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US4144191A
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Amine-resin supported rhodium-cobalt carbonyl bimetallic clusters as novel hydroformylation catalysts
Assignee: Dow Chemical Co
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Filing: 1977-06-06
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Granted: 1979-03-13
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Expires: 1997-06-06
Abstract
Abstract Olefins are converted to alcohols by a one-step, hydroformylation process comprising contacting an olefin, such as 1-hexene, with a gaseous mixture of carbon monoxide and hydrogen in the presence of a catalyst prepared by loading a bimetallic cluster of the formula: RhxCoyCO12 wherein both x and y are independently integers 1-3 with the proviso that SIGMA (x+y)=4, onto an amine resin, such as Dowex TM MWA-1.
Inventors
- 👤 George E. Hartwell
- 👤 Philip E. Garrou
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 17:14
CPC Classifications
B; B01; B01J; B01J31/00; B01J31/16; B01J31/165; B01J31/1658; B01J31/02; B01J31/06; B01J31/08; B01J31/18; B01J31/1805; B01J31/20; C; C07; C07C; C07C29/00; C07C29/16; C07C45/00; C07C45/49; C07C45/50; B01J2231/00; B01J2231/30; B01J2231/32; B01J2231/321; B01J2531/00; B01J2531/02; B01J2531/0202; B01J2531/0208; B01J2531/80; B01J2531/82; B01J2531/822; B01J2531/84; B01J2531/845
Claims Analysis
Total Claims: 21
Claim 1
Independent Claim
15 words
A catalyst consisting essentially of a rhodium-cobalt carbonyl bimetallic cluster loaded on an amine resin.
Claim 2
Dependent Claim
15 words
A catalyst consisting essentially of a rhodium-cobalt carbonyl bimetallic cluster loaded on an amine resin.
Claim 3
Dependent Claim
38 words
The catalyst of claim 1 prepared by loading onto an amine resin a bimetallic cluster of the formula: Rh.sub.x Co.sub.y (CO).sub.12 wherein x and y are individually integers of 1-3 with the proviso that Σ (x+ y)= 4.
Claim 4
Dependent Claim
21 words
The catalyst of claim 2 comprising at least about 1 weight percent rhodium and at least about 0.5 weight percent cobalt.
Claim 5
Dependent Claim
19 words
The catalyst of claim 3 wherein the amine resin comprises cross-linked, essentially water insoluble swellable gell or macroporous beads.
Claim 6
Dependent Claim
24 words
The catalyst of claim 4 wherein the amine resin has an exchange capacity of at least about 3 milliequivalents per gram of dry resin.
Claim 7
Dependent Claim
60 words
The catalyst of claim 5 wherein the amine resin comprises a cross-linked polymer matrix having pendant amine functionality of the formulae --N(R) 2 and/or --NHR'N(R) 2 wherein each R is individually hydrogen or C 1 -C 6 alkyl, R' is C 2 -C 6 alkylene, and the open valence is the bond that joins the functionality to the polymer matrix.
Claim 8
Dependent Claim
12 words
The catalyst of claim 6 wherein x and y are each 2.
Claim 9
Dependent Claim
17 words
The catalyst of claim 7 wherein the pendant amine functionality is of the formula --N(R) 2 .
Claim 10
Dependent Claim
20 words
The catalyst of claim 8 wherein the amine resin comprises a cross-linked polystyrene polymer matrix and each R is methyl.
Claim 11
Dependent Claim
21 words
The catalyst of claim 9 comprising at least about 4 weight percent rhodium and at least about 2.5 weight percent cobalt.
Claim 12
Dependent Claim
27 words
A method of preparing the catalyst of claim 1, the method comprising contacting in an inert, liquid medium a rhodium-cobalt carbonyl bimetallic cluster with an amine resin.
Claim 13
Dependent Claim
36 words
The method of claim 11 wherein the bimetallic cluster is of the formula Rh x Co y (CO) 12 wherein x and y are individually integers of 1-3 with the proviso that Σ (x++ y)= 4.
Claim 14
Dependent Claim
25 words
The method of claim 12 wherein the bimetallic cluster and amine resin are contacted at a cluster:resin mole equivalents ratio of at least about 1:100.
Claim 15
Dependent Claim
21 words
The method of claim 13 wherein the inert liquid medium comprises one or more aliphatic or aromatic hydrocarbon or substituted hydrocarbon.
Claim 16
Dependent Claim
34 words
The method of claim 14 wherein the amine resin comprises cross-linked, essentially water insoluble swellable gell or macroporous beads having an exchange capacity of at least about 3 milliequivalents per gram of dry resin.
Claim 17
Dependent Claim
60 words
The method of claim 15 wherein the amine resin comprises a cross-linked polymer matrix having pendant amine functionality of the formulae --N(R) 2 and/or --NHR'N(R) 2 wherein each R is individually hydrogen or C 1 -C 6 alkyl, R' is C 2 -C 6 alkylene, and the open valence is the bond that joins the functionality to the polymer matrix.
Claim 18
Dependent Claim
12 words
The method of claim 16 wherein x and y are each 2.
Claim 19
Dependent Claim
17 words
The method of claim 17 wherein the pendant amine functionality is of the formula --N(R) 2 .
Claim 20
Dependent Claim
18 words
The method of claim 18 wherein the resin comprises a cross-linked polystyrene matrix and each R is methyl.
Claim 21
Dependent Claim
16 words
The method of claim 19 wherein the contacting is conducted for at least about 2 hours.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1982-03-12 | 1982-09-11 | 1983-03-13 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1986-03-12 | 1986-09-11 | 1987-03-13 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1990-03-12 | 1990-09-11 | 1991-03-13 | $7700.00 | Window Closed / Lapsed |