US4879349A
Expired / Lapsed
US
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Selective hydrogenation process
Assignee: Kraton Polymers US LLC
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Filing: 1987-11-05
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Granted: 1989-11-07
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Expires: 2007-11-05
Abstract
Abstract A method for selectively hydrogenating a polymer containing monomer units from at least two different conjugated diolefins, one of which conjugated diolefins is more substituted at the 2, 3 and/or 4 carbon atoms than is the other. The selective hydrogenation can be accomplished with selective hydrogenation catalysts known in the prior art at selected conditions such that ethylenic unsaturation incorporated into the polymer from the lesser substituted conjugated diolefin is hydrogenated while at least a portion of the ethylenic unsaturation incorporated into the polymer by the more substituted conjugated diolefin remains unsaturated. The polymer containing monomer units from at least two different conjugated diolefins may also contain one or more other monomers, particularly monoalkenyl aromatic hydrocarbon monomers. The hydrogenated polymer may be random, tapered or block. The hydrogenated polymers, which will contain a controlled amount of residual ehtylenic unsaturation in the conjugated diolefin portion, may be used in any application in which a completely hydrogenated polymer would be useful. Moreover, the selectively hydrogenated polymer of this invention may be used in compositions where polymers capable of cross-linking through ethylenic unsaturation are required. The selectively hydrogenated polymer of this invention may also be functionalized using methods requiring reaction with ethylenic unsaturation.
Inventors
- 👤 Ronald J. Hoxmeier
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 13:21
CPC Classifications
C; C08; C08C; C08C19/00; C08C19/02; C08F; C08F8/00; C08F8/04
Claims Analysis
Total Claims: 37
Claim 1
Independent Claim
191 words
A method for preparing a selectively hydrogenated copolymer having a residual ethylenic unsaturation of at least 2 and no more than about 20 percent, the method comprising: (a) providing an unsaturated copolymer comprising monomer units of at least two different conjugated diolefins, at least one of said conjugated diolefins being an unsubstituted linear conjugated diolefin capable of imparting Type I ethylenic unsaturation to the copolymer and the other of said conjugated diolefins selected from monomers capable of imparting 2 to about 20%, based on total copolymer ethylenic unsaturation, Type II ethylenic unsaturation; (b) contacting said unsaturated copolymer, in solution, at a temperature within range of about 40° C. to about 110° C., with hydrogen at a partial pressure within range of from about 100 psig to about 1000 psig in the presence of an amount of a selective hydrogenation catalyst and for a time effective for selective hydrogenation of at least about 90% of the Type I and less than about 10% of the Type II ethylenic unsaturation; and (c) recovering a selectively hydrogenated copolymer having a residual ethylenic unsaturation of at least 2 and not more than about 20 percent.
Claim 2
Independent Claim
191 words
A method for preparing a selectively hydrogenated copolymer having a residual ethylenic unsaturation of at least 2 and no more than about 20 percent, the method comprising: (a) providing an unsaturated copolymer comprising monomer units of at least two different conjugated diolefins, at least one of said conjugated diolefins being an unsubstituted linear conjugated diolefin capable of imparting Type I ethylenic unsaturation to the copolymer and the other of said conjugated diolefins selected from monomers capable of imparting 2 to about 20%, based on total copolymer ethylenic unsaturation, Type II ethylenic unsaturation; (b) contacting said unsaturated copolymer, in solution, at a temperature within range of about 40° C. to about 110° C., with hydrogen at a partial pressure within range of from about 100 psig to about 1000 psig in the presence of an amount of a selective hydrogenation catalyst and for a time effective for selective hydrogenation of at least about 90% of the Type I and less than about 10% of the Type II ethylenic unsaturation; and (c) recovering a selectively hydrogenated copolymer having a residual ethylenic unsaturation of at least 2 and not more than about 20 percent.
Claim 3
Dependent Claim
40 words
The method of claim 1 wherein said selective hydrogenation catalyst is obtained by combining a Group VIII metal compound selected from the Group consisting of nickel alkoxides, cobalt alkoxides, nickel carboxylates, cobalt carboxylates and mixtures thereof with an aluminum alkyl.
Claim 4
Dependent Claim
30 words
The method of claim 2 wherein said Group VIII metal compound is a carboxylate and the hydrocarbyl portion of the carboxylate contains from about 2 to about 20 carbon atoms.
Claim 5
Dependent Claim
24 words
The method of claim 3 wherein said aluminum alkyl is an aluminum trialkyl, each alkyl group containing from 1 to about 4 carbon atoms.
Claim 6
Dependent Claim
13 words
The method of claim 4 wherein said Group VIII metal compound is nickel-2-ethylhexanoate.
Claim 7
Dependent Claim
34 words
The method of claim 2 wherein at least one of said conjugated diolefins is unsubstituted at the 2 and 3 carbon atoms end at least one other is substituted at the 2 carbon atom.
Claim 8
Dependent Claim
17 words
The method of claim 6 wherein one of said conjugated diolefins is butadiene and another is isoprene.
Claim 9
Dependent Claim
38 words
The method of claim 2 wherein at least one of said conjugated diolefins contains no substitution at the 2, 3 and 4 carbon atoms and at least one other contains a substitution at the 3 carbon atom thereof.
Claim 10
Dependent Claim
38 words
The method of claim 2 wherein at least one of said conjugated diolefins has no substitution on the 3 and 4 carbon atoms and at least one other conjugated diolefin is substituted at the number 4 carbon atom.
Claim 11
Dependent Claim
18 words
The method of claim 9 wherein one of said conjugated diolefins is butadiene and the other is 4-methyl-1,3-pentadiene.
Claim 12
Dependent Claim
24 words
The method of claim 1 in which the hydrogen partial pressure is within the range of from about 500 psig to about 700 psig.
Claim 13
Dependent Claim
46 words
The method of claim 2 wherein said catalyst is present in an amount sufficient to provide from about 1×10 -3 to about 2×10 -2 mmoles of Group VIII metal per g of polymer and the selective hydrogenation is between Type I and Type II ethylenic unsatruation.
Claim 14
Dependent Claim
46 words
The method of claim 2 wherein said catalyst is present in an amount sufficient to provide from about 1×10 -3 to about 1×10 -1 mmoles of Group VIII metal per g of polymer and the selective hydrogenation is between Type I and Type II ethylenic unsaturation.
Claim 15
Dependent Claim
76 words
The method of claim 1 wherein said polymer comprising monomer units of at least two different conjugated diolefins is a block copolymer comprising at least one polymer block containing monoalkenyl aromatic hydrocarbon monomer units and at least one monomer block which is a conjugated diolefin copolymer containing monomer units of at least two different conjugated diolefins, one of which conjugated diolefins is more substituted at the 2, 3 and/or 4 carbon atoms than is the other.
Claim 16
Dependent Claim
40 words
The method of claim 14 wherein said selective hydrogenation catalyst is obtained by combining a Group VIII metal compound selected from the Group consisting of nickel alkoxides, cobalt alkoxides, nickel carboxylates, cobalt carboxylates and mixtures thereof with an aluminum alkyl.
Claim 17
Dependent Claim
30 words
The method of claim 15 wherein said Group VIII metal compound is a carboxylate and the hydrocarbyl portion of the carboxylate contains from about 2 to about 20 carbon atoms.
Claim 18
Dependent Claim
24 words
The method of claim 16 wherein said aluminum alkyl is an aluminum trialkyl, each alkyl group containing from 1 to about 4 carbon atoms.
Claim 19
Dependent Claim
13 words
The method of claim 17 wherein said Group VIII metal compound is nickel-2-ethylhexanoate.
Claim 20
Dependent Claim
34 words
The method of claim 15 wherein at least one of said conjugated diolefins is unsubstituted at the 2 and 3 carbon atoms and at least one other is substituted at the 2 carbon atom.
Claim 21
Dependent Claim
19 words
The method of claim 19 wherein one of said conjugated diolefins is butadiene and at least one is isoprene.
Claim 22
Dependent Claim
38 words
The method of claim 15 wherein at least one of said conjugated diolefins contains no substitution at the 2, 3 and 4 carbon atoms and at least one other contains a substitution at the 3 carbon atom thereof.
Claim 23
Dependent Claim
38 words
The method of claim 15 wherein at least one of said conjugated diolefins has no substitution on the 3 and 4 carbon atoms and at least one other conjugated diolefin is substituted at the number 4 carbon atom.
Claim 24
Dependent Claim
18 words
The method of claim 22 wherein one of said conjugated diolefins is butadiene and the other is 4-methyl-1,3-pentadiene.
Claim 25
Dependent Claim
46 words
The method of claim 15 wherein said catalyst is present in an amount sufficient to provide from about 1×10 -3 to about 2×10 -2 mmoles of Group VIII metal per g of polymer and the selective hydrogenation is between Type I and Type II ethylenic unsaturation.
Claim 26
Dependent Claim
46 words
The method of claim 15 wherein said catalyst is present in an amount sufficient to provide from about 1×10 -3 to about 1×10 -1 mmoles of Group VIII metal per g of polymer and the selective hydrogenation is between Type I and Type III ethylenic unsaturation.
Claim 27
Dependent Claim
11 words
A selectively hydrogenated copolymer prepared by the process of claim 1.
Claim 28
Dependent Claim
37 words
The selectively hydrogenated polymer of claim 26 wherein at least one of said conjugated diolefins is unsubstituted at the 2, 3 and 4 carbon atoms and at least one other is substituted at the 2 carbon atom.
Claim 29
Dependent Claim
21 words
The selectively hydrogenated polymer of claim 27 wherein one of said conjugated diolefins is butadiene and at least one is isoprene.
Claim 30
Dependent Claim
40 words
The selectively hydrogenated polymer of claim 26 wherein at least one of said conjugated diolefins contains no substitution at the 2, 3 and 4 carbon atoms and at least one other contains a substitution at the 3 carbon atom thereof.
Claim 31
Dependent Claim
41 words
The selectively hydrogenated polymer of claim 26 wherein at least one of said conjugated diolefins has no substitution on the 2, 3 and 4 carbon atoms and at least one other conjugated diolefin is substituted at the number 4 carbon atom.
Claim 32
Dependent Claim
21 words
The selectively hydrogenated polymer of claim 26 wherein one of said conjugated diolefins is butadiene and the other is 4-methyl- 1,3-pentadiene.
Claim 33
Dependent Claim
103 words
The selectively hydrogenated polymer of claim 26 wherein said conjugated diolefin polymer is a block copolymer comprising at least one block containing monoalkenyl aromatic hydrocarbon monomer units and at least one monomer block which is a conjugated diolefin copolymer containing monomer units of at least two different conjugated diolefins, one of which conjugated diolefins is more substituted at the 2, 3 and/or 4 carbon atoms than is the other, the monomer units derived from the conjugated diolefin having he greater amount of hydrogen being selectively hydrogenated while the monomer units derived from the conjugated diolefin having the lesser amount of hydrogen remain unhydrogenated.
Claim 34
Dependent Claim
37 words
The selectively hydrogenated polymer of claim 32 wherein at least one of said conjugated diolefins is unsubstituted at the 2, 3 and 4 carbon atoms and at least one other is substituted at the 2 carbon atom.
Claim 35
Dependent Claim
21 words
The selectively hydrogenated polymer of claim 33 wherein one of said conjugated diolefins is butadiene and at least one is isoprene.
Claim 36
Dependent Claim
41 words
The selectively hydrogenated polymer of claim 32 wherein at least one of said conjugated diolefins has no substitution on the 2, 3 and 4 carbon atoms and at least one other conjugated diolefin is substituted at the number 4 carbon atom.
Claim 37
Dependent Claim
20 words
The selectively hydrogenated polymer of claim 35 wherein one of said conjugated diolefins is butadiene and the other is 4-methyl-1,3-pentadiene.
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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) | 1992-11-06 | 1993-05-08 | 1993-11-07 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1996-11-06 | 1997-05-08 | 1997-11-07 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2000-11-06 | 2001-05-08 | 2001-11-07 | $7700.00 | Window Closed / Lapsed |