Polymerization of 1,3-cyclodiene with vinylaromatic hydrocarbon
AssigneePhillips Petroleum Company
InventorHenry L. Hsieh
Life of this patent
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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.
Claims44
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.
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.sub.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.
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.
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.
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.
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.
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.
Dependencies are inferred from the claim text.