US4138536A
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Polymerization of 1,3-cyclodiene with vinylaromatic hydrocarbon
Assignee: Phillips Petroleum Co
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Filing: 1977-11-15
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Granted: 1979-02-06
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Expires: 1997-11-15
Abstract
Abstract A 1,3-cyclodiene is polymerized with a vinylaromatic hydrocarbon in the presence of a paraffin or cycloparaffin hydrocarbon diluent and an organolithium initiator. Further, polymerization of a 1,3-cyclodiene with a vinylaromatic hydrocarbon employing an organolithium initiator having a functionally greater than 1 produces a new and useful copolymer. Hydrogenated copolymers are provided.
Inventors
- 👤 Henry L. Hsieh
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-26 18:17
CPC Classifications
C; C08; C08F; C08F232/00; C08F232/02; C08F232/06; C08F8/00; C08F8/04
Claims Analysis
Total Claims: 51
Claim 1
Independent Claim
160 words
A method for the production of a 1,3-cyclodiene/vinylaromatic copolymer which comprises polymerizing a 1,3-cyclodiene comonomer and a vinylaromatic hydrocarbon comonomer in a reaction mixture comprising the 1,3-cyclodiene comonomer represented by the formula ##STR4## wherein n is 1 or 2, R is selected from the group consisting of a hydrogen, methyl or ethyl radical and R' is selected from the group consisting of a hydrogen, alkyl, cycloalkyl, and aryl radical with a maximum of 6 carbon atoms per R' group; the vinylaromatic hydrocarbon comonomer of from about 8 to 14 carbon atoms per molecule; a diluent, wherein the diluent is selected from the group consisting of linear and branched paraffin and cycloparaffin hydrocarbons of 4 to 12 carbon atoms per molecule and wherein the diluent is present in an amount sufficient to produce an increase in conversion as compared to the conversion produced when toluene is used as the diluent; an organolithium initiator; and optionally an ether or a tetiary amine.
Claim 2
Independent Claim
160 words
A method for the production of a 1,3-cyclodiene/vinylaromatic copolymer which comprises polymerizing a 1,3-cyclodiene comonomer and a vinylaromatic hydrocarbon comonomer in a reaction mixture comprising the 1,3-cyclodiene comonomer represented by the formula ##STR4## wherein n is 1 or 2, R is selected from the group consisting of a hydrogen, methyl or ethyl radical and R' is selected from the group consisting of a hydrogen, alkyl, cycloalkyl, and aryl radical with a maximum of 6 carbon atoms per R' group; the vinylaromatic hydrocarbon comonomer of from about 8 to 14 carbon atoms per molecule; a diluent, wherein the diluent is selected from the group consisting of linear and branched paraffin and cycloparaffin hydrocarbons of 4 to 12 carbon atoms per molecule and wherein the diluent is present in an amount sufficient to produce an increase in conversion as compared to the conversion produced when toluene is used as the diluent; an organolithium initiator; and optionally an ether or a tetiary amine.
Claim 3
Independent Claim
200 words
A method for the production of a 1,3-cyclodiene/vinylaromatic copolymer which comprises polymerizing a 1,3-cyclodiene comonomer and a vinylaromatic hydrocarbon comonomer in a reaction mixture consisting essentially of the 1,3-cyclodiene comonomer represented by the formula ##STR5## wherein n is 1 or 2, R is selected from the group consisting of a hydrogen, methyl or ethyl radical and R' is selected from the group consisting of a hydrogen, alkyl, cycloalkyl, and aryl radical with a maximum of 6 carbon atoms per R'0 group; the vinylaromatic hydrocarbon comonomer of from about 8 to 14 carbon atoms per molecule; a diluent selected from the group consisting of 2,3-dimethylbutane, n-heptane, methylcyclopentane, 2,2,4-trimethylpentane and cyclohexane; an organolithium initiator represented by the formula R"Li x wherein R" is selected from the group consisting of an aliphatic, alicyclic and aromatic radical of from 1 to 20 carbon atoms per radical, x is an integer of from 1 to 4 and the valence of R" is equal to x; or an organolithium initiator represented by the formula ##STR6## wherein R"' is a linear or branched alkyl containing 2 to 12 carbon atoms, and n is an integer from 0 to 2; and optionally an ether or a tertiary amine.
Claim 4
Independent Claim
200 words
A method for the production of a 1,3-cyclodiene/vinylaromatic copolymer which comprises polymerizing a 1,3-cyclodiene comonomer and a vinylaromatic hydrocarbon comonomer in a reaction mixture consisting essentially of the 1,3-cyclodiene comonomer represented by the formula ##STR5## wherein n is 1 or 2, R is selected from the group consisting of a hydrogen, methyl or ethyl radical and R' is selected from the group consisting of a hydrogen, alkyl, cycloalkyl, and aryl radical with a maximum of 6 carbon atoms per R'0 group; the vinylaromatic hydrocarbon comonomer of from about 8 to 14 carbon atoms per molecule; a diluent selected from the group consisting of 2,3-dimethylbutane, n-heptane, methylcyclopentane, 2,2,4-trimethylpentane and cyclohexane; an organolithium initiator represented by the formula R"Li x wherein R" is selected from the group consisting of an aliphatic, alicyclic and aromatic radical of from 1 to 20 carbon atoms per radical, x is an integer of from 1 to 4 and the valence of R" is equal to x; or an organolithium initiator represented by the formula ##STR6## wherein R"' is a linear or branched alkyl containing 2 to 12 carbon atoms, and n is an integer from 0 to 2; and optionally an ether or a tertiary amine.
Claim 5
Dependent Claim
25 words
The method of claim 2 wherein the ratio by weight of vinylaromatic compound to 1,3-cyclodiene is in the range of from about 99:1 to 1:99.
Claim 6
Dependent Claim
25 words
The method of claim 3 wherein the ratio by weight of vinylaromatic compound to 1,3-cyclodiene is in the range of from about 95:5 to 25:75.
Claim 7
Dependent Claim
45 words
The method of claim 4 wherein the amount of said ether or said tertinary amine is in the range of from about 0.01 to 50 phm and said polymerization is carried out at a temperature in the range of from about 0 to 300° F.
Claim 8
Dependent Claim
45 words
The method of claim 5 wherein said ether is tetrahydrofuran or the tertiary amine is N,N,N',N'-tetramethylethylenediamine in the range of from about 0.1 to 10 phm and said polymerization is carried out at a temperature in the range of from about 30 to 150° F.
Claim 9
Dependent Claim
14 words
The method of claim 2 wherein said polymerization is carried out at autogenous pressure.
Claim 10
Dependent Claim
25 words
The method of claim 2 wherein said polymerization is carried out at a pressure sufficient to maintain a reaction mixture substantially in a liquid state.
Claim 11
Dependent Claim
19 words
The method of claim 6 wherein 1,3-cyclohexadiene and styrene are polymerized in the presence of n-butyllithium or primarily 1,3-bis(1-lithio-3-methylpentyl)benzene.
Claim 12
Dependent Claim
17 words
The method of claim 9 wherein the copolymer produced is a block copolymer of the form styrene-styrene/1,3-cyclohexadiene-1,3-cyclohexadiene.
Claim 13
Independent Claim
128 words
A method for producing a 1,3-cyclodiene/vinylaromatic copolymer comprising polymerizing a polymerization mixture consisting essentially of a 1,3-cyclodiene represented by the formula ##STR7## wherein n is 1 or 2, R is selected from the group consisting of a hydrogen, methyl or ethyl radical and R' is selected from the group consisting of a hydrogen, alkyl, cycloalkyl, and aryl radical with a maximum of 6 carbon atoms per R' group; a vinylaromatic hydrocarbon of from about 8 to 14 carbon atoms per molecule; optionally an ether or a tertiary amine; optionally a diluent; and an organolithium initiator wherein said organolithium initiator has a lithium functionality greater than 1, said copolymer having improved tensile strength as compared to such copolymers produced employing organolithium initiators having a lithium functionality equal to 1.
Claim 14
Independent Claim
128 words
A method for producing a 1,3-cyclodiene/vinylaromatic copolymer comprising polymerizing a polymerization mixture consisting essentially of a 1,3-cyclodiene represented by the formula ##STR7## wherein n is 1 or 2, R is selected from the group consisting of a hydrogen, methyl or ethyl radical and R' is selected from the group consisting of a hydrogen, alkyl, cycloalkyl, and aryl radical with a maximum of 6 carbon atoms per R' group; a vinylaromatic hydrocarbon of from about 8 to 14 carbon atoms per molecule; optionally an ether or a tertiary amine; optionally a diluent; and an organolithium initiator wherein said organolithium initiator has a lithium functionality greater than 1, said copolymer having improved tensile strength as compared to such copolymers produced employing organolithium initiators having a lithium functionality equal to 1.
Claim 15
Dependent Claim
92 words
The method of claim 11 wherein the organolithium initiator is represented by the formula R"Li x wherein R" is selected from the group consisting of an aliphatic, alicyclic and aromatic radicals of from 1 to 20 carbon atoms per radical, x is an integer of from 2 to 4 and the valence of R is equal to x; or wherein the organolithium initiator is represented by the formula ##STR8## wherein R"' is a linear or branched alkyl containing 2 to 12 carbon atoms, and n is an integer from 0 to 2.
Claim 16
Dependent Claim
25 words
The method of claim 11 wherein the ratio by weight of vinylaromatic compound to 1,3-cyclodiene is in the range of from about 99:1 to 1:99.
Claim 17
Dependent Claim
25 words
The method of claim 11 wherein the ratio by weight of vinylaromatic compound to 1,3-cyclodiene is in the range of from about 95:5 to 25:75.
Claim 18
Dependent Claim
42 words
The method of claim 11 wherein the ether or the tertiary amine is in an amount ranging from about 0.01 to 50 phm and said polymerization is carried out at a temperature in the range of from about 0 to 300° F.
Claim 19
Dependent Claim
55 words
The method of claim 15 wherein said ether is tetrahydrofuran or the tertiary amine is N,N,N',N'-tetramethylethylenediamine and the amount of said ether or tertiary amine is in the range of from about 0.1 to 10 phm and said polymerization is carried out at a temperature in the range of from about 30 to 150° F.
Claim 20
Dependent Claim
16 words
The method of claim 11 wherein 1,3-cyclohexadiene and styrene are polymerized in the presence of 1,3-bis(1-lithio-3-methylpentyl)benzene.
Claim 21
Dependent Claim
30 words
The method of claim 11 wherein the diluent is selected from the group consisting of linear and branched paraffin and cycloparaffin hydrocarbons of 4 to 12 carbon atoms per molecule.
Claim 22
Dependent Claim
21 words
The method of claim 18 wherein said diluent is selected from the group consisting of 2,3-dimethylbutane, n-heptane, methylcyclopentane, 2,2,4-trimethylpentane and cyclohexane.
Claim 23
Dependent Claim
37 words
The method of claim 11 further comprising passing the copolymers 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 hydrogenation catalyst.
Claim 24
Dependent Claim
19 words
The method of claim 20 wherein at least 65 percent of the olefinic unsaturation of said copolymer is hydrogenated.
Claim 25
Dependent Claim
25 words
The method of claim 20 wherein essentially all of the olefinic unsaturation is hydrogenated and at least a portion of the aromatic unsaturation is hydrogenated.
Claim 26
Dependent Claim
16 words
The method of claim 20 wherein at least 80 percent of the aromatic unsaturation is hydrogenated.
Claim 27
Dependent Claim
188 words
A 1,3-cyclodiene/vinylaromatic copolymer produced by polymerizing a reaction mixture consisting essentially of a 1,3-cyclodiene represented by the general formula ##STR9## wherein n is 1 or 2, R is selected from the group consisting of a hydrogen, methyl or ethyl radical and R' is selected from the group consisting of a hydrogen, alkyl, cycloalkyl, and aryl radical with a maximum of 6 carbon atoms per R' group; a vinylaromatic hydrocarbon of from about 8 to 14 carbon atoms per molecule; a polymerization initiator wherein the ratio by weight of vinylaromatic hydrocarbon in the polymerization mixture to 1,3-cyclodiene ranges from about 99:1 to 1:99; and optionally an ether or a tertiary amine in an amount in the range of from about 0.01 to 50 phm; optionally a polymerization diluent selected from the group consisting of linear and branched paraffin and cycloparaffin hydrocarbons of 4 to 12 carbon atoms per molecule; wherein said polymerization initiator consists essentially of an organolithium initiator having a lithium functionality greater than 1, and said copolymer has improved tensile strength as compared to such copolymers produced employing organolithium initiators having a lithium functionality equal to 1.
Claim 28
Dependent Claim
188 words
A 1,3-cyclodiene/vinylaromatic copolymer produced by polymerizing a reaction mixture consisting essentially of a 1,3-cyclodiene represented by the general formula ##STR9## wherein n is 1 or 2, R is selected from the group consisting of a hydrogen, methyl or ethyl radical and R' is selected from the group consisting of a hydrogen, alkyl, cycloalkyl, and aryl radical with a maximum of 6 carbon atoms per R' group; a vinylaromatic hydrocarbon of from about 8 to 14 carbon atoms per molecule; a polymerization initiator wherein the ratio by weight of vinylaromatic hydrocarbon in the polymerization mixture to 1,3-cyclodiene ranges from about 99:1 to 1:99; and optionally an ether or a tertiary amine in an amount in the range of from about 0.01 to 50 phm; optionally a polymerization diluent selected from the group consisting of linear and branched paraffin and cycloparaffin hydrocarbons of 4 to 12 carbon atoms per molecule; wherein said polymerization initiator consists essentially of an organolithium initiator having a lithium functionality greater than 1, and said copolymer has improved tensile strength as compared to such copolymers produced employing organolithium initiators having a lithium functionality equal to 1.
Claim 29
Dependent Claim
14 words
The copolymer of claim 24 wherein a portion of the olefinic unsaturation is hydrogenated.
Claim 30
Dependent Claim
16 words
The copolymer of claim 24 wherein at least 65 percent of the olefinic unsaturation is hydrogenated.
Claim 31
Dependent Claim
25 words
The copolymer of claim 24 wherein essentially all of the olefinic unsaturation is hydrogenated and at least a portion of the aromatic unsaturation is hydrogenated.
Claim 32
Dependent Claim
16 words
The copolymer of claim 24 wherein at least 80 percent of the aromatic unsaturation is hydrogenated.
Claim 33
Dependent Claim
54 words
The copolymer of claim 24 wherein the 1,3-cyclodiene is 1,3-cyclopentadiene or 1,3-cyclohexadiene, the vinylaromatic hydrocarbon is styrene, the polymerization is carried out in presence of an ether or tertiary amine and a diluent selected from the group consisting of linear and branched paraffin and cycloparaffin hydrocarbons of 4 to 12 carbon atoms per molecule.
Claim 34
Dependent Claim
52 words
The copolymer of claim 24 wherein the polymerization mixture comprises a ratio by weight of vinylaromatic compound to 1,3-cyclodiene in the range of from about 99:1 to 1:99, and polymerization is carried out with the amount of initiator ranging from about 0.1 to about 100 millimoles per 100 grams of total monomers.
Claim 35
Dependent Claim
33 words
The copolymer of claim 30 wherein the polymerization temperature ranges from about 0 to about 300° F. and the polymerization pressure is sufficient to maintain the reaction mixture substantially in a liquid state.
Claim 36
Independent Claim
147 words
A method for the production of a 1,3-cyclodiene/vinylaromatic copolymer which comprises polymerizing a 1,3-cyclodiene comonomer and a vinylaromatic hydrocarbon comonomer in a reaction mixture comprising the 1,3-cyclodiene comonomer represented by the formula ##STR10## wherein n is 1 or 2, R is selected from the group consisting of a hydrogen, methyl or ethyl radical and R' is selected from the group consisting of a hydrogen, alkyl, cycloalkyl, and aryl radical with a maximum of 6 carbon atoms per R' group; the vinylaromatic hydrocarbon comonomer of from about 8 to 14 carbon atoms per molecule; a diluent, wherein the diluent is selected from the group consisting of linear and branched paraffin and cycloparaffin hydrocarbons of 4 to 12 carbon atoms per molecule and wherein the amount of diluent employed is at least 500 parts per hundred parts monomers; an organolithium initiator; and optionally an ether or a tertiary amine.
Claim 37
Independent Claim
147 words
A method for the production of a 1,3-cyclodiene/vinylaromatic copolymer which comprises polymerizing a 1,3-cyclodiene comonomer and a vinylaromatic hydrocarbon comonomer in a reaction mixture comprising the 1,3-cyclodiene comonomer represented by the formula ##STR10## wherein n is 1 or 2, R is selected from the group consisting of a hydrogen, methyl or ethyl radical and R' is selected from the group consisting of a hydrogen, alkyl, cycloalkyl, and aryl radical with a maximum of 6 carbon atoms per R' group; the vinylaromatic hydrocarbon comonomer of from about 8 to 14 carbon atoms per molecule; a diluent, wherein the diluent is selected from the group consisting of linear and branched paraffin and cycloparaffin hydrocarbons of 4 to 12 carbon atoms per molecule and wherein the amount of diluent employed is at least 500 parts per hundred parts monomers; an organolithium initiator; and optionally an ether or a tertiary amine.
Claim 38
Dependent Claim
21 words
The method of claim 32 wherein the diluent is selected from the group consisting of 2,3-dimethylbutane, n-heptane, methylcyclopentane, 2,3,4-trimethylpentane and cyclohexane.
Claim 39
Independent Claim
121 words
A method for the production of a 1,3-cyclodiene/vinylaromatic copolymer which comprises polymerizing a reaction mixture consisting of a 1,3-cyclodiene represented by the formula ##STR11## wherein n is 1 or 2, R is selected from the group consisting of a hydrogen, methyl or ethyl radical and R' is selected from the group consisting of a hydrogen, alkyl, cycloalkyl, and aryl radical with a maximum of 6 carbon atoms per R' group; a vinylaromatic hydrocarbon of from about 8 to 14 carbon atoms per molecule; a diluent wherein the diluent is selected from the group consisting of linear and branched paraffin and cycloparaffin hydrocarbons of 4 to 12 carbon atoms per molecule; an organolithium initiator; and optionally an ether or a tertiary amine.
Claim 40
Independent Claim
121 words
A method for the production of a 1,3-cyclodiene/vinylaromatic copolymer which comprises polymerizing a reaction mixture consisting of a 1,3-cyclodiene represented by the formula ##STR11## wherein n is 1 or 2, R is selected from the group consisting of a hydrogen, methyl or ethyl radical and R' is selected from the group consisting of a hydrogen, alkyl, cycloalkyl, and aryl radical with a maximum of 6 carbon atoms per R' group; a vinylaromatic hydrocarbon of from about 8 to 14 carbon atoms per molecule; a diluent wherein the diluent is selected from the group consisting of linear and branched paraffin and cycloparaffin hydrocarbons of 4 to 12 carbon atoms per molecule; an organolithium initiator; and optionally an ether or a tertiary amine.
Claim 41
Dependent Claim
108 words
The method of claim 34 wherein the diluent is selected from the group consisting of 2,3-dimethylbutane, n-heptane, methylcyclopentane, 2,2,4-trimethylpentane and cyclohexane; wherein the organolithium initiator is represented by the formula R"Li x wherein R" is selected from the group consisting of an aliphatic, alicyclic and aromatic radical of from 1 to 20 carbon atoms per radical, x is an integer of from 1 to 4 and the valence of R" is equal to x; or wherein the organolithium initiator is represented by the formula ##STR12## wherein R"' is a linear or branched alkyl containing 2 to 12 carbon atoms, and n is an integer from 0 to 2.
Claim 42
Dependent Claim
25 words
The method of claim 35 wherein the ratio by weight of vinylaromatic compound to 1,3-cyclodiene is in the range of from about 99:1 to 1:99.
Claim 43
Dependent Claim
25 words
The method of claim 36 wherein the ratio by weight of vinylaromatic compound to 1,3-cyclodiene is in the range of from about 95:5 to 25:75.
Claim 44
Dependent Claim
49 words
The method of claim 37 wherein the amount of said ether or said tertiary amine is in the range of from about 0.01 to 50 parts per hundred parts monomers and said polymerization is carried out at a temperature in the range of from about 0 to 300° F.
Claim 45
Dependent Claim
49 words
The method of claim 38 wherein said ether is tetrahydrofuran or the tertiary amine is N,N,N',N'-tetramethylethylenediamine in the range of from about 0.1 to 10 parts per hundred parts monomers and said polymerization is carried out at a temperature in the range of from about 30 to 150° F.
Claim 46
Dependent Claim
14 words
The method of claim 34 wherein said polymerization is carried out at autogeneous pressure.
Claim 47
Dependent Claim
25 words
The method of claim 34 wherein said polymerization is carried out at a pressure sufficient to maintain a reaction mixture substantially in a liquid state.
Claim 48
Dependent Claim
19 words
The method of claim 39 wherein 1,3-cyclohexadiene and styrene are polymerized in the presence of n-butyllithium or primarily 1,3-bis-(1-lithio-3-methylpentyl)benzene.
Claim 49
Dependent Claim
17 words
The method of claim 42 wherein the copolymer produced is a block copolymer of the form styrene-styrene/1,3-cyclohexadiene-1,3-cyclohexadiene.
Claim 50
Independent Claim
133 words
A method for the production of a 1,3-cyclodiene/vinylaromatic copolymer which comprises polymerizing a 1,3-cyclodiene comonomer and a vincylaromatic hydrocarbon comonomer in a reaction mixture consisting essentially of the 1,3-cyclodiene comonomer represented by the formula ##STR13## wherein n is 1 or 2, R is selected from the group consisting of a hydrogen, methyl or ethyl radical and R' is selected from the group consisting of a hydrogen, alkyl, cycloalkyl, and aryl radical with a maximum of 6 carbon atoms per R' group; the vinylaromatic hydrocarbon comonomer of from about 8 to 14 carbon atoms per molecule; a diluent, wherein the diluent is selected from the group consisting of linear and branched paraffin and cycloparaffin hydrocarbons of 4 to 12 carbon atoms per molecule; an organolithium initiator; and optionally an ether or a tertiary amine.
Claim 51
Independent Claim
133 words
A method for the production of a 1,3-cyclodiene/vinylaromatic copolymer which comprises polymerizing a 1,3-cyclodiene comonomer and a vincylaromatic hydrocarbon comonomer in a reaction mixture consisting essentially of the 1,3-cyclodiene comonomer represented by the formula ##STR13## wherein n is 1 or 2, R is selected from the group consisting of a hydrogen, methyl or ethyl radical and R' is selected from the group consisting of a hydrogen, alkyl, cycloalkyl, and aryl radical with a maximum of 6 carbon atoms per R' group; the vinylaromatic hydrocarbon comonomer of from about 8 to 14 carbon atoms per molecule; a diluent, wherein the diluent is selected from the group consisting of linear and branched paraffin and cycloparaffin hydrocarbons of 4 to 12 carbon atoms per molecule; an organolithium initiator; and optionally an ether or a tertiary amine.
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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) | 1982-02-05 | 1982-08-07 | 1983-02-06 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1986-02-05 | 1986-08-07 | 1987-02-06 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1990-02-05 | 1990-08-07 | 1991-02-06 | $7700.00 | Window Closed / Lapsed |