst components are in

an optionally N-alkylated cyclohexylamine form of compounds, which at elevated temperatures

as an inert solvent in a concentration can reduce temperatures with hydrogen, such as oxides,

from 30 to 90 percent by weight, found that thereby hydroxides, oxalates, ammoniates, formates or

is characterized in that, as hydrogenation catalysts, nitrates are mixed to give shaped bodies (e.g. to form strands

In this case, for some time, if necessary, the catalysts used are those that depress cobalt and manganese or pills)

hold, with manganese heated in an amount of 1 to preferably 300 to 1000 ⁰ C and

20 percent by weight, based on the metal content, including hydrogen, advantageously from 200 to

of the catalyst is present. 400 ⁰ C, reduced. To set a specific

3 4

The pore size of the catalyst can be increased again to 400. In a particularly advantageous embodiment

can be heated up to 1000 ° C. It is also possible to use the continuous procedure described Metal compounds on carriers, such as fuller's earth, pumice - the solvent content during the hydrogenation is there, Silica strands, silica gel, aluminum - kept constant by that one with the overoxide or silicates, and, after the excess hydrogen, solvents are discharged heat, e.g. in a muffle furnace, to 300 to 1000 ° C, as continuously replaced or preferably as described above, to reduce with hydrogen. The mixed water content laden with solvent vapor in the supported catalysts is generally in a circle after supplementing the consumed amounts between 5 and 50 percent by weight. gen feeds back to the reaction, with it to

The hydrogenation takes place, for example, at pressures io care that the temperature of the recycled from 150 to 700 atmospheres, preferably from 200 to 350 atmospheres. Hydrogen does not exceed the hydrogenation temperature by more than In general, temperatures below 60 ° C. are used and the total amount supplied 140 to 300 ° C. Particularly good results are obtained with hydrogen at a given pressure and temperature at temperatures of 180 to 250 ° C. a degree of solvent saturation of at least

It is preferred to use cyclic ethers as lo- 15 40%> preferably 80 to 100%> has. It is also a means of teaching. These have one oxygen atom and 4 to partially, part of the reaction mixture in a circle 8 carbon atoms in the ring and, from the oxygen lead.

atom apart, saturated hydrocarbon structure. Be from the discharged reaction mixture

Suitable cyclic ethers are, for example, tetra diaminodicycloalkanes or ethers by fractiohydrofuran, Tetrahydropyran, hexamethylene oxide, 20th distillation obtained.

2-methyltetrahydropyran, 2,4-dimethyltetrahydrofu- diaminodicycloalkane or ethers, which according to the

ran. Particularly good results are obtained when the method of the invention is produced, such as Use of tetrahydrofuran or hexamethylene in U.S. Patent 2,606,928, Example 4, beoxyd as a solvent. is written, valuable raw materials for the manufacture

Particularly good results are also obtained when high-molecular compounds if one uses an N-alkylated cyclohexylamine as The parts given in the following example

Solvent used. Preferred N-alkylated are parts by weight. The parts by weight are related to cyclohexylamines are those that correspond to the space parts on the nitrogen atom such as kilograms to liters, once or twice by alkyl groups with 1 to
4 carbon atoms, such as ethyl, methyl, isopropyl 30

or butyl radicals, are substituted. Suitable connections B e i s ρ i e 1 1

fertilizers are for example N-methylcyclohexylamine,

Ν, Ν-diethylcyclohexylamine, N-methyl-N-butylcyclo- A vertical high pressure pipe is with

hexylamine, N-isopropylcyclohexylamine. The preferred part of the space of a catalytic converter, the 30 weight tens N-alkyl-substituted cyclohexylamines can contain 35 percent cobalt and 6 percent by weight manganese also contains, in a mixture with the mentioned cyclic ethers, the form of oxides on pumice stone, charged, can be applied. It is particularly advantageous to then reduce the catalyst in the course of Mixture of the mentioned cyclic ethers or 60 hours at 320 to 340 ° C without pressure with water-cyclohexylamines and the reaction products as a substance. The high solvent is then dosed at the top to use. In addition, it is not a pressure pipe 0.150 parts per hour of a Gemiweg required that the solvent used cal of 30 percent by weight 4,4'-diamino-3,3'-dimeabsolut are anhydrous. Even with low water-ethyldiphenylmethane and 70 percent by weight tetra content up to 2 percent by weight, based on the hydrofuran and 150 normal space parts of hydrogen. Solvent, the hydrogenation is still successful. The reaction conditions are 220 to 225 ° C at excellent yield. 45 300 at total pressure. The reaction mixture and the

The solvents are in concentrations of hydrogen are drained at the bottom of the reactor via a 30 to 90 percent by weight, based on the total separator. The hydrogen saturated with tetrahydrofuran with solvent and compound to be hydrogenated is used with fresh hydrogen. It is advantageous to work with 60 to 80 percent by weight solvent and return it to the reactor. Can be the solvent 50 After 10 days of run time contains the means by Tetra also ammonia or methylamine to hydrofuran liberated reaction mixture 20 weight percent, based on the solvent, ~ "",., ..., _T.

enforce ° ^'2/0 low-flow,

The method according to the invention is carried out at- ⁹⁵ > ⁰ ° / o ί> ⁴ '- ™ ^^ - άΜΐ ^ £

For example, by placing in a pressure reactor containing 55 hexyl alcohol, b.p. _0> 1-145 C (- ys / ₀

a diaminodiphenylalkane or ether and the an- " _ηΛΙ ^ ^e . ^r , tr. ^eori . ^e · ''"",,. ,,,,,

given amounts of solvent and a suspension ³ > ° / o 4,4-diamino-3,3 -dimethyl-cyclohexyl-

contains one of the catalysts mentioned, water phenylmetnane,

substance under the specified temperature and pressure ^{<: L} ' ^Ü ' ° ^residue

conditions. The procedure can also be 60 ^ _T „.

Carry out continuously, if you get in a drop ^{after 30 days of running time}

right-hand high-pressure pipe from above or from 1% low-boiling flow,

down on a granular carrier mass on 94% 4,4'-diamino-3,3'-dimethyl-dicyclohexyl-

brought catalyst, possibly previously with methane, bp. _{0> 4} = 145 ° C (= 94 ° / or theo-

Hydrogen is reduced at the specified 65 rie),

Pressure and temperature conditions hydrogen, di- 4% 4,4'-diamino-3,3'-dimethyl-cyclohexyl-

aminodiphenylalkanes or ethers and one of the phenylmethane,

called solvent conducts. l ° / o residues.

After a running time of 75 days you will receive

2% low-boiling first runnings,

92% 4,4'-diamino-3,3'-dimethyl-dicyclohexylmethane, boiling point _{0) 4} = 145 ° C (= 92% of theory),
4% 4,4'-diamino-3,3'-dimethyl-cyclohexyl-

phenylmethane,
2% residues.

After 90 days of running time you will receive

3% low-boiling first runnings,
91% 4,4'-diamino-3,3'-dimethyl-dicycIohexyI-methane, boiling point _{0> 4} = 145 ° C (= 91% of theory),

3% 4,4'-diamino-3,3'-dimethyl-cyclohexyl-

phenylmethane,
3% residues.

If the hydrogenation is carried out with a catalyst which, besides cobalt, contains no manganese, so the yield of 4,4'-diamino-3,3'-dimethyl-dicyclohexylmethane decreases after a running time of 90 days 80% of theory.

B e i s ρ i e 1 2

The high-pressure hydrogenation tube from Example 1 is filled with a catalyst which, on a pumice stone support, contains cobalt and manganese in such a quantitative ratio contains that the proportion of cobalt in the total weight 28 and the proportion of manganese 1 percent by weight amounts to. The catalyst is, as described in Example 1, for the hydrogenation reaction prepared by reduction.

A mixture of percent by weight 4,4'-diamino-3,3'-dimethyldiphenylmethane and 70 percent by weight tetrahydrofuran is now pumped into the reactor every hour at a hydrogen pressure of 300 atm and a temperature in the reactor between 220 and 228 ^{0 C} that per part by volume of catalyst per hour 0.15 parts by volume of the liquid mixture is passed over the catalyst. At the same time, hydrogen irU in the direct current is in an amount of

ίο 150 normal room dividers circulated per hour.

. The converted reaction mixture is drawn off at the bottom of the reactor via a customary separator.

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

0.6% low-boiling first run,
92.4% 4,4'-diamino-3,3'-dimethyl-dicyclohexyl-

methane (I), _{boiling point 0.14} = 145 ° C,
4.5% partially hydrogenated intermediates,
2.5% non-distillable residues.

After a running time of 75 days you will receive

2.8% low-boiling first run,

89.1% (I),

6.0% partially hydrogenated intermediates,

2.1% non-distillable residues.

After 90 days of running time you will receive

4.1% low-boiling first run,

87.9% (I),

6.2% partially hydrogenated intermediates,
1.8% non-distillable residues.

Claims (1)

1 2 The new method has the advantage that it deals with Claim: easy to handle, even in technical operations not expensive catalysts diaminodiphenyl Hydrogenate process for the catalytic hydrogenation of di-alkanes or ethers with high yields Leave aminodiphenylalkanes or ethers in the presence of 5. Preserved by the lack of alkaline earth oxides of cobalt containing and without the addition of the catalyst has a long life, especially alkaline earth oxide Hydrogenation catalysts produced are important in a continuous procedure at elevated temperature and under elevated temperature. This is surprising in that in the German Pressure in a cyclic ether with a Sauer patent 842 200 is described that hydrophilic Substance atom and 4 to 8 carbon atoms in the ring io solvents such as tetrahydrofuran, if used or an optionally N-alkylated cyclization of alkaline earth metal oxides lower the yields hexylamine as an inert solvent in and in the Journal of the American Chemical Society, Concentration of 30 to 90 percent by weight, vol. 75, 1953, p. 1156, it is mentioned that the hydration thereby characterized that one tion of diaminodiphenylalkanes only in the presence of Hydrogenation catalysts used, 15 denote by alkaline earth oxyden with good yields Contain cobalt and manganese, with manganese running. in an amount of 1 to 20 percent by weight, Preferred diaminodiphenylalkanes or ethers based on the metal content of the catalyst, too- got the general formula
against is. ■ 30 R,