The Firestone Tire & Rubber Company

Bridgestone Corporation

Bridgestone/firestone, Inc.

Jung W Kang

Takatsugu Hashimoto

Donald N Schulz

James A Davis

Jason T Poulton

David M Roggeman

Gary R Hamed

Binnur Gunesin

James E Hall

Gary B Seaver

William L Hergenrother

David F Lawson

Xiaorong Wang

John W Spiewak

Mark L Stayer

Hideo Takeichi

Naruhiko Mashita

Shinichi Toyosawa

James Oziomek

Arthur E Oberster

Delmar F Lohr, Jr

Takashi Kitamura

Takahiro Matsuse

Thomas J Lynch

Frank J Clark

Dennis L Snyder

Shrikant R Malani

Bonnie L Stuck

Xiao-Liang Luo

Steven X L Luo

Yoichi F Ozawa

Dwayne A Joyner

Kazuaki Yuto

There are disclosed a block copolymer of at least one elastomeric block and at least one syndiotactic polystyrene block which comprises 100 parts by weight of a polymer component comprising 1 to 80% by weight of syndiotactic polystyrene (sPS) block(s) and 99 to 20% by weight of rubbery elastomeric block(s) and at least 30 parts by weight of an extender. These extended block copolymer compositions display the characteristics of thermoplastic elastomers and are useful for high temperature applications possessing unique softness.

Extended syndiotactic polystyrene-elastomeric block copolymers

The instant invention teaches a method for forming a syndiotactic 1,2-polybutadiene product having a syndiotacticity of more than 66.5% and a melting temperature of more than about 100&deg; C. The method includes polymerizing 1,3-butadiene in solution with a solvent, in the presence of catalytically effective amounts of: (a) an organomagnesium compound; (b) a chromium compound; and, (c) a dihydrocarbyl hydrogen phosphite. The present invention also contemplates a product of the method and an article made from the product.

Preparation of syndiotactic 1, 2-polybutadiene using a chromium-containing catalyst system

Novel silicon-containing derivatives of crystalline, high-trans-1,4 polybutadiene in which organosilicon-containing groups are bonded to the 1,2-vinyl carbon atoms along the main chain of the butadiene polymers through the carbon-silicon linkages. These derivatives of butadiene polymers are produced by the addition reaction of an organosilicon-compound having one hydrogen atom directly bonded to the silicon atom in the molecule to the double bonds in the 1,2-vinyl group butadiene polymers. These derivatives having good compatibility with siliceous fillers and when blended with filled diene rubbers are cured to elastomer compositions having excellent properties suitable for the production of tires.

Hydrosilated crystalline high trans polybutadine with silica filler,

Diene polymers having a high content of trans-1,4 addition and two distinct melting points in the ranges of 30.degree. C. to 50.degree. C. and 70.degree. C. to 130.degree. C. are prepared by polymerizing a 1,3-diene monomer in a hydrocarbon solvent in the presence of a catalyst composition comprising (a) a carboxylated nickel oxy borate compound; (b) an orKanoaluminum compound; (c) a triaryloxy phosphorus compound and (d) a carboxylic acid preferably a fluorinated carboxylic acid. The resultant polymers are useful as additives to tire rubbers to improve processability by reducing compound Mooney viscosity and reducing the shrinkage of various compound stocks.

High trans-1,4-polybutadiene and catalyst and process for preparing

Diene polymers having a high content of trans-1,4 addition and two distinct melting points in the ranges of 30.degree. C. to 60.degree. C. and 70.degree. C. to 130.degree. C. are useful as additives to tire rubbers to improve processability by reducing compound Mooney viscosity and reducing the shrinkage of various compound stocks.

Rubber composition for tires

A continuous process is described for preparing copolymer compositions of 1,3-conjugated dienes and aromatic vinyl compounds having a weight average molecular weight of greater than about 100,000, and in one embodiment above about 900,000. The process comprises: (A) continuously introducing into a reactor, a 1,3-conjugated diene, an aromatic vinyl compound, a hydrocarbon solvent and a polymerization catalyst comprising a trimetalated 1-alkyne wherein the catalyst is obtained by reacting at a temperature of above about 70.degree. C., a 1-alkyne containing at least 4 carbon atoms, an organo metallic compound, R.degree. M and a 1,3-conjugated diene wherein the alkyne is characterized by the formula

Copolymers of conjugated dienes and aromatic vinyl compounds prepared by

Elastomer compositions comprising (A) ultra high molecular weight copolymer compositions of 1,3-conjugated dienes and aromatic vinyl compounds having a weight average molecular weight of greater than about 1,000,000 and (B) oil are described. The ultra high molecular weight copolymer compositions which are also characterized as having an intrinsic viscosity in tetrahydrofuran of at least about 4.0 may be obtained by a process which comprises polymerizing a 1,3-conjugated diene and a vinyl aromatic compound in a hydrocarbon solvent in the presence of a trimetalated 1-alkyne catalyst which comprises the reaction product of a 1-alkyne containing at least 4 carbon atoms, an organo metallic compound R.degree.M and a 1,3-conjugated diene wherein R.degree. is a hydrocarbyl group, M is an alkali metal, the mole ratio of R.degree.M to 1-alkyne is about 3:1 and the mole ratio of conjugated diene to 1-alkyne is from about 2:1 to about 30:1. The oil extended elastomer compositions of the present invention preferably contain large amounts of oil such as 80 parts or higher per 100 parts of copolymer.

Oil extended ultra high molecular weight elastomers

High-performance tires comprising treads made of elastomer compositions comprising (A) ultra high molecular weight copolymer compositions of 1,3-conjugated dienes and aromatic vinyl compounds having a weight average molecular weight of greater than about 1,000,000; (B) extender oil; and (C) carbon black are described. The ultra high molecular weight copolymer compositions which are also characterized as having an intrinsic viscosity in tetrahydrofuran of at least about 4.0 may be obtained by a process which comprises polymerizing a 1,3-conjugated diene and a vinyl aromatic compound in a hydrocarbon solvent in the presence of a trimetalated 1-alkyne catalyst which comprises the reaction product of a 1-alkyne containing at least 4 carbon atoms, an organo metallic compound R.sup.o M and a 1,3-conjugated diene wherein R.sup.o is a hydrocarbyl group, M is an alkali metal, the mole ratio of R.sup.o M to 1-alkyne is about 3:1 and the mole ratio of conjugated diene to 1-alkyne is from about 2:1 to about 30:1.

High performance tire treads and tires

Elastomer compositions comprising (A) ultra high molecular weight copolymer compositions of 1,3-conjugated dienes and aromatic vinyl compounds having a weight average molecular weight of greater than about 1,000,000 and (B) oil are described. The ultra high molecular weight copolymer compositions which are also characterized as having an intrinsic viscosity in tetrahydrofuran of at least about 4.0 may be obtained by a process which comprises polymerizing a 1,3-conjugated diene and a vinyl aromatic compound in a hydrocarbon solvent in the presence of a trimetalated 1-alkyne catalyst which comprises the reaction product of a 1-alkyne containing at least 4 carbon atoms, an organo metallic compound R.sup.o M and a 1,3-conjugated diene wherein R.sup.o is a hydrocarby group, M is an alkali metal, the mole ratio of R.sup.o M to 1-alkyne is about 3:1 and th mole ratio of conjugated diene to 1-alkyne is from about 2:1 to about 30:1. The oil extended elastomer compositions of the present invention preferably contain large amounts of oil such as 80 parts or higher per 100 parts of copolymer.

A continuous process is described for preparing copolymer compositions of 1,3-conjugated dienes and aromatic vinyl compounds having a weight average molecular weight of greater than about 100,000, and in one embodiment above about 900,000. The process comprises:

Continuous process for preparing copolymers of conjugated dienes and

An ultra high molecular weight copolymer compositions of 1,3-conjugated dienes and aromatic vinyl compounds having a weight average molecular weight of greater than about 1,000,000 are described. The ultra high molecular weight copolymer compositions which are also characterized as having an intrinsic viscosity in tetrahydrofuran of at least about 4.0 may be obtained by a process which comprises polymerizing a 1,3-conjugated diene and a vinyl aromatic compound in a hydrocarbon solvent in the presence of a trimetalated 1-alkyne catalyst which comprises the reaction product of a 1-alkyne containing at least 4 carbon atoms, an organo metallic compound R.degree.M and 1,3-conjugated diene wherein R.degree. is a hydrocarbyl group, M is an alkali metal, the mole ratio of R.degree.M to 1-alkyne is about 3:1 and the mole ratio of conjugated diene to 1-alkyne is from about 2:1 to about 30:1.

Method for preparing ultra high molecular weight copolymers of

A method for incorporating metal salts of .alpha.,.beta.-ethylenically unsaturated carboxylic acids into polymers and improving the cured physical properties of vulcanizable rubber compositions based on such polymers. The method includes the steps of preparing a polymer cement in a suitable organic solvent, forming a suspension of the metal salt of an .alpha.,.beta.-ethylenically unsaturated carboxylic acid in a suitable aliphatic hydrocarbon solvent miscible with the organic solvent, mixing the polymer cement and the suspension together and thereafter removing the solvents to provide the metal salt uniformly dispersed within the polymer.

Method for incorporating metal salts of .alpha.,.beta.-ethylenically

Hydrocarbon soluble polymetalated 1-alkene compositions are described, and these compositions may be characterized by the formula ##STR1## wherein R is hydrogen, a hydrocarbyl group or R.sup.1 M, M is an alkali metal, R.sup.1 is a divalent oligomeric hydrocarbyl group comprising moieties derived from a conjugated diene, and wherein the total number moieties derived from a conjugated diene in all of the R.sup.1 groups in Formula I is from about 2 to about 30. Preferably, the alkali metal is lithium. Hydrocarbon soluble polymetalated 1-alkene catalysts for anionic polymerizations are also described which comprise the reaction product of a 1-alkyne, an organometallic compount R.degree.M, and a 1,3-conjugated diene wherein R.degree. is a hydrocarbyl group, M is an alkali metal, the mole ratio of conjugated diene to 1-alkyne is at least about 2:1, and the reaction is conducted at a temperature of at least about 70.degree. C.

Polymetalated 1-alkyne compositions

Rubber compositions and metal-reinforced rubber ply members have improved metal adhesion and metal adhesion retention. The improvement comprises admixing from about 0.5 to about 10.0 parts per hundred rubber (phr) of bis(2-mercaptobenzothiazato) nickel with a vulcanizable rubber composition prior to combining the metal and rubber and then curing. A method for improving the metal adhesion and metal adhesion retention between a vulcanizable rubber and metal member includes the step of dispersing from about 0.5 to about 10.0 phr of nickel in a vulcanizable rubber composition prior to curing.

Rubber compositions and related articles having improved metal adhesion

Diene polymers having a high content of cis-1,4 addition are prepared by polymerizing a 1,3-diene monomer in a hydrocarbon solvent in the presence of a catalyst composition comprising (a) a carboxylated metal oxy aluminate compound in which the metal is nickel or cobalt, (b) an organometallic compound of a metal of Groups I, II, and III of the Periodic System, and (c) one or more fluorine containing compounds selected from the group consisting of boron trifluoride complexes with ethers, alcohols or mixtures thereof; hydrogen fluoride; hydrogen fluoride complexes with ethers, alcohols, or mixtures thereof and mixtures of said compounds. The resultant polymers exhibit good green strength and tack and are particularly suitable for use as tire rubbers.

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Clinton, OH, United States of America

Jung W Kang