Butadiene polymerization process

Claim 2

A process of homopolymerizing butadiene or copolymerizing butadiene with other conjugated dienes or with vinyl aromatic compounds to form products having simultaneously a high content of more than about 70% of trans-1,4 linkages and a low content of less than about 5% of 1,2 linkages which comprises reacting the monomers in a reaction medium in the presence of an added anionic catalytic composition consisting of (a) an organo-lithium initiator and (b) a cocatalyst system consisting of a compound of barium or strontium and an organometallic compound of aluminum or zinc.

Claim 3

The process according to claim 1 wherein the cocatalyst system is preformed and added to the reaction medium at the same time as the organo-lithium initiator at the start of the reaction.

Claim 4

The process according to claim 1 wherein the cocatalyst system is preformed and added in one or more batches to the reaction medium during the course of the reaction which had been previously initiated by the organolithium initiator.

Claim 5

The process according to claim 1 wherein the components of the cocatalyst system are added to the reaction medium in one of the following ways: a. separately at the start of the reaction in one or more batches at the same time as the organo-lithium initiator, b. one after the other in any order during the reaction which has been previously initiated by an organo-lithium initiator, or c. jointly in one or more batches during the reaction which has been initiated previously by an organo-lithium initiator.

Claim 6

The process according to claim 1 wherein styrene is used as the vinyl aromatic compound and the catalytic composition consists of n-butyl-lithium, a barium phenate, and a trialkyl aluminum.

Claim 7

The process according to claim 1 wherein the components of the added anionic catalytic composition are present in such quantities that the ratios are within the following limits: ##EQU2##

Claim 8

The process according to claim 1 wherein the components of the added anionic catalytic composition are present in such quantities that the ratios are within the following limits: ##EQU3##

Claim 9

A process of homopolymerizing butadiene or copolymerizing butadiene with other conjugated dienes or with vinyl aromatic compounds to form products having simultaneously a high content of more than about 70% of trans-1,4 linkages and a low content of less than about 5% of 1,2 linkages which comprises reacting the monomers in a reaction medium in the presence of an added anionic catalytic composition consisting of a. an organo-lithium initiator selected from the group consisting of metallic lithium, ethyl-lithium, n-butyl lithium, isobutyl-lithium, sec.-butyl-lithium, ter.-butyl-lithium, isopropyl-lithium, n-amyl-lithium, isoamyl-lithium, allyl-lithium, propenyl-lithium, isobutenyl-lithium, polybutadienyl-lithium, polyisoprenyl-lithium, polystyryl-lithium, 1,4-dilithium butane, 1-5-dilithium pentane, 1,20-dilithium eicosane, benzyl-lithium, phenyl-lithium, 1,1-diphenyl-methyl-lithium, the polylithium reaction product of metallic lithium with 1,1-diphenylethylene, the polylithium reaction product of metallic lithium with trans-stilbene, the polylithium reaction product of metallic lithium with tetraphenylethylene, lithium-naphthalene, lithium-anthracene, lithium-chrysene and lithium-diphenyl; and b. a cocatalyst system consisting of (b 1 ) a compound of barium or strontium selected from the group consisting of barium hydride, strontium hydride; barium naphthenate, barium methanolate, strontium methanolate, barium ethanolate, strontium ethanolate, barium tertio-butanolate, barium nonylphenate, barium acetylacetonate, strontium acetylacetonate, barium dibenzoylmethane, strontium dibenzoylmethane, barium thenoyltrifluoro-acetonate, strontium thenoyltrifluoro-acetonate, barium benzoyltrifluoro-acetonate, strontium benzolytrifluoro-acetonate, barium benzoyl-acetonate, strontium benzoyl-acetonate, barium 1, 1-diphenylethylene, strontium 1, 1-diphenylethylene, barium 1,2-acenaphthylene, strontium 1,2-acenaphthylene, barium tetraphenyl-butane, strontium tetraphenyl-butane, barium alpha-methyl-styrene, strontium alpha-methyl-styrene, diphenyl-barium, diphenyl-strontium, bis-cyclopentadienyl-barium, bis-cyclopentadienyl-strontium, barium triphenylsilyl, strontium triphenylsilyl, phenyl-barium iodide, methyl-strontium iodide, barium-benzophenone, strontium-benzophenone, barium-cinnamone, strontium-cinnamone, barium-naphthalene, strontium-naphthalene, barium-anthracene, strontium-anthracene, barium chrysene and strontium-chrysene; and (b 2 ) an organometallic compound of aluminum or zinc selected from the group consisting of diethyl zinc, triethyl aluminum, tri-isobutyl aluminum, diethyl aluminum chloride, ethyl aluminum dichloride, ethyl aluminum sesquichloride, methyl aluminum sesquichloride, diethyl aluminum hydride and diisobutyl aluminum hydride; said components being present in such quantities that the ratios are within the following limits: ##EQU4##

Claim 10

A process of homopolymerizing butadiene or copolymerizing butadiene with other conjugated dienes or with vinyl aromatic compounds to form products having simultaneously a high content of more than about 70% of trans-1,4 linkages and a low content of less than about 5% of 1,2 linkages which comprises reacting the monomers in a reaction medium in the presence of an added anionic catalytic composition consisting of a. an organo-lithium initiator selected from the group consisting of metallic lithium, ethyl-lithium, n-butyl lithium, isobutyl-lithium, sec.-butyl-lithium, ter.-butyl-lithium, isopropyl-lithium, n-amyl-lithium, isoamyl-lithium, allyl-lithium, propenyl-lithium, isobutenyl-lithium, polybutadienyl-lithium, polyisoprenyl-lithium, polystyryl-lithium, 1,4-dilithium butane, 1-5-dilithium pentane, 1,20-dilithium eicosane, benzyl-lithium, phenyl-lithium, 1,1-diphenyl-methyl-lithium, the polylithium reaction product of metallic lithium with 1,1-diphenylethylene, the polylithium reaction product of metallic lithium with trans-stilbene, the polylithium reaction product of metallic lithium with tetraphenylethylene, lithium-naphthalene, lithium-anthracene, lithium-chrysene and lithium-diphenyl; and b. a cocatalyst system consisting of (b 1 ) a compound of barium or strontium selected from the group consisting of barium hydride, strontium hydride; barium naphthenate, barium methanolate, strontium methanolate, barium ethanolate, strontium ethanolate, barium tertio-butanolate, barium nonylphenate, barium acetylacetonate, strontium acetylacetonate, barium dibenzoylmethane, strontium dibenzoylmethane, barium thenoyltrifluoro-acetonate, strontium thenoyltrifluoro-acetonate, barium benzoyltrifluoro-acetonate, strontium benzolytrifluoro-acetonate, barium benzoyl-acetonate, strontium benzoyl-acetonate, barium 1, 1-diphenylethylene, strontium 1, 1-diphenylethylene, barium 1,2-acenaphthylene, strontium 1,2-acenaphthylene, barium tetraphenyl-butane, strontium tetraphenyl-butane, barium alpha-methyl-styrene, strontium alpha-methyl-styrene, diphenyl-barium, diphenyl-strontium, bis-cyclopentadienyl-barium, bis-cyclopentadienyl-strontium, barium triphenylsilyl, strontium triphenylsilyl, phenyl-barium iodide, methyl-strontium iodide, barium-benzophenone, strontium-benzophenone, barium-cinnamone, strontium-cinnamone, barium-naphthalene, strontium-naphthalene, barium-anthracene, strontium-anthracene, barium chrysene and strontium-chrysene; and (b 2 ) an organometallic compound of aluminum or zinc selected from the group consisting of diethyl zinc, triethyl aluminum, tri-isobutyl aluminum, diethyl aluminum chloride, ethyl aluminum dichloride, ethyl aluminum sesquichloride, methyl aluminum sesquichloride, diethyl aluminum hydride and diisobutyl aluminum hydride; said components being present in such quantities that the ratios are within the following limits: ##EQU4##

Claim 11

The process according to claim 10 wherein 8 cocatalyst system is preformed and added to the reaction medium at the same time as the organo-lithium initiator at the start of the reaction.

Claim 12

The process according to claim 8 wherein the cocatalyst system is preformed and added in one or more batches to the reaction medium during the course of the reaction which has been previously initiated by the organo-lithium initiator.

Claim 13

The process according to claim 8 wherein the components of the cocatalyst system are added to the reaction medium in one of the following ways: a. separately at the start of the reaction in one or more batches at the same time as the organo-lithium initiator, b. one after the other in any order during the reaction which has been previously initiated by an organo-lithium initiator, or c. jointly in one or more batches during the reaction which has been initiated previously by an organo-lithium initiator.

Claim 14

The process according to claim 8 wherein styrene is used as the vinyl aromatic compound and the catalytic composition consists of n-butyl-lithium, a barium phenate, and a trialkyl aluminum.

Claim 15

The process according to claim 8 wherein the catalytic composition consists of n-butyl lithium, barium nonylphenate and triethyl aluminum.

Claim 16

The process according to claim 8 wherein the catalytic composition consists of n-butyl lithium, dibenzoylmethane barium and triethyl aluminum.

Claim 17

The process according to claim 8 wherein the components of the added anionic catalytic composition are present in such quantities that the ratios are within the following limits: ##EQU5##