The Goodyear & Tire Rubber Company

Laurie Elizabeth Austin

Adel Farhan Halasa

Wen-Liang Hsu

Bill B Gross

Barry A Matrana

Scott M Christian

David John Zanzig

Chad Aaron Jasiunas

Paul Harry Sandstrom

Susan A Weakland

Steven Kristofer Henning

John Robert Zuppo, Iii

Brian John Doucet

Gerald L Allen

The present invention is directed to a catalyst system for synthesizing rubbery polymers, such as polybutadiene rubber, styrene-butadiene rubber, isoprene-butadiene rubber, or styrene-isoprene-butadiene rubber, that are amine functionalized and have a high trans microstructure. The catalyst system, in one embodiment, includes (a) an organolithium amine compound, (b) a group IIa metal salt of an amino glycol or a glycol ether, (c) an organoaluminum compound, and optionally (d) an amine compound. The amine functionalized rubbery polymers can be utilized in tire tread rubbers where the rubbery polymers may provide desirable wear properties without substantially sacrificing other performance characteristic(s), e.g., traction properties.

Catalyst system for synthesizing amine functionalized rubbery polymers having a high trans microstructure

The present invention is directed to a catalyst system for synthesizing rubbery polymers, such as polybutadiene rubber and styrene-butadiene rubber, having a high trans microstructure. The catalyst system, in one embodiment, includes (a) a barium salt of an alcohol that is soluble in a hydrocarbon solvent, and (b) an organomagnesium compound. In one example, the alcohol is a primary or secondary alcohol. The catalyst system can further optionally include an alkali metal alkoxide, an organolithium compound, an amine compound, or mixtures thereof.

Catalyst system for synthesizing rubbery polymers having a high trans microstructure content

The process and catalyst of this invention can be utilized to synthesize homo and copolymers of conjugated diene monomers and vinyl aromatic monomers having high trans contents of greater than 60% with low melting points. These homo and copolymers of conjugated diene monomers and vinyl aromatic monomers can be utilized in tire tread and sidewall rubbers that exhibit outstanding wear and tear characteristics in the tread and excellent flexing properties in the sidewall. The rubber polymers of this invention are made utilizing an improved catalyst system. This catalyst system is comprised of (a) organo aluminum compounds, (b) organo lithium compounds, (c) a barium compound selected from barium salts of (i) di(ethylene glycol) ethyl ether, (ii) di(ethylene glycol) propyl ether, (iii) di(ethylene glycol) hexyl ether, (iv) di(N,N-dimethyl amino glycol) ethyl ether, (v) menthol and thymol in the presence of polar modifier consisting of water, alcohols, amines, thiols, phosphates and phosphites. The trans polymers and copolymers of this invention made with the above catalyst system typically have a glass transition temperature ranging from &#x2212;97&#xb0; C. to &#x2212;40&#xb0; C., a melt temperature ranging from &#x2212;30&#xb0; C. to +30&#xb0; C., and a number average molecular weight from 20,000 to 250,000. The inclusion of such polar modifiers in the barium catalyst system results in a high styrene content in copolymerization, a high trans content, and high molecular weight. Copolymers of conjugated diolefin monomers and vinyl aromatic monomers made with the catalyst system of this invention also have a tapered macrostructure.

Catalyst for synthesizing high trans polymers

The group IIa metal containing catalyst system of this invention can be utilized to synthesize rubbery polymers having a high trans microstructure by solution polymerization. Such rubbery polymers having a high trans microstructure content, such as polybutadiene rubber, styrene-isoprene-butadiene rubber, styrene-butadiene rubber, can be utilized in tire tread rubbers that exhibit improved wear and tear characteristics. This invention more specifically reveals a catalyst system which is comprised of (a) an organolithium compound, including organolithium functionalized compounds, (b) a group IIa metal salt selected from the group consisting of group IIa metal salts of di(alkylene glycol)alkylethers and group IIa metal salts of tri(alkylene glycol) alkylethers, and (c) an organoaluminum compound, and optionally an organomagnesium compound. The subject invention further discloses a process for synthesizing rubbery polymers having a high trans microstructure by a process that comprises polymerizing a conjugated diolefin monomer in an organic solvent in the presence of a catalyst system that is comprised of (a) an organolithium compound, (b) a group IIa metal salt selected from the group consisting of group IIa metal salts of amino glycols and group IIa metal salts of glycol ethers, and (c) an organoaluminum compound.

Group IIa metal containing catalyst system

The process and catalyst system of this invention can be utilized to synthesize polybutadiene rubber having a high trans content and a low melting point by solution polymerization. The trans-polybutadiene rubber made by the process of this invention can be utilized in tire tread rubbers that exhibit outstanding wear characteristics. More importantly, the trans-polybutadiene rubber of this invention can be easily processed because of its low level of crystallinity. In fact, the trans-polybutadiene made by the process of this invention does not need to be heated in a &ldquo;hot-house&rdquo; before being used in making rubber compounds. The process and catalyst system of this invention can also be used in the synthesis of trans-styrene-butadiene rubber (SBR). This invention more specifically reveals a process for synthesizing trans-polybutadiene rubber which comprises polymerizing 1,3-butadiene in an organic solvent in the presence of a catalyst system which comprises (a) an organolithium compound, (b) a barium compound selected from the group consisting of (i) barium salts of cyclic alcohols, such as barium mentholate, and (ii) barium thymol, and (c) an organoaluminum compound.

Process for synthesizing trans polydiene rubber

The process and catalyst system of this invention can be utilized to synthesize a highly random styrene-butadiene rubber having a high trans content by solution polymerization. The styrene-butadiene rubber made by the process of this invention can be utilized in tire tread rubbers that exhibit improved wear characteristics. This invention more specifically reveals a catalyst system for use in exothermal polymerizations which consists essentially of (a) an organolithium compound, (b) a barium alkoxide and (c) a lithium alkoxide. The subject invention further discloses a process for synthesizing a random styrene-butadiene rubber having a low vinyl content by a process which comprises copolymerizing styrene and 1,3-butadiene under isothermal conditions in an organic solvent in the presence of a catalyst system which consists essentially of (a) an organolithium compound, (b) a barium alkoxide and (c) a lithium alkoxide.

Process and catalyst system for synthesizing random trans SBR with low

The subject invention discloses a pneumatic tire having an outer circumferential tread wherein said tread is a sulfur-cured rubber composition comprised of (a) an isoprene-butadiene diblock rubber, said isoprene-butadiene diblock rubber being comprised of a butadiene block and an isoprene-butadiene block, wherein said butadiene block has a number average molecular weight which is within the range of about 25,000 to about 350,000, wherein said isoprene-butadiene block has a number average molecular weight which is within the range of about 25,000 to about 350,000, wherein said isoprene-butadiene diblock rubber has essentially one glass transition temperature which is within the range of about -100.degree. C. to about -70.degree. C., wherein said isoprene-butadiene diblock polymer has a Mooney ML-4 viscosity at 100.degree. C. which is within the range of about 50 to about 140, and wherein the repeat units derived from isoprene and 1,3-butadiene in the isoprene-butadiene block are in essentially random order; and (b) a second rubber selected from the group consisting of high vinyl polybutadiene rubber, styrene-isoprene-butadiene rubber, solution styrene-butadiene rubber and emulsion styrene-butadiene rubber.

Tire tread compound

The subject invention discloses a pneumatic tire having an outer circumferential tread wherein said tread is a sulfur-cured rubber composition comprised of (a) an isoprene-butadiene diblock rubber, said isoprene-butadiene diblock rubber being comprised of a butadiene block and an isoprene-butadiene block, wherein said butadiene block has a number average molecular weight which is within the range of about 25,000 to about 350,000, wherein said isoprene-butadiene block has a number average molecular weight which is within the range of about 25,000 to about 350,000, wherein said isoprene-butadiene diblock rubber has essentially one glass transition temperature which is within the range of about -100.degree. C. to about -70.degree. C., wherein said isoprene-butadiene diblock polymer has a Mooney ML-4 viscosity at 100.degree. C. which is within the range of about 50 to about 140, wherein the repeat units derived from isoprene and 1,3-butadiene in the isoprene-butadiene block are in essentially random order, and wherein said isoprene-butadiene diblock polymer does not contain any blocks which are derived solely from isoprene; and (b) a second rubber selected from the group consisting of high vinyl polybutadiene rubber, styrene-isoprene-butadiene rubber, solution styrene-butadiene rubber and emulsion styrene-butadiene rubber.

The subject invention relates to a technique for synthesizing rubbery copolymers of styrene and butadiene and/or isoprene. These rubbers exhibit an excellent combination of properties for utilization in high performance tire tread rubber compounds. The subject invention specifically discloses a process for preparing a styrene-butadiene rubber (SBR) which comprises: copolymerizing from about 30 weight percent to about 55 weight percent styrene and from about 45 weight percent to about 70 weight percent 1,3-butadiene in an alkane solvent, such as hexane, at a temperature which is within the range of about -10.degree. C. to about 150.degree. C. in the presence of (a) an alkali metal alkoxide, and (b) an organolithium compound, wherein the molar ratio of the alkali metal alkoxide to the organolithium compound is within the range of about 0.01:1 to about 1:1. The subject invention further discloses a process for preparing a rubbery copolymer of styrene and isoprene having an excellent combination of properties for use in making tire treads by a solution polymerization process which comprises: copolymerizing from about 30 weight percent to about 55 weight percent styrene and from about 45 weight percent to about 70 weight percent isoprene in an alkane solvent at a temperature which is within the range of about -10.degree. C. to about 150.degree. C. in the presence of (a) an alkali metal alkoxide, and (b) an organolithium compound, wherein the molar ratio of the alkali metal alkoxide to the organolithium compound is within the range of about 0.01:1 to about 1:1.

Solution polymerization process for synthesis of styrene-butadiene or

The subject invention relates to an anionic polymerization technique for synthesizing rubbery polymers of conjugated diolefin monomers, such as an rubbery copolymer of .alpha.-methylstyrene and 1,3-butadiene. These rubbery copolymers exhibit an excellent combination of properties for utilization in tire tread rubber compounds. They have high trans-isomer contents which leads to good treadwear characteristics and a broad molecular weight distribution which enhances processability. This invention more specifically discloses a process for the synthesis of rubbery polymers which have a broad molecular weight distribution and which are particularly useful in tire tread rubber compounds, said process comprising the polymerization of at least one conjugated diolefin monomer in an organic solvent in the presence of a catalyst system which is comprised of (a) a dialkyl magnesium compound and (b) an alkali metal containing compound selected from the group consisting of alkali metal alkoxides, alkali metal phenoxides, alkali metal sulfoxides, alkali metal sulfonates, alkali metal carboxylates, alkyl substituted alkali metal phenoxides, alkali metal alkylamines, and alkali metal dialkylamines; wherein the molar ratio of the alkali metal containing compound to the dialkyl magnesium compound is within the range of about 6:1 to about 1:5. In cases where rubbery copolymers containing .alpha.-methylstyrene are being synthesized the alkali metal in the alkali metal containing compound will normally be potassium, rubidium, or cesium with cesium being most preferred.

Pneumatic tire

The subject invention relates to an anionic polymerization technique for synthesizing rubbery polymers of conjugated diolefin monomers, such as rubbery copolymer of .alpha.-methylstyrene and 1,3-butadiene. These rubbery copolymers exhibit an excellent combination of properties for utilization in tire tread rubber compounds. They have high trans-isomer contents which leads to good treadwear characteristics and a broad molecular weight distribution which enhances processability. This invention more specifically discloses a process for the synthesis of rubbery polymers which have a broad molecular weight distribution and which are particularly useful in tire tread rubber compounds, said process comprising the polymerization of at least one conjugated diolefin monomer in an organic solvent in the presence of a catalyst system which is comprised of (a) a dialkyl magnesium compound and (b) an alkali metal containing compound selected from the group consisting of alkali metal alkoxides, alkali metal phenoxides, alkali metal sulfoxides, alkali metal sulfonates, alkali metal carboxylates, alkyl substituted alkali metal phenoxides, alkali metal alkylamines, and alkali metal dialkylamines; wherein the molar ratio of the alkali metal containing compound to the dialkyl magnesium compound is within the range of about 6:1 to about 1:5. In cases where rubbery copolymers containing .alpha.-methylstyrene are being synthesized the alkali metal in the alkali metal containing compound will normally be potassium, rubidium, or cesium with cesium being most preferred.

Catalyst system for the synthesis of rubbery polymers

This invention reveals a pneumatic tire having an outer circumferential tread wherein said tread is a sulfur-cured rubber composition comprised of, based on 100 parts by weight of rubber, (1) from about 5 to about 50 parts of 3,4-polyisoprene rubber, wherein said 3,4-polyisoprene rubber has (a) a 3,4-isomer content of from 75 percent to 95 percent, (b) a 1,2-isomer content of from 5 percent to 25 percent, (c) a glass transition temperature from 0.degree. to 25.degree. C. and (d) a number average molecular weight which is within the range of 30,000 to 180,000; and (2) from about 50 to about 95 parts of a rubbery polymer which is co-curable with the 3,4-polyisoprene rubber. The subject invention further discloses a pneumatic tire having an outer circumferential tread wherein said tread is a sulfur-cured rubber composition comprised of, based on 100 parts by weight of rubber, (1) from about 20 to about 60 parts of natural rubber, (2) from about 5 to about 30 parts of high cis-1,4-polybutadiene rubber, (3) from about 10 to about 50 parts of styrene-butadiene rubber, and (4) from about 5 to about 30 parts of 3,4-polyisoprene rubber, wherein the 3,4-polyisoprene rubber has (a) a 3,4-isomer content of from 75 percent to 95 percent, (b) a 1,2-isomer content of from 5 percent to 25 percent, (c) a glass transition temperature from 0.degree. to 25.degree. C. and (d) a number average molecular weight which is within the range of 30,000 to 180,000.

Tire tread containing 3.4-polyisoprene rubber

The subject invention relates to an anionic polymerization technique for synthesizing rubbery polymers of conjugated diolefin monomers, such as a rubbery copolymer of .alpha.-methylstyrene and 1,3-butadiene. These rubbery copolymers exhibit an excellent combination of properties for utilization in tire tread rubber compounds. They have high trans-isomer contents which leads to good treadwear characteristics and a broad molecular weight distribution which enhances processability. This invention more specifically discloses a process for the synthesis of rubbery polymers which have a broad molecular weight distribution and which are particularly useful in tire tread rubber compounds, said process comprising the polymerization of at least one conjugated diolefin monomer in an organic solvent in the presence of a catalyst system which is comprised of (a) a dialkyl magnesium compound and (b) an alkali metal containing compound selected from the group consisting of alkali metal alkoxides, alkali metal phenoxides, alkali metal sulfoxides, alkali metal sulfonates, alkali metal carboxylates, alkyl substituted alkali metal phenoxides, alkali metal alkylamines, and alkali metal dialkylamines; wherein the molar ratio of the alkali metal containing compound to the dialkyl magnesium compound is within the range of about 6:1 to about 1:5. In cases where rubbery copolymers containing .alpha.-methylstyrene are being synthesized, the alkali metal in the alkali metal containing compound will normally be potassium, rubidium, or cesium, with cesium being most preferred.

Process for the synthesis of rubbery polymers

The subject invention discloses a process for preparing a coupled styrene-isoprene-butadiene rubber which is particularly valuable for use in making automobile tire tread rubber compounds which comprises the steps of (1) solution terpolymerizing in an organic solvent from about 5 weight percent to about 40 weight percent styrene, from about 1 weight percent to about 10 weight percent isoprene, and from about 50 weight percent to about 94 weight percent 1,3-butadiene, based on total monomers, to a conversion of at least about 90% to produce a living styrene-isoprene-butadiene polymer, wherein the terpolymerization is initiated with an organolithium compound, and wherein the terpolymerization is conducted in the presence of a polar modifier at a molar ratio of the polar modifier to the organolithium compound, which is within the range of about 0.5:1 to about 5:1, and wherein the terpolymerization is conducted at a temperature which is within the range of about 20.degree. C. to about 150.degree. C.; and (2) coupling the living styrene-isoprene-butadiene polymer with a coupling agent selected from the group consisting of tin tetrachloride and silicon tetrachloride, wherein the molar ratio of the coupling agent to the organolithium compound is within the range of about 1:3 to 1:6.

Coupled styrene-isoprene-butadiene rubber

The subject invention discloses an isoprene-butadiene diblock rubber which is particularly valuable for use in making treads for tires which have improved wear characteristics without compromising traction characteristics or rolling resistance. Said isoprene-butadiene diblock rubber is comprised of (1) a first block which is comprised of repeat units which are derived from 1,3-butadiene and (2) a second block which is comprised of repeat units which are derived from both 1,3-butadiene and isoprene, wherein the repeat units derived from isoprene and 1,3-butadiene in the second block are in an essentially random order, wherein the diblock rubber has a glass transition temperature which is within the range of about -100.degree. C. to about -70.degree. C., and wherein the diblock rubber has a Mooney viscosity which is within the range of about 50 to about 140. In cases where the isoprene-butadiene diblock rubber of this invention is employed in automobile tires it will preferably have a second glass transition temperature which is within the range of about -50.degree. C. to about 0.degree. C. The Mooney viscosity will preferably be within the range of about 80 to about 135 and in the case of oil extended polymers will more preferably be within the range of about 100 to about 130 before oil extension.

Growing community of inventors

Hartville, OH, United States of America

Laurie Elizabeth Austin