Process for hydrogenating aromatic di- and polyamines to cycloaliphatic di- and polyamines

Patent metadata

Field	Value
Publication number	US-9278906-B2
Application number	US-201514614183-A
Country	US
Kind code	B2
Filing date	Feb 4, 2015
Priority date	Feb 5, 2014
Publication date	Mar 8, 2016
Grant date	Mar 8, 2016

Abstract

A process for hydrogenating aromatic di- and polyamines is provided comprising the steps of reacting the aromatic amine with hydrogen in the presence of a catalytic system, wherein the catalytic system comprises a heterogeneous catalyst comprising a metal selected from the group consisting of Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and/or Pt and a support, and wherein the catalyst system further comprises an organic nitro compound. Hydrogenation of aromatic di- and polyamines having two or more amino groups bound to the aromatic ring produces cycloaliphatic di- and polyamines, which are useful chemical intermediates, e.g., for further reaction with epoxides or isocyanates. The amino groups may also be converted to isocyanates via reaction with phosgene. The resulting cycloaliphatic di- and polyisocyanates may also be used as monomers for making polymers.

First claim

The invention claimed is:

1. A process for hydrogenating aromatic di- and polyamines comprising the steps of:
reacting, in a reactor, at least one aromatic amine with hydrogen in the presence of a catalytic system, wherein the catalytic system comprises at least one heterogeneous catalyst,
wherein the heterogeneous catalyst comprises a metal selected from the group consisting of Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt and combinations thereof, and
wherein the catalyst system further comprises an organic nitro compound; and obtaining a reaction product from the reaction.

2. The process according to claim 1 , wherein the aromatic amine is selected from the group consisting of o-, m-, and p-phenylenediamine, 2,3-diaminotoluene, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,4-diaminotoluene, 2,3-diamino-p-xylene, 2,5-diamino-p-xylene, 2,6-diamino-p-xylene, N-methyl-o-phenylenediamine, N-ethyl-o-phenylenediamine, 4-methoxy-m-phenylenediamine, N-methyl-m-phenylenediamine, N-ethyl-m-phenylenediamine, N-isobutyl-p-phenylenediamine, N-isoamyl-p-phenylenediamine, N-cyclohexyl-p-phenylenediamine, N-benzyl-p-phenylenediamine, N-phenyl-p-phenylenediamine, N,N′-diethyl-p-phenylenediamine, N,N′-di(n-propyl)-p-phenylenediamine, N-methyl-N′-(n-propyl)-p-phenylenediamine, N-(n-butyl)-N′-benzyl-p-phenylenediamine, N,N′-dibenzyl-p-phenylenediamine, benzidine, N,N,N′,N′-tetramethylbenzidine, 4,4′-oxydianiline, 4,4′-, 2,4′- and/or 2,2′-methylenedianiline, 4,4′-methylene-bis(N,N-dimethylaniline), 4,4′-methylene-bis(N-methylaniline), bis(3-methyl-4-aminophenyl)methane, 4,4′-ethylenedianiline, 2,4-diamino-N-phenylaniline, 2,4-bis(4-aminobenzyl)aniline, 1,2,4,5-tetraaminobenzene, bis(3,4-diaminophenyl)methane and combinations thereof.

3. The process according to claim 2 , wherein the aromatic amine is 2,4-diaminotoluene and/or 2,6-diaminotoluene and the reaction product comprises a mixture of 2,4-diamino-1-methyl-cyclohexane and 2,6-diamino-1-methyl-cyclohexane, wherein ≦50 mol % of said diamino-1-methyl-cyclohexane reaction products are in the cis-cis-isomer configuration and ≦15 mol % of said diamino-1-methyl-cyclohexanes reaction products are in the trans-trans-isomer configuration.

4. The process according to claim 1 , wherein the metal of the heterogeneous catalyst is on a support selected from the group consisting of alumina, silica, titania, ceria, carbon and combinations thereof.

5. The process according to claim 1 , wherein the metal of the first heterogeneous catalyst is ruthenium, rhodium, nickel or cobalt.

6. The process according to claim 1 , wherein two heterogeneous catalysts are utilized, wherein the first heterogeneous catalyst is a supported ruthenium catalyst and the second heterogeneous catalyst is comprised of rhodium on silica, rhodium on alumina, nickel on silica, nickel on alumina, cobalt on silica or cobalt on alumina.

7. The process according claim 1 , wherein the organic nitro compound is selected from the group consisting of nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, all isomers of nitrobutane, nitropentane and nitrohexane, 2-nitroheptane, 2-nitrooctane, nitrocyclopentane, nitrocyclohexane, 4-nitropyridine, 4-nitropiperidine, nitromethylbenzene, nitrobenzene, 4-fluoronitrobenzene, 4-chloronitrobenzene, 4-bromonitrobenzene, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2-nitrophenol, 3-nitrophenol, 4-nitrophenol, 1-methoxy-2-nitrobenzene, 1-methoxy-3-nitrobenzene, 1-methoxy-4-nitrobenzene, N-cyclohexylmethyl-4-nitroaniline, N-(1(4-nitrophenyl)ethyl)cyclohexaneamine, 2- and/or 4-nitrotoluene, 4-isopropylnitrobenzene, nitrostyrene, 4-nitrodiphenylmethane, 1-nitro-4-phenoxybenzene, 2,3-, 2,4-, 2,6- and 3,4-dinitrotoluene, and combinations thereof.

8. The process according to any one of the preceding claims, wherein the process is conducted in the absence of at least one of Pd and Pt.

9. The process according to claim 1 , wherein the organic nitro compound is added to the reactor during the course of the reaction.

10. The process according to claim 1 , wherein the reactor is a trickle bed reactor.

11. The process according to claim 1 , wherein the reaction is carried out at a temperature in the range from ≧120° C. to ≦250° C.

12. The process according to claim 1 , wherein the molar ratio of catalytically active metal or metals in the heterogeneous catalyst or catalysts to organic nitro compound or organic nitro compounds is in a range of ≧0.01 to ≦10.

13. The process according to claim 1 , wherein the catalytic system comprises a mixture of at least two heterogeneous catalysts, wherein the first and the second heterogeneous catalyst comprise a metal selected from the group consisting of Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt and combinations thereof with the further proviso that the metal selected for the second heterogeneous catalyst is different from the metal selected for the first heterogeneous catalyst.

14. The process according to claim 13 , wherein the first heterogeneous catalyst and the second heterogeneous catalyst are spatially separated from each other in the reactor.

Assignees

• Bayer Materialscience Ag

Inventors

• Müller Thomas E
• Gürtler Christoph
• Halpaap Reinhard
• Gebauer-Henke Ewa
• Leitner Walter
• Tomkins Patrick
• Thiebes Christoph

Classifications

• C07C209/72 Primary

  by reduction of six-membered aromatic rings · CPC title

• C07C211/35

  containing only non-condensed rings · CPC title

• C07C2101/14

  Chemistry & Metallurgy · mapped topic

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• C07C2601/14

  The ring being saturated · CPC title