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US4201728A Expired / Lapsed US ⏱️ 0.0 years remaining

Hydroformylation catalyst and process

Assignee: Celanese Corp
•
Filing: 1977-08-19
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Granted: 1980-05-06
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Expires: 1997-08-19
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Abstract

Abstract This invention provides a catalyst and process for achieving highly selective straight chain aldehyde formation from alpha-olefins under hydroformylation conditions. The improved hydroformylation results are obtained under mild conditions of temperature and pressure in the presence of a stabilized catalyst complex of rhodium metal, bidentate ligand and monodentate ligand represented by the formula: <IMAGE> Illustrative of a preferred bidentate ligand is trans 1,2-bis(diphenylphosphinomethyl)cyclobutane. Illustrative of a preferred monodentate ligand is diphenylethylphosphine. It is an essential feature of the invention process that the monodentate ligand is provided in a molar excess with respect to the rhodium metal in the stabilized catalyst complex.

Inventors

  • 👤 O. Richard Hughes

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-23 23:03
CPC Classifications
C; C07; C07F; C07F15/00; C07F15/0006; C07F15/0073; C07F15/008; B; B01; B01J; B01J23/00; B01J23/16; C07C; C07C45/00; C07C45/49; C07C45/50

Claims Analysis

Total Claims: 30
Claim 1
Independent Claim 230 words
In a process for the production of an alkanal- 1 by hydroformylation of an alpha-olefin, the improvement which comprises contacting an alpha-olefin containing between about 3-30 carbon atoms with hydrogen and carbon monoxide at a temperature between about 25° C. and 150° C. and a pressure between about 15 and 3000 psi in the presence of a catalyst consisting essentially of a stabilized complex of rhodium metal, bidentate ligand and monodentate ligand, which catalyst components are provided in a molar ratio of 1 mole of bidentate ligand and between about 1.2-800 moles of monodentate ligand per gram atom of rhodium metal in the hydroformylation medium, and said catalyst complex corresponding to the structural formula: ##STR13## wherein L is a bidentate ligand having the formula: ##STR14## wherein Z is an alicyclic structure; Q is a group VA element selected from nitrogen, phosphorus and arsenic; and R is an organic radical selected from aliphatic, alicyclic and aromatic groups containing between one and about 20 carbon atoms; and wherein L' is a monodentate ligand having the formula: Q'R'.sub.3 where Q' is a group VA element selected from nitrogen, phosphorus and arsenic; R' is an organic radical selected from aliphatic, alicyclic and aromatic groups containing between one and about 20 carbon atoms; and the steric parameter θ of Q'R' 3 in the catalyst complex is an apex angle between about 135 and 150 degrees.
Claim 2
Dependent Claim 230 words
In a process for the production of an alkanal- 1 by hydroformylation of an alpha-olefin, the improvement which comprises contacting an alpha-olefin containing between about 3-30 carbon atoms with hydrogen and carbon monoxide at a temperature between about 25° C. and 150° C. and a pressure between about 15 and 3000 psi in the presence of a catalyst consisting essentially of a stabilized complex of rhodium metal, bidentate ligand and monodentate ligand, which catalyst components are provided in a molar ratio of 1 mole of bidentate ligand and between about 1.2-800 moles of monodentate ligand per gram atom of rhodium metal in the hydroformylation medium, and said catalyst complex corresponding to the structural formula: ##STR13## wherein L is a bidentate ligand having the formula: ##STR14## wherein Z is an alicyclic structure; Q is a group VA element selected from nitrogen, phosphorus and arsenic; and R is an organic radical selected from aliphatic, alicyclic and aromatic groups containing between one and about 20 carbon atoms; and wherein L' is a monodentate ligand having the formula: Q'R'.sub.3 where Q' is a group VA element selected from nitrogen, phosphorus and arsenic; R' is an organic radical selected from aliphatic, alicyclic and aromatic groups containing between one and about 20 carbon atoms; and the steric parameter θ of Q'R' 3 in the catalyst complex is an apex angle between about 135 and 150 degrees.
Claim 3
Dependent Claim 13 words
A process in accordance with claim 1 wherein the alpha-olefin reactant is hexene-1.
Claim 4
Dependent Claim 13 words
A process in accordance with claim 1 wherein the alpha-olefin reactant is styrene.
Claim 5
Dependent Claim 14 words
A process in accordance with claim 1 wherein the alpha-olefin reactant is acrolein acetal.
Claim 6
Dependent Claim 14 words
A process in accordance with claim 1 wherein the alpha-olefin reactant is allyl alcohol.
Claim 7
Dependent Claim 14 words
A process in accordance with claim 1 wherein the alpha-olefin reactant is acrylic acid.
Claim 8
Dependent Claim 14 words
A process in accordance with claim 1 wherein the alpha-olefin reactant is vinyl acetate.
Claim 9
Dependent Claim 41 words
A process in accordance with claim 1 wherein the molar ratio of hydrogen to carbon monoxide is in the range between about 10:1 and 1:10, and the hydrogen and carbon monoxide are provided in a stoichiometric excess in the hydroformylation medium.
Claim 10
Dependent Claim 14 words
A process in accordance with claim 1 wherein the bidentate ligand is trans 1,2-bis(diphenylphosphinomethyl)-cyclobutane.
Claim 11
Dependent Claim 14 words
A process in accordance with claim 1 wherein the bidentate ligand is trans 1,2-bis(diphenylphosphinomethyl)-3,5-dioxa-4,4-dimethylcyclopentane.
Claim 12
Dependent Claim 13 words
A process in accordance with claim 1 wherein the monodentate ligand is diphenylmethylphosphine.
Claim 13
Dependent Claim 13 words
A process in accordance with claim 1 wherein the monodentate ligand is diphenylethylphosphine.
Claim 14
Dependent Claim 13 words
A process in accordance with claim 1 wherein the monodentate ligand is diethylphenylphosphine.
Claim 15
Dependent Claim 13 words
A process in accordance with claim 1 wherein the monodentate ligand is tris(trifluoromethyl)phosphine.
Claim 16
Dependent Claim 13 words
A process in accordance with claim 1 wherein the monodentate ligand is tri(o-tolyl)phosphite.
Claim 17
Dependent Claim 13 words
A process in accordance with claim 1 wherein the monodentate ligand is tri(isobutyl)phosphine.
Claim 18
Dependent Claim 13 words
A process in accordance with claim 1 wherein the monodentate ligand is tri(isobutyl)amine.
Claim 19
Dependent Claim 13 words
A process in accordance with claim 1 wherein the monodentate ligand is tri(isobutyl)arsine.
Claim 20
Dependent Claim 13 words
A process in accordance with claim 1 wherein the monodentate ligand is triphenylamine.
Claim 21
Dependent Claim 13 words
A process in accordance with claim 1 wherein the monodentate ligand is triphenylphosphine.
Claim 22
Dependent Claim 13 words
A process in accordance with claim 1 wherein the monodentate ligand is tri(p-tolyl)phosphine.
Claim 23
Dependent Claim 13 words
A process in accordance with claim 1 wherein the monodentate ligand is tri(m-fluorophenyl)phosphine.
Claim 24
Dependent Claim 13 words
A process in accordance with claim 1 wherein the monodentate ligand is tri(o-isopropylphenyl)phosphite.
Claim 25
Dependent Claim 13 words
A process in accordance with claim 1 wherein the monodentate ligand is isopropyldiphenylphosphine.
Claim 26
Dependent Claim 41 words
A process in accordance with claim 1 wherein the catalyst components are provided in a molar ratio of 1 mole of bidentate ligand and between about 5-100 moles of monodentate ligand per gram atom of rhodium metal in the hydroformylation medium.
Claim 27
Dependent Claim 24 words
A process in accordance with claim 1 wherein the alpha-olefin is hexene-1, the bidentate ligand is trans 1,2-bis(diphenylphosphinomethyl)cyclobutane, and the monodentate ligand is diphenylethylphosphine.
Claim 28
Dependent Claim 13 words
A process in accordance with claim 26 wherein the monodentate ligand is tri(isobutyl)phosphine.
Claim 29
Dependent Claim 13 words
A process in accordance with claim 26 wherein the monodentate ligand is triphenylphosphine.
Claim 30
Dependent Claim 24 words
A process in accordance with claim 1 wherein the alpha-olefin is hexene-1, the bidentate ligand is trans 1,2-bis(diphenylphosphinomethyl)-3,5-dioxa-4,4-dimethylcyclopentane, and the monodentate ligand is diphenylethylphosphine.

References Cited (Backward Citations)

US3239566A Cited
US3480659A Cited
US3527809A Cited
US3939188A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1983-05-06 1983-11-05 1984-05-06 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1987-05-06 1987-11-05 1988-05-06 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1991-05-06 1991-11-05 1992-05-06 $7700.00 Window Closed / Lapsed

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