The Goodyear & Tire Rubber Company

Enichimica S.p.a.

Enichem Polimeri

Morford C Throckmorton

William M Saltman

Charles J Suchma

Paul Harry Sandstrom

Ken W Donbar

Joginder Lal

Karl C Kauffman

There is disclosed a process for the regulation of the molecular weight of a high-cis 1,4-polybutadiene prepared by polymerizing 1,3-butadiene in a solution of an aliphatic and/or cycloaliphatic or aromatic solvent system employing as a catalyst system a mixture of (1) an organonickel compound, (2) an organoaluminum compound, and (3) a fluorine containing compound selected from the group consisting of hydrogen fluoride and hydrogen fluoride complexes which are prepared by complexing hydrogen fluoride with a ketone, an aldehyde, a nitrile, a mineral acid containing oxygen, an ester, an ether, an alcohol, a phenol or water; said polymerization being conducted in the presence of small amounts of olefins selected from the group consisting of 1-butene, isobutylene, cis and trans-2-butene and allene.

Controlling the molecular weight of polybutadiene

Lanthanide and actinide catalyst systems normally appear to be 'pseudo-living' when they are used to polymerize conjugated diolefin monomers into polymers. Polymerizations which are catalyzed with such catalyst systems produce polymers which have increasingly high molecular weight as monomer conversions are increased. Consequently, any change in polymerization time or conversion may affect the polymer's ultimate molecular weight. This has made controlling the molecular weight of polymers which are made utilizing lanthanide and actinide catalysts difficult. It has been unexpectedly discovered that vinyl halides can be used as molecular weight regulators for polymerizations which are catalyzed with lanthanide and actinide catalyst systems. Accordingly, the present invention relates to a process which comprises polymerizing at least one conjugated diolefin monomer in the presence of (a) a catalyst system which is comprised of (1) an organoaluminum compound, (2) an organometallic compound which contains a metal from Group III-B of the Periodic System, and (3) at least one compound which contains at least one labile halide ion; and (b) a vinyl halide.

Molecular weight modifier for use with lanthanide and actinide catalysts

A nonaqueous dispersion polymerization process can offer many distinct advantages over other polymerization techniques including: improved heat transfer, increased production capacity, and energy savings. This invention discloses a process for the nonaqueous dispersion polymerization of butadiene monomer in a reaction mixture containing a liquid nonaqueous dispersion medium, the improvement which comprises carrying out the polymerization of the butadiene monomer in the presence of random copolymers of butadiene and isoprene, to produce very high cis-1,4-polybutadiene.

Process for nonaqueous dispersion polymerization of butadiene in the

The presence of cyclopentadiene in unsaturated C.sub.5 -hydrocarbons is often very undesirable. This is because cyclopentadiene is a poison to many of the catalysts used to polymerize C.sub.5 -hydrocarbon monomers. This invention reveals a process for reducing the concentration of cyclopentadiene in impure unsaturated C.sub.5 -hydrocarbons containing cyclopentadiene, comprising adding to said impure unsaturated C.sub.5 -hydrocarbon (a) at least one member selected from the group consisting of trialkylaluminum compounds, dialkylaluminum hydride compounds, dialkylmagnesium compounds, and dialkylzinc compounds; and (b) an organonickel compound.

Process for the removal of cyclopentadiene from unsaturated C.sub.5

This invention discloses a process for the nonaqueous dispersion polymerization of butadiene monomer in a reaction mixture containing a liquid nonaqueous dispersion medium, the improvement which comprises carrying out the polymerization of the butadiene monomer in the presence of at least one member selected from the group consisting of cis-1,4-poly(1,3-pentadiene), trans-1,4-poly(1,3-pentadiene), trans-1,2-poly(1,3-pentadiene), moderately high trans-1,4-polyisoprene, poly(2,3-dimethyl-1,3-butadiene), syndiotactic 1,2-polybutadiene, atactic 1,2-polybutadiene, butadiene/isoprene copolymers, butadiene/dimethylbutadiene/pentadiene terpolymers, styrene/1,3-pentadiene copolymers, mixtures of from 20% to 65% 3,4-polyisoprene and from 35% to 80% 1,4-polyisoprene, EPDM rubbers, and butyl rubbers to produce very high cis-1,4-polybutadiene.

This invention discloses a process for the nonaqueous dispersion polymerization of butadiene monomer in a reaction mixture containing a liquid nonaqueous dispersion medium, the improvement which comprises carrying out the polymerization of the butadiene monomer in the presence of at least one carbonylated polymer.

This invention discloses a process for the nonaqueous dispersion polymerization of butadiene monomer in a reaction mixture containing a liquid nonaqueous dispersion medium, a catalyst system, butadiene monomer, and at least one polymeric dispersing agent, the improvement which comprises carrying out the polymerization of the butadiene monomer in the presence of the reaction product of (1) an alkylbenzene sulfonic acid wherein said alkyl moiety contains from 6 to 20 carbon atoms and (2) a polyalkylene amine that contains from 6 to 20 carbon atoms and 2 to 8 amine moieties. The presence of a small amount of this reaction product very substantially reduces the amount of polymeric dispersing agent needed in such a polymerization.

Process for nonaqueous dispersion polymerization of butadiene

This invention reveals a process for the nonaqueous dispersion polymerization of butadiene monomer in a reaction mixture containing a liquid nonaqueous dispersion medium, the improvement which comprises carrying out the polymerization of the butadiene monomer in the presence of high cis-1,4-polyisoprene to produce very high cis-1,4-polybutadiene.

Method of polymerizing conjugated diolefinic monomers containing from 4 to about 12 carbon atoms to high molecular weight polymers by bringing said monomers into contact with a catalyst system consisting of (1) an iron-containing compound, (2) an organometallic reducing agent from Groups I and III of the Periodic Table, and (3) a nitrogen-containing ligand.

Catalyst composition consisting essentially of iron compounds,

There is disclosed a method for copolymerizing cis-1,3-pentadiene and trans-1,3-pentadiene to prepare cis-1,4-polypentadienes. Other conjugated diolefins, including butadiene, isoprene, 2-ethyl-1,3-butadiene and 2-methyl-1,3-pentadiene also may be copolymerized with the cis-1,3-pentadiene isomer to prepare elastomeric copolymers. The polymerization catalyst is a ternary catalyst system comprising (A) a soluble chromium compound, (B) organometallic compounds such as a trihydrocarbylaluminum, and (C) a dihydrocarbyl hydrogen phosphite.

Copolymerization of conjugated diolefins using a chromium-containing

There is disclosed a method for the preparation of very high cis-1,4-polypentadiene which comprises polymerizing cis-1,3-pentadiene, also known as cis-piperylene, with a ternary catalyst system comprising (A) a soluble chromium compound such as chromium salts of organic acids, organic complex compounds of chromium containing tridentate organic ligands, and .pi.-bonded organochromium compounds, (B) an organometallic, such as trialkylaluminums, dialkylmagnesiums or dialkylzincs, and (C) dialkyl hydrogen phosphites.

Preparation of high cis-1,4-polypentadiene

A process for producing cis-1,4 polybutadiene by contacting butadiene with a catalyst consisting of (1) at least one organoaluminum compound, (2) at least one nickel compound selected from the class consisting of nickel salts of carboxylic acids, organic complex compounds of nickel, nickel tetracarbonyl, and (3) at least one hydrogen fluoride complex prepared by complexing hydrogen fluoride with a member of the class consisting of ketones, esters, ethers, alcohols, nitriles and water.

Catalyst composition comprising an organoaluminum compound/an

There is disclosed a method for the polymerization and copolymerization of diolefins selected from the group of monomers consisting of trans-1,3-pentadiene and isoprene employing as a catalyst a mixture of (A) an organometallic compound selected from the group consisting of aluminum trialkyls, magnesium dialkyls and zinc dialkyls, (B) a soluble chromium compound selected from the group consisting of chromium salts of organic acids containing from 2 to 20 carbon atoms, organic complex compounds of chromium containing tridentate ligands and .pi.-bonded organochromium compounds, and (C) a member selected from dialkyl hydrogen phosphites, diaryl hydrogen phosphites and tris(2-chloroethyl)phosphite.

Polymerization and copolymerization of trans-piperylene and isoprene

Catalyst composition for the preparation of butadiene

A process for producing cis-1,4-polybutadiene by contacting butadiene with a catalyst consisting of (1) at least one organoaluminum compound, (2) at least one organonickel compound selected from the class consisting of nickel salts of carboxylic acids, organic complex compounds of nickel and nickel tetracarbonyl, (3) boron trifluoride gas or a boron trifluoride etherate complex, and (4) at least one alkyl substituted hydroxy containing aromatic compound wherein the alkyl groups leave the hydroxy groups unhindered for chemical activity in that no alkyl groups are present simultaneously on both positions ortho to the hydroxy groups.

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Akron, OH, United States of America

Morford C Throckmorton