Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From carboxylic acid or derivative thereof
Reexamination Certificate
1999-09-20
2001-09-04
Truong, Duc (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From carboxylic acid or derivative thereof
C528S398000, C528S491000, C525S418000, C525S420000, C525S434000, C525S437000
Reexamination Certificate
active
06284865
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to a polymeric phosphite composition and polymeric phosphite catalyst composition that can be useful for a variety of catalytic processes, to a process for producing the composition, and to a process for using the composition in the hydrocyanation of unsaturated organic compounds and the isomerization of unsaturated nitrites.
BACKGROUND OF THE INVENTION
Phosphorus-based ligands are ubiquitous in catalysis, finding use for a number of commerically important chemical transformations. Phosphorus-based ligands commonly encountered in catalysis include phosphines and phosphites. Monophosphine and monophosphite ligands are compounds which contain a single phosphorus atom which serves as a donor to a transition metal. Bisphosphine, bisphosphite, and bisphosphorus) ligands in general, contain two phosphorus donor atoms and typically form cyclic chelate structures with transition metals.
Two industrially important catalytic reactions using phosphorus ligands of particular importance are olefin hydrocyanation and isomerization of branched nitrites to linear nitrites. Phosphite ligands are particularly good ligands for both reactions. The hydrocyanation of ethylenically unsaturated compounds using transition metal complexes with monodentate phosphite ligands is well documented in the prior art. See for example U.S. Pat. Nos. 3,496,215; 3,631,191; 3655,723; 3,766,237; and 5,543,536. Bidentate phosphite ligands have also been shown to be particularly useful ligands in the hydrocyanation of activated ethylenically unsaturated compounds. See for example, Baker, M. J., and Pringle, P. G.,
J. Chem. Soc., Chem. Commun
., 1292, 1991; Baker et al.,
J. Chem. Soc., Chem. Commun
., 803, 1991; WO 93,03839; U.S. Pat. Nos. 5,512,696; 5,723,641; 5,688,986.
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, Pergarnon Press, 1982, Chapter 55; and Beller, M., Cornils, B., Frohning, C. D., Kohlpaintner, C. W.,
Journal of Molecular Catalysis A
, 104, 1995, 17-85 and
Macromol. Symp
. 1994, 80, 241. Specifically, monophosphine and monophosphite ligands attached to solid supports are described in these references. Bisphospine 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
, 1996, 112,217; 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. The prior art discloses side-chain polymers containing multidentate phosphorus ligands as pendant groups.
There is always a need to develop a composition that can be used as or in a catalyst with substantially reduced loss during a catalytic reaction or separation of product from the catalyst. An object of the present invention is, therefore, to provide such a composition and to provide processes for making and for using the composition.
An advantage of the invention composition is that varying the molecular weight and degree of branching can control the solubility of the composition. Another advantage of the invention is that the catalyst produced by the composition can be substantially recovered by 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 composition is provided. The composition is selected from the group consisting of composition A, composition B, and combinations thereof. Composition A comprises repeat units derived from (1) a carbonyl compound, (2) a monomer, and (3) phosphorochloridite. Composition B comprises repeat units derived from (1) phosphorus trichloride, (2) a polyhydric alcohol, and (3) an aromatic diol. The monomer can be a first polyhydric alcohol, an amine, or combinations thereof.
According to a second embodiment of the invention, a composition that can be used as a catalyst is provided, which comprises (1) composition disclosed in the first embodiment, (2) a Group VIII metal selected from Ni, Co, Pd, and combinations of two or more thereof, and optionally (3) a Lewis acid.
According to a third embodiment of the invention, a process that can be used for producing composition A is provided, which comprises (1) contacting a carbonyl compound with a monomer to produce an intermediate and (2) contacting the intermediate with phosphorochloridite.
According to a fourth embodiment of the invention, a process that can be used for producing composition B is provided, which comprises (1) contacting phosphorus trichloride with a second polyhydric alcohol under a condition sufficient to produce a phosphorus-containing polymer and (2) contacting the phosphorus-containing polymer with an aromatic diol.
According to a fifth embodiment of the invention, a process that can be used for producing composition B is provided, which comprises (1) contacting an N,N-dialkyl dichlorophosphoramidite with a second polyhydric alcohol under a condition sufficient to produce a polymeric phosphoramidite, (2) contacting the polymeric phosphoramidite with an acid, and (3) contacting the resultant polymer with an aromatic diol.
According to a sixth embodiment of the invention, a process is provided. The process comprises contacting, in the presence of a catalyst disclosed in the second embodiment of the invention, an unsaturated organic compound with a hydrogen cyanide-containing fluid under a condition sufficient to produce a nitrile.
According to a seventh embodiment of the invention, a process is provided. The process comprises contacting a nitrile with the catalyst disclosed in the second embodiment of the invention to produce linear 3-alkenenitrile.
DETAILED DESCRIPTION OF THE INVENTION
The polymeric phosphite compositions disclosed in the invention are also referred to as ligands in the application. According to the first embodiment of the invention, composition A comprises, consist essentially of, or consist of repeat units derived from (1) a carbonyl compound, (2) a monomer, and (3) phosphorchmoridite.
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 monomer is selected from the group consisting of a first polyhydric alcohol, a diamine, a triamine, a tetra amine, and combinations 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.
T
Greene Robin Nikolas
Kristjansdottir Sigridur Soley
Tam Wilson
E. I. Du Pont de Nemours and Company
Truong Duc
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