US4020251A
Expired / Lapsed
US
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1,3-Cyclodiene-acyclic conjugated diene copolymers
Assignee: Phillips Petroleum Co
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Filing: 1975-03-17
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Granted: 1977-04-26
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Expires: 1995-03-17
Abstract
Abstract A copolymer is produced by polymerization of a mixture comprising a 1,3-cyclodiene and an acyclic conjugated diene wherein a substantial percentage by weight of the acyclic conjugated diene units of the copolymer is in the trans and vinyl configurations. A method for producing the copolymer is provided employing an organolithium initiator. A hydrogenated copolymer and method of its production is also provided.
Inventors
- 👤 Henry L. Hsieh
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-25 22:35
CPC Classifications
C; C08; C08F; C08F297/00; C08F297/02; C08F232/00; C08F232/02; C08F232/06; C08F236/00; C08F236/02; C08F236/04; C08F8/00; C08F8/04
Claims Analysis
Total Claims: 23
Claim 1
Independent Claim
187 words
A method for the production of a copolymer by polymerizing a monomer mixture consisting essentially of 1,3-butadiene; a 1,3-cyclodiene represented by the general formulas ##STR4## wherein R is selected from the group consisting of hydrogen, methyl and ethyl radicals, R' is selected from the group consisting of hydrogen, cycloalkyl, aryl and linear and branced alkyl radicals such that the maximum number of carbon atoms per R' radical is about 6 and the total number of carbon atoms per cyclodiene monomer is in the range of from about 5 to 20; an organolithium initiator consisting of alpha-lithio multisubstituted dialkylbenzenes and dialkylbenzene oligomers represented by the general formula ##STR5## wherein R"' is a linear or branched alkyl containing 2 to 12 carbon atoms, and n is an integer from 0 to 2; optionally a vinylaromatic compound containing in the range of from about 8 to 14 carbon atoms per molecule; optionally an ether or tertiary amine in an amount in the range of from about 0.01 to 50 parts by weight per 100 parts by weight monomer; and optionally a hydrocarbon diluent which is not detrimental to said polymerization.
Claim 2
Independent Claim
187 words
A method for the production of a copolymer by polymerizing a monomer mixture consisting essentially of 1,3-butadiene; a 1,3-cyclodiene represented by the general formulas ##STR4## wherein R is selected from the group consisting of hydrogen, methyl and ethyl radicals, R' is selected from the group consisting of hydrogen, cycloalkyl, aryl and linear and branced alkyl radicals such that the maximum number of carbon atoms per R' radical is about 6 and the total number of carbon atoms per cyclodiene monomer is in the range of from about 5 to 20; an organolithium initiator consisting of alpha-lithio multisubstituted dialkylbenzenes and dialkylbenzene oligomers represented by the general formula ##STR5## wherein R"' is a linear or branched alkyl containing 2 to 12 carbon atoms, and n is an integer from 0 to 2; optionally a vinylaromatic compound containing in the range of from about 8 to 14 carbon atoms per molecule; optionally an ether or tertiary amine in an amount in the range of from about 0.01 to 50 parts by weight per 100 parts by weight monomer; and optionally a hydrocarbon diluent which is not detrimental to said polymerization.
Claim 3
Dependent Claim
24 words
The method of claim 1 wherein said polymerization is carried out at a temperature in the range of from about 0° to 300° F.
Claim 4
Dependent Claim
25 words
The method of claim 2 wherein said temperature is in the range of from about 30° to 150° F and said diluent is a cycloparaffin.
Claim 5
Dependent Claim
35 words
The method of claim 1 wherein said ether is tetrahydrofuran or N,N,N', N'-tetramethylethylenediamine and the amount is in the range of from about 0.1 to 10 parts by weight per hundred parts by weight monomer.
Claim 6
Dependent Claim
58 words
The method of claim 1 wherein the weight ratio of 1,3-butadiene units to 1,3-cyclodiene units in the copolymer is in the range of from about 99:1 to 1:99; wherein the amount of organolithium initiator is in the range of from about 0.1 to 100 millimoles per hundred grams monomer; and wherein the copolymer produced is a block copolymer.
Claim 7
Dependent Claim
19 words
The method of claim 5 wherein said weight ratio is in the range of from about 95:5 to 40:60.
Claim 8
Dependent Claim
37 words
The method of claim 1 wherein the weight ratio of 1,3-butadiene units to vinylaromatic compound units in the copolymer is in the range of from about 100:0 to 1:99 and the copolymer produced is a block copolymer.
Claim 9
Dependent Claim
19 words
The method of claim 7 wherein the weight ratio is in the range of from about 100:0 to 50:50.
Claim 10
Dependent Claim
19 words
The method of claim 1 wherein the 1,3-cyclodiene is 1,3-cyclohexadiene and the organolithium initiator is principally 1,3-bis(1-lithio-3-methylpentyl)benzene or secbutyllithium.
Claim 11
Dependent Claim
11 words
The method of claim 1 wherein the vinylaromatic compound is styrene.
Claim 12
Dependent Claim
37 words
The method of claim 1 further comprising passing the copolymer produced by said polymerization to a hydrogenation zone wherein a portion of the olefinic unsaturation of said copolymer is hydrogenated in the presence of a suitable catalyst.
Claim 13
Dependent Claim
19 words
The method of claim 11 wherein at least 65 percent of the olefinic unsaturation of said copolymer is hydrogenated.
Claim 14
Dependent Claim
16 words
The method of claim 11 wherein at least 90 percent of the aromatic unsaturation is hydrogenated.
Claim 15
Dependent Claim
150 words
A copolymer consisting essentially of units of 1,3-butadiene; units of a 1,3-cyclodiene represented by the general formulas ##STR6## wherein R is selected from the group consisting of hydrogen, methyl and ethyl radicals, R' is selected from the group consisting of hydrogen, cycloalkyl, aryl and linear and branched alkyl radicals such that the maximum number of carbon atoms per R' radical is about 6 and the total number of carbon atoms per cyclodiene monomer is in the range of from about 5 to 20; optionally units of a vinylaromatic compound containing in the range of from about 8 to 14 carbon atoms per molecule; and wherein the 1,3-butadiene portion of said copolymer has a trans and vinyl content ranging from about 48 to 99 percent when said copolymer does not contain units of said vinylaromatic compound and 39 to 99 percent when said copolymer does contain units of said vinylaromatic compound.
Claim 16
Dependent Claim
150 words
A copolymer consisting essentially of units of 1,3-butadiene; units of a 1,3-cyclodiene represented by the general formulas ##STR6## wherein R is selected from the group consisting of hydrogen, methyl and ethyl radicals, R' is selected from the group consisting of hydrogen, cycloalkyl, aryl and linear and branched alkyl radicals such that the maximum number of carbon atoms per R' radical is about 6 and the total number of carbon atoms per cyclodiene monomer is in the range of from about 5 to 20; optionally units of a vinylaromatic compound containing in the range of from about 8 to 14 carbon atoms per molecule; and wherein the 1,3-butadiene portion of said copolymer has a trans and vinyl content ranging from about 48 to 99 percent when said copolymer does not contain units of said vinylaromatic compound and 39 to 99 percent when said copolymer does contain units of said vinylaromatic compound.
Claim 17
Dependent Claim
25 words
The copolymers of claim 14 wherein the weight ratio of 1,3-butadiene units to 1,3-cyclodiene units is in the range of from about 99:1 to 1:99.
Claim 18
Dependent Claim
25 words
The copolymer of claim 15 wherein the weight ratio of 1,3-butadiene units to 1,3-cyclodiene units is in the range of from about 95:5 to 40:60.
Claim 19
Dependent Claim
10 words
The copolymer of claim 16 wherein the 1,3-cyclodiene is 1,3-cyclohexadiene.
Claim 20
Dependent Claim
32 words
The copolymer of claim 14 wherein the vinyl aromatic compound is styrene, and the weight ratio of 1,3-butadiene units to styrene units is in the range of from about 100:0 to 50:50.
Claim 21
Dependent Claim
16 words
The copolymer of claim 14 containing olefinic unsaturation of which a portion is removed by hydrogenation.
Claim 22
Dependent Claim
16 words
The copolymer of claim 19 wherein at least 65 percent of the olefinic unsaturation is hydrogenated.
Claim 23
Dependent Claim
16 words
The copolymer of claim 14 wherein at least 90 percent of the aromatic unsaturation is 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) | 1980-04-25 | 1980-10-25 | 1981-04-26 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1984-04-25 | 1984-10-25 | 1985-04-26 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1988-04-25 | 1988-10-25 | 1989-04-26 | $7700.00 | Window Closed / Lapsed |