The Goodyear & Tire Rubber Company

Other

Kenneth Floyd Castner

Joseph P Kennedy

Howard Allen Colvin

Nissim Calderon

Joel Muse, Jr

Anthony J Bell

Paul Harry Sandstrom

Adel Farhan Halasa

Lawson G Wideman

Dane Kenton Parker

Richard G Bauer

George Frank Balogh

Michael Joseph Rachita

Michael Lester Kerns

Tang Hong Wong

Joseph Frank Geiser

Jean Steininger Clites

Michael Paul Mallamaci

Leonard J Kuzma

Kimberly M Glenn

Craig William Burkhart

It has been unexpectedly discovered that cis-1,4-polybutadiene that is synthesized utilizing Zeigler-Natta catalyst systems has superior characteristics for utilization in solid golf ball cores if the polymerization is terminated utilizing a carboxylic acid of the structural formula RCOOH, wherein R represents an alkyl group containing from 1 to about 30 carbon atoms.

Golf ball

This invention is based upon the unexpected discovery that elastomeric trans-1,4-polybutadiene can be made by utilizing a catalyst system that is comprised of an organocobalt compound, an organoaluminum compound, a para-alkyl substituted phenol, and ortho-phenyl phenol wherein the molar ratio of the para-substituted phenol to the organoaluminum compound is within the range of about 1.2:1 to about 1.8:1, and wherein the molar ratio of the ortho-phenyl phenol to the organoaluminum compound is within the range of about 0.7:1 to about 1.3:1. Accordingly, the elastomeric trans-1,4-polybutadiene made by the process of this invention does not need to be heated, such as in a hot-house, before being used in making rubber stocks.

Synthesis of elastomeric high trans-1,4-polybutadiene

This invention is based upon the unexpected discovery that elastomeric trans-1,4-polybutadiene can be made by utilizing a catalyst system that is comprised of an organocobalt compound, an organoaluminum compound, a para-alkyl substituted phenol, and ortho-phenyl phenol wherein the molar ratio of the para-substituted phenol to the organoaluminum compound is within the range of about 1.2:1 to about 1.8:1, and wherein the molar ratio of the ortho-phenyl phenol to the organoaluminum compound is within the range of about 0.7:1 to about 1.3:1. Accordingly, the elastomeric trans-1,4-polybutadiene made by the process of this invention does not need to be heated, such as in a hot-house, before being used in making rubber stocks. This invention more specifically discloses a process for synthesizing elastomeric trans-1-4-polybutadiene by polymerizing 1,3-butadiene monomer in the presence of a catalyst system that is comprised of an organocobalt compound, an organoaluminum compound, a para-alkyl substituted phenol, and ortho-phenyl phenol, wherein the molar ratio of the para-substituted phenol to the organoaluminum compound is within the range of about 1.2:1 to about 1.8:1, and wherein the molar ratio of the ortho-phenyl phenol to the organoaluminum compound is within the range of about 0.7:1 to about 1.3:1.

Syndiotactic 1,2-polybutadiene is a thermoplastic resin which has double bonds attached in an alternating fashion to its polymeric backbone. Films, fibers and molded articles can be made utilizing syndiotactic 1,2-polybutadiene. It can also be blended into rubbers and cocured therewith. It is generally preferred to synthesize syndiotactic 1,2-polybutadiene in an aqueous medium by suspension or emulsion polymerization utilizing a cobalt-based catalyst system. This invention is based upon the unexpected finding that certain substituted benzoic acids can be employed to deactivate such cobalt based catalyst systems. This invention more specifically discloses a process for synthesizing and deactivating syndiotactic 1,2-polybutadiene which comprises (1) polymerizing 1,3-butadiene monomer in the aqueous medium in the presence of a catalyst system which is comprised of (a) transition metal compound, (b) an organoaluminum compound and (c) at least one member selected from the group consisting of carbon disulfide, phenyl isothiocyanate and xanthic acid to produce an aqueous medium which contains the syndiotactic 1,2-polybutadiene; and (2) subsequently adding a substituted benzoic acid to the aqueous medium which contains the syndiotactic 1,2-polybutadiene to deactivate the catalyst system.

Deactivation of syndiotactic&mdash;1, 2&mdash;polybutadiene

By utilizing the vapor phase polymerization techniques of the present invention, numerous distinct and highly beneficial advantages are realized. For instance, cis-1,4-polyisoprene rubber and high cis-1,4-polybutadiene rubber having a consistent and controllable molecular weight can be easily and practically prepared without utilizing a solvent. The subject invention more specifically discloses a method for vapor phase polymerizing isoprene into cis-1,4-polyisoprene in a process comprising the steps of:

Vapor phase synthesis of cis-1, 4-Polyisoprene

Various benefits can be attained by utilizing trans-1,4-polybutadiene in tire rubber compounds. For instance, the green strength of tire rubber compounds can be improved by including trans-1,4-polybutadiene therein. The inclusion of trans-1,4-polybutadiene in tire rubber compounds is also beneficial because it is strain crystallizable. However, due to its high melting point, it is normally necessary to heat trans-1,4-polybutadiene in order for it to be processed using conventional mixing equipment. This heating step is typically carried out by storing the trans-1,4-polybutadiene in a 'hothouse' for a few days prior to its usage. During this storage period, the polymer typically undergoes undesirable oxidative crosslinking which is caused by residual cobalt catalyst and leads to gelation. In fact, the gelation can render the trans-1,4-polybutadiene unprocessable. This invention is based upon the unexpected finding that certain substituted benzoic acids, such as salicylic acid, thiosalicylic acid and acetylsalicylic acid, will act as metal deactivators in polymers. By utilizing the technique of this invention, residual cobalt and/or other metals, such as nickel, that act as prooxidants in polymers, such as trans-1,4-polybutadiene, can be deactivated. This invention more specifically discloses a stabilized trans-1,4-polybutadiene composition which is comprised of trans-1,4-polybutadiene and a substituted benzoic acid selected from the group consisting of salicylic acid, thiosalicylic acid and acetylsalicylic acid.

Metal deactivator for cobalt catalyzed polymers

The synthesis of cis-1,4-polyisoprene by polymerizing isoprene with a catalyst system which is comprised of a titanium tetrahalide, a trialkylaluminum compound and diphenylether is plagued with the formation of gel. This invention is based upon the unexpected discovery that gel formation can be reduced by conducting such polymerizations in the presence of a diarylamine, such as para-styrenated diphenylamine. The subject invention more specifically discloses a process for synthesizing cis-1,4-polyisoprene having a low gel content which comprises polymerizing isoprene in an inert organic solvent with a preformed catalyst system which is made by reacting an organoaluminum compound with titanium tetrahalide, such as titanium tetrachloride, in the presence of at least one ether, wherein said polymerization is conducted at a temperature which is within the range of about 0.degree. C. to about 100.degree. C., and wherein said polymerization is conducted in the presence of a diarylamine.

Synthesis of cis-1,4-polyisoprene rubber

By utilizing the vapor phase polymerization techniques of the present invention, numerous distinct and highly beneficial advantages are realized. For instance, cis-1,4-polyisoprene rubber and high cis-1,4-polybutadiene rubber having a consistent and controllable molecular weight can be easily and practically prepared without utilizing a solvent. The subject invention more specifically discloses a method for vapor phase polymerizing isoprene into cis-1,4-polyisoprene in a process comprising the steps of: (1) charging into a reaction zone said isoprene and a preformed catalyst system which is made by reacting an organoaluminum compound with titanium tetrachloride, preferably in the presence of at least one ether; wherein the isoprene is maintained in the vapor phase in said reaction zone by a suitable combination of temperature and pressure; (2) allowing said isoprene to polymerize into cis-1,4-polyisoprene in said reaction zone at a temperature within the range of about 0.degree. C. to about 100.degree. C. in the presence of a diarylamine, wherein said reaction zone is a horizontal, stirred reactor of substantially circular cross section containing a centrally-located drive shaft extending longitudinally through said reactor to which are attached a plurality of adjacently located paddles, which paddles cause essentially no forward or backward movement of the cis-1,4-polyisoprene contained in said reactor; and (3) withdrawing said cis-1,4-polyisoprene from said reaction zone.

Vapor phase synthesis of rubbery polymers

By utilizing the techniques of this invention, trans-1,4-polybutadiene can be synthesized continuously to a high level of conversion utilizing a low level of a highly active cobalt-based catalyst system. The trans-1,4-polybutadiene made with the cobalt-based catalyst system of this invention also typically has a molecular weight which is acceptable for use in tire applications without the need for employing a molecular weight regulator. It is also not typically necessary to utilize a gel inhibitor, such as carbon disulfide, in the polymerizations of this invention. Since a low level of residual cobalt is present in the trans-1,4-polybutadiene which is made utilizing the catalyst system of this invention, it is much more stable than trans-1,4-polybutadiene made with standard cobalt-based catalyst systems. This invention specifically relates to a process for synthesizing trans-1,4-polybutadiene by polymerizing 1,3-butadiene monomer in the presence of a catalyst system which is comprised of cobalt (III) acetylacetonate, an organoaluminum compound and a para-alkyl-substituted phenol, wherein the cobalt (III) acetylacetonate is mixed with the para-substituted phenol prior to the polymerization. Such polymerizations can be conducted on a batch or a continuous basis.

Synthesis of trans-1,4-polybutadiene

It has been determined that 1,3-butadiene monomer can be polymerized into cis-l,4-polybutadiene rubber utilizing a cobalt-based catalyst system which is comprised of (a) an organocobalt compound, (b) a trialkylaluminum compound and (c) hexafluoro-2-propanol. The use of this catalyst system results in extremely fast rates of polymerization. The molecular weight of the cis-1,4- polybutadiene rubber made utilizing this cobalt-based catalyst system can be regulated by conducting the polymerization in the presence of 1,5-cyclooctadiene. This present invention more specifically discloses a catalyst system which is particularly useful for polymerizing 1,3-butadiene monomer into cis-1,4-polybutadiene, said catalyst system being comprised of (a) an organocobalt compound, (b) a trialkylaluminum compound and (c) hexafluoro-2-propanol. The subject invention further discloses a process for synthesizing cis-1,4-polybutadiene rubber which comprises polymerizing 1,3-butadiene in the presence of (a) an organocobalt compound, (b) a trialkylaluminum compound and (c) hexafluoro-2-propanol.

Synthesis of cis-1,4-polybutadiene rubber in presence of cobalt

It has been determined that 1,3-butadiene monomer can be polymerized into cis-1,4-polybutadiene rubber utilizing a cobalt-based catalyst system which is comprised of (a) an organocobalt compound, (b) a trialkylaluminum compound and (c) hexafluoro-2-propanol. The use of this catalyst system results in extremely fast rates of polymerization. The molecular weight of the cis-1,4-polybutadiene rubber made utilizing this cobalt-based catalyst system can be regulated by conducting the polymerization in the presence of 1,5-cyclooctadiene. This present invention more specifically discloses a catalyst system which is particularly useful for polymerizing 1,3-butadiene monomer into cis-1,4-polybutadiene, said catalyst system being comprised of (a) an organocobalt compound, (b) a trialkylaluminum compound and (c) hexafluoro-2-propanol. The subject invention further discloses a process for synthesizing cis-1,4-polybutadiene rubber which comprises polymerizing 1,3-butadiene in the presence of (a) an organocobalt compound, (b) a trialkylaluminum compound and (c) hexafluoro-2-propanol.

Cobalt containing catalyst system

The subject invention discloses a technique for controlling the molecular weight of synthetic polymers which are made by anionic polymerization. This invention is based upon the discovery that the molecular weight of diene polymers made by anionic polymerization utilizing organolithium initiators can be reduced by conducting the polymerization in the presence of bis(1,5-cyclooctadiene) nickel. The present invention more specifically discloses a process for producing a polymer of controlled molecular weight by anionic polymerization, said process comprising initiating the anionic polymerization of at least one conjugated diolefin monomer with an organolithium compound, wherein the polymerization is conducted in the presence of bis(1,5-cyclooctadiene) nickel. This technique is particularly useful in synthesizing liquid polymers but can also be used to reduce the molecular weight of rubbery polymers.

Molecular weight regulator for anionic polymerizations

Cis-1,4-polybutadiene can be synthesized by polymerizing 1,3-butadiene monomer with a three component nickel catalyst system containing (a) an organonickel compound, (b) an organoaluminum compound, and (c) a fluorine containing compound. However, the molecular weight of the cis-1,4-polybutadiene prepared is typically too high to be utilized as a non-oil extended rubber. This invention is based upon the discovery that para-styrenated diphenylamine acts to reduce the molecular weight and to improve the processability of cis-1,4-polybutadiene prepared with such nickel based catalyst systems. The use of para-styrenated diphenylamine as a modifier in such polymerizations does not change the microstructure of the cis-1,4-polybutadiene produced. Accordingly, the present invention specifically discloses a process for producing cis-1,4-polybutadiene having a reduced molecular weight and improved processability which comprises polymerizing 1,3-butadiene in the presence of (a) an organonickel compound, (b) an organoaluminum compound, (c) a fluorine containing compound, and (d) para-styrenated diphenylamine; wherein the organoaluminum compound and the fluorine containing compound are brought together in the presence of the para-styrenated diphenylamine. Since para-styrenated diphenylamine is an excellent antidegradant, it also provides the rubber synthesized in its presence with antioxidant protection.

Technique for reducing the molecular weight and improving the

Trans-1,4-polybutadiene is normally synthesized utilizing transition metal or rare earth catalysts. However, molecular weight control is difficult to achieve with such catalysts and the molecular weight of the polymer produced is frequently much higher than desired. By utilizing the catalyst system and techniques of this invention, trans-1,4-polybutadiene can be synthesized continuously to a high level of conversion with molecular weight control being possible. This invention specifically relates to a process for synthesizing trans-1,4-polybutadiene by polymerizing 1,3-butadiene monomer in the presence of a catalyst system which is comprised of an organocobalt compound, an organoaluminum compound and a para-substituted phenol with molecular weight being controlled by conducting the polymerization in the presence of at least one dialkyl sulfoxide, diaryl sulfoxide or dialkaryl sulfoxide. Such polymerizations can be conducted on a batch or a continuous basis. In the case of continuous processes, it is normally desirable to conduct the polymerization in the presence of carbon disulfide as a gel inhibitor.

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Uniontown, OH, United States of America

Kenneth Floyd Castner