Using Catalyst Containing Metal Bonded To Or Complexed With C, C-containing Compound, Or H Patents (Class 585/511)
  • Patent number: 4594469
    Abstract: A process for oligomerizing alpha-olefins comprising contacting in a reactor zone under reaction conditions: (a) alpha-olefins having at least three carbon atoms; (b) an alkyl aluminum bromine or iodine compound having the formula R.sub.3 Al.sub.2 X.sub.3 or R.sub.n AlX.sub.3-n, wherein n is 1 or 2; R is an hydrocarbyl group and X is a reactive halogen selected from bromine and iodine; and (c) a cocatalyst which is (i) bromine, (ii) iodine, (iii) hydrocarbyl bromide having at least one halogen group reactive with said aluminum compound or (iv) hydrocarbyl iodide having at least one halogen group reactive with said aluminum compound.
    Type: Grant
    Filed: September 8, 1983
    Date of Patent: June 10, 1986
    Assignee: Uniroyal Chemical Company, Inc.
    Inventors: Frederick C. Loveless, Aspet V. Merijanian, David J. Smudin, Walter Nudenberg
  • Patent number: 4544789
    Abstract: Regioselective and stereoselective synthesis of trans-internal olefins is effected with transition metal catalyst complexes having pairs of associated active sites. Photolytic conditions are generally employed.
    Type: Grant
    Filed: September 6, 1983
    Date of Patent: October 1, 1985
    Assignee: University of Illinois Board of Trustees
    Inventors: Theodore L. Brown, Philip O. Nubel
  • Patent number: 4535135
    Abstract: The invention relates to new associations of strong bases, having the following general formula:n' RLi--n MZin which: n and n' are the numbers of mols of each compound, R is an alkyl or aryl radical, M is an alkali metal chosen from amongst lithium, sodium or potassium and Z is a hydride or an inorganic amide, the ratio n/n' being between 0.2 and 50.It is preferred to use bases in which the metal of the alkali metal amide or hydride is potassium or sodium. These associations are formed very rapidly and can be applied to anionic polymerization, in particular of conjugated dienes, in a solvent of low polarity or an apolar solvent.The polymers thus obtained contain a high percentage of 1,2 or 3,4 structures.
    Type: Grant
    Filed: October 24, 1983
    Date of Patent: August 13, 1985
    Assignee: Societe Nationale des Poudres et Explosifs
    Inventors: Serge Lecolier, Serge Raynal
  • Patent number: 4528415
    Abstract: A novel ethylene dimerization catalyst is provided consisting essentially of a nickel compound, a phosphine compound, and an acidic compound. In addition, an improved ethylene dimerization process is provided which comprises contacting ethylene with the novel catalyst composition present, in an effective solvent, at a temperature from about 0.degree. C. to about 200.degree. C. As a result of the inventive precess, high catalyst productivity and good selectivity to the desired dimerized product, 1-butene, is obtained.
    Type: Grant
    Filed: August 20, 1981
    Date of Patent: July 9, 1985
    Assignee: Phillips Petroleum Company
    Inventor: Ronald D. Knudsen
  • Patent number: 4469910
    Abstract: A process is provided for oligomerizing alpha-olefins comprising contacting in a reaction zone under reaction conditions: (a) alpha-olefins having at least three carbon atoms; (b) an aluminum compound having the formula R.sub.3 Al, wherein R is an hydrocarbyl group and (c) a cocatalyst which is hydrocarbyl halide having at least one halogen group reactive with said aluminum compound, elemental bromine or elemental iodine.
    Type: Grant
    Filed: September 8, 1983
    Date of Patent: September 4, 1984
    Assignee: Uniroyal, Inc.
    Inventor: Frederick C. Loveless
  • Patent number: 4451688
    Abstract: Olefins are polymerized in the presence of a catalyst which comprises the combination of:[I] a solid substance obtained by the reaction of at least the following two components:(i) a magnesium compound represented by the general formula R.sup.1.sub.m (OR.sup.2).sub.n MgX.sub.2-m-n wherein R.sup.1 and R.sup.2 are each a hydrocarbon radical having 1 to 24 carbon atoms, X is a halogen atom, m is 0.ltoreq.m.ltoreq.2 and n is 0.ltoreq.n.ltoreq.2, provided 0.ltoreq.m+n.ltoreq.2, and(ii) a titanium compound and/or a vanadium compound;[II] a silicon compound represented by general formula R.sup.1 mSi(OR.sup.2).sub.n X.sub.4-m-n wherein R.sup.1 and R.sup.2 are each hydrocarbon radical having 1 to 24 carbon atoms, X is a halogen atom, m is 0.ltoreq.m<4 and n is 0<n.ltoreq.4, provided 0 m+n 4;[III] an organometallic compound, where said catalyst comprises a product obtained by pre-reacting said silicon compound (II) and said organometallic compound (III).
    Type: Grant
    Filed: September 1, 1982
    Date of Patent: May 29, 1984
    Assignee: Nippon Oil Company, Limited
    Inventors: Nobuyuki Kuroda, Toru Nakamura, Yutaka Shikatani, Kazuo Matsuura, Mituji Miyoshi
  • Patent number: 4409415
    Abstract: Olefin oligomers suitable as lubricants are prepared with a catalyst comprising boron trifluoride and a mixture of an alcohol, and a polyol. 1-Decene is oligomerized to a liquid product having an improved trimer to tetramer ratio using boron trifluoride and a mixture of n-butanol, and ethylene glycol.
    Type: Grant
    Filed: September 18, 1981
    Date of Patent: October 11, 1983
    Assignee: Gulf Research & Development Company
    Inventors: Neal E. Morganson, Adam V. Vayda
  • Patent number: 4382132
    Abstract: A process for the high pressure polymerization of ethylene in a reactor in the presence of conventional free radical generating initiators, wherein the initiator material is admixed with certain additives in small concentrations to lower the polymerization initiation temperature.
    Type: Grant
    Filed: June 1, 1981
    Date of Patent: May 3, 1983
    Assignee: El Paso Polyolefins Company
    Inventors: Joseph M. Kelley, John J. Roderick
  • Patent number: 4382153
    Abstract: Ethylene is oligomerizied by reacting ethylene under an elevated pressure greater than about 700 pounds per square inch gauge (4826 kPa) in methanol in contact with a nickel ylide defined by the following Formula: ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7 and R.sub.
    Type: Grant
    Filed: April 5, 1982
    Date of Patent: May 3, 1983
    Assignee: Gulf Research & Development Company
    Inventors: David L. Beach, James J. Harrison
  • Patent number: 4377719
    Abstract: A process for preparing 1,7-octadiene by dimerizing butadiene in the presence of a catalytic amount of palladium acetate and a tertiary phosphine, a solvent in an amount sufficient to dissolve the catalyst, a strong base and formic acid, wherein: (a) the molar ratio of the strong base to the formic acid is 1:1-2, (b) the mole ratio of tertiary phosphine to palladium is at least 1, (c) the amount of strong base present is such that the pH of the reaction medium is from 7.5 to 10.5 and (d) the solvent is at least one member selected from the group consisting of aromatic hydrocarbons, lower alkyl substituted aromatic hydrocarbon, halogenated aromatic hydrocarbons, halogenated lower aliphatic hydrocarbons, nitriles, amides, dilower alkyl ethers, lower alkyl phenyl ethers, lower alkyl esters of lower alkanoic acids, ketones and lower alkanols.
    Type: Grant
    Filed: December 13, 1978
    Date of Patent: March 22, 1983
    Assignee: Charles U. Pittman, Jr.
    Inventors: Charles U. Pittman, Jr., Ronald Hanes
  • Patent number: 4361714
    Abstract: A process for preparing linear alpha olefins and waxes having a total product M.sub.n in the range 200 to 700 which includes polymerizing an ethylene-containing gas in the presence of the reaction product of a zirconium halide with R.sub.2 Zn, wherein R is an alkyl group having about 1 to about 20 carbon atoms, in the presence of a diluent at a temperature of about 50.degree. to 200.degree. C. and an ethylene pressure above about 3.5 MPa, wherein the M.sub.n of said reaction product is controlled by the molar ratio of said R.sub.2 Zn/ZrCl.sub.4, said molar ratio being less than about 1.
    Type: Grant
    Filed: December 14, 1981
    Date of Patent: November 30, 1982
    Assignee: Exxon Research and Engineering Co.
    Inventors: Arthur W. Langer, John J. Steger, Terry J. Burkhardt
  • Patent number: 4334117
    Abstract: This invention provides an improved process for producing alkadienes which comprises (1) contacting butadiene or isoprene with a catalyst such as platinum or palladium or a compound of one of said metals in a sulfolane solution, in the presence of a tertiary lower alkylamine formate and at least one phosphine compound of the formula: ##STR1## wherein R.sup.1 is a substituted or unsubstituted C.sub.1-10 hydrocarbon group; R.sup.2 is H, a saturated aliphatic C.sub.1-5 hydrocarbon group, nitro or halogen; m is 1, 2 or 3; n is 0 or 1; x is 0, 1 or 2; y and z each is 0, 1, 2 or 3 (provided that y and z are not zero concurrently and x+y+z=3); A is --SO.sub.3 M wherein M is a cation selected from among H, alkali metals, alkaline earth metals and NH.sub.4 or the formate or an inorganic acid salt of ##STR2## wherein R.sup.3 and R.sup.4 each means a saturated aliphatic C.sub.
    Type: Grant
    Filed: September 4, 1980
    Date of Patent: June 8, 1982
    Assignee: Kuraray Co., Ltd.
    Inventors: Noriaki Yoshimura, Masuhiko Tamura
  • Patent number: 4311613
    Abstract: A catalyst is prepared by reacting tungsten hexafluoride with a branched-chain aliphatic alcohol in a molar ratio of 2:1 to 20:1. This catalyst can be used to oligomerize 1-butene to produce synthetic hydrocarbon oils.
    Type: Grant
    Filed: December 15, 1980
    Date of Patent: January 19, 1982
    Assignee: Gulf Research & Development Company
    Inventors: John P. Pellegrini, Jr., Richard G. Austin, David L. Beach
  • Patent number: 4310716
    Abstract: Ethylene is oligomerized by reacting ethylene in methanol under oligomerization conditions in contact with a nickel ylide defined by the following Formula I: ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7 and R.sub.
    Type: Grant
    Filed: August 18, 1980
    Date of Patent: January 12, 1982
    Assignee: Gulf Research & Development Company
    Inventors: David L. Beach, James J. Harrison
  • Patent number: 4301318
    Abstract: Ammonium hydroxide is used to remove nickel ylide residue from an oligomerization reaction product obtained by contacting ethylene with a nickel ylide catalyst under oligomerization conditions. The oligomerization reaction product is contacted with ammonium hydroxide to obtain a product composed of two layers, an upper layer containing normal alpha olefins and a lower layer containing nickel ylide residue. The two layers are then separated from each other to recover the desired normal alpha olefins.
    Type: Grant
    Filed: November 25, 1980
    Date of Patent: November 17, 1981
    Assignee: Gulf Research & Development Company
    Inventors: David L. Beach, James J. Harrison
  • Patent number: 4293726
    Abstract: An alpha olefin containing three to 10 carbon atoms, or higher, is oligomerized by intimately contacting the alpha olefin, e.g., in a non-aromatic solvent, with a catalyst produced by contacting (a) a refractory metal oxide/silica support such as alumina/silica wherein the silica content of the support is from about 2 to about 95 weight percent and the metal oxide content of the support is from about 5 to about 98 percent with (b) a tris(cyclopentadienyl)trinickel dicarbonyl. This process is characterized by a relatively high reaction rate at moderate temperatures and pressures and results in the production of significant quantities of dimers, trimers and tetramers.
    Type: Grant
    Filed: May 21, 1980
    Date of Patent: October 6, 1981
    Assignee: Gulf Research & Development Company
    Inventors: David L. Beach, Thaddeus P. Kobylinski
  • Patent number: 4293725
    Abstract: Ethylene is oligomerized by intimately contacting ethylene with a metal modified catalyst. The catalyst is produced by contacting (a) a refractory metal oxide/silica support, such as alumina/silica wherein the silica content of the support is from about 2 to about 95 weight percent and the metal oxide content of the support is from about 5 to about 98 percent with (b) a solution of a basic metal and then (c) contacting the resulting metal modified support with a tris(cyclopentadienyl)trinickel dicarbonyl.
    Type: Grant
    Filed: May 21, 1980
    Date of Patent: October 6, 1981
    Assignee: Gulf Research & Development Company
    Inventors: David L. Beach, Thaddeus P. Kobylinski
  • Patent number: 4288648
    Abstract: Ethylene is oligomerized by contacting ethylene with a catalyst produced by contacting (a) a refractory metal oxide/silica support such as alumina/silica wherein the silica content of the support is from about 2 to about 95 weight percent and the metal oxide content of the support is from about 5 to about 98 percent with (b) a tris(cyclopentadienyl)trinickel dicarbony. This process is characterized by a relatively high reaction rate at moderate temperatures and pressures and results in the production of relatively high proportions of desirable trimer, tetramer, pentamer, and higher olefinic products.
    Type: Grant
    Filed: May 21, 1980
    Date of Patent: September 8, 1981
    Assignee: Gulf Research & Development Company
    Inventors: David L. Beach, Thaddeus P. Kobylinski
  • Patent number: 4272406
    Abstract: A catalyst that is highly active at low operating temperatures and pressures in the oligomerization of lower olefins such as ethylene is produced by contacting (a) a refractory metal oxide/silica support such as alumina/silica wherein the silica content of the support is from about 2 to about 95 weight percent and the metal oxide content of the support is from about 5 to about 98 percent with (b) a tris(cyclopentadienyl)trinickel dicarbonyl. When used to oligomerize ethylene, these catalysts are characterized by a relatively high reaction rate at moderate temperatures and pressures. Their use permits the production of relatively high proportions of desirable trimer, tetramer, pentamer, and higher olefinic products.
    Type: Grant
    Filed: May 21, 1980
    Date of Patent: June 9, 1981
    Assignee: Gulf Research & Development Company
    Inventors: David L. Beach, Thaddeus P. Kobylinski
  • Patent number: 4272407
    Abstract: A catalyst that is highly active in the oligomerization of lower olefins such as ethylene is produced by contacting (a) a refractory metal oxide/silica support, such as alumina/silica wherein the silica content of the support is from about 2 to about 95 weight percent and the metal oxide content of the support is from about 5 to about 98 percent with (b) a solution of a basic metal and then (c) contacting the resulting metal modified support with a tris(cyclopentadienyl)trinickel dicarbonyl.
    Type: Grant
    Filed: May 21, 1980
    Date of Patent: June 9, 1981
    Assignee: Gulf Research & Development Company
    Inventors: David L. Beach, Thaddeus P. Kobylinski
  • Patent number: 4245131
    Abstract: Tantalum and niobium catalysts or catalyst precursors of the formula: ##STR1## wherein R is cyclopentadienyl, which can be substituted with methyl up to five positions, or neopentylidene, R.sup.1 is neopentyl or benzyl, n is 0 or 1, R.sup.2 is neopentylidene, benzylidene, tetramethylene, or 2,3-dimethyltetramethylene, A is halo or a moiety of the formula YR.sup.3 R.sup.4 R.sup.5 wherein Y is a group 5 element including N, P, As, Sb and Bi and R.sup.3, R.sup.4, R.sup.5 can be the same or different and are C.sub.1 -C.sub.4 alkyl, aralkyl such as naphthyl, neophyl, tolyl or xylyl, aryl such as benzyl or phenyl or bipyridyl and Z is tantalum or niobium. The compounds selectively dimerize 1-olefins to 1-butenes; m=1 or 2.
    Type: Grant
    Filed: July 2, 1979
    Date of Patent: January 13, 1981
    Assignee: Massachusetts Institute of Technology
    Inventor: Richard R. Schrock
  • Patent number: 4243829
    Abstract: A process for preparing 1,7-octadiene by dimerizing butadiene in the presence of a catalytic amount of palladium acetate and a tertiary phosphine, a solvent in an amount sufficient to dissolve the catalyst, a strong base and formic acid, wherein: (a) the molar ratio of the strong base to the formic acid is 1:1-2, (b) the mole ratio of tertiary phosphine to palladium is at least 1, (c) the amount of strong base present is such that the pH of the reaction medium is from 7.5 to 10.5 and (d) the solvent is at least one member selected from the group consisting of aromatic hydrocarbons, lower alkyl substituted aromatic hydrocarbons, halogenated aromatic hydrocarbons, halogenated lower aliphatic hydrocarbons, nitriles, amides, dilower alkyl ethers, lower alkyl phenyl ethers, lower alkyl esters of lower alkanoic acids, ketones and lower alkanols.
    Type: Grant
    Filed: October 4, 1976
    Date of Patent: January 6, 1981
    Assignee: Charles U. Pittman, Jr.
    Inventors: Charles U. Pittman, Jr., Ronald Hanes
  • Patent number: 4242481
    Abstract: Novel organoaluminum compounds having the formula XYA1 ##STR1## in which X is a halogen, Y is an alkyl group having from 1 to 10 carbon atoms, a phenyl group or a halogen, R is an alkyl group having from 2 to 9 carbon atoms, and n is an integer from 1 to 20. These compounds are less viscous and more soluble in hydrocarbon solvents than are corresponding ethylene-based or butadiene-based compounds. The novel compounds are prepared by the reaction of alkylaluminum dihalides or aluminum trihalides with a terminal olefin having from 3 to 10 carbon atoms in the presence of aluminum metal.
    Type: Grant
    Filed: May 7, 1979
    Date of Patent: December 30, 1980
    Assignee: Texas Alkyls, Inc.
    Inventor: Loyd W. Fannin
  • Patent number: 4238628
    Abstract: Process for the production of undegraded alkylated aromatic compounds by alkylating an aromatic compound with a C.sub.3 or higher olefin polymer having terminal ethylene units.
    Type: Grant
    Filed: September 28, 1978
    Date of Patent: December 9, 1980
    Assignee: Standard Oil Company (Indiana)
    Inventors: Paul J. Cahill, Carl E. Johnson
  • Patent number: 4225743
    Abstract: In a dimerization of butenes containing isobutene, a formation of 2,2,4-trimethyl pentenes is minimized by using a specific nickel catalyst solution and an organoaluminum catalyst. The specific nickel catalyst is a nickel salt of a fatty acid having 1.5 to 40 wt. % of a free fatty acid and less than 0.1 wt. % of water.The C.sub.8 olefins having less 2,2,4-trimethyl pentenes obtained by the dimerization are quite important to produce excellent plasticizer.
    Type: Grant
    Filed: December 15, 1978
    Date of Patent: September 30, 1980
    Assignee: Nissan Chemical Industries Limited
    Inventors: Satoshi Hoshiyama, Shuichi Fukushima, Hiroshi Kobayashi, Hideki Takamatsu
  • Patent number: 4197419
    Abstract: Tantalum catalysts or catalyst precursors of the formula ##STR1## wherein X is a halide, or alkoxide and L is an alkene (CH.sub.2 .dbd.CHR) having from 2 to 20 carbon atoms, react with 1-olefins to give catalysts of the formula ##STR2## wherein R.sup.2 is hydrogen or a C.sub.1 to C.sub.18 alkyl such as methyl, ethyl, or propyl. The catalysts or catalyst precursors selectively dimerize 1-olefins to the two possible disubstituted .alpha.-olefin dimers, the ratio of which depends on the nature of R.
    Type: Grant
    Filed: December 15, 1978
    Date of Patent: April 8, 1980
    Assignee: Massachusetts Institute of Technology
    Inventor: Richard R. Schrock
  • Patent number: 4180694
    Abstract: Butadiene is hydrodimerized to 1,7-octadiene in high yield by contacting the butadiene with a formate of an alkali metal, alkaline earth metal or ammonia, a palladium catalyst, tertiary phosphine, a solvent selected from dialkyl sulfoxides, N,N-dialkylalkanamides, substituted and unsubstituted pyridines and sulfolanes and at least one mole of water per mole of formate salt.
    Type: Grant
    Filed: July 24, 1978
    Date of Patent: December 25, 1979
    Assignee: Shell Oil Company
    Inventor: Kenzie Nozaki
  • Patent number: 4176086
    Abstract: Preparation of a hydrocarbon-soluble nickel complex substantially free of moisture comprising reacting a nickel compound with an organic complexing agent in a hydrocarbon solvent to form a complex, allowing the complex to settle and separate into a water phase and a hydrocarbon solution of the complex, then drying the hydrocarbon solution of complex by azeotropic distillation. The substantially anhydrous nickel complex obtained can be mixed with an alkylaluminum halide to form a catalyst system useful for the dimerization of olefins.
    Type: Grant
    Filed: August 25, 1977
    Date of Patent: November 27, 1979
    Assignee: Phillips Petroleum Company
    Inventor: Cecil O. Carter
  • Patent number: 4172855
    Abstract: A process for making a low viscosity, low volatility .alpha.-olefin oligomer suitable for use as a functional fluid or lubricating oil comprising dimerizing a C.sub.6-12 .alpha.-olefin, reacting the resultant dimer with a C.sub.6-18 .alpha.-olefin in the presence of a Friedel-Crafts catalyst, distilling out volatile components and hydrogenating the residual product.
    Type: Grant
    Filed: April 10, 1978
    Date of Patent: October 30, 1979
    Assignee: Ethyl Corporation
    Inventors: Ronald L. Shubkin, Ellis B. Rifkin, Martin E. Gluckstein
  • Patent number: 4170603
    Abstract: Novel organoaluminum compounds having the formula ##STR1## in which X is a halogen, Y is an alkyl group having from 1 to 10 carbon atoms, a phenyl group or a halogen, R is an alkyl group having from 2 to 9 carbon atoms, and n is an integer from 1 to 20. These compounds are less viscous and more soluble in hydrocarbon solvents than are corresponding ethylene-based or butadiene-based compounds.The novel compounds are prepared by the reaction of alkylaluminum dihalides or aluminum trihalides with a terminal olefin having from 3 to 10 carbon atoms in the presence of aluminum metal.
    Type: Grant
    Filed: March 3, 1977
    Date of Patent: October 9, 1979
    Assignee: Stauffer Chemical Company
    Inventor: Loyd W. Fannin