DE1618174C

DE1618174C - Process for the continuous Her position of diamino dicyclohexylalkanes

Info

Publication number: DE1618174C
Authority: DE
Inventors: Hubert Dr Grosskmsky Otto Alfred Dr Losch Norbert Dr Pilch Kurt Dr 6700 Ludwigshafen Corr
Original assignee: Badische Anilin and Sodafabrik AG
Current assignee: BASF SE
Publication date: 1971-12-09

Description

1 21 2

Gegenstand der Erfindung ist ein kontinuierliches · Ν,Ν,Ν', N'-TetramethyM^'-diaminodiphenylmethan, Verfahren zur Herstellung von Diamino-dicyclohexyl- N,N'-DibutyI-4,4'-diamino-diphenylmethan, 4',4"-Dialkanen durch Hydrieren von Diamino-diphenyl- amino-diphenylpropan-(l,3), 4',4"-Diamino-diphenylalkanen. butan-(1,4), 4',4"-Diamino-diphenylpropan-(2,2),The invention relates to a continuous Ν, Ν, Ν ', N'-TetramethyM ^' - diaminodiphenylmethane, Process for the preparation of diamino-dicyclohexyl-N, N'-dibutyl-4,4'-diamino-diphenylmethane, 4 ', 4 "-dialcanes by hydrogenation of diamino-diphenylamino-diphenylpropane- (1,3), 4 ', 4 "-diaminodiphenylalkanes. butane (1,4), 4 ', 4 "-diaminodiphenylpropane- (2,2),

Aus der USA.-Patentschrift 2 606 927 ist bekannt, 5 2,2'-Diamino-diphenylmethan, 2,4'-Diamino-diphedaß man Aminodiphenylalkane in Gegenwart von nylmethan, 2,2'-Diamino-4,4'-dimethyldiphenylme-Äthern, wie Dioxan, und Kobalt- oder Nickelkataly- than. Besondere Bedeutung hat das Verfahren für satoren hydrieren kann. Die nach diesem Verfahren die Hydrierung von 4,4'-Diamino-diphenylmethan und erhaltenen Ausbeuten sind jedoch unbefriedigend. 4',4"-Diamino-diphenylpropan-(2,2). Nach einem anderen Verfahren (deutsche Patent- io Die Hydrierung wird bei Temperaturen über 180⁰C schrift 888.767) erzielt man bei der Hydrierung von durchgeführt. Vorteilhaft wendet man Temperaturen 4,4-Diamino-diphenylmetha.n mit Rutheniumkataly- von t90 bis 280⁰C an. Besonders gute Ergebnisse satoren in Gegenwart von Dioxan gute Ausbeuten. erhält man, wenn man bei Temperaturen von 200 bis Rutheniumkatalysatoren sind jedoch für technische 250⁰C arbeitet. Die Hydrierung verläuft bei Drücken Zwecke weniger geeignet, da sie sehr aufwendig sind. 15 über 50 at. Im allgemeinen arbeitet man bei Weiter ist aus der deutschen Patentschrift 842 200 Drücken zwischen 50 und 500, insbesondere zwischen bekannt, daß die Hydrierung von 4,4'-Diaminodi- 100 und 300 at.From US Pat. No. 2,606,927 it is known that 5 2,2'-diamino-diphenylmethane, 2,4'-diamino-diphedas are aminodiphenylalkanes in the presence of nylmethane, 2,2'-diamino-4,4'-dimethyldiphenylme Ethers, such as dioxane, and cobalt or nickel catalysis. The process is of particular importance for the hydrogenation of aerators. However, the hydrogenation of 4,4'-diaminodiphenylmethane and the yields obtained by this process are unsatisfactory. 4 ', 4 "diamino-diphenylpropane (2,2). According to another process (German Patent io The hydrogenation is writing at temperatures above 180 C ⁰ 888 767) is obtained in the hydrogenation of performed. Advantageously applies to temperatures 4 , 4-diamino-diphenylmetha.n with ruthenium-of t90 to 280 ⁰ C on. particularly good results catalysts in the presence of dioxane in good yields. is obtained if you're at temperatures of 200 to ruthenium catalysts, however, works for technical 250 ⁰ C. The hydrogenation is less suitable at pressures, since it is very expensive, 15 over 50 atm. In general, the German patent 842 200 pressures between 50 and 500, in particular between, know that the hydrogenation of 4.4 '-Diaminodi- 100 and 300 at.

phenylmethan mit Kobalt- oder Nickelkatalysatoren Bevorzugte Katalysatoren enthalten 80 bis 100,phenylmethane with cobalt or nickel catalysts Preferred catalysts contain 80 to 100,

in Gegenwart von hydrophoben Lösungsmitteln und insbesondere 90 bis 100 Gewichtsprozent Kobalt, von Erdalkalimetalloxyden mit guten Ausbeuten ver- 20 Daneben können die Katalysatoren noch Aktivatoren läuft. Dieses Verfahren ist für eine kontinuierliche Ar- enthalten, wie Mangan oder Chrom, z. B. bis zu 20 Gebeitsweise weniger geeignet, da die Katalysatormasse wichtsprozent. Die Katalysatoren können als sogein kontinuierlichem Betrieb nach kurzer Zeit zusam- nannte Voll katalysatoren angewandt werden oder auf menbackt und dadurch ihre Wirkung verliert. Bei Trägern, wie Tonerde, Aluminiumoxyd oder Bimsallen bekannten Verfahren bilden sich bei der Hydrie- 25 stein, gebunden verwendet werden. Trägerkatalysatorung, insbesondere in der Schmelze, Desaminierungs- ren enthalten vorteilhaft 10 bis 50 Gewichtsprozent produkte, die schwer abzutrennen sind. der aktiven Katalysatormasse, bezogen auf die Summein the presence of hydrophobic solvents and in particular 90 to 100 percent by weight cobalt, of alkaline earth metal oxides with good yields. In addition, the catalysts can also activate activators running. This method is for a continuous Ar- contained, such as manganese or chromium, e.g. B. up to 20 parts less suitable because the catalyst mass is weight percent. The catalysts can be used as so Continuous operation after a short period of time called full catalysts can be applied or on baked and thereby loses its effect. For carriers such as clay, aluminum oxide or pumice known processes are formed in the case of hydration stones, which are used in bound form. Supported catalyst, in particular in the melt, deamination ren contain advantageously 10 to 50 percent by weight products that are difficult to separate. the active catalyst mass, based on the total

Es wurde nun gefunden, daß man Diamino-dicyclo- von Katalysatormasse und Träger. Es ist von Vorteil, hexylalkane durch kontinuierliches Hydrieren von Di- wenn die Katalysatoren äußer den genannten Metallen amino-diphenylalkanen bei Temperaturen über 180⁰C 30 noch einen Gehalt, z. B. bis zu 20 Gewichtsprozent und Drücken über 50 at in Gegenwart von Kobalt und an in wäßriger Lösung basisch reagierenden Alkali-Kupfer enthaltenden Hydrierungskatalysatoren, ge- salzen, z. B. Natriumcarbonat, enthalten, gebenenfalls in Anwesenheit inerter Lösungsmittel, Ein wesentliches Merkmal der Erfindung ist es, daßIt has now been found that diamino-dicyclo can be obtained from the catalyst composition and carrier. It is advantageous to add hexylalkanes by continuous hydrogenation of di- if the catalysts outside of the metals mentioned amino-diphenylalkanes at temperatures above 180 ⁰ C 30 still a content, z. B. up to 20 percent by weight and pressures above 50 atm in the presence of cobalt and in aqueous solution containing alkali copper containing hydrogenation catalysts, salts, z. B. sodium carbonate, optionally in the presence of inert solvents, An essential feature of the invention is that

vorteilhafter als bisher erhält, wenn man Kobalt ent- die Katalysatoren weniger als 0,5 Gewichtsprozent, haltende Hydrierungskatalysatoren verwendet, deren 35 jedoch mindestens 0,02 Gewichtsprozent Kupfer, be-Kupfergehalt <0,5 Gewichtsprozent, jedoch minde- zogen auf den Gehalt an Kobalt, haben. Es ist richtig, stens 0,02 Gewichtsprozent, bezogen auf Kobalt, ist, hierauf zu achten, da Kupfer häufig ein Begleitmetall und in dem Reaktionsgemisch einen Wassergehalt von Kobalt ist.more advantageous than before when cobalt contains less than 0.5 percent by weight of the catalysts, Holding hydrogenation catalysts are used, but their 35 is at least 0.02 percent by weight copper, be-copper content <0.5 percent by weight, but less based on the cobalt content. That's right, At least 0.02 percent by weight, based on cobalt, should be taken into account, since copper is often an accompanying metal and there is a water content of cobalt in the reaction mixture.

unter 0,4 Gewichtsprozent, vorteilhaft von 0,001 bis Ein weiteres, wesentliches Merkmal der Erfindungbelow 0.4 percent by weight, advantageously from 0.001 to Another essential feature of the invention

JD,2 Gewichtsprozent, einhält. 4° ist es, daß die Hydrierung unter weitgehendem Aus-JD, 2 percent by weight. 4 ° it is that the hydrogenation is largely effective

Das neue Verfahren hat den Vorteil, daß man Di- Schluß von Wasser durchgeführt wird, wobei die Reamino-dicyclohexylalkane in hohen Ausbeuten er- aktionsgemische während der Hydrierung einen Washält. Das Verfahren hat insbesondere den Vorteil, daß sergehalt unter 0,4 Gewichtsprozent haben. Besonders es unter Beibehaltung der Aktivität des Katalysators gute Ergebnisse werden erzielt, wenn der Wasserkontinuierlich durchgeführt werden kann. Außerdem 45 gehalt 0,001 bis 0,2 Gewichtsprozent beträgt. Man erentstehen neben den Diamino-dicyclohexylalkanen reicht die genannten Wassergehalte am einfachsten, nahezu keine Desaminierungsprodukte, die schwer von indem man entsprechend wasserarme Ausgangsstoffe dem Reaktionsprodukt abgetrennt werden können. zuführt. Die Entfernung des Wassers aus den Aus-The new process has the advantage that it is carried out with water, the reamino-dicyclohexylalkanes er action mixtures in high yields during the hydrogenation. The method has the particular advantage that the water content is less than 0.4 percent by weight. Especially good results are achieved while maintaining the activity of the catalyst if the water can be carried out continuously. In addition, the content is 0.001 to 0.2 percent by weight. One emerges In addition to the diamino-dicyclohexylalkanes, the water content mentioned is the easiest, almost no deamination products that are difficult to obtain by using raw materials that are correspondingly low in water the reaction product can be separated. feeds. The removal of the water from the

Bevorzugte Diamino-diphenylalkane haben die all- gangsstoffen wird beispielsweise, durch Durchleiten gemeine Formel ,, . .50 von inerten Gasen, wie Stickstoff oder Wasserstoff,Preferred diamino-diphenylalkanes have the general substances, for example, by passing them through common formula ,,. .50 of inert gases, such as nitrogen or hydrogen,

<⁵ erreicht. Es ist auch möglich, wasseradsorbierende< ⁵ reached. It is also possible to use water-absorbent

R4¹ ^⁴ Stoffe oder Stoffe, die mit Wasser unter Bildung vonR4 ¹ ^ ⁴ substances or substances that react with water to form

Verbindungen reagieren, wie Calciumoxyd, zu verwenden. Als besonders vorteilhaft hat es sich auch er-55 wiesen, wenn der Wassergehalt im verwendeten Wasserstoff 0,1 Molprozent nicht überschreitet. Einen niedrigen Wassergehalt im verwendeten Wasserstoff erreicht man beispielsweise, wenn man den Wasserworin R₁ für einen Alkylen- oder Alkylidenrest mit stoff im Kreis führt und dabei durch Abkühlen das 1 bis 4 Kohlenstoffatomen, insbesondere mit 1 bis 60 enthaltene Wasser auskondensiert und anschließend 3 Kohlenstoffatomen, steht, R₂ und R₃ Wasserstoff- den Wasserstoff über Wasser adsorbierende Stoffe, atome oder Alkylreste mit 1 bis 4 Kohlenstoffatomen wie Kieselsäuregel, leitet.Compounds react like calcium oxide to use. It has also proven to be particularly advantageous if the water content in the hydrogen used does not exceed 0.1 mol percent. A low water content in the hydrogen used is achieved, for example, if the water word R ₁ for an alkylene or alkylidene radical is circulated with substance and the 1 to 4 carbon atoms, in particular with 1 to 60 contained water, are condensed out by cooling and then 3 carbon atoms, stands, R ₂ and R ₃ hydrogen conducts the hydrogen via water-adsorbing substances, atoms or alkyl radicals with 1 to 4 carbon atoms such as silica gel.

bedeuten und R₄ ein Wasserstoffatom oder einen Al- Es ist möglich, die Hydrierung in Gegenwart vonand R _{4 is} a hydrogen atom or an Al- It is possible to carry out the hydrogenation in the presence of

kylrest mit 1 bis 4 Kohlenstoffatomen bezeichnet. Lösungsmitteln, die unter den Reaktionsbedingungen Besonders bevorzugt sind Ausgangsstoffe, in denen Rj 65 inert sind, durchzuführen. Die Mitverwendung von und R₃ Wasserstoffatome bedeuten. Für die Hydrie- Lösungsmitteln ist jedoch nicht unbedingt erforderrung sind beispielsweise geeignet 4,4'-Diamino-diphe- lieh. Geeignete Lösungsmittel sind beispielsweise Kohnylmethan, 4,4'-Diamino-2,2'-dibutyldiphenylmethan, lenwasserstoffe, wie Toluol oder Cyclohexan, sowiekyl radical with 1 to 4 carbon atoms. Solvents which are particularly preferred under the reaction conditions, starting materials in which Rj 65 are inert, to carry out. The use of and R ₃ mean hydrogen atoms. However, it is not absolutely necessary for the hydrogen solvents to be, for example, 4,4'-diamino-diphe- lent. Suitable solvents are, for example, Kohnylmethane, 4,4'-diamino-2,2'-dibutyldiphenylmethane, lenwasserstoffe, such as toluene or cyclohexane, and

Claims

3 43 4

cyclic ethers, such as tetrahydrofuran or dioxane, ditolylmethane, which by treating with for 2 hours

also amines, such as cyclohexylamine or alkylated nitrogen at 150 ^° C. to 0.02 percent by weight of water

Cyclohexylamines. were dewatered, used as an inlet. The im

The method of the invention leads to examples circle guided hydrogen (2.7 x 10 ^e parts) is by way of playing out by reacting, in a perpendicular STE 5-cooling to 20 ⁰ C followed by treatment

The existing high-pressure pipe is drained from above or below via a silica-filled pipe. The yield of qi-

the fixed Hydrierungskata- amino-dimethyldicyclohexylmethane amounts to 84 ° / ₀ of the described

analyzers at the specified pressure and temperature theory.

conditions hydrogen and diamino-diphenylal- For comparison, the procedure is as described in Example 2, if necessary in the presence of an inert lion, but using a catalyst that conducts solvent, taking care that 1.4 percent by weight of copper, based on cobalt, reaction mixture does not contain the specified water content. The yield decreases within 2 weeks is exceeded. It is advantageous to take the comparable at 54 ° / ₀ of theory, used hydrogen in the circuit and condensed before. , I ₁ its reuse water by cooling 15 B e 1 s ρ ι e 1 3 from. The diamino process is carried out as described in Example 2 and verdicyclohexylalkanes by fractional distillation are used, a catalyst which isolates 0.02 weight. The recovered solvent and percentage of copper, based on cobalt, contains, partially hydrogenated products are returned to the reman diamino-diemethyldicyclohexylmethane in one action. 20 yield of 89 ° / ₀ of theory. The yield drops

The produced by the process of the invention after 4 months to 85% of theory,

th diamino-dicyclohexylalkanes are suitable as Aus.

raw materials for high polymers. 'B e 1 s ρ 1 c I 4

The parts given in the following examples of a high pressure pipe with a catalyst are parts by weight. They relate to the room 25 charged, the 40 percent by weight cobalt oxide, 1.7 parts as kilograms to liters. Contains weight percent sodium carbonate on pumice stone. ... The copper content is 0.2 percent by weight, bebe 1 s ρ 1 e 1 1 moved on to cobalt. The catalyst was 48 hours. A high-pressure tube is charged with a catalyst with hydrogen at 300 ^° C. and 50 atm, the 40 percent by weight of cobalt oxide and 30 percent by weight of the hydrogen was circulated and the 17 percent by weight of sodium carbonate on pumice stone formed in the reaction contains by cooling. The copper content is from 0.2 Gewichtspro- of hydrogen at 2O ⁰ C condensed been centered with respect to cobalt. The catalyst was then reduced hourly at a hydrogen pressure of 230 at and a 48 hours with hydrogen at 300 ⁰ C and 50 at temperature of 227 ⁰ C is passed. The hydrogen was guided 35 52 parts of a dried calcium oxide on the melt in the circuit and the resulting during the reaction of bis (4-amino-phenyl) -methane auskon- together with 3 x by cooling of the hydrogen to 70 ⁰ C 10 * Parts of the volume of hydrogen that has been condensed on silica gel. At a hydrogen pressure of was dried over the catalyst. 230 at and a temperature of 227 ° C. are obtained, bis- (4-amino then 18 parts per hour of a mixture of diamino-cyclohexyl methane in a yield of 92 ° / ₀ of ditolyl methane are passed over an operating time of 6 weeks the catalyst. The starting theory. With a gradual increase in the reactants, they were dried over calcium oxide. They have a temperature of 245 ° C. over the course of a further water content of 0.07 percent by weight. 1.8 · 10 weeks the yield drops to only 89%. 10 * parts of hydrogen are circulated and cooled to 20 ° C. and then dried over an example of 45. The water content of the hydrogen described in Example 1 is 0.01 mol percent reduced catalyst is in the water content of the liquid reaction mixture is 230 ⁰ C and under a Druck'von 230 per hour at 0.1 percent by weight. After a week of operating time a ⁰ to 180 C preheated solution of 24 parts, the feed amount is increased to 33 parts. The reaction mixture, which is 50 bis (4-aminophenyl-hexane) - (1,6), dissolved in 26 parts, is fractionally distilled. Aniline, which was dried over calcium oxide. With an hourly feed of 33 parts, at the same time 2 · 10 * parts by volume of Wasman per hour 28 parts (82% of theory) of an iso-hydrogen which has been dried over silica gel, a mixture of diamino-dimethyldicyclohexyl- are introduced. After the aniline has been distilled off, methanes with a boiling point of 200 to 212 ° C. at 55 are obtained in 91% yield of bis (4-aminocyclohexyl) -20 Torr. hexane (1.6).

For comparison, the same procedure is used as in Example 1 with respect to D i e 1 6 wrote and used a non-drained one

Feed with 0.5 percent by weight of water. Furthermore, the procedure is as described in Example 5,

is hydrogen only at 70 ⁰ C without him Toggle 6 ° applies, however, a solution of 20 parts of bis- (4-amino-

then pass over silica, so that a phenyl) ethane (l, 2) in 30 parts of aniline, which over

Adjusts water content of 17 mol. This gives calcium oxide that has been dried. According to ana-

Diamino - dimethyldicyclohexylmethane with a logical work-up bis- (4-aminocyclohexyl) -ethane- (l, 2)

Yield of 63% of theory. in a yield of 90% of theory.

Example 2 claim:

1- The procedure described in Example 1, with processes for the continuous production of

ie the difference that molten diamino-diamino-dicyclohexylalkanes by hydrogenating

Diamino-diphenylalkanes at temperatures above 180 ^p C and pressures above -50 atm in the presence of cobalt and copper-containing hydrogenation catalysts, optionally in the presence of inert solvents, since this indicates that cobalt-containing hydrogenation catalysts are used, the copper content of which is <0.5 percent by weight, but at least 0.02 percent by weight, based on cobalt, and maintains a water content of less than 0.4 percent by weight, advantageously from 0.001 to 0.2 percent by weight, in the reaction mixture.