The Goodyear & Tire Rubber Company

Lehigh Technologies, Inc.

Chad Aaron Jasiunas

Adel Farhan Halasa

Wen-Liang Hsu

Jin-Ping Zhou

Laurie Elizabeth Austin

John Robert Zuppo, Iii

Charles Rosenmayer

Frank Papp

Paul Harry Sandstrom

Corey Stanton Yon

Aaron Michael Ryba

David John Zanzig

Shingo Futamura

Steven Kristofer Henning

Leh-Yeh Hsu, Legal Representative

Glenn Denstaedt

Kedar D Murthy

Charles T Rosenmayer

Joe Zhou

Lauire Elizabeth Austin

Frank P Papp

The renewed rubber of this invention can be used in rubber formulations that are used in manufacturing a wide array of rubber products, including tires, power transmission belts, conveyor belts, hoses, and a wide array of other products. The present invention more specifically discloses a method for manufacturing an environmentally friendly, chemically functionalized, renewed rubber composition having a highly desirable combination of physical properties and which exhibits excellent processability comprising the steps of (1) blending a micronized rubber powder with a processing aid and a chemical functionalizing agent to produce a blended mixture; (2) processing the blended mixture under conditions of high shear and low temperature to produce a reacted mixture; (3) adding a stabilizer to the reacted mixture to produce the chemically functionalized renewed rubber composition.

Chemically functionalized renewed rubber composition

This invention is based upon the discovery that micronized solution styrene-butadiene rubber from postconsumer sources can be included in rubber formulations without severely compromising abrasion resistance. The micronized solution styrene-butadiene rubber utilized in the rubber formulations of this invention can be made by cryogenic grinding postconsumer rubber products using conventional procedures. For instance, it can be made by cryogenically grinding a tire tread containing a high level of solution styrene-butadiene rubber. The micronized solution styrene-butadiene rubber can then be blending into desired virgin rubbers and cured without significantly compromising the abrasion resistance of the rubber formulation. The rubber formulation of this invention is comprised of a natural or synthetic rubber and from 1 weight percent to 30 weight percent of a micronized rubber composition containing at least 10 weight percent solution styrene-butadiene rubber and having a particle size of 40 mesh to 200 mesh.

Recycled micronized rubber formulation having improved abrasion resistance

This invention relates to certain rubber formulations which exhibit a low level of hysteresis which are comprised of a chemically functionalized renewed rubber and virgin solution styrene-butadiene rubber. These rubber formulations are loaded with a reinforcing silica. The rubber formulations of this invention can be utilized in making rubber products such as, tires, tracks, and conveyor belts which will promote energy savings by virtue of their low hysteretic properties. The present invention more specifically discloses a rubber composition which is comprised of (1) a solution styrene-butadiene rubber; (2) a functionalized renewed rubber composition which is comprised of an elastomeric polymer and a stabilizer; wherein the rubber composition has a crosslink density which is within the range of 0.05 to 2.0&#xd7;10mole/g, and wherein the rubber composition has a solubility fraction of less than 90 percent; and (3) a reinforcing filler including reinforcing silica.

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

This invention discloses a process for synthesizing a dendrimer of a rubbery polymer comprising: (a) reacting a lithium terminated rubbery polymer with a halogenated tin containing compound to produce a polymer which is terminated with halogenated tin moieties, wherein the halogenated tin containing compound is of the structural formula: wherein X represents a halogen atom, wherein Zgroups can be the same or different and are selected from alkyl groups containing from 1 to 8 carbon atoms, wherein x represents an integer from 1 to 20, wherein the molar ratio of the lithium terminated rubbery polymer to halogen atoms in the halogenated tin containing compound is within the range of 2:n to (n&#x2212;1):n, wherein n represents the number of halogen atoms that are bonded directly to tin atoms in the halogenated tin containing compound; (b) reacting the polymer which is terminated with halogenated tin moieties with a molar excess of a tertiary alcohol to produce a polymer which is terminated with hydroxy tin moieties; and (c) allowing the polymer which is terminated with the hydroxy tin moieties to couple under conditions sufficient to produce a dendrimer of the rubbery polymer.

Dendrimers of rubbery polymers

This invention discloses a process for synthesizing a dendrimer of a rubbery polymer comprising: (a) reacting a lithium terminated rubbery polymer with a halogenated silicon containing compound to produce a polymer which is terminated with halogenated silicon moieties, wherein the halogenated silicon contain compound has at least four halogen atoms which are bonded directly to silicon atoms, wherein the ratio of the lithium terminated rubbery polymer to halogen atoms in the halogenated silicon containing compound is within the range of 2:n to (n-1):n, wherein n represents the number of halogen atoms that are bonded directly to silicon atoms in the halogenated silicon containing compound, wherein the halogenated silicon containing compound contains at least three halogen atoms which are bonded directly to a silicon atom; (b) reacting the polymer which is terminated with halogenated silicon moieties with a molar excess of a tertiary alcohol to produce a polymer which is terminated with hydroxy silyl moieties; and (c) allowing the polymer which is terminated with the hydroxy silyl moieties to couple under conditions sufficient to produce a dendrimer containing siloxane linkages. It has also be found that similar dendrimers having improved processability can be make utilizing halogenated tin containing compounds in stead of the halogenated silicon containing compound.

Rubbery polymers can be formed having the general formula:RRN&#x2014;(CH)&#x2014;X&#x2014;CH&#x2014;CHRRwherein Rand Rare independently selected from a group consisting of alkyls, cycloalkyls, alkenyls, cycloalkenyls, aryls, phenyls, heterocycles, acyls, and silanes, or Rin combination with Rforms a heterocyclic ring; n is an integer from 1 to 20; X is selected from a group consisting of sulfur, a phosphorus moiety, and a silicon moiety; Rand Rare one of hydrogen, alkyls, alkenyls, and at least one of which includes reactive unsaturation such as an alkenyl group. Moreover, this invention discloses a process of making functionalized rubbery polymers from the functionalized monomers.

Functionalized monomers and functionalized rubbery polymers made therewith

This invention discloses a process for synthesizing a dendrimer of a rubbery polymer comprising: (a) reacting a lithium terminated rubbery polymer with a halogenated silicon containing compound to produce a polymer which is terminated with halogenated silicon moieties, wherein the halogenated silicon contain compound has at least four halogen atoms which are bonded directly to silicon atoms, wherein the ratio of the lithium terminated rubbery polymer to halogen atoms in the halogenated silicon containing compound is within the range of 2:n to (n&#x2212;1):n, wherein n represents the number of halogen atoms that are bonded directly to silicon atoms in the halogenated silicon containing compound, wherein the halogenated silicon containing compound contains at least three halogen atoms which are bonded directly to a silicon atom; (b) reacting the polymer which is terminated with halogenated silicon moieties with a molar excess of a tertiary alcohol to produce a polymer which is terminated with hydroxy silyl moieties; and (c) allowing the polymer which is terminated with the hydroxy silyl moieties to couple under conditions sufficient to produce a dendrimer containing siloxane linkages. It has also be found that similar dendrimers having improved processability can be make utilizing halogenated tin containing compounds in stead of the halogenated silicon containing compound.

The present invention is directed to an amine containing 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) an organolithium compound, (b) a group IIa metal salt, (c) an organoaluminum compound, and (d) an amine compound which can be selected from (1) a heterocyclic aromatic compound which includes a ring structure with one or more nitrogen atoms as part of the ring; (2) a heterocyclic non-aromatic compound which includes a ring structure with two or more nitrogen atoms as part of the ring; (3) an aromatic compound including a ring structure substituted with at least one amine and at least one polar functionality containing group selected from a carboxyl group or a hydroxyl group; (4) a bicyclic chelating diamine compound; or (5) an aliphatic amine which includes a C-Calkyl group.

Amine containing catalyst system and methods of use thereof

The neodymium catalyst system prepared by the technique of this invention can be used in the polymerization of isoprene monomer into synthetic polyisoprene rubber having an extremely high cis-microstructure content and high stereo regularity. This polyisoprene rubber will crystallize under strain and can be compounded into rubber formulations in a manner similar to natural rubber. This invention more specifically discloses a process for the synthesis of polyisoprene rubber which comprises polymerizing isoprene monomer in the presence of a neodymium catalyst system, wherein the neodymium catalyst system is prepared by a process that comprises (1) reacting a neodymium carboxylate with an organoaluminum compound in an organic solvent to produce neodymium-aluminum catalyst component, and (2) subsequently reacting the neodymium-aluminum catalyst component with an elemental halogen to produce the neodymium catalyst system, wherein the neodymium catalyst system is void of nickel-containing compounds.

Synthetic polyisoprene rubber

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 subject invention relates to a process for preparing a catalyst system that comprises the sequential steps of (I) reacting an organometalic compound that contains a metal from Group III-B of the Periodic System with an organoaluminum compound at a temperature which is within the range of 50&#xb0; C. to 100&#xb0; C. to produce an aluminum modified Group III-B metal containing catalyst component, and (II) mixing the aluminum modified Group III-B metal containing catalyst component with a halogen containing compound to produce the Group III-B metal containing catalyst system, wherein the catalyst system is void of compounds selected from the group consisting of aliphatic alcohols, cycloaliphatic alcohols, aliphatic thiols, cycloaliphatic thiols, trialkyl silanols, and triaryl silanols, wherein the organometalic compound that contains a metal from Group III-B of the Periodic System is reacted with the organoaluminum compound in the absence of conjugated diene monomers, and wherein the catalyst system is prepared in the absence of compounds that contain labile halogen atoms.

Group III-B metal catalyst system

The neodymium catalyst system prepared by the technique of this invention can be used in the polymerization of isoprene monomer into synthetic polyisoprene rubber having an extremely high cis-microstructure content and high stereo regularity. This polyisoprene rubber will crystallize under strain and can be compounded into rubber formulations in a manner similar to natural rubber. This invention more specifically discloses a process for preparing a neodymium catalyst system which comprises (1) reacting a neodymium carboxylate with an organoaluminum compound in an organic solvent to produce neodymium-aluminum catalyst component, and (2) subsequently reacting the neodymium-aluminum catalyst component with an elemental halogen to produce the neodymium catalyst system. The present invention further discloses a synthetic polyisoprene rubber which is comprised of repeat units that are derived from isoprene, wherein the synthetic polyisoprene rubber has a cis-microstructure content which is within the range of 98.0% to 99.5%, a 3,4-microstructure content which is within the range of 0.5% to 2.0%, and a trans-microstructure content which is within the range of 0.0% to 0.5%.

The subject invention relates to a technique for synthesizing rubbery non-tapered, random, copolymers of 1,3-butadiene and isoprene. These rubbery copolymers exhibit an excellent combination of properties for utilization in tire sidewall rubber compounds for truck tires. By utilizing these isoprene-butadiene rubbers in tire sidewalls, tires having improved cut growth resistance can be built without sacrificing rolling resistance. Such rubbers can also be employed in tire tread compounds to improve tread wear characteristics and decrease rolling resistance without sacrificing traction characteristics. This invention more specifically discloses a process for the synthesis of isoprene-butadiene rubber which comprises copolymerizing isoprene monomer and 1,3-butadiene monomer in an organic solvent in the presence of a Group III-B metal containing catalyst system that is made by the sequential steps of (I) reacting an organometalic compound that contains a metal from Group III-B of the Periodic System with an organoaluminum compound at a temperature which is within the range of 50&#xb0; C. to 100&#xb0; C. to produce an aluminum modified Group III-B metal containing catalyst component, and (II) mixing the aluminum modified Group III-B metal containing catalyst component with a halogen containing compound, wherein the catalyst system is void of compounds selected from the group consisting of aliphatic alcohols, cycloaliphatic alcohols, aliphatic thiols, cycloaliphatic thiols, trialkyl silanols, and triaryl silanols.

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Copley, OH, United States of America

Chad Aaron Jasiunas