Process for hydrogenating aromatic di- and polyamines

Patent metadata

Field	Value
Publication number	US-9403754-B2
Application number	US-201514614013-A
Country	US
Kind code	B2
Filing date	Feb 4, 2015
Priority date	Feb 5, 2014
Publication date	Aug 2, 2016
Grant date	Aug 2, 2016

Abstract

A catalytic process for hydrogenating aromatic di- and polyamines with the aid of a selected catalyst system is provided, which comprises a mixture of a first heterogeneous catalyst and a second heterogeneous catalyst and a nitro compound (nitrate and/or nitrite salt). The first and second heterogeneous catalyst each independently comprise 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 the metal selected for the second heterogeneous catalyst is different from the metal selected for the first heterogeneous catalyst. Hydrogenation of aromatic rings 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 amines comprising the steps of:
reacting, in a reactor, a mixture of 2,4-diaminotoluene and 2,6-diaminotoluene with hydrogen in the presence of a catalytic system,
wherein the catalytic system comprises a mixture of a first heterogeneous catalyst comprising Ru and a second heterogeneous catalyst comprising Rh,
wherein the catalytic system further comprises a nitrate salt, a nitrite salt or a combination thereof, and
obtaining from the reaction a reaction product comprising a mixture of 2,4-diamino-1-methyl-cyclohexane and 2,6-diamino-1-methyl-cyclohexane, wherein ≦45 mol % of said diamino-1-methyl-cyclohexane reaction products are in the cis-cis-isomer configuration and ≦22 mol % of said diamino-1-methyl-cyclohexane reaction products are in the trans-trans-isomer configuration,
wherein the initial rate of the reaction is ≧0.0052 mol H 2 /min/g of the catalytic system.

2. The process according to claim 1 , wherein ≦20 mol % of said diamino-1-methyl-cyclohexane reaction products are in the trans-trans-isomer configuration.

3. The process according to claim 1 , wherein the metal of the first and/or second heterogeneous catalyst is on a support selected from the group consisting of alumina, silica, titania, ceria, carbon, and combination thereof.

4. The process according to claim 1 , wherein the first heterogeneous catalyst is comprised of ruthenium on silica or ruthenium on alumina and the second heterogeneous catalyst is comprised of rhodium on silica or rhodium on alumina.

5. The process according to claim 1 , wherein the first heterogeneous catalyst and the second heterogeneous catalyst are spatially separated from each other in the reactor.

6. The process according to claim 1 , wherein the metal of the first heterogeneous catalyst and the metal of the second heterogeneous catalyst are present as individual nanoparticles on a common support.

7. The process according to claim 1 , wherein the process is conducted in the absence of at least one of Pd and Pt.

8. The process according to claim 1 , wherein either the nitrate salt, the nitrite salt, or both, are selected as follows:
the nitrate salt is selected from the group consisting of LiNO 3 , NaNO 3 , KNO 3 , NR′ 4 NO 3 , PR′ 4 NO 3 , and combinations thereof, wherein R′ is a C1 to C18 alkyl or aryl group and each R′ may be different,
and
the nitrite salt is selected from the group of LiNO 2 , NaNO 2 , KNO 2 , NR′ 4 NO 2 , PR′ 4 NO 2 , wherein R′ is a C1 to C18 alkyl or aryl group and each R′ may be different.

9. The process according to claim 8 , wherein the nitrate salt and/or nitrite salt is added into 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 reaction is carried out in the presence of a solvent having ether or alcohol groups.

Assignees

• Bayer Materialscience Ag

Inventors

• Müller Thomas E
• Gürtler Christoph
• Halpaap Reinhard
• Thiebes Christoph
• Gebauer-Henke Ewa
• Castro Cevallos Isabel U
• Leitner Walter

Classifications

• C07C2101/14

  Chemistry & Metallurgy · mapped topic

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• C07C209/72 Primary

  by reduction of six-membered aromatic rings · CPC title

• B01J23/464

  Rhodium · CPC title

• C07C211/36

  containing at least two amino groups bound to the carbon skeleton · CPC title