The General Tire & Rubber Company

Gencorp, Inc.

Sundar L Aggarwal

Russell A Livigni

Ivan G Hargis

Hubert J Fabris

Robert E Bingham

Richard R Durst

Francis J Vitus

John A Wilson

George B Thomas

Robert J Herold

Thomas J Dudek

Leon F Marker

Rubbery high trans-high vinyl diblock copolymers, blends of rubbery high trans copolymers and rubbery high vinyl polymers, and mixtures (alloys or blends) of said diblock copolymers, high trans copolymers and high vinyl polymers are useful in producing tire treads exhibiting good processibility, good rolling resistance, skid resistance and abrasion resistance. The high trans block or copolymer comprises a copolymer of butadiene-1,3 and styrene and/or isoprene and the high vinyl block or polymer comprises polybutadiene or copolymers of butadiene and styrene and/or isoprene. These di-block copolymers, copolymers and polymers are made by solution polymerization. The diblock copolymer may be made by copolymerizing butadiene and styrene and/or isoprene using a Ba, Ca or Sr alcoholate, R.sub.2 Mg and R.sub.3 Al to from about 60 to 95% conversion to a high trans block and then adding (optionally more Bd with or without Sty and/or isoprene) a strong Lewis base and a Na, K or Rb alkoxide and continuing the polymerization to completion to obtain the high vinyl block of the di-block copolymer.

High trans butadiene based carbon black reinforced compositions

Tire tread having high trans butadiene based elastomeric block

High trans butadiene based elastomeric block copolymers and blends

A tire having a tread exhibiting substantial low rolling resistance, traction and wear comprises a cured compounded carbon black reinforced blend of (A) a star-shaped substantially random vinyl containing rubbery solution polymerized polymer selected from the group consisting of polybutadienes, polyisoprenes, butadiene-styrene copolymers, butadiene-isoprene copolymers, isoprene-styrene copolymers, butadiene-isoprene-styrene copolymers and mixtures of the same and (B) at least one other rubbery diene polymer.

Star-shaped polymers for improved tire treads

A composition useful as a catalyst in solution polymerization comprises (1) a barium, calcium and/or strontium alcoholate, (2) an organoaluminum compound and (3) an organomagnesium compound. (2) and (3) may be used as a complex with (1). The compositions can be used to polymerize ethylenically unsaturated monomers like butadiene, butadiene and styrene, and isoprene and heterocyclic monomers like oxiranes, thiiranes, siloxanes, thiatanes and lactams. The catalyst composition can produce polybutadienes and butadiene-styrene copolymers having a trans-1,4 content as high as 90%. The non-terminating features of the polymerization of this invention permit the preparation of functionally terminated butadiene based polymers and block polymers containing sufficient amounts of trans-1,4 butadiene units to crystallize.

Solution polymerization

Divinyl benzene and/or diisopropenyl benzene in hydrocarbon solvent is added over a period of time at low temperature to a hydrocarbon solvent containing a C.sub.2-20 normal, secondary or tertiary alkyl or cycloalkyl lithium compound and a tertiary alkylamine having 2-4 carbon atoms prepared at low temperature to provide an initiator having an average of from 4 to 9 C-Li sites and a VPO Mn of from about 750 to 4,000. These initiators are useful in polymerizing dienes and vinyl monomers to provide star polymers having an average of from about 4 to 9 arms or branches. These star polymers among other things are useful low profile or low shrink additives for FRPs, e.g., glass fiber reinforced plastics.

Preparation of lithium initiator for the preparation of star polymers

Divinyl benzene and/or diisopropenyl benzene in hydrocarbon solvent is added over a period of time at low temperature to a hydrocarbon solvent containing a C.sub.2-20 normal, secondary or tertiary alkyl or cycloalkyl lithium compound and a tertiary alkylamine having 2-4 carbon atoms prepared at low temperature to provide an initiator having an average of from 4 to 9 C-Li sites and a VPO Mn of from about 750 to 4,000. These initiators a re useful in polymerizing dienes and vinyl monomers to provide star polymers having an average of from about 4 to 9 arms or branches. These star polymers among other things are useful low profile or low shrink additives for FRPs, e.g., glass fiber reinforced plastics.

Preparation of star polymers

Divinyl benzene and/or diisopropenyl benzene in hydrocarbon solvent is added over a period of time at low temperature to a hydrocarbon solvent containing a C.sub.2-20 normal, secondary or tertiary alkyl or cycloalkyl lithium compound and a tertiary alkylamine having 2-4 carbon atoms prepared at low temperature to provide an initiator having an average of from 4 to 9 C-Li sites and a VPO Mn of from about 750 to 4,000. These initiators are useful in polymerizing dienes and vinyl monomers to provide star polymers having an average of from about 4 to 9 arms or branches. These star polymers among other things are useful low profile or low shrink additives of FRPs, e.g., glass fiber reinforced plastics.

A composition useful as a catalyst in solution polymerization comprises (1) a barium, calcium and/or strontium alcoholate, (2) an organoaluminum compound and (3) an organomagnesium compound. (2) and (3) may be used as a complex with (1). The compositions can be used to polymerize ethylenically unsaturated monomers like butadiene, butadiene and styrene, and isoprene and heterocyclic monomers like oxiranes, thiiranes, siloxanes, thiatanes and lactams. The catalyst composition can product polybutadienes and butadiene-styrene copolymers having a trans-1,4 content as high as 90%. The non-terminating features of the polymerization of this invention permit the preparation of functionally terminated butadiene based polymers and block polymers containing sufficient amounts of trans-1,4 butadiene units to crystallize.

A block copolymer of polyalkalene oxide and a polydiene is made by the lithium catalyzed anionic polymerization of a diene followed by polymerization of an alkalene oxide using a double metal cyanide catalyst. The dispersant can be used in forming a crude oil methanol dispersion for transport through unheated pipelines from the North Slope oil fields to Prudhoe Bay.

Polydiene polyalkylene oxide block copolymers and their use as alcohol

A laminated product such as a tire is cast from chemically extending liquids which form a laminated solid in a mold. The mold cavity is closed in preparation for use except for casting fluid inlet ports and exhaust vents. The mold cavity defines the shape of the product to be cast. Two or more chemically extendable liquids are injected into the mold without mixing through the inlet ports. Each liquid is injected through a different port. After injection, the liquids are arranged in alternate circumferential segments within the annular space. At least one of the inner and outer surfaces which define the mold cavity is then rotated about the common axis to impart a spiral configuration to each of the injected liquids. The liqiuds are then allowed to chemically extend to solids and form a laminated product such as a tire. The products, when they comprise alternate layers of high and low elastic modulus materials, have better resistance to flex cracking than non-layered materials of similar composition having similar average stiffness.

Apparatus for making cast annular laminates

The characteristics of barium t-alkoxide salts used with organolithium compounds as catalyst complexes in the solution polymerization of unsaturated or oxirane monomers to make polymers such as rubbers is improved by reducing or eliminating the nitrogen content of the barium salt and, further, by using a certain mixture of tertiary carbinols and water in forming the barium salt. In certain instances water may be eliminated.

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Akron, OH, United States of America

Sundar L Aggarwal