Title of Invention	CO-PRODUCTION OF CYCLOHEXYLAMINE AND BIS-(PARA-AMINOCYCLOHEXYL)METHANE
Abstract	Embodiments of the present invention disclose a process for the co-production of bis(para-aminocyclohexyl) methane (PACM). Also disclosed are articles of manufacture made using PACM produced by methods of this invention. The methods of the present invention generally include using a first mixture having methylene di-aniline (MDA) and a second aromatic amine. The first mixture has less than 15% polymeric MDA by weight and the second aromatic amine is present in an amount to render the first mixture a liquid. The first mixture is hydrogenated to produce a product mixture comprising PACM and at least one second non-aromatic amine.

Title of Invention

CO-PRODUCTION OF CYCLOHEXYLAMINE AND BIS-(PARA-AMINOCYCLOHEXYL)METHANE

Abstract

Embodiments of the present invention disclose a process for the co-production of bis(para-aminocyclohexyl) methane (PACM). Also disclosed are articles of manufacture made using PACM produced by methods of this invention. The methods of the present invention generally include using a first mixture having methylene di-aniline (MDA) and a second aromatic amine. The first mixture has less than 15% polymeric MDA by weight and the second aromatic amine is present in an amount to render the first mixture a liquid. The first mixture is hydrogenated to produce a product mixture comprising PACM and at least one second non-aromatic amine.

Full Text	Co-production of Cvclohexvlamine and bis-fpara-aminocvclohexvl) Methane This application claims priority to US Provisional Patent Application No. 60/636,759 which was filed on December 16,2004 and which is currently still pending. Field of the Invention The present invention relates to an improved process to co-produce bis(para-aminocyclohexyl) methane ("PACM") from a mixture of methylene di-aruline (MDA) and a second aromatic amine, hi particular, embodiments of this invention allow more efficient processes for producing PACM and more control over the isomer content of the PACM. Background Information PACM is traditionally made from MDA via hydrogenation. Methods of making PACM typically include using a MDA feed that includes mixtures of MDA and co-products such as polymeric MDA. This MDA feed with polymeric MDA impurities comes from isocyanate plants that react aniline with formaldehyde to produce the MDA and polymeric MDA Typically these co-products are then phosogenated to produce methyl diphenyl diisocyanate (MDI) and polymeric MDL However, if these co-products are recovered before the phosogenation stage they may be used as a MDA feed that is hydrogenated to produce PACM. This feed is typically 60% to 85% MDA and 15% to 40% polymeric MDA High polymeric MDA is undesirable in the feed when producing PACM because the polymeric MDA results in more unwanted products and the polymeric MDA will typically deactivate the catalyst used in the hydrogenation reaction. In order to decrease the polymeric MDA content of the feed, an operator may remove the polymeric Summary of the Invention Embodiments of the present invention include a process for the co-production of PACM which provides a first mixture having MDA and at least one second aromatic amine. The first mixture has less than 15% by weight polymeric MDA. The second aromatic amine is present in an amount to render the first mixture a liquid. The first mixture is hydrogenated to produce a product mixture having PACM and at least one second non-aromatic amine. Further embodiments may separate the PACM from the product mixture. Embodiments of the present invention have the advantages of a MDA feed with reactants already in a liquid phase. Additionally, the MDA feeds may have minimal polymeric MDA content, allowing purer product and less catalyst deactivation. The processes may also be controlled to allow a desired isomer content in the PACM product Embodiments of the present invention also include articles of manufacture that use PACM produced by the above processes. These articles may include nylons, nylons blends, fabrics, films, molded materials, epoxies, polyurethanes, coatings, lacquers, dispersants, oil additives, viscosity improvers, powder coatings and cosmetic compositions. the purposes of this application, minimal shall mean less than .01% by weight of the first mixture. The first mixture also includes at least one second aromatic amine. In embodiments of the present invention, the second aromatic amine has the benefit as serving as a solvent, thereby reducing the need for an additional solvent in the reaction. In some embodiments of the present invention, the second aromatic amine comprises aniline and expected derivatives and impurities found in aniline. One skilled in the art, with the benefit of this disclosure, will recognize other suitable second aromatic amines for use in this invention. The at least one second aromatic amine is present in the first mixture in an amount to render the first mixture a liquid. This amount may be around 40-50% by weight of the first mixture, however, it may be lower depending on the temperature of the first mixture. MDA is typically a solid at standard temperature and pressure. However, the second aromatic amine acts a solvent to dissolve tlie MDA, making the first mixture easier to handle. In a further embodiment, the first mixture is a liquid at ambient temperature. As discussed by the'examples below, the amount of second aromatic amine used may influence the isomer content (trans-trans, trans-cis, or cis-cis) of PACM produced. In embodiments of the present invention, the second aromatic amine is present in an amount of at least about 30%, 50%, or 70% by weight based on the total weight of the first mixture, including all percentages above 30%. In further embodiments, the second aromatic amine is present in the first mixture in an amount effective for modifying the isomer content to be less than 25% by weight of the trans-trans isomer of PACM, based on the total weight of all isomers of PACM present in the product mixture. Adjusting the aniline content in the first mixture may also have the advantage of increasing the rate of hydrogenation of the MDA. embodiment of the present invention, the preferred catalyst is ruthenium on alumina which is available from Huntsman International LLC of The Woodlands, Texas. For this hydrogenation a hydrogen feed may be used According to embodiments of the present invention, the hydrogenation may occur at any temperature in the range of between about 75°C to about 200°C. Some preferred temperature ranges may be in the range of between about 90°C to about 130°C or in the range of between about 105°C to about 115°C. The hydrogenation according to the present invention may be carried out at any pressure in the range of about 200 to about 5000 pounds per square inch gauge (psig), with about 1500 to about 2500 psig being preferable. One skilled in the art, with the benefit of this disclosure will recognize other suitable methods of hydrogenating the first mixture. By manipulating variables of the hydrogenation reaction, the isomers of PACM produced may be selectively controlled In particular, the aniline concentration, feed rate and temperature can be varied, alone or in combination, to produce a PACM with a desired isomer ratio. As stated above, the aniline content may be used to vary the isomer content of the PACM produced The feed rate may also be adjusted to control the PACM isomers produced. The examples below show that a higher feed rate, resulting in shorter residence time may reduce the amount of trans-trans isomer produced For the production of PACM with a higher trans-trans isomer ratio a slower feed rate, resulting in a longer residence time, may be preferable. Additionally, adjusting the temperature of the hydrogenation may influence the isomers of PACM produced As described in the examples below, lower temperature may lead to a lower trans-trans isomer produced The hydrogenation produces a product mixture that has PACM and a second non-aromatic amine. The second non-aromatic amine may be cyclohexyl amine (CHA) and/or To a tubular reactor filled with 200 cubic centimeters (cc) of glass beads on the bottom served as a preheat zone and 300 cc of a 1% ruthenium/alumina catalyst (commercially available from the Engelhard Corporation of Iselin, New Jersey) was fed a mixture of aniline and methylene dianiline (1 to 1 by weight) and hydrogen at 2000 psig continuously. Various temperatures and feed rates were evaluated The reactor effluent was analyzed by gas chromatography. The results are in Table 1 below. Cyclohexylamine is abbreviated as "CHA" and dicyclohexylamine is abbreviated as lfDCHA,f. The above results indicate that at higher temperature, higher trans-trans isomer PACM product would be obtained. However, by lowering both the feed rate and temperature, a lower trans-trans isomer PACM may be obtained composition of PACM can be achieved. Example II— Preparation of PACM About 2800 grams (gm) of reactor effluent were collected from Run #4 in Table 1. About 1571 gm of the mixture was fractionally distilled. About 624.34 gm of cyclohexylamine and 760.66 gm of colorless liquid PACM were recovered at room What is claimed is: 1) A process for the co-production of bis(para-aminocyclohexyl) methane which comprises the steps of: providing a first mixture having methylene di-aniline and at least one second aromatic amine, wherein the at least one second aromatic amine is present in an amount to render the first mixture a liquid, and wherein the first mixture has less than 15% polymeric methylene di-aniline by weight based on the total weight of the first mixture; and hydrogenating the first mixture to produce a product mixture comprising bis(para-aminocyclohexyl) methane and at least one second non-aromatic amine. 2) A process according to claim 1 further comprising separating the product mixture to recover bis(para-aminocyclohexyl) methane ftom the product mixture. 3) A process according to claim 1 further comprising separating the product mixture to recover the at least one second non-aromatic amine firom the product mixture. 4) A process according to claim 1 wherein the first mixture is liquid at ambient temperature. 5) A process according to claim 1 wherein the at least one second aromatic amine comprises aniline. 6) A process according to claim 1 wherein the at least one second aromatic amine is present in an amount of at least about 50% by weight based on the total weight of the first mixture. 7) A process according to claim 1 wherein the at"least one second aromatic amine is present in an amount of at least about 70% by weight based on the total weight of the first mixture. 8) A process according to claim 1 wherein the first mixture has less than about 5% polymeric methylene di-aniline by weight of the first mixture. 9) A process according to claim 1 wherein the first mixture has less than about 1% polymeric methylene di-aniline by weight of the first mixture, 10) A process according to claim 1 wherein the first mixture contains less than about .01% polymeric methylene di-aniline by weight of the first mixture. 11) A process according to claim 1 wherein hydrogenating the first mixture comprises using a catalyst, wherein the catalyst is selected from group consisting of: iron, cobalt, nickel, ruthenium, titanium, palladium, rhodium, platinum, iridium and combinations thereof. total weight of the first mixture and wherein the aniline is present in an amount to render the first mixture a liquid; hydrogenating the first mixture to produce a product mixture comprising bis(para-aminocyclohexyl) methane and a second non-aromatic amine; and separating the product mixture to recover bis(para-aminocyclohexyl) methane from the product mixture. 25) An article of manufacture produced using bis(para-aminocyclohexyl) methane produced by: providing a first mixture having methylene di-aniline and at least one second aromatic amine, wherein the at least one second aromatic amine is present in an amount to render the first mixture a liquid, and wherein the first mixture has less than 15% polymeric methylene di-aniline by weight based on the total weight of the first mixture; and hydrogenating the first mixture to produce a product mixture comprising bis(para-aminocyclohexyl) methane and at least one second non-aromatic amine. 26) The article of claim 25 wherein the article of manufacture is selected from the group consisting of: a nylon, a nylons blend, a fabric, a film, a molded material, an epoxy, a polyurethane, a coating, a lacquer, a dispersant, an oil additive, a viscosity improver, a powder coating and a cosmetic composition.

Full Text

Co-production of Cvclohexvlamine and bis-fpara-aminocvclohexvl) Methane
This application claims priority to US Provisional Patent Application No. 60/636,759 which was filed on December 16,2004 and which is currently still pending.
Field of the Invention
The present invention relates to an improved process to co-produce bis(para-aminocyclohexyl) methane ("PACM") from a mixture of methylene di-aruline (MDA) and a second aromatic amine, hi particular, embodiments of this invention allow more efficient processes for producing PACM and more control over the isomer content of the PACM.
Background Information
PACM is traditionally made from MDA via hydrogenation. Methods of making PACM typically include using a MDA feed that includes mixtures of MDA and co-products such as polymeric MDA. This MDA feed with polymeric MDA impurities comes from isocyanate plants that react aniline with formaldehyde to produce the MDA and polymeric MDA Typically these co-products are then phosogenated to produce methyl diphenyl diisocyanate (MDI) and polymeric MDL However, if these co-products are recovered before the phosogenation stage they may be used as a MDA feed that is hydrogenated to produce PACM. This feed is typically 60% to 85% MDA and 15% to 40% polymeric MDA High polymeric MDA is undesirable in the feed when producing PACM because the polymeric MDA results in more unwanted products and the polymeric MDA will typically deactivate the catalyst used in the hydrogenation reaction. In order to decrease the polymeric MDA content of the feed, an operator may remove the polymeric

Summary of the Invention
Embodiments of the present invention include a process for the co-production of PACM which provides a first mixture having MDA and at least one second aromatic amine. The first mixture has less than 15% by weight polymeric MDA. The second aromatic amine is present in an amount to render the first mixture a liquid. The first mixture is hydrogenated to produce a product mixture having PACM and at least one second non-aromatic amine. Further embodiments may separate the PACM from the product mixture.
Embodiments of the present invention have the advantages of a MDA feed with reactants already in a liquid phase. Additionally, the MDA feeds may have minimal polymeric MDA content, allowing purer product and less catalyst deactivation. The processes may also be controlled to allow a desired isomer content in the PACM product
Embodiments of the present invention also include articles of manufacture that use PACM produced by the above processes. These articles may include nylons, nylons blends, fabrics, films, molded materials, epoxies, polyurethanes, coatings, lacquers, dispersants, oil additives, viscosity improvers, powder coatings and cosmetic compositions.

the purposes of this application, minimal shall mean less than .01% by weight of the first mixture.
The first mixture also includes at least one second aromatic amine. In embodiments of the present invention, the second aromatic amine has the benefit as serving as a solvent, thereby reducing the need for an additional solvent in the reaction. In some embodiments of the present invention, the second aromatic amine comprises aniline and expected derivatives and impurities found in aniline. One skilled in the art, with the benefit of this disclosure, will recognize other suitable second aromatic amines for use in this invention.
The at least one second aromatic amine is present in the first mixture in an amount to render the first mixture a liquid. This amount may be around 40-50% by weight of the first mixture, however, it may be lower depending on the temperature of the first mixture. MDA is typically a solid at standard temperature and pressure. However, the second aromatic amine acts a solvent to dissolve tlie MDA, making the first mixture easier to handle. In a further embodiment, the first mixture is a liquid at ambient temperature.
As discussed by the'examples below, the amount of second aromatic amine used may influence the isomer content (trans-trans, trans-cis, or cis-cis) of PACM produced. In embodiments of the present invention, the second aromatic amine is present in an amount of at least about 30%, 50%, or 70% by weight based on the total weight of the first mixture, including all percentages above 30%. In further embodiments, the second aromatic amine is present in the first mixture in an amount effective for modifying the isomer content to be less than 25% by weight of the trans-trans isomer of PACM, based on the total weight of all isomers of PACM present in the product mixture. Adjusting the aniline content in the first mixture may also have the advantage of increasing the rate of hydrogenation of the MDA.

embodiment of the present invention, the preferred catalyst is ruthenium on alumina which is available from Huntsman International LLC of The Woodlands, Texas. For this hydrogenation a hydrogen feed may be used According to embodiments of the present invention, the hydrogenation may occur at any temperature in the range of between about 75°C to about 200°C. Some preferred temperature ranges may be in the range of between about 90°C to about 130°C or in the range of between about 105°C to about 115°C. The hydrogenation according to the present invention may be carried out at any pressure in the range of about 200 to about 5000 pounds per square inch gauge (psig), with about 1500 to about 2500 psig being preferable. One skilled in the art, with the benefit of this disclosure will recognize other suitable methods of hydrogenating the first mixture.
By manipulating variables of the hydrogenation reaction, the isomers of PACM produced may be selectively controlled In particular, the aniline concentration, feed rate and temperature can be varied, alone or in combination, to produce a PACM with a desired isomer ratio. As stated above, the aniline content may be used to vary the isomer content of the PACM produced The feed rate may also be adjusted to control the PACM isomers produced. The examples below show that a higher feed rate, resulting in shorter residence time may reduce the amount of trans-trans isomer produced For the production of PACM with a higher trans-trans isomer ratio a slower feed rate, resulting in a longer residence time, may be preferable. Additionally, adjusting the temperature of the hydrogenation may influence the isomers of PACM produced As described in the examples below, lower temperature may lead to a lower trans-trans isomer produced
The hydrogenation produces a product mixture that has PACM and a second non-aromatic amine. The second non-aromatic amine may be cyclohexyl amine (CHA) and/or

To a tubular reactor filled with 200 cubic centimeters (cc) of glass beads on the bottom served as a preheat zone and 300 cc of a 1% ruthenium/alumina catalyst (commercially available from the Engelhard Corporation of Iselin, New Jersey) was fed a mixture of aniline and methylene dianiline (1 to 1 by weight) and hydrogen at 2000 psig continuously. Various temperatures and feed rates were evaluated The reactor effluent was analyzed by gas chromatography. The results are in Table 1 below. Cyclohexylamine is abbreviated as "CHA" and dicyclohexylamine is abbreviated as lfDCHA,f.

The above results indicate that at higher temperature, higher trans-trans isomer PACM product would be obtained. However, by lowering both the feed rate and temperature, a lower trans-trans isomer PACM may be obtained composition of PACM can be achieved.
Example II— Preparation of PACM About 2800 grams (gm) of reactor effluent were collected from Run #4 in Table 1. About 1571 gm of the mixture was fractionally distilled. About 624.34 gm of cyclohexylamine and 760.66 gm of colorless liquid PACM were recovered at room

What is claimed is:
1) A process for the co-production of bis(para-aminocyclohexyl) methane which comprises the steps of:
providing a first mixture having methylene di-aniline and at least one second aromatic amine,
wherein the at least one second aromatic amine is present in an amount to render the first mixture a liquid, and
wherein the first mixture has less than 15% polymeric methylene di-aniline by weight based on the total weight of the first mixture; and
hydrogenating the first mixture to produce a product mixture comprising bis(para-aminocyclohexyl) methane and at least one second non-aromatic amine.
2) A process according to claim 1 further comprising separating the product mixture to recover bis(para-aminocyclohexyl) methane ftom the product mixture.
3) A process according to claim 1 further comprising separating the product mixture to recover the at least one second non-aromatic amine firom the product mixture.
4) A process according to claim 1 wherein the first mixture is liquid at ambient temperature.
5) A process according to claim 1 wherein the at least one second aromatic amine comprises aniline.

6) A process according to claim 1 wherein the at least one second aromatic amine is present in an amount of at least about 50% by weight based on the total weight of the first mixture.
7) A process according to claim 1 wherein the at"least one second aromatic amine is present in an amount of at least about 70% by weight based on the total weight of the first mixture.
8) A process according to claim 1 wherein the first mixture has less than about 5% polymeric methylene di-aniline by weight of the first mixture.
9) A process according to claim 1 wherein the first mixture has less than about 1% polymeric methylene di-aniline by weight of the first mixture,
10) A process according to claim 1 wherein the first mixture contains less than about .01% polymeric methylene di-aniline by weight of the first mixture.
11) A process according to claim 1 wherein hydrogenating the first mixture comprises using a catalyst, wherein the catalyst is selected from group consisting of: iron, cobalt, nickel, ruthenium, titanium, palladium, rhodium, platinum, iridium and combinations thereof.

total weight of the first mixture and wherein the aniline is present in an amount to render the first mixture a liquid;
hydrogenating the first mixture to produce a product mixture comprising bis(para-aminocyclohexyl) methane and a second non-aromatic amine; and
separating the product mixture to recover bis(para-aminocyclohexyl) methane from the product mixture.
25) An article of manufacture produced using bis(para-aminocyclohexyl) methane
produced by:
providing a first mixture having methylene di-aniline and at least one second aromatic amine,
wherein the at least one second aromatic amine is present in an amount to render the first mixture a liquid, and
wherein the first mixture has less than 15% polymeric methylene di-aniline by weight based on the total weight of the first mixture; and
hydrogenating the first mixture to produce a product mixture comprising bis(para-aminocyclohexyl) methane and at least one second non-aromatic amine.
26) The article of claim 25 wherein the article of manufacture is selected from the group
consisting of: a nylon, a nylons blend, a fabric, a film, a molded material, an epoxy, a
polyurethane, a coating, a lacquer, a dispersant, an oil additive, a viscosity improver, a
powder coating and a cosmetic composition.

Documents:

2591-CHENP-2007 FORM-3 19-07-2013.pdf

2591-CHENP-2007 OTHER PATENT DOCUMENT 19-07-2013.pdf

2591-CHENP-2007 AMENDED PAGES OF SPECIFICATION 17-09-2013.pdf

2591-CHENP-2007 AMENDED CLAIMS 17-09-2013.pdf

2591-CHENP-2007 CORRESPONDENCE OTHERS 19-03-2013.pdf

2591-CHENP-2007 CORRESPONDENCE OTHERS 19-07-2013.pdf

2591-CHENP-2007 CORRESPONDENCE OTHERS 24-07-2012.pdf

2591-CHENP-2007 EXAMINATION REPORT REPLY RECEIVED 17-09-2013.pdf

2591-CHENP-2007 FORM-1 24-07-2012.pdf

2591-CHENP-2007 FORM-13 24-07-2012.pdf

2591-CHENP-2007 FORM-2 15-06-2007.pdf

2591-CHENP-2007 POWER OF ATTORNEY 17-09-2013.pdf

2591-CHENP-2007 AMENDED PAGES OF SPECIFICATION 24-07-2012.pdf

2591-CHENP-2007 OTHER DOCUMENT 24-07-2012.pdf

2591-CHENP-2007 ABSTRACT 18-12-2012.pdf

2591-CHENP-2007 CLAIMS 18-12-2012.pdf

2591-CHENP-2007 DESCRIPTION (COMPLET) 18-12-2012.pdf

2591-chenp-2007-correspondnece-others.pdf

2591-chenp-2007-form 1.pdf

2591-chenp-2007-form 26.pdf

2591-chenp-2007-form 3.pdf

2591-chenp-2007-form 5.pdf

2591-chenp-2007-pct.pdf

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Patent Number

257348

Indian Patent Application Number

2591/CHENP/2007

PG Journal Number

39/2013

Publication Date

27-Sep-2013

Grant Date

26-Sep-2013

Date of Filing

15-Jun-2007

Name of Patentee

HUNTSMAN PETROCHEMICAL LLC

Applicant Address

10003 WOODLOCH FOREST DRIVE, THE WOODLANDS, TEXAS 77380.

Inventors:

#	Inventor's Name	Inventor's Address
1	MORFORD, PETER, S	105 CRESTWOOD COURT, AUSTIN, TX, 78746, USA
2	SU, WEI-YANG	5722 DESERT OAK WAY, SPRING, TX 77379.
3	DIGUILIO, RALPH, M	30115 NORTH LAKE FALLS LANE, SPRING, TX 77386, USA

PCT International Classification Number

C07C 209/00

PCT International Application Number

PCT/US05/45360

PCT International Filing date

2005-12-15

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	60/636,759	2004-12-16	U.S.A.