US4131743A
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Process for preparing unsaturated diesters
Assignee: JSR Corp
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Filing: 1976-07-06
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Granted: 1978-12-26
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Expires: 1996-07-06
Abstract
Abstract Unsaturated diesters are produced by a process which comprises reacting, in a flowing gaseous phase, a gaseous mixture comprising a conjugated diene, a carboxylic acid and molecular oxygen in the presence of (A) a catalyst comprising palladium, vanadium, antimony and at least one alkali metal carboxylate, or in the presence of (B) a catalyst comprising palladium, vandium, antimony, at least one alkali metal carboxylate and at least one alkali metal halide. The catalyst (A) maintains a high activity and a high selectivity for a long time. The catalyst (B), in which further the alkali metal halide is added, shows a higher activity and a higher selectivity for a longer time. And its activity and selectivity are stable and durable at high temperatures such as 160° - 200° C. Furthermore, the addition of the alkali metal halide suppresses combustion reaction of dienes such as butadiene remarkably. Additionally, the catalysts (A) and (B), especially (B) can be easily reactivated when they lose activity.
Inventors
- 👤 Yoshinori Yoshida
- 👤 Tutomu Kobayashi
- 👤 Hironobu Shinohara
- 👤 Izumi Hanari
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-23 17:08
CPC Classifications
B; B01; B01J; B01J23/00; B01J23/38; B01J23/40; B01J23/44; C; C07; C07C; C07C67/00; C07C67/04; C07C67/05; C07C67/055
Claims Analysis
Total Claims: 27
Claim 1
Independent Claim
181 words
A process for producing unsaturated glycol diesters which comprises reacting in a flowing gaseous phase, a gaseous mixture comprising a conjugated diene of the formula: ##STR3## wherein, each of the R 1 -R 6 groups is independently hydrogen or a hydrocarbon group of 1 to 6 carbon atoms, or wherein two of such groups are joined so that said formula includes cyclopentadiene and cyclohexadiene; and aliphatic, alicyclic or aromatic carboxylic acid; and molecular oxygen at a temperature of 100° C. to 300° C. in the presence of a catalyst carrier, and a catalyst consisting essentially of: (a) palladium in the proportion of 0.1 to 10% by weight based on the weight of the carrier; (b) vanadium in the amount of 0.01 to 20 gram atoms per gram atom of palladium; (c) antimony in an amount of 0.01 to 20 grams per gram atom of palladium, the ratio of antimony to vanadium being 0.1 to 10 in terms of gram atoms, and (d) at least one alkali metal carboxylate in the proportion of 0.01 to 40 m mole per gram of carrier.
Claim 2
Dependent Claim
181 words
A process for producing unsaturated glycol diesters which comprises reacting in a flowing gaseous phase, a gaseous mixture comprising a conjugated diene of the formula: ##STR3## wherein, each of the R 1 -R 6 groups is independently hydrogen or a hydrocarbon group of 1 to 6 carbon atoms, or wherein two of such groups are joined so that said formula includes cyclopentadiene and cyclohexadiene; and aliphatic, alicyclic or aromatic carboxylic acid; and molecular oxygen at a temperature of 100° C. to 300° C. in the presence of a catalyst carrier, and a catalyst consisting essentially of: (a) palladium in the proportion of 0.1 to 10% by weight based on the weight of the carrier; (b) vanadium in the amount of 0.01 to 20 gram atoms per gram atom of palladium; (c) antimony in an amount of 0.01 to 20 grams per gram atom of palladium, the ratio of antimony to vanadium being 0.1 to 10 in terms of gram atoms, and (d) at least one alkali metal carboxylate in the proportion of 0.01 to 40 m mole per gram of carrier.
Claim 3
Dependent Claim
15 words
A process according to claim 1, wherein the carboxylic acid is lower aliphatic carboxylic acid.
Claim 4
Dependent Claim
36 words
A process according to claim 1, wherein said conjugated diene is presented by the following formula: ##STR4## wherein R 1 - R 6 individually are hydrogen or a hydrocarbon group having 1 to 6 carbon atoms.
Claim 5
Dependent Claim
14 words
A process according to claim 1, wherein said conjugated diene is a cyclic diene.
Claim 6
Dependent Claim
20 words
A process according to claim 1, wherein said conjugated diene is butadiene, isoprene, 2,3 dimethyl butadiene, piperylene, cyclopentadiene or cyclohexadiene.
Claim 7
Dependent Claim
18 words
A process according to claim 1, wherein said carboxylic acid is acetic acid, propionic acid or butyric acid.
Claim 8
Dependent Claim
18 words
A process according to claim 1, wherein said alkali metal carboxylate is lithium-, sodium-, potassium-, rubidium- or caesium-carboxylate.
Claim 9
Dependent Claim
14 words
A process according to claim 1, wherein said vanadium is produced from ammonium metavanadate.
Claim 10
Dependent Claim
30 words
A process according to claim 1, wherein said catalyst is carried on a carrier selected from the group consisting of alumina, silica-alumina silica, active carbon, magnesia, diatomaceous earth and carborundum.
Claim 11
Dependent Claim
26 words
A process according to claim 1, wherein said catalyst contains vanadium in the ratio of 0.1 to 10 gram atoms per 1 gram atom of palladium.
Claim 12
Dependent Claim
26 words
A process according to claim 1, wherein said catalyst contains antimony in the ratio of 0.1 to 10 gram atoms per 1 gram atom of palladium.
Claim 13
Dependent Claim
21 words
A process according to claim 1, wherein said reaction is carried out at a temperature of from 100 to 200° C.
Claim 14
Dependent Claim
202 words
A process for producing unsaturated glycol diesters which comprises reacting in a flowing gaseous phase, a gaseous mixture comprising a conjugated diene of the formula: ##STR5## wherein, each of the R 1 -R 6 groups is independently hydrogen or a hydrocarbon group of 1 to 6 carbon atoms, or wherein two of such groups are joined so that said formula includes cyclopentadiene and cyclohexadiene; and aliphatic, alicyclic or aromatic carboxylic acid; and molecular oxygen at a temperature of 100° C. to 300° C. in the presence of a catalyst carrier, and a catalyst consisting essentially of: (a) palladium in the proportion of 0.1 to 10% by weight based on the weight of the carrier; (b) vanadium in the amount of 0.01 to 20 gram atoms per gram atom of palladium; (c) antimony in an amount of 0.01 to 20 gram atoms per gram atom of palladium, the ratio of antimony to vanadium being 0.1 to 10 in terms of gram atoms; (d) at least one alkali metal carboxylate in the proportion of 0.01 to 40 m mole per gram of carrier; and (e) at least one alkali metal halide in an amount of 0.01 to 40 m mole per gram of carrier.
Claim 15
Dependent Claim
202 words
A process for producing unsaturated glycol diesters which comprises reacting in a flowing gaseous phase, a gaseous mixture comprising a conjugated diene of the formula: ##STR5## wherein, each of the R 1 -R 6 groups is independently hydrogen or a hydrocarbon group of 1 to 6 carbon atoms, or wherein two of such groups are joined so that said formula includes cyclopentadiene and cyclohexadiene; and aliphatic, alicyclic or aromatic carboxylic acid; and molecular oxygen at a temperature of 100° C. to 300° C. in the presence of a catalyst carrier, and a catalyst consisting essentially of: (a) palladium in the proportion of 0.1 to 10% by weight based on the weight of the carrier; (b) vanadium in the amount of 0.01 to 20 gram atoms per gram atom of palladium; (c) antimony in an amount of 0.01 to 20 gram atoms per gram atom of palladium, the ratio of antimony to vanadium being 0.1 to 10 in terms of gram atoms; (d) at least one alkali metal carboxylate in the proportion of 0.01 to 40 m mole per gram of carrier; and (e) at least one alkali metal halide in an amount of 0.01 to 40 m mole per gram of carrier.
Claim 16
Dependent Claim
18 words
A process according to claim 13, wherein said alkali metal halide is lithium-, sodium-, potassium-, rubidium- or caesium-halide.
Claim 17
Dependent Claim
36 words
A process according to claim 13, wherein said conjugated diene is represented by the following formula: ##STR6## wherein R 1 - R 6 individually are hydrogen or a hydrocarbon group having 1 to 6 carbon atoms.
Claim 18
Dependent Claim
14 words
A process according to claim 13, wherein said conjugated diene is a cyclic diene.
Claim 19
Dependent Claim
20 words
A process according to claim 13, wherein said conjugated diene is butadiene, isoprene, 2,3 diemethyl butadiene, piperylene, cyclopentadiene or cyclohexadiene.
Claim 20
Dependent Claim
16 words
A process according to claim 13, wherein said carboxylic acid is a lower aliphatic carboxylic acid.
Claim 21
Dependent Claim
18 words
A process according to claim 13, wherein said carboxylic acid is acetic acid, propionic acid or butyric acid.
Claim 22
Dependent Claim
18 words
A process according to claim 13, wherein said alkali metal carboxylate is lithium-, sodium-, potassium-, rubidium- or caesium-carboxylate.
Claim 23
Dependent Claim
14 words
A process according to claim 13, wherein said vanadium is produced from ammonium metavanadate.
Claim 24
Dependent Claim
19 words
A process according to claim 13, wherein said catalyst is carried on a carrier which is alumina or silica-alumina.
Claim 25
Dependent Claim
26 words
A process according to claim 13, wherein said catalyst contains vanadium in the ratio of 0.1 to 10 gram atoms per 1 gram atom of palladium.
Claim 26
Dependent Claim
26 words
A process according to claim 13, wherein said catalyst contains antimony in the ratio of 0.1 to 10 gram atoms per 1 gram atom of palladium.
Claim 27
Dependent Claim
21 words
A process according to claim 13, wherein said reaction is carried out at a temperature of from 100 to 200° C.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1981-12-25 | 1982-06-26 | 1982-12-26 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-12-25 | 1986-06-26 | 1986-12-26 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-12-25 | 1990-06-26 | 1990-12-26 | $7700.00 | Window Closed / Lapsed |