Prepared By Disproportionation Patents (Class 562/481)
  • Patent number: 10710971
    Abstract: A method for synthesizing a dicarboxylate containing an aromatic heterocycle is provided. A carboxylic acid containing a heterocycle is provided. A CO32? salt is provided to form a mixture, which converts the carboxylic acid containing an aromatic heterocycle to a carboxylate containing an aromatic heterocycle. CO2 gas is provided to the mixture. The mixture is heated to a temperature to at least partially melt the carboxylate containing an aromatic heterocycle.
    Type: Grant
    Filed: November 19, 2018
    Date of Patent: July 14, 2020
    Assignee: The Board of the Trustees of the Leland Stanford Junior University
    Inventors: Matthew W. Kanan, Aanindeeta Banerjee
  • Patent number: 6562999
    Abstract: Disclosed is a process for purifying 2,6-naphthalene dicarboxylic acid produced by disproportionation and more efficiently recycling byproduct dipotassium salts which includes the steps of: a) Contacting an aqueous solution containing the disalt of 2,6-NDA(2,6-K2NDA) with carbon dioxide to form as a precipitate the monopotassium salt of 2,6-NDA (KHNDA) and an aqueous solution containing 2,3-KHNDA, K2NDA, and potassium bicarbonate; b) Disproportionating said monopotassium salt (KHNDA) to form 2,6-NDA and an aqueous solution containing K2NDA, and potassium bicarbonate; c) Separating said 2,6-NDA and concentrating said aqueous solution containing K2NDA and potassium bicarbonate by reverse osmosis.
    Type: Grant
    Filed: January 9, 2002
    Date of Patent: May 13, 2003
    Assignee: Mossi & Ghisolfi Overseas S.A.
    Inventors: Zaida Diaz, John B. Rodden
  • Patent number: 6479699
    Abstract: Disclosed is a method for selective carboxylation of naphthoic acid, or other aromatic mono-acids to form primarily 2,3-naphthalene dicarboxylic acid (2,3-NDA) or other aromatic diacids which comprises reacting said aromatic mono-acid in the presence of one or more metal oxide catalysts, alone, or in combination, and in the presence of about 0.2 to 0.8 moles excess of base over aromatic mono-acid, at a temperature of about 380° C. to about 420° C., and, in a second step, disproportionating the product of said selective carboxylation at a temperature above about 420° C. to form a product with a greatly improved yield of 2,6-naphthalene dicarboxylic acid, or other aromatic dicarboxylic acid.
    Type: Grant
    Filed: July 3, 2001
    Date of Patent: November 12, 2002
    Assignee: Mossi & Ghisolfi Overseas S.A.
    Inventors: Thomas Fairchild Brownscombe, Donn Anthony DuBois, Susan Secor Pfrehm, William Larry King
  • Patent number: 6452045
    Abstract: Disclosed is a process for disproportionation of potassium naphthoate to the dipotassium salt of 2,6-NDA which gives reproducible improved yields of up to 40% which comprises: a) reacting naphthoic acid in the presence of excess base to produce a disproportionation feed comprising a finely dispersed disordered salt mixture of excess base salts and naphthoic acid salts, wherein the feed is prepared by the steps of: (1) Reacting naphthoic acid in the presence of excess base selected from the group consisting of carbonates and bicarbonates to form a salt; (2) Drying said salt mixture by a method which forms a highly mixed disordered salt mixture characterized by a differential scanning calorimeter(DSC) signature characterized by low melting peaks not previously observed in the salt; and b) Disproportionating said solid salts in the presence of a disproportionation catalyst to form the dipotassium salts of 2,6-NDA.
    Type: Grant
    Filed: August 22, 2000
    Date of Patent: September 17, 2002
    Assignee: M & G USA Corporation
    Inventors: Thomas Fairchild Brownscombe, James Laurel Buechele, Donn Anthony DuBois, Susan Secor Pfrehm, William Larry King
  • Patent number: 6448437
    Abstract: Disclosed are halide-free catalyst compositions for the disproportionation/isomerization of aromatic carboxylic acid salts. In one embodiment the catalyst comprises a mixed catalyst of compounds of copper, zinc, and zirconium; and, in a second embodiment, the catalyst comprises a copper compound treated with a base, optionally used with a promoter. Both halide-free catalysts provide advantages with respect to metallurgic problems, as well as good stability, activity and selectivity, and the later is faster kinetically at lower temperatures.
    Type: Grant
    Filed: August 22, 2000
    Date of Patent: September 10, 2002
    Assignee: Mossi & Ghisolfi Overseas S.A.
    Inventors: Donn Anthony DuBois, Brendan Dermot Murray
  • Publication number: 20020123646
    Abstract: Disclosed is a process for purifying 2,6-naphthalene dicarboxylic acid produced by disproportionation and more efficiently recycling byproduct dipotassium salts which includes the steps of:
    Type: Application
    Filed: January 9, 2002
    Publication date: September 5, 2002
    Applicant: Mossi & Ghisolfi Overseas, S.A.
    Inventors: Zaida Diaz, John B. Rodden
  • Patent number: 6441224
    Abstract: Disclosed is a method for selective carboxylation of naphthoic acid, or other aromatic mono-acids to form primarily 2,3-naphthalene dicarboxylic acid (2,3-NDA) or other aromatic diacids which comprises reacting said aromatic mono-acid in the presence of one or more metal oxide catalysts, alone, or in combination, and in the presence of about 0.2 to 0.8 moles excess of base over aromatic mono-acid, at a temperature of about 380° C. to about 420° C., and, in a second step, disproportionating the product of said selective carboxylation at a temperature above about 420° C. to form a product with a greatly improved yield of 2,6-naphthalene dicarboxylic acid, or other aromatic dicarboxylic acid.
    Type: Grant
    Filed: August 22, 2000
    Date of Patent: August 27, 2002
    Assignee: Mossi & Ghisolfi Overseas, S. A.
    Inventors: Thomas Fairchild Brownscombe, Donn Anthony DuBois, Susan Secor Pfrehm, William Larry King
  • Patent number: 6426430
    Abstract: Disclosed is a method for reducing alkali metals in aromatic dicarboxylic acids produced by disproportionation or rearrangement of an alkali salt of a mono- or dicarboxylic acid to levels acceptable for polymerization which comprises: a) Washing the aromatic dicarboxylic acid with water in a ratio of about 5:1 water to acid at a temperature of about 70-200° C.; b) Introducing the washed aromatic dicarboxylic acid into a reactor characterized by minimal backmixing, such as a pipe reactor, and reacting the washed aromatic dicarboxylic acid in the pipe reactor at about 100-200° C.; c) Directing the aromatic dicarboxylic acid exiting the pipe reactor to a centrifuge to separate the solid aromatic dicarboxylic acid from water containing contaminants; d) Optionally, combining the solid aromatic dicarboxylic acid again with water in a ratio of about 5:1 at a temperature of about 100-200° C. to further reduce levels of alkali metals.
    Type: Grant
    Filed: August 22, 2000
    Date of Patent: July 30, 2002
    Assignee: Mossi & Ghisolfi Oversears, S.A.
    Inventors: Robert Lawrence Blackbourn, Raymond Lawrence June
  • Patent number: 6426431
    Abstract: Disclosed is a method of increasing the yield of 2,6-NDA which comprises: a) Dissolving a disproportionation reaction product containing a dialkali salt of 2,6-NDA in water and filtering off insoluble matter from the resulting solution; b) Precipitating the monoalkali salt of 2,6-NDA (KHNDA) with CO2; c) Suspending said monoalkali salt in water in a weight ratio higher than 8:1, water: monosalt; and d) Heating at a temperature above 100° C. and at a pressure above 100 psig. The improvements in yield are from about 20% to as high as 45%.
    Type: Grant
    Filed: August 22, 2000
    Date of Patent: July 30, 2002
    Assignee: Mossi & Ghisolfi Overseas S.A.
    Inventors: Zaida Diaz, Thomas F. Brownscombe
  • Patent number: 5668186
    Abstract: The invention relates to a novel process for depolymerizing polyesters by subjecting the polyesters to catalysts and organic solvents which are substantially free of oxygen and water in order to produce macrocyclic polyester oligomers substantially free of hydroxybutyl terminated linear impurities.
    Type: Grant
    Filed: March 20, 1996
    Date of Patent: September 16, 1997
    Assignee: General Electric Company
    Inventors: Daniel Joseph Brunelle, Ganesh Kailasam, Judith Ann Serth-Guzzo, Paul Russell Wilson
  • Patent number: 5243067
    Abstract: A 3,4,3',4'-substituted biphenyl compound represented by the general formula (II): ##STR1## wherein, one of R.sup.1 and R.sup.2 is a -CH.sub.3 group and the one other is a --COOR.sup.5 group, --COOH group, or --COCl group, and one of R.sup.3 and R.sup.4 is a -CH.sub.3 group and the other one is a --COOR.sup.5 group, --COOH group, or --COCl group, is produced by the steps of oxidatively coupling an o-toluic acid alkyl ester in the presence of a catalyst containing a mixture of palladium salts with 1,10-phenanthroline or .alpha.,.alpha.'-bipyridine, a chelating product of a palladium salt with 1,10-phenanthroline, or a chelating products of a palladium salt with .alpha.,.alpha.
    Type: Grant
    Filed: February 20, 1991
    Date of Patent: September 7, 1993
    Assignee: Ube Industries, Ltd.
    Inventors: Akinori Shiotani, Michinori Suzuki, Fumio Matsuo
  • Patent number: 5175354
    Abstract: The process of this invention for preparing 2,6-naphthalene-dicarboxylic acid comprises a reaction step (Step A) wherein 2,6-naphthalene-dicarboxylic acid potassium salts consisting of 2,6-naphthalene-dicarboxylic acid dipotassium salt and/or 2,6-naphthalene-dicarboxylic acid monopotassium salt are allowed to react with benzene-carboxylic acids in the presence of water to yield 2,6-naphthalene-dicarboxylic acid and benzene-carboxylic acid potassium salts and a separation step (Step B) wherein the crystallized 2,6-naphthalene-dicarboxylic acid is separated from the benzene-carboxylic acid potassium salts dissolved in the aqueous solution and provides 2,6-naphthalene-dicarboxylic acid, useful as raw material for polymers, at low cost on a commerical scale with recycle of potassium.
    Type: Grant
    Filed: April 1, 1991
    Date of Patent: December 29, 1992
    Assignees: Nippon Steel Chemical Co., Ltd., Nippon Steel Corporation
    Inventors: Shuichi Mitamura, Yasuhisa Tsutsumi, Yoshimi Kata, Atsushi Kawada, Naoya Okabayashi
  • Patent number: 5095144
    Abstract: A process for dimerizing an aromatic halogen compound is disclosed, which comprises the step of: subjecting an aromatic halogen compound having at least one halogen atom bonded to an aromatic nucleus carbon to a dehalogenation-dimerization reaction in the presence of a catalyst, water, a reducing agent, and a halogen acceptor, the catalyst comprising a carrier supported thereon palladium and iron.
    Type: Grant
    Filed: July 17, 1990
    Date of Patent: March 10, 1992
    Assignee: Mitsubishi Kasei Corporation
    Inventors: Keiichi Sato, Takahiko Takewaki, Yoshio Katsuro
  • Patent number: 5081291
    Abstract: A process for the preparation of 3,3',4,4'-biphenyltetracarboxylic acid salt by the dehalodimerization of a 4-halophthalic acid salt. The process uses hydroxylamine or one of its salts as the reducing agent in an alkaline solution, preferably of pH 10 or above, and palladium catalyst. The reaction is carried out between 50.degree. and 150.degree. C.
    Type: Grant
    Filed: September 21, 1990
    Date of Patent: January 14, 1992
    Assignee: E. I. Du Pont de Nemours and Company
    Inventor: John H. Freudenberger
  • Patent number: 4942257
    Abstract: A method of manufacturing an alkali metal salt of 2,3,6,7-naphthalenetetracarboxylic acid. Either a sodium salt or a mixture of sodium salt and potassium salt of at least one naphthalenecarboxylic acid selected form the group consisting of naphthoic acids and naphthalenepolycarboxylic acids is heated to an elevated temperature in an inert gas atmosphere in the presence of a Henkel reaction catalyst and halogenated sodium.
    Type: Grant
    Filed: August 31, 1989
    Date of Patent: July 17, 1990
    Assignee: NKK Corporation
    Inventors: Yakudo Tachibana, Kazuhiko Tate, Toshifumi Suzuki, Kouji Chiba
  • Patent number: 4900843
    Abstract: A method of dehalogeno-dimerizing an aromatic halide compound substituted by at least one halogen atom substituted on the aromatic ring using a palladium catalyst on support in the presence of water, a reducing agent and a halogen acceptor is disclosed. The method is characterized by using the palladium catalyst on support immersed in a hydrohalogenic acid prior to the dehalogeno-dimerization reaction.
    Type: Grant
    Filed: May 31, 1988
    Date of Patent: February 13, 1990
    Assignee: Mitsubishi Chemical Industries Limited
    Inventors: Mitsumasa Kitai, Yoshio Katsuro, Shigenori Kawamura, Masumi Hino, Keiichi Sato
  • Patent number: 4820868
    Abstract: Disclosed is a process for the preparation of a naphthalene-2,6-dicarboxylic acid dialkali metal salt which comprises heating an alkali metal salt of naphthoic acid and/or a dialkali metal salt of naphthalene-dicarboxylic acid under pressure with carbon dioxide gas in the presence of a catalyst, wherein an aprotic polycyclic aromatic compound having 2 or 3 rings is used as a reaction medium. Naphthalene-2,6-dicarboxylic acid dialkali metal salt can be obtained in high yield and selectivity with a good reproducibility of the reaction.
    Type: Grant
    Filed: September 29, 1986
    Date of Patent: April 11, 1989
    Assignee: Nippon Steel Corporation
    Inventors: Shuichi Mitamura, Koichi Fujishiro, Hiroharu Inoue
  • Patent number: 4727185
    Abstract: When a 4-halogenoorthophthalic acid salt is dissolved together with a base in an alkaline aqueous solution and the solution is heated in the presence of a catalyst comprising a noble metal supported on a carrier, a formic acid salt and a small amount of an aliphatic compound containing a hydroxyl group, a 3,3',4,4'-biphenyltetracarboxylic acid salt is obtained in a high yield.
    Type: Grant
    Filed: January 21, 1986
    Date of Patent: February 23, 1988
    Assignee: Hitachi, Ltd.
    Inventors: Fusaji Shoji, Fumio Kataoka
  • Patent number: 4720576
    Abstract: A process for dehalogeno-dimerization reaction of an aromatic halide compound which comprises dimerizing aromatic halide compound having at least one halogen atom attached to a carbon atom in the aromatic nucleus, and optionally having a substituent other than the halogen atom, in the presence of a platinum group metal catalyst, carbon monoxide, and an alkali metal compound and/or an alkaline earth metal compound.
    Type: Grant
    Filed: September 18, 1986
    Date of Patent: January 19, 1988
    Assignee: Mitsubishi Chemical Industries Limited
    Inventors: Keisuke Wada, Keiichi Sato
  • Patent number: 4683339
    Abstract: Novel 2,2-bis(2-perfluoroalkylethylthio)acetaldehydes having the formula: ##STR1## wherein R.sub.F and R'.sub.F are the same or different perfluoroalkyl groups, together with processes for producing the same and using the same to prepare surface active agents and products with hydrophobic and lipophobic properties.
    Type: Grant
    Filed: November 26, 1985
    Date of Patent: July 28, 1987
    Assignee: Atochem
    Inventors: Brigitte Bertaina, Aime Cambon, Andre Lantz
  • Patent number: 4435596
    Abstract: A method for producing terephthalic acid from potassium benzoate in which the potassium benzoate is charged to the reactor in powdered form as a low viscosity slurry of potassium benzoate in terphenyl.
    Type: Grant
    Filed: August 23, 1982
    Date of Patent: March 6, 1984
    Assignee: Phillips Petroleum Company
    Inventors: Yulin Wu, Ernest A. Zuech
  • Patent number: 4430511
    Abstract: A low viscosity slurry of aggregates of crystals in a dispersant is prepared by first making aggregates of crystals by the method of direct precipitation, the shape of the aggregates being granular, and then mixing the aggregates and the dispersant.
    Type: Grant
    Filed: August 23, 1982
    Date of Patent: February 7, 1984
    Assignee: Phillips Petroleum Company
    Inventor: Yulin Wu
  • Patent number: 4357257
    Abstract: A low viscosity slurry is prepared by first making a powder such that the shape of the particles of the powder is granular and then mixing the powder and a suitable dispersant.
    Type: Grant
    Filed: April 6, 1978
    Date of Patent: November 2, 1982
    Assignee: Phillips Petroleum Company
    Inventors: Yulin Wu, Ernest A. Zuech
  • Patent number: 4356105
    Abstract: A low viscosity slurry of aggregates of crystals in a dispersant is prepared by first making aggregates of crystals by the method of direct precipitation, the shape of the aggregates being granular, and then mixing the aggregates and the dispersant.
    Type: Grant
    Filed: April 6, 1978
    Date of Patent: October 26, 1982
    Assignee: Phillips Petroleum Company
    Inventor: Yulin Wu
  • Patent number: 4345098
    Abstract: A process for producing an isomerized benzene carboxylic acid salt by treating a mixture of an aromatic material, water, and a water soluble reagent comprising a Group Ia or IIa metal with oxygen under conditions sufficient to convert at least a portion of the aromatic material to a benzene carboxylic acid salt of the metal; isomerizing the benzene carboxylic acid salt by heating without converting the benzene carboxylic acid salt to a benzene carboxylic acid salt of a different Group Ia or IIa metal prior to isomerizing; and recovering the benzene carboxylic acid salt. Another embodiment further comprises converting the isomerized benzene carboxylic acid salt to isomerized benzene carboxylic acid; regenerating the reagent; recovering the isomerized benzene carboxylic acid; and recycling the reagent thusly regenerated to supply a portion of the reagent required for producing the benzene carboxylic acid salt.
    Type: Grant
    Filed: February 29, 1980
    Date of Patent: August 17, 1982
    Assignee: Occidental Research Corporation
    Inventor: Raymond A. Schep
  • Patent number: 4271316
    Abstract: A process for the continuous rearrangement of alkali metal salts of aromatic carboxylic acids is disclosed. The process is conducted under an atmosphere of carbon dioxide and in the presence of an organic diluent and results in high conversion rates and practically quantitative yields of the rearranged alkali metal salt of the aromatic carboxylic acid.
    Type: Grant
    Filed: July 20, 1979
    Date of Patent: June 2, 1981
    Assignee: Rhone-Poulenc Industries
    Inventors: Jean-Claude Choulet, Jacques Nouvel
  • Patent number: 4263451
    Abstract: A method for removing carbonaceous impurity from zinc oxide by contacting a water slurry of contaminated zinc oxide with oxygen in a reactor at reaction conditions sufficient to produce oxide products of the carbon contaminants and passing the reactor effluent through a filter to collect solid zinc oxide while passing the oxides of carbon through the filter. In a preferred embodiment, contaminated zinc oxide separated from the reaction product in the preparation of terephthalic acid from benzoic acid using zinc benzoate catalyst is subjected to treatment for removal of carbonaceous contaminants before being recycled to reaction with molten benzoic acid to produce zinc benzoate catalyst used in the reaction.
    Type: Grant
    Filed: October 15, 1979
    Date of Patent: April 21, 1981
    Assignee: Phillips Petroleum Company
    Inventors: Ronnie L. Lewis, Fred T. Sherk
  • Patent number: 4239915
    Abstract: Gem-perfluoroalkylthio group containing acids of the formula(R.sub.f --R.sub.1 --X--.sub.2 C(R.sub.2)--B--(COOH).sub.gand alkyl esters thereof, wherein R.sub.f is a perfluoroalkyl, R.sub.1 is alkylene or alkylenethio- or oxy- or imino- alkylene, R.sub.2 is hydrogen, alkyl or phenyl, B is a covalent bond, alkylene or alkanetriyl and g is 1 or 2, can be prepared by the addition of a perfluoroalkylthiol to aldehydo or keto acids or esters. The compounds are useful as surface active agents, as intermediates to fluorochemical chromium complexes with low surface energies, or as oil and water repellents for textiles.
    Type: Grant
    Filed: December 2, 1976
    Date of Patent: December 16, 1980
    Assignee: Ciba-Geigy Corporation
    Inventor: Robert A. Falk
  • Patent number: 4230885
    Abstract: Mixture of salts of aromatic mono- or polycarboxylic acids are converted to terephthalate salts in presence of selected catalyst or catalyst mixture, e.g., a mixture of potassium, sodium and cesium benzoates, is disproportionated in the presence of zinc and/or a zinc salt or a mixture of zinc and/or cadmium and a zinc and/or cadmium salt. The mixture of compounds which are to be converted to terephthalate salts will contain at least those of two different alkali metals. A formula m+n is equal to at least 4 is given for determining the catalyst, or catalysts, to be employed. In one embodiment, now preferred, a mixture of sodium, potassium, and cesium benzoates is heated at a reaction temperature of the order of 350.degree.-430.degree. C., more preferably 380.degree.-415.degree. C., in presence of a catalytic mixture of zinc and cadmium benzoates to obtain high yields and rates of reaction at temperatures substantially below those needed in the prior art for similar or better yields, etc.
    Type: Grant
    Filed: June 12, 1978
    Date of Patent: October 28, 1980
    Assignee: Phillips Petroleum Company
    Inventor: Yulin Wu
  • Patent number: 4212991
    Abstract: Highly pure terephthalic acid is prepared from di-potassium terephthalate. The terephthalic acid so produced aids in the direct production of high quality polyester fiber.
    Type: Grant
    Filed: May 5, 1977
    Date of Patent: July 15, 1980
    Assignee: Rhone-Poulenc Industries
    Inventors: Jean-Claude Choulet, Andre Laily