Patent US4268689A successfully refreshed from Google Patents.
US4268689A
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US
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Manufacture of vicinal glycol esters from synthesis gas
Assignee: Huntsman Corp
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Filing: 1979-12-14
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Granted: 1981-05-19
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Expires: 1999-12-14
Abstract
Abstract This invention concerns the improved preparation of glycol esters, such as ethylene glycol diesters, by reaction of carbon monoxide and hydrogen in the presence of a ruthenium or osmium-containing catalyst and a liquid phase medium containing a carboxylic acid co-reactant. The improvement which comprises the invention here also involves use of a co-catalyst species selected from the group consisting of one or more alkali metal salts, alkaline earth metal salts, quaternary ammonium salts, iminium salts and quaternary aliphatic phosphonium salts.
Inventors
- 👤 John F. Knifton
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 04:06
CPC Classifications
C; C07; C07C; C07C67/00; C07C67/36
Claims Analysis
Total Claims: 26
Claim 1
Independent Claim
143 words
In a process for the synthesis of vicinal glycol esters from mixtures of carbon monoxide and hydrogen which comprises the following steps: (a) Contacting said mixtures of carbon monoxide and hydroigen with a liquid medium containing one or more aliphatic carboxylic acids and a catalyst containing a ruthenium or osmium transition-metal or mixtures thereof, (b) Heating said reaction mixture to a temperature of between about 100° C. and 350° C., at superatmospheric pressures of 500 psi or greater with sufficient carbon monoxide and hydrogen to satisfy the stoichiometry of the desired ester syntheses, until substantial formation of the desired esters of the vicinal glycols has been achieved, (c) The improvement which comprises also contacting said mixture with a co-catalyst species selected from the group consisting of alkali metal salts, alkaline earth metal salts, quaternary ammonium salts, iminium salts and quaternary aliphatic phosphonium salts.
Claim 2
Dependent Claim
143 words
In a process for the synthesis of vicinal glycol esters from mixtures of carbon monoxide and hydrogen which comprises the following steps: (a) Contacting said mixtures of carbon monoxide and hydroigen with a liquid medium containing one or more aliphatic carboxylic acids and a catalyst containing a ruthenium or osmium transition-metal or mixtures thereof, (b) Heating said reaction mixture to a temperature of between about 100° C. and 350° C., at superatmospheric pressures of 500 psi or greater with sufficient carbon monoxide and hydrogen to satisfy the stoichiometry of the desired ester syntheses, until substantial formation of the desired esters of the vicinal glycols has been achieved, (c) The improvement which comprises also contacting said mixture with a co-catalyst species selected from the group consisting of alkali metal salts, alkaline earth metal salts, quaternary ammonium salts, iminium salts and quaternary aliphatic phosphonium salts.
Claim 3
Dependent Claim
12 words
The method of claim 1 wherein said vicinal glycol esters are isolated.
Claim 4
Dependent Claim
13 words
The process of claim 1 wherein the ruthenium-containing catalyst is a ruthenium oxide.
Claim 5
Dependent Claim
23 words
The process of claim 3 wherein the ruthenium oxide is selected from the group consisting of ruthenium(IV) dioxide, ruthenium(IV)dioxided hydrate and ruthenium(VIII) tetraoxide.
Claim 6
Dependent Claim
16 words
The process of claim 1 wherein the ruthenium-containing catalyst is the salt of a carboxylic acid.
Claim 7
Dependent Claim
29 words
The process of claim 5 wherein the ruthenium salt is selected from the group consisting of ruthenium acetate, ruthenium propionate, ruthenium butyrate, ruthenium trifluoroacetate, ruthenium acetylacetonate and ruthenium hexafluoroacetylacetonate.
Claim 8
Dependent Claim
16 words
The process of claim 1 wherein the ruthenium-containing catalyst is the salt of a mineral acid.
Claim 9
Dependent Claim
25 words
The process of claim 7 wherein the ruthenium salt is selected from the group consisting of ruthenium chloride hydrate, ruthenium bromide and anhydrous ruthenium chloride.
Claim 10
Dependent Claim
19 words
The process of claim 1 wherein the ruthenium-containing catalyst also contains one or more Group VB tertiary donor ligands.
Claim 11
Dependent Claim
30 words
The process of claim 9 wherein the Group VB tertiary donor ligands are selected from the group consisting of triphenylphosphine, tri-n-butylphosphine, triphenylphosphite, triethylphosphite, trimethylphosphine, triphenylarsine, trimethylamine, triethylamine, tripropylamine, and tri-n-octylamine.
Claim 12
Dependent Claim
21 words
The process of claim 1 wherein the carboxylic acid co-reactant is an aliphatic carboxylic acid of 1 to 12 carbon atoms.
Claim 13
Dependent Claim
24 words
The process of claim 11 wherein the aliphatic carboxylic acid is selected from the group consisting of acetic acid, propionic acid and butyric acid.
Claim 14
Dependent Claim
27 words
The process of claim 11 where the carboxylic acid co-reactant is a substituted aliphatic carboxylic acid selected from the group consisting of trifluoroacetic, dichloroacetic and monofluoroacetic acids.
Claim 15
Dependent Claim
26 words
The process of claim 1 wherein the ruthenium catalyst precursor is residual catalyst from previous syntheses of alcohol and vicinal glycol esters from CO/H 2 mixtures.
Claim 16
Dependent Claim
19 words
The process of claim 1 wherein the alkali metal co-catalyst is an alkali metal salt of a carboxylic acid.
Claim 17
Dependent Claim
28 words
The process of claim 15 wherein the alkali metal salt is selected from the group consisting of cesium acetate, cesium propionate, cesium butyrate, sodium acetate and cesium trifluoroacetate.
Claim 18
Dependent Claim
19 words
The process of claim 1 wherein the quaternary ammonium co-catalyst is a quaternary ammonium salt of a carboxylic acid.
Claim 19
Dependent Claim
22 words
The process of claim 17 wherein the quaternary ammonium salt is selected from the group consisting of tetramethylammonium acetate and tetrapropylammonium acetate.
Claim 20
Dependent Claim
22 words
The process of claim 1 wherein the iminium salt co-catalyst is selected from the group consisting of bis(triphenylphosphine)iminium acetate and bis(triphenylphosphine)iminium nitrate.
Claim 21
Dependent Claim
24 words
The process of claim 1 wherein the alkali metal co-catalyst is present in about 5 to about 15 moles per gram atom of ruthenium.
Claim 22
Dependent Claim
19 words
The process of claim 1 wherein the quaternary phosphonium co-catalyst is a quaternary phosphonium salt of a carboxylic acid.
Claim 23
Dependent Claim
22 words
The process of claim 21 wherein the quaternary phosphonium salt is selected from the group consisting of tetramethylphosphonium acetate and tetrabutylphosphonium acetate.
Claim 24
Dependent Claim
139 words
A process for the synthesis of ethylene glycol diacetate from mixtures of carbon monoxide and hydrogen which comprises the following steps: (a) Contacting said mixtures of carbon monoxide and hydrogen with acetic acid and a catalyst containing ruthenium or osmium transition-metal or mixtures thereof, (b) Heating said reaction mixture to a temperature of between about 100° C. and 350° C., at superatmospheric pressures of 500 psi or greater with sufficient carbon monoxide and hydrogen to satisfy the stoichiometry of the desired ester synthesis until substantial formation of the desired ethylene glycol diacetate has been achieved along with methyl acetate and ethyl acetate co-products; (c) The improvement which comprises also contacting said mixture with a co-catalyst species selected from the group consisting of alkali metal salts, alkaline earth metal salts, quaternary ammonium salts, iminium salts and quaternary aliphatic phosphonium salts.
Claim 25
Dependent Claim
139 words
A process for the synthesis of ethylene glycol diacetate from mixtures of carbon monoxide and hydrogen which comprises the following steps: (a) Contacting said mixtures of carbon monoxide and hydrogen with acetic acid and a catalyst containing ruthenium or osmium transition-metal or mixtures thereof, (b) Heating said reaction mixture to a temperature of between about 100° C. and 350° C., at superatmospheric pressures of 500 psi or greater with sufficient carbon monoxide and hydrogen to satisfy the stoichiometry of the desired ester synthesis until substantial formation of the desired ethylene glycol diacetate has been achieved along with methyl acetate and ethyl acetate co-products; (c) The improvement which comprises also contacting said mixture with a co-catalyst species selected from the group consisting of alkali metal salts, alkaline earth metal salts, quaternary ammonium salts, iminium salts and quaternary aliphatic phosphonium salts.
Claim 26
Dependent Claim
15 words
The process of claim 23 wherein said ethylene glycol diacetate is isolated from said co-products.
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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) | 1984-05-18 | 1984-11-17 | 1985-05-19 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-05-18 | 1988-11-17 | 1989-05-19 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-05-18 | 1992-11-17 | 1993-05-19 | $7700.00 | Window Closed / Lapsed |