Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
1999-09-20
2002-07-16
Padmanabhan, Sreeni (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C502S155000, C556S016000, C556S136000
Reexamination Certificate
active
06420611
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to a process for the preparation of aldehydes by hydroformylation of unsaturated organic compounds in the presence of a Group VIII metal and selected polymeric phosphite ligands. The invention also relates to composition of selected hydroformylation catalysts derived from polymeric phosphite ligands and Group VIII metal.
BACKGROUND OF THE INVENTION
Phosphorus-based ligands are ubiquitous in catalysis and are used for a number of commerically important chemical transformations. Phosphorus-based ligands commonly encountered in catalysis include phosphines and phosphites. These ligands include monophosphine and monophosphite ligands, which are compounds that contain a single phosphorus atom that serves as a donor to a transition metal, and bisphosphine, bisphosphite, and bis(phosphorus) ligands, which contain two phosphorus donor atoms and normally form cyclic chelate structures with transition metals.
An industrially important catalytic reaction using phosphorus-based ligands of particular importance is olefin hydroformylation. Phosphite ligands are particularly good ligands for these reactions. For example, U.S. Pat. No. 5,235,113 describes a hydroformylation process in which an organic bidentate ligand containing two phosphorus atoms linked with an organic dihydroxyl bridging group is used in a homogeneous hydroformylation catalyst system also comprising rhodium. See also Cuny et al.,
J. Am. Chem. Soc.,
1993, 115, 2066; U.S. Pat. Nos. 4,769,498; 4,668,651; 4,885,401; 5,113,022; 5,059,710; 5,235,113; 5,264,616; 4,885,401; and published international applications WO-A-9303839 and WO-A-9518089.
Hydroformylation processes involving organic bidentate ligands containing two trivalent phosphorus atoms, in which the two phosphorous atoms are linked with a 2,2′-dihydroxyl-1,1′-binaphthalene bridging group, are described in U.S. Pat. No. 5,874,641 and the prior art referenced therein. U.S. Pat. No. 5,874,641 describes ligands containing substituents such as esters or ketones on the 3,3′-positions of the 2,2′-dihydroxyl-1,1′-binaphthalene bridging group. Such ligands provide reasonably good selectivity in the hydroformylation of internal olefins to terminal aldehydes.
Recovery of the ligand and catalyst is important for a successful process. Typical separation procedures to remove the product(s) from the catalyst and ligand involve extraction with an immiscible solvent or distillation. It is usually difficult to recover the catalyst and ligand quantitatively. For instance, distillation of a volatile product from a non-volatile catalyst results in thermal degradation of the catalyst. Similarly, extraction results in some loss of catalyst into the product phase. For extraction, one would like to be able to tune the solubility of the ligand and catalyst to disfavor solubility in the product phase. These ligands and metals are often very expensive and thus it is important to keep such losses to a minimum for a commercially viable process.
One method to solve the problem of catalyst and product separation is to attach the catalyst to an insoluble support. Examples of this approach have been previously described, and general references on this subject can be found in “Supported Metal Complexes”, D. Reidel Publishing, 1985, Acta Polymer., 1996, 47, 1; Comprehensive Organometallic Chemistry, Pergamon Press, 1982,553;
J. of Mol. Catal. A,
104, 1995, 17-85 and
Macromol. Symp.
80, 1994, 241. Specifically, monophosphine and monophosphite ligands attached to solid supports are described in these references. Bisphosphine ligands have also been attached to solid supports and used for catalysis, as described in for example U.S. Pat. No. 5,432,289;
J. Mol. Catal. A,
112, 1996, 217; and
J. Chem. Soc., Chem. Commun.,
1996, 653. The solid support in these prior art examples can be organic, e.g., a polymer resin, or inorganic in nature.
Polymer-supported multidentate phosphorus ligands may be prepared by a variety of methods known in the art. See U.S. Pat. Nos. 4,769,498 and 4,668,651 and published international applications WO9303839 and WO9906146 and EP 0864577 A2 and EP0877029 A2. These prior art disclose side-chain polymers containing multidentate phosphorus ligands as pendant groups.
The present invention involves another approach to improving recovery of the catalyst by providing polymeric forms of the bidentate ligands themselves.
There is an increasing need to develop a catalytic process in which the loss of catalyst composition can be substantially reduced during separation of product from the catalyst. An object of the invention is to provide a hydroformylation process. An advantage of the invention is that varying the molecular weight and degree of branching can control the solubility of the catalyst composition. Another advantage of the invention is that the catalyst composition can be substantially recovered by, for example, filtration. Other objects and advantages of the present invention will become apparent as the invention is more fully disclosed below.
SUMMARY OF THE INVENTION
According to a first embodiment of the invention, a process is provided. The process comprises contacting, in the presence of a catalyst, an unsaturated organic compound with a fluid containing hydrogen and carbon monoxide under a condition sufficient to produce an aldehyde wherein said catalyst is selected from the group consisting of catalyst A, catalyst B, and combinations thereof. Catalyst A comprises a Group VIII metal and polymer A that comprises repeat units derived from (1) a carbonyl compound, (2) a monomer, and (3) phosphochloridite. Catalyst B comprises a Group VIII metal and polymer B which comprises repeat units derived from (1) phosphorus trichloride, (2) a polyhydric alcohol, and (3) an aromatic diol.
According to a second embodiment of the invention, a composition is provided that comprises a Group VIII metal and a phosphite polymeric composition selected from the group consisting of polymer A, polymer B, and combinations thereof; the polymer A comprises repeat units derived from (1) a carbonyl compound, (2) a monomer, and (3) phosphochloridite; and the polymer B comprises repeat units derived from (1) phosphorus trichloride, (2) a polyhydric alcohol, and (3) an aromatic diol.
DETAILED DESCRIPTION OF THE INVENTION
The polymeric phosphite composition is also referred to herein as ligand. The ligands suitable for use in the process of the invention are polymer A and polymer B. Polymer A comprises repeat units derived from (1) a carbonyl compound, (2) a monomer, and (3) phosphorochloridite. The monomer is selected from the group consisting of a first polyhydric alcohol, an amine, and combinations thereof. Polymer B comprises repeat units derived from (1) phosphorus trichloride, (2) a second polyhydric alcohol, and (3) an aromatic diol.
The carbonyl compound has the formula of (R
1
O
2
C)
m
(OH)—Ar
1
—(OH)(CO
2
R
1
)
m
, (R
1
O
2
C)
m
(OH)—Ar
2
—A
2
—Ar
2
—(OH)(CO
2
R
1
)
m
, (R
1
O
2
C)
m
(OH)—Ar
2
—Ar
2
—(OH)(CO
2
R
1
)
m
, and combinations of two or more thereof;
The term “polyhydric alcohol” used herein refers to, unless otherwise indicated, a molecule having two or more hydroxyl groups. Generally a polyhydric alcohol can be selected from the group consisting of dialcohols, trialcohols, tetraalcohols, and combinations of two or more thereof.
The first polyhydric alcohol has the formula selected from the group consisting of (HO)
m
—A
1
—(OH)
m
, (HO)
m
—Ar
2
—A
1
—Ar
2
—(OH)
m
, (HO)
m
—Ar
2
—(O)—A
1
—(O)—Ar
2
—(OH)
m
, (HO)
m
—(A
1
—O)
p
—A
1
—(OH)
m
,(HO—A
1
)
m
(OH)—Ar
1
—(OH)(A
1
—OH)
m
, (HO—A
1
)
m
(OH)—Ar
2
—A
2
—Ar
2
—(OH)(A
1
—OH)
m
, (HO—A
1
)
m
(OH)—Ar
2
—Ar
2
—(OH)(A
1
—OH)
m
, (HO)
m
—Ar
2
—(O—A
1
)
p
—O—Ar
2
—(OH)
m
, (OH)
m
—Ar
2
—Ar
2
—(OH)
m
, (OH)
m
—Ar
2
—A
2
—Ar
2
—(OH)
m
, (HO)
m
—Ar
2
—A
1
—C(O)—O—A
1
—O—C(O)—A
1
—Ar
2
—(OH)
m
, (OH)—Ar
1
(OH), and combinations of two or more thereof.
Each Ar
1
is selected from the group consisting of C
6
to C
40
phenylene group, C
12
to C
40
biphenylene gro
Schwierbert Kathryn Eileen
Tam Wilson
E. I. du Pont de Nemours and Company
Padmanabhan Sreeni
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