Process for hydroformylation using a catalyst based on...

Details Process for hydroformylation using a catalyst based on... Process for hydroformylation using a catalyst based on...

2000-12-07

2002-10-22

Padmanabhan, Sreeni (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Oxygen containing

C568S451000

Reexamination Certificate

active

06469216

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an improved process for hydroformylation of olefinically unsaturated compounds employing a catalyst based on cobalt and/or rhodium used in a two-phase medium. The catalyst based on cobalt and/or rhodium, which comprises at least one cobalt and/or rhodium complex co-ordinated with at least one nitrogen-containing ligand, is dissolved in a non-aqueous ionic solvent which is liquid at a temperature of less than 90° C., in which the aldehydes formed are slightly soluble or insoluble.
Hydroformylation of olefinic compounds is a reaction of major industrial importance and the majority of processes use homogeneous catalysts dissolved in an organic phase constituted by the reactants, products and possibly excess ligand, although difficulties are encountered in separating and recovering the catalyst, in particular when it is used in relatively large quantities, as is the case with catalysts based on cobalt or on a noble metal, as is the case with rhodium-based catalysts.
2. Description of the Prior Art
One solution aimed at solving that problem has been developed by Bartik et al., Organometallics (1993), 12, 164-170, J. Organometal. Chem. (1994), 480, 15-21, and by Beller et al., J. molecular Catal. A: Chemical (1999), 143, 31-39. It consists of carrying out hydroformylation in the presence of an aqueous solution containing a cobalt complex which is rendered water-soluble by the presence of a phosphine-sulfonate ligand such as the sodium salt of trisulfonated triphenylphosphine or a trisulfonated tris-(alkylphenyl)phosphine. International Patent Application WO 97/00132 describes cobalt clusters substituted by trialkoxysilylmethyl groups which render them water-soluble. In that manner, the organic phase containing the aldehydes is readily separated from the aqueous phase containing the catalyst.
A further solution aimed at solving that problem has been described in French Patent No. 2 314 910. It consists of carrying out hydroformylation in the presence of an aqueous solution containing a rhodium complex which is rendered water-soluble by the presence of a sulfonated phosphine ligand which is itself water-soluble, such as the sodium salt of trisulfonated triphenylphosphine. In that manner, the organic phase containing the aldehydes is readily separated from the aqueous phase containing the catalyst. That technique has been studied widely and those studies have been discussed in an article by W. A. Herrmann in “Angewandte Chemie International”, 1993, volume 32, pages 1524 ff.
Despite the huge industrial importance of such techniques for hydroformylation of propylene, such two-phase systems suffer from a lack of solubility of olefins in water, leading to relatively low reaction rates, which render them unsuitable for long chain olefins.
U.S. Pat. No. 3,565,823 describes a technique consisting of dispersing a transition metal compound in a quaternary ammonium or phosphonium salt of tin or germanium with formula (R
1
R
2
R
3
R
4
Z)YX
3
where R
1
, R
2
, R
3
, and R
4
are hydrocarbyl residues containing up to 18 carbon atoms, Z is nitrogen or phosphorous, Y is tin or germanium and X is a halogen, for example chlorine or bromine.
U.S. Pat. No. 3,832,391 claims a process for olefin carbonylation using the same composition. The above compositions have the disadvantage of having a relatively high melting point, for example over 90° C., which complicates manipulation of the catalyst solutions and the reaction products.
Assignee's U.S. Pat. No. 5,874,638 describes that it is possible to benefit both from the advantages of a two-phase operation while avoiding the disadvantages linked to using water and to using compounds with a high melting point, by dissolving certain catalytic compounds of transition metals from groups 8, 9 and 10, known to catalyze hydroformylation, in non-aqueous ionic solvents which are constituted by organic-inorganic salts which are liquid at ambient temperature. This patent on column 3, lines 25-50 states as follows, with respect to the organic ligand associated or complexed with the transition metals:
Organic ligands such as tertiary phosphines, stibines and arsines, phosphites, and in particular arylphosphites can advantageously be associated with all these compounds. They can be mono- or bidentate. These ligands can carry at least one other function such as an amine, ammonium, alcohol, carboxylic acid or sulphonate on the heteroatom and/or on the carbon chain. Examples are triphenylphosphine, triphenylphosphite, trimethylphosphite, the sodium salt of monosulphonated triphenylphosphine, and the sodium salt of monosulphonated triphenylphosphine, and the sodium salt of monosulphonated triphenylphosphine. The choice of transition metal catalytic compound is not critical. Examples are HRh(CO)(PR
3
)
3
, HRh(CO)
2
(PR
3
), HRh(CO)[P(OR)
3
]
3
, Rh(acac)(CO)
2
, (acac represents acetylaccetonate), Rh
6
(CO)
16
, [Rh(norbonadiene)(PPh
3
)
2
]
+
[PF
6
]
−
, [Rh(CO)
3
(PPh
3
)
2
]
+
[BPh
4
]
−
, Rhcl(CO)(PEt
3
)
2
, [RhCl(cyclooctadiene)]
2
, [Rh(CO)
3
(PR
3
)
2
]
+
BPh
4
1
, [Rh(CO)
3
(PR
3
)
2
]
+
PF
6
−
,HCo(CO)
4
, Ru
3
(CO)
12
, [RuH(CO)(acetonitrile)
2
(PPh
3
)
3
]
+
[BF
4
]
−
, PtCl
2
(cyclooctadiene), [Ir(CO)
3
(PPh
3
)]
+
[PF
6
]
−
, [HPt(PEt
3
)
3
]
+
[PF
6
], where R is a hydrocarbyl radical, for example alkyl, cycloalkyl, aryl, which may or may not be substituted. Completely inorganic salts may also be used, such as Rh
2
O
3
, Pd(NO
3
)
2
and Rh(NO
3
)
3
, also halides such as RHCl
3
, 3H
2
O, although halides are not preferred. The transition metal compound and/or the ligand can also be already dissolved in an organic solvent.
SUMMARY OF THE INVENTION
It has now been discovered that the activity and selectivity for the hydroformylation reaction of catalysts based on cobalt and/or rhodium used in an ionic non-aqueous solvent which is liquid at a temperature of less than 90° C. are greatly improved by using nitrogen-containing ligand to complex the cobalt and/or rhodium.
More precisely, the invention provides a process for hydroformylation in the liquid phase of olefinically unsaturated compounds in which the reaction is carried out in the presence of at least one complex of cobalt and/or rhodium co-ordinated by at least one nitrogen-containing ligand, and of at least one non-aqueous ionic solvent comprising at least one organic-inorganic salt with general formula Q
+
A
−
, where Q
+
represents a quaternary ammonium and/or quaternary phosphonium cation and A
−
represents an anion.
The cobalt and/or rhodium precursor compounds of the catalyst are selected from the group formed by cobalt and/or rhodium salts such as acetylacetonates, carboxylates, in particular formate or acetate, and carbonyl complexes, such as dicobalt-octacarbonyl, cobalt-tetracarbonyl hydride, rhodium-dicarbonyl acetylacetonate and carbonyl clusters. The choice of the cobalt and/or rhodium precursor compound is not critical, but in general it is preferable to avoid halides.
The nitrogen-containing ligand is preferably selected from the group formed by monoamines, di-, tri- and polyamines, imines, diimines, pyridine and substituted pyridines, bipyridine, imidazole and substituted imidazoles, pyrrole and substituted pyrroles, pyrazole and substituted pyrazoles. Non limiting examples which can be cited are triethylamine, ethylene diamine, tetramethylethylenediamine, diethylenetriamine, diazabicyclooctane, 1,4,7-trimethyl-1,4,7-triazacyclononane, N,N′-dimethyl-ethane-1,2-diimine, N,N′-di-tert-butyl-ethane-1,2-diimine, N,N′-di-t-butyl-butane-2,3-diimine, N,N′-diphenyl-ethane-1,2-diimine, N,N′-bis-(2,6-dimethylphenyl)-ethane-1,2-diimine, N,N′-bis-(2,6-diisopropyl-phenyl)-ethane-1,2-diimine, N,N′-bis-(2,6-di-t-butyl-phenyl)-ethane-1,2-diimine, N

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