From Polyolefins Patents (Class 560/244)
  • Patent number: 8491758
    Abstract: A process for inhibiting polymerization of (meth)acrylic acid and/or (meth)acrylic esters by introducing an oxygenous gas into the (meth)acrylic acid and/or the (meth)acrylic ester, in which the (meth)acrylic acid and/or the (meth)acrylic ester has a degree of purity of at least 95% and is in the liquid state.
    Type: Grant
    Filed: December 9, 2010
    Date of Patent: July 23, 2013
    Assignee: BASF SE
    Inventors: Gunter Lipowsky, Steffen Rissel, Volker Schliephake, Ulrich Jäger, Sylke Haremza
  • Patent number: 7541506
    Abstract: The invention relates to a process for the telomerization of acyclic olefins having at least two conjugated double bonds (I) or mixtures in which such olefins are present with nucleophiles (II) using a metal-carbene complex as catalyst.
    Type: Grant
    Filed: June 17, 2003
    Date of Patent: June 2, 2009
    Assignee: OXENO Olefinchemie GmbH
    Inventors: Dirk Roettger, Ralf Jackstell, Holger Klein, Matthias Beller
  • Patent number: 7026523
    Abstract: The invention provides a process for the telomerization of acyclic olefins having at least two conjugated double bonds (I) or mixtures comprising such olefins by means of nucleophiles (II) using a palladium-carbene complex as catalyst.
    Type: Grant
    Filed: May 4, 2002
    Date of Patent: April 11, 2006
    Assignee: OXENO Olefinchemie GmbH
    Inventors: Dirk Röttger, Matthias Beller, Ralf Jackstell, Holger Klein, Klaus-Diether Wiese
  • Patent number: 6914156
    Abstract: In yielding diacetoxybutene by feeding butadiene, acetic acid, and oxygen in the presence of a solid catalyst containing palladium, the butadiene can be efficiently reacted to produce diacetoxybutene in high yield by feeding an oxygen-containing gas containing 7 mol % or more oxygen as fine bubbles to a reaction zone containing the solid catalyst.
    Type: Grant
    Filed: April 14, 2003
    Date of Patent: July 5, 2005
    Assignee: Mitsubishi Chemical Corporation
    Inventors: Kazuhiro Makino, Hiroshi Iwasaka, Kazuyuki Okubo, Koji Hata
  • Patent number: 6770791
    Abstract: Disclosed is an olefin containing stream from an oxygenate to olefin process, and a process for making olefin dimer and oligomer product from the olefin containing stream using a nickel based oligomerization catalyst. The dimer/oligomer product is optionally converted to hydroformylated product. The olefin containing stream that is used to make the higher olefin product has low levels of impurities including nitrogen, sulfur and/or chlorine.
    Type: Grant
    Filed: April 29, 2003
    Date of Patent: August 3, 2004
    Assignee: ExxonMobil Chemical Patents Inc.
    Inventors: Georges Mathys, John Stephen Godsmark, Marcel Janssen, Luc Roger Martens, Hubertus Joseph Beckers, Eddy Theophile Andrea Van Driessche, Raphael Frans Ivo Caers, John Richard Shutt
  • Patent number: 6534672
    Abstract: A catalytically active material useful to prepare vinyl acetate monomer from ethylene, acetic acid, and an oxygen-containing gas under fluid bed conditions comprises a porous microspheroidal support containing catalytically active palladium crystallites finely dispersed within the support. This catalyst material does not require incorporation of gold to maintain activity and selectivity. A process to produce a vinyl acetate fluid bed catalyst in which catalytically active small palladium crystallites are finely dispersed within the support comprises dispersing selected metal species within the support which have an affinity to palladium to form very fine crystallites of palladium. The affinity metal species may be dispersed by impregnation onto a preformed microspheroidal support or may be intimately incorporated within the support before impregnation with a soluble palladium species.
    Type: Grant
    Filed: December 4, 2001
    Date of Patent: March 18, 2003
    Assignee: The Standard Oil Company
    Inventors: George Frederick Salem, Michael James Baker
  • Patent number: 6300515
    Abstract: The invention provides a process that includes isomerizing at least one allylic substrate having an acyloxyl group or a hydroxyl group at the allyl position thereof, to produce a corresponding allylic isomer, wherein the isomerizing is conducted in the presence of a catalyst that includes a Group VIII-X metal compound and a phosphite compound.
    Type: Grant
    Filed: April 17, 2000
    Date of Patent: October 9, 2001
    Assignee: Mitsubishi Chemical Corporation
    Inventors: Mikael Retboll, Yoshinori Hara, Hisao Urata, Hironobu Ohno
  • Patent number: 6239324
    Abstract: The invention provides a chain diene compound with desirable regioselectivity, in the presence of a specific ruthenium compound. This chain diene compound is a promising raw material for terpene. It has a structure represented by the general formula (IX): wherein R1 represents H, a C1-C6 alkyl group which may be substituted or a C2-C6 alkenyl group which may be substituted, R2 represents a phenyl group which may have a C1-C4 alkyl group or a C1-C12 acyloxy group which may have a phenyl group or a naphthyl group, or a benzyl group or R2 is a hydroxy group which reversibly forms an aldehyde group through shifting of the position of the double bond adjacent to said hydroxy group. The chain diene compound is produced by reacting 2-substituted-1,3-butadienes with terminal olefins in the presence of a ruthenium compound in a hydrophilic solvent.
    Type: Grant
    Filed: August 26, 1999
    Date of Patent: May 29, 2001
    Assignee: Takasago International Corporation
    Inventors: Mitsuhiko Fujiwhara, Takenobu Nishikawa, Yoji Hori, Toshimitsu Hagiwara, Hisao Iwai, Takashi Miura
  • Patent number: 5808136
    Abstract: A catalyst and method of its production for use in making vinyl acetate monomer. The carrier is impregnated with a basic solution and a solution containing gold salts and palladium salts and finally impregnated with alkali acetate. The activity and selectivity of the catalyst, its mechanical strength, the noble-metal adhesion and the dispersion of noble metal on the carrier can be improved if the carrier is impregnated in a pretreatment with salts containing as cation elements of groups IA, IIA, IIIA and IVB of the periodic table and as anions elements of group VIIA or complex anions such as nitrate, sulfate or anions of organic acids such as acetate and lactate and is subsequently dried and calcined at temperatures of at least 160.degree. C.
    Type: Grant
    Filed: January 23, 1996
    Date of Patent: September 15, 1998
    Assignee: Degussa Aktiengesellschaft
    Inventors: Thomas Tacke, Herbert Mueller, Uwe Ohlrogge, Francis P. Daly, Hans Lansink Rotgerink, Helmfried Krause
  • Patent number: 5777155
    Abstract: A process for producing an unsaturated glycol diester disclosed, which process comprises reacting a conjugated diene with a carboxylic acid and molecular oxygen in the presence of a solid catalyst comprising (1) palladium and (2) tellurium as active components supported on a carrier, wherein a said carrier is a solid carrier in which a proportion of the volume of pores having a pore radius in the range of from 5 to 50 nm is 80% or more relative to the total volume of pores having a pore radius in the range of from 1.8 to 10,000 nm.
    Type: Grant
    Filed: March 17, 1997
    Date of Patent: July 7, 1998
    Assignee: Mitsubishi Chemical Corporation
    Inventors: Masato Sato, Hironobu Ohno, Nobuyuki Murai, Hiroshi Iwasaka
  • Patent number: 5429721
    Abstract: A process for preparing diacetoxybutene, including:reacting butadiene, acetic acid and oxygen in the presence of a palladium-based catalyst;feeding continuously the resulting reaction product into a first distillation tower;feeding continuously a withdrawn bottoms withdrawn from the first distillation tower into a second distillation tower;withdrawing bottoms containing high boiling point materials from the bottom of the second distillation tower, so that the content of the high boiling point materials in the bottoms of the second distillation tower is not more than 20 wt %;feeding continuously the withdrawn bottoms into a thin-film evaporator whose internal pressure is kept lower than the bottom pressure of the second distillation tower to carry out evaporation treatment; andrecycling the evaporated materials mainly containing diacetoxybutene into the second distillation tower.
    Type: Grant
    Filed: May 18, 1994
    Date of Patent: July 4, 1995
    Assignee: Mitsubishi Chemical Corporation
    Inventors: Hiroaki Kandori, Nobuyuki Murai
  • Patent number: 5206396
    Abstract: Octyl ethers and octadienyl ethers of glucose, sucrose, bisphenol A, 4-substituted-2,2,6,6-tetramethylpiperidines are disclosed. Compositions comprised of a mixture of octyl ethers of glucose and sucrose and those containing octadienyl ethers of sugar acids and ring-opened epoxidized octadienyl ethers are also disclosed as are telomerization processes.
    Type: Grant
    Filed: July 25, 1990
    Date of Patent: April 27, 1993
    Assignee: Henkel Research Corporation
    Inventors: Bert Gruber, Kenneth J. Weese, Steven M. Hoagland, Hans-Peter Mueller, Karlheinz Hill, Arno Behr, James R. Tucker
  • Patent number: 5177254
    Abstract: A method for producing an unsaturated glycol diester by reacting molecular oxygen, a carboxylic acid and a conjugated diene in the presence of a solid catalyst containing palladium and tellurium supported on a carrier, wherein an active carbon with the total pore volume of pores having radii of from 18 to 100,000 .ANG. being at least 0.45 cc/g and with the volume of pores having radii of at least 3,000 .ANG. constituting at least 50% of the total pore volume, is used as the carrier for the solid catalyst.
    Type: Grant
    Filed: February 4, 1988
    Date of Patent: January 5, 1993
    Assignee: Mitsubishi Chemical Industries Limited
    Inventors: Junzo Haji, Ichiro Yokotake, Takahiro Yamaguchi, Masato Sato, Nobuyuki Murai
  • Patent number: 5030792
    Abstract: This invention relates to a process for producing 1-octenes comprising reacting conjugated dienes and carboxylic acids in the presence of palladium, platinum or ruthenium catalysts to produce 2,7-alkadienyl esters, contacting the 2,7-alkadienyl esters with hydrogen to produce alkyl esters and subsequently pyrolyzing the alkyl esters to produce 1-octene and carboxylic acid.
    Type: Grant
    Filed: June 22, 1987
    Date of Patent: July 9, 1991
    Assignee: Shell Oil Company
    Inventor: Lynn H. Slaugh
  • Patent number: 4658053
    Abstract: A process for the production of an ester comprises reacting an olefin with carbon monoxide, hydrogen and another ester at elevated temperature and pressure in the presence of a catalyst comprising (1) a rhodium source, (2) a ruthenium source, and (3) cobalt or zinc iodide. The product ester comprises the acid group of the ester used as reactant esterified with a hydrocarbyl group derived from the olefin, hydrogen and carbon monoxide.
    Type: Grant
    Filed: February 25, 1985
    Date of Patent: April 14, 1987
    Assignee: BP Chemicals Limited
    Inventor: Michael J. Green
  • Patent number: 4554375
    Abstract: A method for preparing 2,7-octadienyl formate by reacting 1,3-butadiene with formic acid in the presence of a platinum(II) catalyst is described. The platinum(II) catalyst is preferably platinum acetylacetonate. A reaction temperature between 50.degree. and 150.degree. C. is preferred, and carbon dioxide and a solvent may also be employed. Tetrahydrofuran and acetone are the preferred aprotic solvents.
    Type: Grant
    Filed: March 15, 1984
    Date of Patent: November 19, 1985
    Assignee: Texaco Inc.
    Inventors: Jiang-Jen Lin, David C. Alexander
  • Patent number: 4504676
    Abstract: 1,4-diacyloxybutenes are prepared by reacting a 1,3-butadiene with a carboxylic acid and oxygen in the presence of a catalyst in a reactor, by a process in which the 3,4-diacyloxybutene formed as a by-product in the reaction is separated off from the reaction mixture, and some or all of this 3,4-diacyloxybutene is recycled to the reactor.
    Type: Grant
    Filed: March 9, 1984
    Date of Patent: March 12, 1985
    Assignee: BASF Aktiengesellschaft
    Inventors: Rolf Schnabel, Gerd Kissau, Hans-Martin Weitz, Rolf Fischer
  • Patent number: 4480123
    Abstract: A process for preparing diacyloxyalkadienes of the formula ##STR1## where R.sup.1 to R.sup.6 are each hydrogen or a hydrocarbon radical, which contain one or more hydrocarbon radicals having one or more non-conjugated double bonds, by reacting an aliphatic triene of the formula ##STR2## in which R.sup.1 to R.sup.6 have the same meanings given above with a carboxylic acid of the formulaR.sup.7 -COOHin which R.sup.7 has the same meaning given above, in the presence of a catalyst which contains palladium, platinum or salts of these metals and in the presence of oxygen.
    Type: Grant
    Filed: July 25, 1983
    Date of Patent: October 30, 1984
    Assignee: BASF Aktiengesellschaft
    Inventors: Rolf Fischer, Hans-Martin Weitz
  • Patent number: 4468525
    Abstract: A process for the preparation of a diacyloxyhexadiene of the formula ##STR1## where X is R.sup.9 -CO- and R.sup.1 to R.sup.9 are hydrogen or alkyl of 1 to 3 carbon atoms, by reacting a hexatriene of the formula ##STR2## with oxygen and a carboxylic acid of the formula R.sup.9 COOH in the presence of a catalyst which contains palladium, platinum or a salt of these metals.
    Type: Grant
    Filed: April 29, 1983
    Date of Patent: August 28, 1984
    Assignee: BASF Aktiengesellschaft
    Inventors: Hans-Martin Weitz, Rolf Fischer
  • Patent number: 4399301
    Abstract: Methylenically-substituted undecadiene compounds having the structural formula: ##STR1## wherein X is selected from the group consisting of lower acyloxy, aryloxy having from 6 to 14 carbon atoms, lower alkoxy and hydroxy, and R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13, R.sub.14, R.sub.15 and R.sub.16 are independently selected from the group consisting of hydrogen and lower alkyl, with the proviso that at least one of R.sub.3, R.sub.5 and R.sub.6 and at least one of R.sub.9, R.sub.10, R.sub.11 and R.sub.12 must be hydrogen, are prepared by reacting a diene having the structural formula: ##STR2## with a conjugated diene having the structural formula: ##STR3## in the presence of a rhodium/trivalent phosphorus catalyst, with the atomic ratio of the trivalent phosphorus to the rhodium therein being at least 1.5. The compounds can be hydrogenated and saponified to form known alcohols which are precursors for biodegradable detergents.
    Type: Grant
    Filed: September 13, 1979
    Date of Patent: August 16, 1983
    Assignee: Rhone-Poulenc Industries
    Inventor: Didier Morel
  • Patent number: 4394290
    Abstract: A process for regenerating a supported catalyst for acyloxylations, which contains palladium and/or platinum and tellurium, with or without copper, wherein copper is applied to the catalyst to be regenerated.
    Type: Grant
    Filed: December 29, 1981
    Date of Patent: July 19, 1983
    Assignee: BASF Aktiengesellschaft
    Inventors: Rolf Schnabel, Hans-Martin Weitz, Rolf Fischer
  • Patent number: 4321409
    Abstract: A process for producing a conjugated diene monoester by reacting a gaseous mixture comprising a conjugated diene, a carboxylic acid and oxygen as reactive components, in which the fraction of said conjugated diene is preferably 12-60 mole % and the fraction of oxygen is preferably 5-30 mole %, in the gas phase in the presence of a catalyst, characterized by carrying out the reaction in the presence of a catalyst which comprises, as active components, (a) palladium, (b) at least one member selected from the group consisting of magnesium, calcium, barium, cerium, lanthanum, tungsten, copper, zinc, cadmium, boron, thallium, molybdenum, tin, lead, phosphorous, arsenic and selenium and (c) at least one alkali metal carboxylate, or a catalyst which comprises, as active components, these three components (a), (b) and (c) together with (d) at least one alkali metal halide.
    Type: Grant
    Filed: December 14, 1979
    Date of Patent: March 23, 1982
    Assignee: Japan Synthetic Rubber Co., Ltd.
    Inventors: Yoshinori Yoshida, Hironobu Shinohara
  • Patent number: 4287356
    Abstract: Vinylglycol esters are prepared by reacting butadiene with oxygen and a carboxylic acid in the gas phase or liquid phase over a supported catalyst which contains from 0.1 to 20 percent by weight of palladium and from 2.5 to 7 percent by weight of cobalt.
    Type: Grant
    Filed: November 27, 1979
    Date of Patent: September 1, 1981
    Assignee: BASF Aktiengesellschaft
    Inventors: Hans-Martin Weitz, Rolf Fischer
  • Patent number: 4262139
    Abstract: A process for the preparation of butenediol diacetate by reacting butadiene with oxygen and acetic acid or with a compound which liberates acetic acid under the reaction conditions, over a solid catalyst which contains a platinum metal and one or more elements of main group 5 or 6, in the presence of butanediol diacetate, butanediol monoacetate, butanediol or a mixture of these, and the use of the butenediol diacetate, thus obtained, to prepare butane-1,4-diol by hydrogenating and then hydrolyzing the diacetate.
    Type: Grant
    Filed: October 22, 1979
    Date of Patent: April 14, 1981
    Assignee: BASF Aktiengesellschaft
    Inventors: Juergen Hartig, Hans-Martin Weitz, Rolf Schnabel
  • Patent number: 4260750
    Abstract: A process for the telomerization of dienes with a telomerizing compound containing a mobile hydrogen atom is disclosed wherein the reaction between the diene and the telomerizing agent is effected in the presence of a catalytic system comprising a water-soluble sulfonated triaryl phosphine compound, preferably a water-soluble salt of a mono-, di-, or trisulfonated triphenyl phosphine and a transition metal compound, preferably palladium or a palladium-containing compound. Water is added either before or after the reaction is completed and the reaction products can easily be separated from the aqueous catalyst solution.
    Type: Grant
    Filed: March 13, 1980
    Date of Patent: April 7, 1981
    Assignee: Rhone-Poulenc Industries
    Inventor: Emile Kuntz
  • Patent number: 4239910
    Abstract: In a process for the manufacture of butenediol-dicarboxylic acid esters by reacting butadiene with oxygen and a carboxylic acid in the presence of a noble metal catalyst containing platinum or palladium, the carboxylic acid is added to the reaction mixture in the form of the ester of the acid with a low molecular weight aliphatic alcohol such as methanol and the reaction is carried out under conditions under which the ester undergoes hydrolysis, or the hydrolysis is carried out before the main reaction. This enables the carboxylic acid obtained on further processing of the butenediol esters to be recycled.
    Type: Grant
    Filed: March 18, 1977
    Date of Patent: December 16, 1980
    Assignee: BASF Aktiengesellschaft
    Inventors: Hans-Martin Weitz, Rolf Platz, Juergen Hartig
  • Patent number: 4236024
    Abstract: Diacetoxybutene is prepared in a high yield with a high selectivity from butadiene, acetic acid and oxygen in the presence of a solid catalyst comprising sulfur, at least one noble metal selected from palladium, platinum and rhodium, and a carrier.
    Type: Grant
    Filed: February 27, 1979
    Date of Patent: November 25, 1980
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Teruo Matsuda, Kuniyoshi Manabe
  • Patent number: 4233455
    Abstract: Diesters of olefinically unsaturated 1,2- and/or 1,4-diols are prepared by reacting a conjugated diolefin, oxygen and a fatty acid, in the gas phase or liquid phase, over a solid catalyst which contains palladium and/or platinum and a further metal, which has an atomic number of from 21 to 30, from 39 to 48 or from 57 to 80, but is not a platinum metal, the catalyst having been obtained by reduction of compounds, applied to a carrier, of platinum and/or palladium and the further metal, and heating at 400.degree. C. or above.
    Type: Grant
    Filed: April 4, 1979
    Date of Patent: November 11, 1980
    Assignee: BASF Aktiengesellschaft
    Inventors: Hans-Martin Weitz, Juergen Hartig, Laszlo Marosi
  • Patent number: 4228301
    Abstract: In a process for preparing diacetoxybutene by subjecting butadiene, acetic acid and oxygen to reaction, the discharge gas from the reaction system or purification system, containing butadiene and/or acetic acid, is treated by contacting with diacetoxybutene and/or diacetoxybutane (absorbent) to allow butadiene and/or acetic acid to be absorbed by said absorbent. A part of the diacetoxybutene separated in a distillation tower from the reaction product solution containing diacetoxybutene produced by said three-component reaction can be used as said absorbent. In this case, butadiene and/or acetic acid can be recovered from said discharge gas by supplying the absorption solution into said distillation tower. Also usable as said absorbent is diacetoxybutane obtained by hydrogenation of diacetoxybutene.
    Type: Grant
    Filed: October 11, 1978
    Date of Patent: October 14, 1980
    Assignee: Japan Synthetic Rubber Co., Ltd.
    Inventors: Yoshinori Yoshida, Hironobu Shinohara
  • Patent number: 4225727
    Abstract: The invention relates to a process for the production of an unsaturated glycol diester by the reaction of a conjugated diene compound, a carboxylic acid and molecular oxygen in the presence of a solid catalyst. For example, 1,4-diacetoxy-2-butene is prepared at high conversion and high selectivity by reacting butadiene, molecular oxygen and acetic acid in the presence of a solid catalyst containing palladium, tellurium and at least one element selected from the group consisting of tin, germanium and lead. The product is an intermediate for the preparation of 1,4-butanediol.
    Type: Grant
    Filed: October 5, 1979
    Date of Patent: September 30, 1980
    Assignee: Toa Nenryo Kogyo Kabushiki Kaisha
    Inventors: Setsuo Kamiyama, Kouji Shiozawa, Yoshiharu Okumura, Katsumi Kaneko
  • Patent number: 4225729
    Abstract: Diacetoxybutane is prepared by a process for hydrogenating diacetoxybutene in the presence of a supported hydrogenation catalyst comprising catalytically reacting diacetoxybutene with hydrogen continuously in an insulation reaction apparatus utilizing a fixed-bed of said hydrogenation catalyst, withdrawing the reaction effluent continuously from said reaction apparatus, circulating at least a part of said reaction effluent to said reaction apparatus while controlling the temperature of influx of said reaction apparatus at a temperature lower than the temperature of efflux from said reaction apparatus by 5.degree. to 100.degree. C.
    Type: Grant
    Filed: December 2, 1976
    Date of Patent: September 30, 1980
    Assignee: Mitsubishi Chemical Industries, Limited
    Inventors: Jun Toriya, Ken Shiraga, Takeru Onoda, Akihisa Ohno
  • Patent number: 4182919
    Abstract: A reaction in a catalyst suspension system is carried out by using a reactor equipped with a filter for separating the catalyst in the reactor.
    Type: Grant
    Filed: March 16, 1978
    Date of Patent: January 8, 1980
    Assignee: Toyo Soda Manufacturing Co., Ltd.
    Inventors: Shunsuke Mabuchi, Sadakatsu Kumoi, Kenji Tsuzuki
  • Patent number: 4152525
    Abstract: Disclosed is a method of recovering butadiene gas from an acetoxylation process which method comprises steps: (a) contacting a butadiene-containing gas with acetic acid to effect the absorption of butadiene in acetic acid, (b) recycling the acetic acid containing butadiene to the acetoxylation process, (c) contacting the waste gas containing acetic acid from step (a) with water to effect the absorption of acetic acid in water and (d) recycling the water containing acetic acid to hydrolysis step of the acetoxylation product.
    Type: Grant
    Filed: January 30, 1975
    Date of Patent: May 1, 1979
    Assignee: Mitsubishi Chemical Industries Ltd.
    Inventors: Yasuo Tanabe, Jun Toriya, Ikuo Kasahara
  • Patent number: 4150239
    Abstract: A process for producing 1,4-glycol diester from unsaturated glycol diesters prepared by reacting butadiene, acetic acid and oxygen or an oxygen-containing gas in the presence of a palladium catalyst or, from saturated glycol diesters prepared by hydrogenating said unsaturated glycol diesters, wherein, 1,4-glycol diester is separated from the isomer mixture of glycol diesters prepared, the residual glycol diester isomers are decomposed by heating and butadiene and/or acetic acid produced on decomposition are recycled to the process for the production of glycol diesters.
    Type: Grant
    Filed: May 27, 1977
    Date of Patent: April 17, 1979
    Assignee: Mitsubishi Chemical Industries Ltd.
    Inventors: Yasuo Tanabe, Jun Toriya
  • Patent number: 4142060
    Abstract: A process for the telomerization of dienes with a telomerizing compound containing a mobile hydrogen atom is disclosed wherein the reaction between the diene and the telomerizing agent is effected in the presence of a catalytic system comprising a water-soluble sulfonated triaryl phosphine compound, preferably a water-soluble salt of a mono-, di-, or trisulfonated triphenyl phosphine and a transition metal compound, preferably palladium or a palladium-containing compound. Water is added either before or after the reaction is completed and the reaction products can easily be separated from the aqueous catalyst solution.
    Type: Grant
    Filed: July 21, 1977
    Date of Patent: February 27, 1979
    Assignee: Rhone-Poulenc Industries
    Inventor: Emile Kuntz
  • Patent number: 4131743
    Abstract: Unsaturated diesters are produced by a process which comprises reacting, in a flowing gaseous phase, a gaseous mixture comprising a conjugated diene, a carboxylic acid and molecular oxygen in the presence of (A) a catalyst comprising palladium, vanadium, antimony and at least one alkali metal carboxylate, or in the presence of (B) a catalyst comprising palladium, vandium, antimony, at least one alkali metal carboxylate and at least one alkali metal halide. The catalyst (A) maintains a high activity and a high selectivity for a long time. The catalyst (B), in which further the alkali metal halide is added, shows a higher activity and a higher selectivity for a longer time. And its activity and selectivity are stable and durable at high temperatures such as 160.degree. - 200.degree. C. Furthermore, the addition of the alkali metal halide suppresses combustion reaction of dienes such as butadiene remarkably.
    Type: Grant
    Filed: July 6, 1976
    Date of Patent: December 26, 1978
    Assignee: Japan Synthetic Rubber Co., Ltd.
    Inventors: Yoshinori Yoshida, Tutomu Kobayashi, Hironobu Shinohara, Izumi Hanari
  • Patent number: 4122285
    Abstract: Butenediol diacetate is manufactured by reaction of butadiene, oxygen and acetic acid over a palladium or platinum catalyst, only liquid, and no gases, being present in the reaction chamber.
    Type: Grant
    Filed: August 13, 1976
    Date of Patent: October 24, 1978
    Assignee: BASF Aktiengesellschaft
    Inventors: Hans-Martin Weitz, Ludwig Vogel, Juergen Hartig, Eckhard Hetzel
  • Patent number: 4121039
    Abstract: Unsaturated glycol diesters are prepared at high reaction rates, high degrees of conversion and high selectivity, by reacting a conjugated diene, a carboxylic acid and oxygen, in the presence of an improved active solid catalyst, in the liquid phase. The improved catalyst of the invention comprises palladium containing thorium as a promotor. In the preferred embodiment, butadiene and acetic acid are reacted with oxygen to produce the desired 1,4-diacetoxy-2-butene at high conversions and selectivity.
    Type: Grant
    Filed: September 26, 1977
    Date of Patent: October 17, 1978
    Assignee: GAF Corporation
    Inventors: R. Parthasarathy, Eugene Victor Hort
  • Patent number: 4113970
    Abstract: 1,4-Diacyloxybutene-2 is produced with a high yield by reacting 1,3-butadiene with a carboxylic acid, for example, acetic acid, and molecular oxygen in the presence of a catalyst containing metallic palladium and at least one iodine-containing substance selected from the group consisting of iodine, iodic acid, iodates, for example, alkali metal iodates and substituted and unsubstituted ammonium iodate, and iodides, for example, hydrogen iodide, alkali metal iodide and substituted and unsubstituted ammonium iodides, the ratio in gram-atom, of iodine to palladium in the above-mentioned catalyst being 0.1 to 1.5:1.
    Type: Grant
    Filed: April 11, 1977
    Date of Patent: September 12, 1978
    Assignee: Asahi Kasei Kogyo Kabushiki Kaisha
    Inventors: Masanori Tanabe, Masanori Ikeda, Nobuhiro Tamura
  • Patent number: 4100361
    Abstract: A process for the manufacture of butenediol diacetates, especially but-2-ene-1,4-diol diacetate and but-1-ene-3,4-diol diacetate, by reacting butadiene with oxygen and acetic acid in the gas phase or liquid phase over a solid catalyst which contains platinum and at least one element of main group 5 or 6, as well as nickel.
    Type: Grant
    Filed: September 29, 1976
    Date of Patent: July 11, 1978
    Assignee: BASF Aktiengesellschaft
    Inventors: Hans-Martin Weitz, Juergen Hartig
  • Patent number: 4075413
    Abstract: Diacetoxybutene is prepared by a catalytic reaction of butadiene, acetic acid and oxygen or an oxygen containing gas in the presence of a supported palladium catalyst.In said reaction, the use of butadiene containing vinylcyclohexene in an amount of not more than 5,000 parts by weight per million parts by weight of butadiene and at least one polymerization inhibitor prevents the lowering of the activity of the catalyst thereby prolonging its useful life.
    Type: Grant
    Filed: June 10, 1976
    Date of Patent: February 21, 1978
    Assignee: Mitsubishi Chemical Industries Limited
    Inventor: Yasuo Tanabe
  • Patent number: 4075412
    Abstract: Diacyloxy olefins are prepared by the reaction of a conjugated diolefin with a carboxylic acid in the presence of free oxygen and a catalyst system consisting essentially of an indium compound, a halide source and an alkali metal compound.
    Type: Grant
    Filed: April 21, 1976
    Date of Patent: February 21, 1978
    Assignee: Phillips Petroleum Company
    Inventor: Paul R. Stapp
  • Patent number: 4057472
    Abstract: A fractional distillation method of separating diacetoxybutene isomers from a reaction mixture produced from the reaction of butadiene, acetic acid and molecular oxygen comprises employing a series of at least two distillation towers, one of said towers being used for distillation of water and acetic acid under a pressure of 30 - 250 Torr and a tower bottom temperature of 190.degree. - 120.degree. C and the other being used for separation of high boiling point materials under a pressure of 2 - 100 Torr and a tower bottom temperature of 190.degree. - 120.degree. C, the temperature of all tower bottoms being from 190.degree. - 120.degree. C.
    Type: Grant
    Filed: February 6, 1976
    Date of Patent: November 8, 1977
    Assignees: Noboru Haji, Mitsubishi Chemical Industries Ltd.
    Inventors: Jun Toriya, Masato Sato, Ken Shiraga, Setsuo Matsunaga