High trans butadiene based elastomeric block copolymers and blends

Claim 1

A composition of matter comprising a rubbery solution polymer selected from the group consisting of I. a high trans copolymer-high vinyl polymer diblock copolymer, II. a blend of a high trans copolymer and a high vinyl polymer and III. a blend or mixture of a high trans copolymer-high vinyl polymer diblock copolymer, a high trans copolymer and a high vinyl polymer a. where said high trans copolymer is a copolymer of butadiene-1,3 and at least one copolymerizable monomer selected from the group consisting of styrene and isoprene, has a Tg of less than about -70° C., has an overall content of about 75 to 85% trans units and not over about 8% vinyl units in the butadiene segments and comprises about 25 to 80% by weight of the composition, b. where said high vinyl polymer is at least one polymer selected from the group consisting of homo polybutadiene and copolymers of butadiene-1,3 and at least one monomer selected from the group consisting of styrene and isoprene, has a Tg of greater than about -70° C. and not above about -35° C. and has about 40 to 80% vinyl units in the butadiene segments and c. where in said composition the total overall amount of styrene and/or isoprene is from about 5 to 20% by weight and the total overall amount of vinyl groups is from about 30 to 60%.

Claim 6

The method which comprises, (I) polymerizing under inert conditions in a hydrocarbon solvent at a temperature of from about 25° to 80° C. butadiene-1,3 and at least one monomer selected from the group consisting of styrene and isoprene with a catalyst in a minor effective amount sufficient to polymerize said monomers to obtain a polymer, said catalyst comprising (1) an alcoholate selected from the group consisting of barium alcoholate, calcium alcoholate and strontium alcoholate and mixtures thereof, (2) an organolaluminum compound selected from the group consisting of alkyl and cycloalkyl aluminum compounds and mixtures of the same in which the organic moieties have from 1 to 20, preferably from 1 to 10, carbon atoms and (3) an organomagnesium compound selected from the group consisting of alkyl and cycloalkyl magnesium compounds and mixtures of the same in which the organic moieties have from 1 to 20, preferably from 1 to 10, carbon atoms, and complexes of (2) and (3) where the mole ratio computed as metal of barium, calcium and/or strontium to magnesium is from about 1:10 to 1:2 and where the mole ratio computed as metal of magnesium to aluminum is from about 105:1 to 1.5:1 to obtain a high trans copolymer block and to a conversion of from about 60 to 95%, preferably about 85%, and (II) then adding to the resulting living high trans copolymer or carbanions additional monomer selected from the group consisting of butadiene-1,3 and a mixture of butadiene-1,3 and at least one monomer selected from the group consisting of styrene and isoprene, and minor amounts by weight, based on the weight of the monomers, sufficient to obtain a high vinyl content polymer block, of at least one strong Lewis base and at least one alkoxide selected from the group consisting of sodium, potassium and rubidium alkoxides having from 3 to 6 carbon atoms in the organic moieties of the alkoxide group and continuing the polymerization to obtain a high trans copolymer-high vinyl polymer diblock copolymer a. where said high trans copolymer block has a Tg of less than about -70° C., has an overall content of from about 75 to 85% trans units and not over about 8% vinyl units in the butadiene segments and comprises about 25 to 80% by weight of the diblock copolymer, b. where said high vinyl polymer block has a Tg of greater than about -70° C. and not above about -35° C. and has about 40 to 80% vinyl units in the butadiene segments of the high vinyl block, and c. where in said diblock copolymer the total overall amount of styrene and/or isoprene is from about 5 to 20% by weight and the total overall amount of vinyl groups is from about 30 to 60%.

Claim 7

The method which comprises, (I) polymerizing under inert conditions in a hydrocarbon solvent at a temperature of from about 25° to 80° C. butadiene-1,3 and at least one monomer selected from the group consisting of styrene and isoprene with a catalyst in a minor effective amount sufficient to polymerize said monomers to obtain a polymer, said catalyst comprising (1) an alcoholate selected from the group consisting of barium alcoholate, calcium alcoholate and strontium alcoholate and mixtures thereof, (2) an organolaluminum compound selected from the group consisting of alkyl and cycloalkyl aluminum compounds and mixtures of the same in which the organic moieties have from 1 to 20, preferably from 1 to 10, carbon atoms and (3) an organomagnesium compound selected from the group consisting of alkyl and cycloalkyl magnesium compounds and mixtures of the same in which the organic moieties have from 1 to 20, preferably from 1 to 10, carbon atoms, and complexes of (2) and (3) where the mole ratio computed as metal of barium, calcium and/or strontium to magnesium is from about 1:10 to 1:2 and where the mole ratio computed as metal of magnesium to aluminum is from about 105:1 to 1.5:1 to obtain a high trans copolymer block and to a conversion of from about 60 to 95%, preferably about 85%, and (II) then adding to the resulting living high trans copolymer or carbanions additional monomer selected from the group consisting of butadiene-1,3 and a mixture of butadiene-1,3 and at least one monomer selected from the group consisting of styrene and isoprene, and minor amounts by weight, based on the weight of the monomers, sufficient to obtain a high vinyl content polymer block, of at least one strong Lewis base and at least one alkoxide selected from the group consisting of sodium, potassium and rubidium alkoxides having from 3 to 6 carbon atoms in the organic moieties of the alkoxide group and continuing the polymerization to obtain a high trans copolymer-high vinyl polymer diblock copolymer a. where said high trans copolymer block has a Tg of less than about -70° C., has an overall content of from about 75 to 85% trans units and not over about 8% vinyl units in the butadiene segments and comprises about 25 to 80% by weight of the diblock copolymer, b. where said high vinyl polymer block has a Tg of greater than about -70° C. and not above about -35° C. and has about 40 to 80% vinyl units in the butadiene segments of the high vinyl block, and c. where in said diblock copolymer the total overall amount of styrene and/or isoprene is from about 5 to 20% by weight and the total overall amount of vinyl groups is from about 30 to 60%.

Claim 10

The method which comprises, polymerizing under inert conditions in a hydrocarbon solvent at a temperature of from about 25° to 80° C. butadiene-1,3 and at least one monomer selected from the group consisting of styrene and isoprene with a catalyst in a minor effective amount sufficient to polymerize said monomers to obtain a polymer, said catalyst comprising (1) an alcoholate selected from the group consisting of barium alcoholate, calcium alcoholate and strontium alcoholate and mixtures thereof, (2) an organolaluminum compound selected from the group consisting of alkyl and cycloalkyl aluminum compounds and mixtures of the same in which the organic moieties have from 1 to 20, preferably from 1 to 10, carbon atoms and (3) an organomagnesium compound selected from the group consisting of alkyl and cycloalkyl magnesium compounds and mixtures of the same in which the organic moieties have from 1 to 20, preferably from 1 to 10, carbon atoms, and complexes of (2) and (3) where the mole ratio computed as metal of barium, calcium and/or strontium to magnesium is from about 1:10 to 1:2 and where the mole ratio computed as metal of magnesium to aluminum is from about 105:1 to 1.5:1 to obtain a high trans copolymer block and to a conversion of from about 60 to 95%, preferably about 85%, and then adding to the resulting living high trans copolymer or carbanions minor amounts by weight, based on the weight of the monomers, of at least one strong Lewis base and at least one alkoxide selected from the group consisting of sodium, potassium and rubidium alkoxides having from 3 to 6 carbon atoms in the organic moieties of the alkoxide group and continuing the copolymerization to completion.

Claim 11

The method which comprises, polymerizing under inert conditions in a hydrocarbon solvent at a temperature of from about 25° to 80° C. butadiene-1,3 and at least one monomer selected from the group consisting of styrene and isoprene with a catalyst in a minor effective amount sufficient to polymerize said monomers to obtain a polymer, said catalyst comprising (1) an alcoholate selected from the group consisting of barium alcoholate, calcium alcoholate and strontium alcoholate and mixtures thereof, (2) an organolaluminum compound selected from the group consisting of alkyl and cycloalkyl aluminum compounds and mixtures of the same in which the organic moieties have from 1 to 20, preferably from 1 to 10, carbon atoms and (3) an organomagnesium compound selected from the group consisting of alkyl and cycloalkyl magnesium compounds and mixtures of the same in which the organic moieties have from 1 to 20, preferably from 1 to 10, carbon atoms, and complexes of (2) and (3) where the mole ratio computed as metal of barium, calcium and/or strontium to magnesium is from about 1:10 to 1:2 and where the mole ratio computed as metal of magnesium to aluminum is from about 105:1 to 1.5:1 to obtain a high trans copolymer block and to a conversion of from about 60 to 95%, preferably about 85%, and then adding to the resulting living high trans copolymer or carbanions minor amounts by weight, based on the weight of the monomers, of at least one strong Lewis base and at least one alkoxide selected from the group consisting of sodium, potassium and rubidium alkoxides having from 3 to 6 carbon atoms in the organic moieties of the alkoxide group and continuing the copolymerization to completion.