US5039755A
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Selective hydrogenation of conjugated diolefin polymers
Assignee: Kraton Polymers US LLC
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Filing: 1990-05-29
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Granted: 1991-08-13
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Expires: 2010-05-29
Abstract
Abstract This is a process for the preparation of hydrogenated conjugated diolefin polymers which comprises terminating a living polymer obtained by polymerizing or copolymerizing at least a conjugated diolefin with an organo-alkali metal polymerization initiator in a suitable solvent, by the addition of hydrogen, and effecting selective hydrogenation of the unsaturated double bonds in the conjugated diolefin units of the terminated polymer by contacting the polymer, in the absence of hydrocarbon lithium and alkoxy lithium compounds, with hydrogen in the presence of at least one bis(cyclopentadienyl)titanium compound.
Inventors
- 👤 Linda R. Chamberlain
- 👤 Carma J. Gibler
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 16:23
CPC Classifications
C; C08; C08F; C08F10/00; C08C; C08C19/00; C08C19/02; C08F36/00; C08F36/02; C08F36/04
Claims Analysis
Total Claims: 29
Claim 1
Independent Claim
139 words
A process for the hydrogenation of conjugated diolefin polymers which comprises: (a) polymerizing or copolymerizing at least one conjugated diolefin with an organo-alkali metal polymerization initiator in a suitable solvent thereby creating a living polymer, (b) terminating the polymerization by the addition of H 2 prior to hydrogenation, and (c) after termination selectively hydrogenating the unsaturated double bonds in the conjugated diolefin units of said terminated polymer by contacting the polymer, in the absence of hydrocarbon lithium and alkoxy lithium compounds, with hydrogen in the presence of at least one bis(cyclopentadienyl)titanium compound of the formula: ##STR3## wherein R 1 and R 2 are the same or different and are selected from the group consisting of halogen groups, C 1 -C 8 alkyl and alkoxy groups, C 6 -C 8 aryloxy groups, aralkyl, cycloalkyl groups, silyl groups and carbonyl groups.
Claim 2
Dependent Claim
139 words
A process for the hydrogenation of conjugated diolefin polymers which comprises: (a) polymerizing or copolymerizing at least one conjugated diolefin with an organo-alkali metal polymerization initiator in a suitable solvent thereby creating a living polymer, (b) terminating the polymerization by the addition of H 2 prior to hydrogenation, and (c) after termination selectively hydrogenating the unsaturated double bonds in the conjugated diolefin units of said terminated polymer by contacting the polymer, in the absence of hydrocarbon lithium and alkoxy lithium compounds, with hydrogen in the presence of at least one bis(cyclopentadienyl)titanium compound of the formula: ##STR3## wherein R 1 and R 2 are the same or different and are selected from the group consisting of halogen groups, C 1 -C 8 alkyl and alkoxy groups, C 6 -C 8 aryloxy groups, aralkyl, cycloalkyl groups, silyl groups and carbonyl groups.
Claim 3
Dependent Claim
74 words
The process of claim 1 wherein the hydrogenation is carried out at a temperature from about 0° C. to about 120° C. and a pressure of from about 1 psig to about 1200 psig and the catalyst concentration is from about 0.01 mM to about 20 mM of titanium per 100 g of polymer and the contacting takes place for a period of time within the range from about 15 to about 1440 minutes.
Claim 4
Dependent Claim
66 words
The process of claim 2 wherein the hydrogenation is carried out at a temperature from about 60°-90° C. and a pressure from about 100-200 psig, the catalyst concentration is from about 0.04-1.0 mM titanium per 100 g of polymer, the alkali metal to titanium molar ratio is from about 3-30 and the contacting takes place for a period of time from about 30 to 360 minutes.
Claim 5
Dependent Claim
15 words
The process of claim 1 wherein the alkali metal initiator is an organo lithium compound.
Claim 6
Dependent Claim
12 words
The process of claim 4 wherein the organo lithium compound is sec-butyllithium.
Claim 7
Dependent Claim
54 words
The process of claim 1 wherein the titanium compound is selected from the group consisting of bis(cyclopentadienyl)titanium dichloride, bis(cyclopentadienyl)titanium dibromide, bis(cyclopentadienyl)titanium diiodide, bis(cyclopentadienyl)titanium difluoride, bis(cyclopentadienyl)titanium dicarbonyl, bis(cyclopentadienyl)titanium dimethyl, bis(cyclopentadienyl)titanium diethyl, bis(cyclopentadienyl)titanium dibutyl, bis(cyclopentadienyl)titanium bis(trimethylsilylmethyl), bis(cyclopentadienyl)titanium dibenzyl, bis(cyclopentadienyl)titanium dihexyl, bis(cyclopentadienyl)titanium dimethoxide, bis(cyclopentadienyl)titanium diethoxide, bis(cyclopentadienyl)titanium dibutoxide, bis(cyclopentadienyl)titanium dipentoxide, bis(cyclopentadienyl)titanium dineopentoxide, bis(cyclopentadienyl)titanium diphenoxide and all mixtures thereof.
Claim 8
Dependent Claim
12 words
The process of claim 6 wherein the titanium compound is bis(cyclopentadienyl)titanium dichloride.
Claim 9
Dependent Claim
15 words
The process of claim 6 wherein the alkali metal initiator is an organo lithium compound.
Claim 10
Dependent Claim
12 words
The process of claim 8 wherein the organo lithium compound is sec-butyllithium.
Claim 11
Dependent Claim
19 words
The process of claim 1 wherein a metal hydride is created in-situ by the termination of the living polymer.
Claim 12
Dependent Claim
17 words
The process of claim 10 wherein lithium hydride is created in-situ by termination of the living polymer.
Claim 13
Dependent Claim
18 words
The process of claim 1 wherein the alkali metal:titanium metal ratio during the hydrogenation is at least 2:1.
Claim 14
Dependent Claim
36 words
The process of claim 12 wherein alkali metal hydride is added to the polymer to be hydrogenated by adding an organo alkali metal compound and hydrogen to the polymer prior to addition of the hydrogenation catalyst.
Claim 15
Dependent Claim
22 words
The process of claim 13 wherein the metal hydride is created in-situ by the reaction of an organo alkali metal with hydrogen.
Claim 16
Dependent Claim
21 words
The process of claim 14 wherein lithium hydride is created in-situ by the reaction of a lithium alkali metal with hydrogen.
Claim 17
Dependent Claim
18 words
The process of claim 15 wherein lithium hydride is created in-situ by the reaction of sec-butyllithium with hydrogen.
Claim 18
Dependent Claim
59 words
The process of claim 12 wherein the titanium compound is selected from the group consisting of bis(cyclopentadienyl)titanium dichloride, bis(cyclopentadienyl)titanium dibromide, bis(cyclopentadienyl)titanium diiodide, bis(cyclopentadienyl)titanium difluoride, bis(cyclopentadienyl)titanium dicarbonyl, bis(cyclopentadienyl)titanium dimethyl, bis(cyclopentadienyl)titanium diethyl, bis(cyclopentadienyl)titanium dibutyl (including n-butyl, sec-butyl, tert-butyl), bis(cyclopentadienyl)titanium bis(trimethylsilylmethyl), bis(cyclopentadienyl)titanium dibenzyl, bis(cyclopentadienyl)titanium dihexyl, bis(cyclopentadienyl)titanium dimethoxide, bis(cyclopentadienyl)titanium diethoxide, bis(cyclopentadienyl)titanium dibutoxide, bis(cyclopentadienyl) titanium dipentoxide, bis(cyclopentadienyl)titanium dineopentoxide, bis(cyclopentadienyl)titanium diphenoxide and all mixtures thereof.
Claim 19
Dependent Claim
12 words
The process of claim 17 wherein the titanium compound is bis(cyclopentadienyl)titanium dichloride.
Claim 20
Dependent Claim
15 words
The process of claim 18 wherein the alkali metal initiator is an organo lithium compound.
Claim 21
Dependent Claim
12 words
The process of claim 18 wherein the organo lithium compound is sec-butyllithium.
Claim 22
Dependent Claim
22 words
The process of claims 1, 6 or 13 wherein the conjugated diolefin is selected from the group consisting of butadiene and isoprene.
Claim 23
Dependent Claim
15 words
The process of claim 1 wherein the diolefin is copolymerized with a vinyl-substituted aromatic hydrocarbon.
Claim 24
Dependent Claim
23 words
The process of claim 22 wherein the diolefin is copolymerized with a monomer selected from the group consisting of styrene and styrene derivatives.
Claim 25
Dependent Claim
29 words
The process of claim 23 wherein the copolymer is a block copolymer having at least one conjugated diene polymer block and at least one styrene or styrene derivative block.
Claim 26
Dependent Claim
27 words
A process of claim 24 wherein the styrene or styrene derivatives block is about 3 to 90% by weight based on the total weight of the polymer.
Claim 27
Dependent Claim
19 words
The process of claim 24 wherein the conjugated diolefin is selected from the group consisting of butadiene and isoprene.
Claim 28
Dependent Claim
20 words
The process of claim 1 wherein at least 50% of the unsaturated bonds in the conjugated diene units are hydrogenated.
Claim 29
Dependent Claim
20 words
The process of claim 27 wherein at least 95% of the unsaturated bonds in the conjugated diene units are hydrogenated.
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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) | 1994-08-12 | 1995-02-11 | 1995-08-13 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1998-08-12 | 1999-02-11 | 1999-08-13 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2002-08-12 | 2003-02-11 | 2003-08-13 | $7700.00 | Window Closed / Lapsed |