Preparing Esters By Ester Interchange Patents (Class 560/234)
  • Patent number: 9630890
    Abstract: The present disclosure provides for a process for an equilibrium limited reaction using reactive chromatography unit (RCU) in which a first organic donor reactant (FODR) and a second organic acceptor reactant (SOAR) react to form a product mixture of a first acceptor product (FAP) and a second donor co-product (SDCP). The equilibrium-limited reaction does not produce water. The RCU has separation media to separate the product mixture into a raffinate and an extract. The FODR is in a stoichiometric deficit relative to the SOAR for the equilibrium limited reaction, so that the SOAR acts as the eluent for both the raffinate and the extract, and so as not to produce an azeotrope of FODR and the SDCP in the extract.
    Type: Grant
    Filed: May 2, 2014
    Date of Patent: April 25, 2017
    Assignee: Dow Global Technologies LLC
    Inventors: Timothy C. Frank, Megan E. Donaldson
  • Patent number: 9365487
    Abstract: Methods and systems for making dibasic esters and/or dibasic acids using metathesis are generally disclosed. In some embodiments, the methods comprise reacting a terminal olefin ester with an internal olefin ester in the presence of a metathesis catalyst to form a dibasic ester and/or dibasic acid. In some embodiments, the terminal olefin ester or the internal olefin ester are derived from a renewable feedstock, such as a natural oil feedstock. In some such embodiments, the natural oil feedstock, or a transesterified derivative thereof, is metathesized to make the terminal olefin ester or the internal olefin ester.
    Type: Grant
    Filed: October 8, 2013
    Date of Patent: June 14, 2016
    Assignee: Elevance Renewable Sciences, Inc.
    Inventors: Thomas E. Snead, Steven A. Cohen, Demond L. Gildon
  • Patent number: 8975437
    Abstract: A continuous process is provided for selective formation of a vinyl ester by reactive distillation from a corresponding carboxylic acid. Carboxylic acid, vinyl acetate, and a palladium acetate—bidentate ligand catalyst complex are provided and reacted in a typical embodiment. Acetic acid and vinyl acetate are continuously removed from the reaction mixture and vinyl acetate is recycled to the reaction mixture. The vinyl ester product is separated from the vinyl acetate, residual carboxylic acid, residual acetic acid, and catalyst.
    Type: Grant
    Filed: May 3, 2011
    Date of Patent: March 10, 2015
    Assignee: Celanese International Corporation
    Inventors: Ilias S. Kotsianis, Barbara F. M. Kimmich, Melchior A. Meilchen, Hang Wang, Prashant P. Barve, Bhaskar D. Kulkarni, Gopal M. Chaphekar, Ravindra W. Shinde, Milind Y. Gupte, Sanjay P. Kamble, Satish N. Shintre
  • Patent number: 8921593
    Abstract: A semi-continuous process is provided for selective formation of a vinyl ester by reactive distillation from a corresponding carboxylic acid. Carboxylic acid, vinyl acetate, and a palladium acetate—bidentate ligand catalyst complex are provided and reacted in a typical embodiment. Acetic acid and vinyl acetate are continuously removed from the reaction mixture and vinyl acetate is recycled to the reaction mixture. The vinyl ester product is separated from the vinyl acetate, residual carboxylic acid, residual acetic acid, and catalyst.
    Type: Grant
    Filed: May 3, 2011
    Date of Patent: December 30, 2014
    Assignee: Celanese International Corporation
    Inventors: Ilias S. Kotsianis, Barbara F. M. Kimmich, Melchior A. Meilchen, Hang Wang, Prashant P. Barve, Bhaskar D. Kulkarni, Gopal M. Chaphekar, Ravindra W. Shinde, Milind Y. Gupte, Sanjay P. Kamble, Satish N. Shintre
  • Patent number: 8865931
    Abstract: This invention is directed to a process for the production of a variety of esters, particularly acrylate and methacrylate-based esters, by a transesterification reaction. This objective is achieved by reaction of an ester of a carboxylic or a carbonic acid, in particular of a saturated or unsaturated, typically, a 3 to 4 carbon atom carboxylic acid; with an alcohol in the presence of a catalyst comprising the combination of a metal 1,3-dicarbonyl complex (pref. Zn or Fe acetylacetonate) and a salt, in particular an inorganic salt, pref. ZnCl2, LiCI, NaCI, NH4CI or Lil. These catalysts are prepared from readily available starting materials within the reaction medium without the need for isolation (in-situ preparation).
    Type: Grant
    Filed: June 10, 2011
    Date of Patent: October 21, 2014
    Assignee: Ecosynth bvba
    Inventors: Thomas Peter Anne Goossens, Freek Annie Camiel Vrielynck, Noel Gabriel Cornelius Hosten, Koen Jeanne Alfons Van Aken
  • Patent number: 8729295
    Abstract: The present invention provides methods of using a novel sulfonated resin catalyst, showing improved performance. The catalyst has reduced or partial functionalization, throughout the sulfonated region of the polymer, leading to reduced by-product formation and other desirable features. This catalyst has particular usefulness in reactions or processes sensitive to high acidity, e.g., esterification-transesterification.
    Type: Grant
    Filed: October 24, 2008
    Date of Patent: May 20, 2014
    Assignee: The Purolite Company
    Inventors: James A. Dale, Luc Froment, Satish Bapat
  • Patent number: 8722924
    Abstract: An integrated facility for the co-production of ethanol and biodiesel fuel is provided. Ethanol and corn oil, the primary product and a by-product from the ethanol plant, are utilized as feedstocks for a biodiesel plant operating within the same general facility as the corn ethanol plant. By-products of the biodiesel plant, principally crude liquid glycerol and gaseous ethanol or methanol, are recycled to various parts of the ethanol plant.
    Type: Grant
    Filed: January 30, 2014
    Date of Patent: May 13, 2014
    Assignee: WB Technologies LLC
    Inventors: Rachel Overheul, Brandon Awtrey, Daniel Johnson
  • Patent number: 8461376
    Abstract: In one embodiment, a method for the production of alkyl esters comprises: introducing liquid biomass and an alcohol to a first transesterification reactor at a point in a lower 25% of the reactor; reacting the liquid biomass and the alcohol to form a liquid glycerol and a liquid alkyl ester, wherein greater than or equal to about 75 mass % of the liquid glycerol moves towards a bottom of the first transesterification reactor; removing a liquid alkyl ester stream from the first transesterification reactor; and removing the liquid glycerol from the first transesterification reactor. The liquid biomass and the alcohol form a combined liquid stream that flows through the first transesterification reactor in a laminar flow.
    Type: Grant
    Filed: February 15, 2012
    Date of Patent: June 11, 2013
    Assignee: The University of Connecticut
    Inventors: Richard Parnas, Clifford Weed, Nicholas Leadbeater, Matthew Boucher
  • Patent number: 8455676
    Abstract: In a process for preparing carboxylic esters by transesterification, a first feed stream comprising a first carboxylic ester, e.g. methyl formate, is introduced laterally into a reaction column at least one first feed point located between top and bottom of the reaction column and a second feed stream comprising a first alcohol, e.g. ethanol, is introduced laterally into the reaction column at a second feed point located above the first feed point and are reacted in a reaction zone of the reaction column to form a second carboxylic ester and a second alcohol. The first alcohol has a higher molecular weight than the second alcohol. A product fraction comprising the second carboxylic ester and unreacted first carboxylic ester is taken off at an offtake point located above the second feed point. At the bottom of the reaction column, a bottom fraction comprising the second alcohol and unreacted first alcohol is taken off.
    Type: Grant
    Filed: April 18, 2011
    Date of Patent: June 4, 2013
    Assignee: BASF SE
    Inventors: Helmut Kronemayer, Ellen Dahlhoff, Andreas Lanver
  • Patent number: 8436202
    Abstract: The present invention includes a process to dry a feed steam containing alcohol and a small quantity of water. The process includes the step of using pressure swing adsorption to produce a first alcohol stream of substantially dehydrated alcohol and a second mixed stream of water and alcohol. The second mixed stream is distilled in a distillation column to produce a relatively purified water stream and a wet alcohol stream. The wet alcohol stream is added to the feed stream. Optionally the present invention is used to recover excess methanol from a biodiesel reactor that uses one or both of the transesterification reaction and the esterification reaction. The biodiesel reactor produces a product stream comprising fatty acid esters, water and alcohol. Water and alcohol is separated from the product stream. The alcohol is dried as noted above. Dried alcohol is recycled to one or both of the transesterification reaction and the esterification reaction.
    Type: Grant
    Filed: August 18, 2011
    Date of Patent: May 7, 2013
    Inventors: Christopher J Brown, Marion Simo
  • Publication number: 20130090492
    Abstract: This invention is directed to a general catalyst of high activity and selectivity for the production of a variety of esters, particularly acrylate and methacrylate-based esters, by a transesterification reaction. This objective is achieved by reaction of an ester of a carboxylic or a carbonic acid, in particular of a saturated or unsaturated, typically, a 3 to 4 carbon atom carboxylic acid; with an alcohol in the presence of a catalyst comprising the combination of a metal 1,3-dicarbonyl complex (pref. Zn or Fe acetylacetonate) and a salt, in particular an inorganic salt, pref. ZnCl2, LiCI, NaCI, NH4CI or Lil. These catalysts are prepared from readily available starting materials within the reaction medium without the need for isolation (in-situ preparation).
    Type: Application
    Filed: June 10, 2011
    Publication date: April 11, 2013
    Applicant: ECOSYNTH BVBA
    Inventors: Thomas Peter Anne Goossens, Freek Annie Camiel Vrielynck, Noel Gabriel Cornelius Hosten, Koen Jeanne Alfons Van Aken
  • Patent number: 8309755
    Abstract: The invention relates to a process in which a compound R1COOR3 (I) is made by a transesterification reaction of an ester compound R1COOR2 (II) with an alcohol R3OH (III) in the presence of a transesterification catalyst, wherein R1 is H or C1-4 alkyl or CH2?CR4—; R2 is C1-4 alkyl; R3 is selected from the group consisting of alkyl having at least 4 carbon atoms, cycloalkyl having at least 5 carbon atoms, aryl, aralkyl, alkaryl and amino alkyl; and R4 is —H or —C1-4 alkyl, wherein alcohol R2OH (IV) is formed as a byproduct and in which said byproduct (IV) is removed by distillation in the presence of an entrainer, in which the entrainer is a compound that suppresses the formation of an azeotrope between compound (II) and byproduct (IV). The process can be useful in the preparation of esters such as dimethyl amino ethyl (meth)acrylate. The invention also provides a method of separating alcohols and esters.
    Type: Grant
    Filed: April 22, 2011
    Date of Patent: November 13, 2012
    Assignee: BASF SE
    Inventors: John Colin Dunn, Dinesh Mistry, Martin Gower, Roger Prétôt, Markus Schmid
  • Publication number: 20120253042
    Abstract: A process for preparing amides by reacting a primary amine and a primary alcohol in the presence of a Ruthenium complex to generate the amide and molecular hydrogen. Primary amines are directly acylated by equimolar amounts of alcohols to produce amides and molecular hydrogen (the only byproduct) in high yields and high turnover numbers. Also disclosed are processes for hydrogenation of amides to alcohols and amines; hydrogenation of organic carbonates to alcohols; hydrogenation of carbamates or urea derivatives to alcohols and amines; amidation of esters; acylation of alcohols using esters; coupling of alcohols with water and a base to form carboxylic acids; dehydrogenation of beta-amino alcohols to form pyrazines and cyclic dipeptides; and dehydrogenation of secondary alcohols to ketones. These reactions are catalyzed by a Ruthenium complex which is based on a dearomatized PNN-type ligand of formula A1 or precursors thereof of formulae A2 or A3.
    Type: Application
    Filed: May 14, 2012
    Publication date: October 4, 2012
    Applicant: YEDA RESEARCH AND DEVELOPMENT CO. LTD.
    Inventors: David Milstein, Chidambaram Gunanathan, Yehoshua Ben-David, Ekambaram Balaraman, Boopathy Gnanaprakasam, Jing Zhang
  • Patent number: 8124801
    Abstract: Processes for preparation of fatty acid alkyl esters are described herein. The processes include contacting fatty acid glycerides with alcohols in the presence of a catalyst separating the reaction products from the catalyst, and separating the fatty acid alkyl esters from the reaction products. The catalyst includes a metal from Group VIB of the Periodic Table and an element from Group VA of the Periodic Table.
    Type: Grant
    Filed: June 24, 2009
    Date of Patent: February 28, 2012
    Assignee: Benefuel Inc.
    Inventors: Darbha Srinivas, Paul Ratnassamy, Sanjeevani Amrit Pardhy, Thirumalaiswamy Raja, Shilpa Shirish Deshpande, Vijay Vasant Bokade, Kashinath Joti Wagmare, Arshia Altaf Lalljee, Surya Prakash Babu, Karukappadath Kunjimoideen Abdul Rashid, Khaliji Anas, Chennampilly Ummer Aniz
  • Patent number: 8119832
    Abstract: In one embodiment, an alkyl ester production system can comprise: a first transesterification reactor comprising a liquid biomass inlet located between a liquid glycerol outlet and a liquid alkyl ester outlet, a water wash vessel comprising an alkyl ester inlet, a water inlet located near a top of the water wash vessel, and a washed alkyl ester outlet located near the top of the water wash vessel, wherein the alkyl ester inlet is located near a bottom of the water wash vessel, and a drier comprising a washed alkyl ester inlet located near a top of the drier, and a gas inlet and a dried alkyl ester outlet located near the bottom of the drier. The first transesterification reactor can be configured for laminar flow and for liquid reactants and products. The alkyl ester inlet can be in fluid communication with the washed alkyl ester outlet.
    Type: Grant
    Filed: April 28, 2009
    Date of Patent: February 21, 2012
    Assignee: The University of Connecticut
    Inventors: Richard Parnas, Clifford Weed, Nicholas Leadbeater
  • Publication number: 20110275852
    Abstract: A semi-continuous process is provided for selective formation of a vinyl ester by reactive distillation from a corresponding carboxylic acid. Carboxylic acid, vinyl acetate, and a palladium acetate—bidentate ligand catalyst complex are provided and reacted in a typical embodiment. Acetic acid and vinyl acetate are continuously removed from the reaction mixture and vinyl acetate is recycled to the reaction mixture. The vinyl ester product is separated from the vinyl acetate, residual carboxylic acid, residual acetic acid, and catalyst.
    Type: Application
    Filed: May 3, 2011
    Publication date: November 10, 2011
    Inventors: Ilias S. Kotsianis, Barbara F.M. Kimmich, Melchior A. Meilchen, Hang Wang, Prashant P. Barve, Bhaskar D. Kulkarni, Gopal M. Chaphekar, Ravindra W. Shinde, Milind Y. Gupte, Sanjay P. Kamble, Satish N. Shintre
  • Publication number: 20110275853
    Abstract: A continuous process is provided for selective formation of a vinyl ester by reactive distillation from a corresponding carboxylic acid. Carboxylic acid, vinyl acetate, and a palladium acetate—bidentate ligand catalyst complex are provided and reacted in a typical embodiment. Acetic acid and vinyl acetate are continuously removed from the reaction mixture and vinyl acetate is recycled to the reaction mixture. The vinyl ester product is separated from the vinyl acetate, residual carboxylic acid, residual acetic acid, and catalyst.
    Type: Application
    Filed: May 3, 2011
    Publication date: November 10, 2011
    Inventors: Ilias S. Kotsianis, Barbara F.M. Kimmich, Melchior A. Meilchen, Hang Wang, Prashant P. Barve, Bhaskar D. Kulkarni, Gopal M. Chaphekar, Ravindra W. Shinde, Milind Y. Gupte, Sanjay P. Kamble, Satish N. Shintre
  • Publication number: 20110257426
    Abstract: In a process for preparing carboxylic esters by transesterification, a first feed stream comprising a first carboxylic ester, e.g. methyl formate, is introduced laterally into a reaction column at least one first feed point located between top and bottom of the reaction column and a second feed stream comprising a first alcohol, e.g. ethanol, is introduced laterally into the reaction column at a second feed point located above the first feed point and are reacted in a reaction zone of the reaction column to form a second carboxylic ester and a second alcohol. The first alcohol has a higher molecular weight than the second alcohol. A product fraction comprising the second carboxylic ester and unreacted first carboxylic ester is taken off at an offtake point located above the second feed point. At the bottom of the reaction column, a bottom fraction comprising the second alcohol and unreacted first alcohol is taken off.
    Type: Application
    Filed: April 18, 2011
    Publication date: October 20, 2011
    Applicant: BASF SE
    Inventors: Helmut KRONEMAYER, Ellen DAHLHOFF, Andreas LANVER
  • Patent number: 7999131
    Abstract: The invention relates to a process in which a compound R1COOR3 (I) is made by a transesterification reaction of an ester compound R1COOR2 (II) with an alcohol R3OH (III) in the presence of a transesterification catalyst, wherein R1 is H or C1-4 alkyl or CH2?CR4—; R2 is C1-4 alkyl; R3 is selected from the group consisting of alkyl having at least 4 carbon atoms, cycloalkyl having at least 5 carbon atoms, aryl, aralkyl, alkaryl and amino alkyl; and R4 is —H or —C1-4 alkyl, wherein alcohol R2OH (IV) is formed as a byproduct and in which said byproduct (IV) is removed by distillation in the presence of an entrainer, in which the entrainer is a compound that suppresses the formation of an azeotrope between compound (II) and byproduct (IV). The process can be useful in the preparation of esters such as dimethyl amino ethyl(meth)acrylate. The invention also provides a method of separating alcohols and esters.
    Type: Grant
    Filed: November 9, 2006
    Date of Patent: August 16, 2011
    Assignee: BASF SE
    Inventors: John Colin Dunn, Dinesh Mistry, Martin Gower, Roger Prétôt, Markus Schmid
  • Patent number: 7781610
    Abstract: Supported heterogeneous organotin catalysts of the formula X1, X2, or X3: wherein Z is a spacer group; Y is an insoluble phenyl-group containing copolymer; R1, R2, R3, R5, and R6 are independently selected from halogen, alkyl, alkylene, phenyl, vinyl, allyl, naphthyl, aralkyl, and Z; and R4 is alkyl, alkylene, phenyl, vinyl, allyl, naphthyl, or aralkyl.
    Type: Grant
    Filed: February 19, 2010
    Date of Patent: August 24, 2010
    Assignee: Chemtura Corporation
    Inventors: Uwe Schneider, Bernard Jousseaume, Karine Darriet, Thierry Toupance
  • Patent number: 7696376
    Abstract: A method for the manufacture of an ester by transesterification allows the transesterification reaction to proceed within a short reaction time and under a pressure of the order of normal pressure. It was found that transesterification proceeds when a starting material ester and an alcohol are brought into contact with a catalyst comprising (A) an amorphous zirconium oxide and (B) an oxide of a Group II element, an oxide of a Group V element, and/or an oxide of a Group IV element other than zirconium and hafnium. In this method, it is preferred that the starting material ester in a liquid-phase state and the alcohol in a vapor-phase state be brought into contact with a solid acid catalyst comprising the above components (A) and (B), the starting material ester be an oil or fat, and the alcohol be methanol or ethanol. An oxide of titanium, silicon, germanium, or tin is the preferred oxide of the Group IV element other than zirconium and hafnium.
    Type: Grant
    Filed: June 23, 2004
    Date of Patent: April 13, 2010
    Assignee: Japan Energy Corporation
    Inventor: Satoshi Furuta
  • Patent number: 7592470
    Abstract: A novel process is described for producing esters of linear monocarboxylic acids containing 6 to 26 carbon atoms, by reacting vegetable or animal oils, neutral or otherwise, with monoalcohols containing 1 to 18 carbon atoms in the presence of a catalyst selected from: mixtures of titanium oxide and alumina having formula: (TiOx)y(Al2O3)1-y where x has the value 1.5 to 2.2 and y, representing the weight ratio of the two oxides, has a value of 0.005 to 0.995; mixtures of zirconium oxide and alumina having formula: (ZrOx)y(Al2O3)1-y where x has the value 1.5 to 2.2 and y has a value of 0.005 to 0.995; and mixtures of antimony oxide and alumina having formula: (SbOx)y(Al2O3)1-y where x has the value 1.2 to 2.6 and y has a value of 0.005 to 0.995, in order to directly produce, in one or more steps, an ester for use as a fuel and a pure glycerin.
    Type: Grant
    Filed: May 26, 2004
    Date of Patent: September 22, 2009
    Assignee: Institut Francais du Petrole
    Inventors: Thierry Lacome, Gerard Hillion, Bruno Delfort, Renaud Revel, Serge Leporq, Gustave Acakpo
  • Patent number: 7544830
    Abstract: In one embodiment, the method comprises: combining liquid biomass with an alcohol to form a combined liquid stream, introducing the combined liquid stream to a first transesterification reactor between a liquid glycerol outlet and a liquid alkyl ester outlet, reacting the liquid biomass and the alcohol to form liquid glycerol and liquid alkyl ester, and removing a liquid alkyl ester stream from an upper portion of the first transesterification reactor. The combined liquid stream flows upward through the reactor at a rate that is less than a settling velocity of the liquid glycerol.
    Type: Grant
    Filed: September 19, 2007
    Date of Patent: June 9, 2009
    Assignee: The University of Connecticut
    Inventors: Richard Parnas, Clifford Weed, Nicholas Leadbeater, Matthew Boucher
  • Patent number: 7399881
    Abstract: A transesterification process of methyl acetate is provided. The process comprises: (a) performing a first reactive distillation of a methyl acetate solution and a first alcohol to generate a first ester and a first mixture; (b) performing a first distillation of a first part of the first mixture to generate a second mixture; and (c) performing a second reactive distillation of a first part of the second mixture and a second alcohol to generate a second ester; wherein the respective one of the first and second alcohols is a limiting reagent. The transesterification process provided in the present invention could highly reduce the investing production cost of the transesterification of the by-product, methyl acetate, in the conventional polyvinyl alcohol plants.
    Type: Grant
    Filed: March 8, 2007
    Date of Patent: July 15, 2008
    Assignee: National Taiwan University
    Inventors: Hsiao-Ping Huang, Cheng-Ching Yu, Ming-Jer Lee, Jyun-Hong Chen, Jian-Kai Cheng
  • Patent number: 7312355
    Abstract: The invention relates to a method of producing fatty acid monoesters and polyhydroxylic alcohols by means of transesterification between a polyhydroxylic alcohol and a compound that is selected from a fat of animal origin, a fat of vegetable origin, and a fatty acid methyl ester. The invention is characterised in that the transesterification reaction is performed in the presence of basic solid catalysts, said basic solids being oxides that are selected from mixed oxides of one or more monovalent metals and one or more trivalent metals, mixed oxides of one or more divalent metals and one or more trivalent metals, and mixtures of same.
    Type: Grant
    Filed: April 12, 2006
    Date of Patent: December 25, 2007
    Assignees: Consejo Superior de Investigaciones Cientificas, Universidad Politecnica de Valencia, Universiti Malaya
    Inventors: Avelino Corma Canòs, Sara Iborra Chornet, Alexandra Isabelle Velty, Sharifah Bee Abd Hamid
  • Patent number: 7253305
    Abstract: Esters are formed by reaction of acetic anhydride with tertiary butyl or tertiary anyl alcohol in the presence of tertiary amine catalyst such as DMAP or NMI catalyst and acetic acid in amount sufficient to present catalyst degradation; in preferred practice a mixed acetic anhydride and acetic acid stream is recycled to the esterfication.
    Type: Grant
    Filed: July 26, 2005
    Date of Patent: August 7, 2007
    Inventor: Stephen H. Harris
  • Patent number: 7211681
    Abstract: It is an object of this invention to provide a method for producing an ester by a transesterification reaction in which the reaction can be stably performed in a short time at a pressure approximately equal to normal pressure. The ester is produced by a transesterification reaction in which a starting material ester and an alcohol are brought into contact with a solid acid catalyst that displays the characteristics of a very strong acid in terms of the absolute value of argon adsorption heat ranging from 15 to 22 kJ/mol. In particular, it is preferable that the starting material ester in a liquid phase and alcohol in a vapor phase be brought into contact with the solid acid catalyst, and that the starting material ester be oil or fat, and the alcohol be methanol or ethanol.
    Type: Grant
    Filed: March 19, 2004
    Date of Patent: May 1, 2007
    Assignee: Japan Energy Corporation
    Inventor: Satoshi Furuta
  • Patent number: 6992212
    Abstract: Formic acid and a carboxylic acid having at least two carbon atoms and/or derivatives thereof are prepared jointly by a process in which (a) a formic ester (I) is transesterified with a carboxylic acid having at least two carbon atoms (II) to form formic acid (III) and the corresponding carboxylic ester (IV); and (b) at least part of the carboxylic ester (IV) formed in step (a) is carbonylated to give the corresponding carboxylic anhydride (V).
    Type: Grant
    Filed: July 24, 2002
    Date of Patent: January 31, 2006
    Assignee: BASF Aktiengesellschaft
    Inventors: Peter Zehner, Jörg Pastre, Wolfram Stüer
  • Patent number: 6710204
    Abstract: There is provided a superior decreasing method of an N-oxyl compound contained in an easily polymerizable material, according to which the N-oxyl compound contained in an easily polymerizable material can be sufficiently decreased and loss of the easily polymerizable material is little. The easily polymerizable material containing an N-oxyl compound and an acid are contacted with each other. In addition, not only the N-oxyl compound but also an organic titanium group compound contained in the easily polymerizable material can be sufficiently decreased.
    Type: Grant
    Filed: March 25, 2002
    Date of Patent: March 23, 2004
    Assignee: Mitsubishi Rayon Co., Ltd.
    Inventors: Masanori Tokuda, Yasukazu Yoshida, Junichi Doi, Motomu Oh-Kita
  • Patent number: 6706910
    Abstract: There is provided a method for producing a cyclopropanecarboxylate of formula (1): which comprises contacting a cyclopropanecarboxylate of formula (2): with a monohydroxy compound of formula (3): R7OH  (3) in the presence of a lithium compound of formula (4): R8OLi  (4), wherein R1, R2, R3, R4 and R5 each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group; R6 represents an alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted phenyl group; R7 and R8 do not simultaneously represent the same and each independently represent a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.
    Type: Grant
    Filed: October 31, 2001
    Date of Patent: March 16, 2004
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Kazunori Iwakura, Hiroshi Souda, Tohei Takagaki, Yoshimi Yamada
  • Publication number: 20030144543
    Abstract: An accelerated process for preparing a methyl ester having formula (III) 1
    Type: Application
    Filed: August 8, 2002
    Publication date: July 31, 2003
    Inventors: Wen-Chung Shieh, Steven Dell
  • Patent number: 6441220
    Abstract: There is provided a method for producing a cyclopropanecarboxylate of formula (3): wherein R1, R2, R3, R4 and R5 each independently represent: a hydrogen atom, halogen atom, an optionally substituted alkyl group and the like; and R7 represents: an optionally substituted alkyl group, and the like, which is characterized by reacting a cyclopropanecarboxylate of the formula (1) wherein R1, R2, R3, R4 and R5 are as defined above, and R6 represents an alkyl group having 1 to 10 carbon atoms or an optionally substituted phenyl group, with a monohydroxy compound of the formula (2): R7OH   (2) wherein R7 is the same as defined above, in the presence of an alkali metal hydroxide.
    Type: Grant
    Filed: June 16, 2000
    Date of Patent: August 27, 2002
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Hiroshi Souda, Kazunori Iwakura
  • Publication number: 20020055649
    Abstract: A carboxylic acid tertiary alkyl ester (Chemical formula 1) of high purity is obtained at a high yield ratio, by continually adding an esterification agent possessing a monovalent acid group, which agent is ester-interchangeable with a tertiary alcohol, to a mixed fluid of a carboxylic acid and a tertiary alcohol:
    Type: Application
    Filed: August 21, 2001
    Publication date: May 9, 2002
    Inventors: Sachiko Miyagi, Masayuki Maeda, Seiji Kawano, Taiichi Shiomi
  • Publication number: 20020028961
    Abstract: The present invention pertains to a process for making an alkyl ester of a carboxylic acid via transesterification comprising the steps of: (1) reacting a carboxylic acid ester with an alcohol and an effective amount of a transesterification catalyst in a reaction zone to form a reaction mixture comprised of a product ester and a product alcohol; (2) passing the reaction mixture from step (1) through a centrifugal separation zone wherein the second alcohol is separated from the second ester. The process according to the invention allows for shorter reaction times and improved product yields.
    Type: Application
    Filed: June 26, 2001
    Publication date: March 7, 2002
    Inventors: Jeffrey A. Barnhorst, Michael D. Staley, Dean A. Oester
  • Publication number: 20020022741
    Abstract: The present invention relates to metathesis syntheses for insect sex-attractant pheromones or their components, such as E-5-decenyl acetate, the major component of the Peach Twig Borer pheromone; (5R, 6S)-6-acetoxy-5-hexadecanolide, the mosquito oviposition attractant pheromone; E9, Z11-hexadecadienal, the pecan nut casebearer moth pheromone; 9-tetradecenyl formate, an analog of the Diamondback Moth (DBM) pheromone; 11-tetradecenyl acetate, the Omnivorous Leafroller (OLR) pheromone; E-4-tridecenyl acetate, the major component of the Tomato Pinworm (TPW) pheromone; E,E-8,10-dodecadienol, the Codling Moth (CM) pheromone. The syntheses preferably employ a Class I-IV metathesis catalyst, entail few reaction steps, use generally commercially available starting materials, and have relatively short process times. These syntheses produce good yields without the need for expensive or sophisticated equipment.
    Type: Application
    Filed: April 10, 2001
    Publication date: February 21, 2002
    Inventors: Richard L. Pederson, Robert H. Grubbs
  • Patent number: 6342199
    Abstract: The invention relates to a process for conducting a chemical reaction characterized by an equilibrium in a reaction system designed as a loop reactor, said loop reactor comprising a reactor vessel (1), at least one loop connected to said reactor vessel (1) each by means of an outlet and an inlet, said loop comprising means (3) for pumping over a fluid reaction material, at least one he exchanger (4), optionally means (5) for feeding said reaction material into Me reactor vessel (1) and a separate gas loop (8) which is connected to the gas space of the reactor vessel (1) above the reaction mixture and has separate means for feeding a gas into the gas loop (8), for withdrawing gas from the gas loop (8) and/or for treating said gas circulating in the gas loop (8), said process comprising the steps of circulating and/or treating said gas in said gas loop (8), feeding said gas into the reactor vessel (1) for influencing the equilibrium of a reaction conducted in said reactor vessel (1) and being characterized by t
    Type: Grant
    Filed: June 18, 1999
    Date of Patent: January 29, 2002
    Inventor: Vincent Simon Ellis
  • Publication number: 20020010359
    Abstract: The present invention provides a heterogeneous catalyst which is highly active, excellent in selectivity and free from elution of its catalyst-components during reaction and which has long lifetime. That is, a phosphate of a metal selected from the group consisting of aluminum, gallium and iron is used as the catalyst for transesterification of the present invention.
    Type: Application
    Filed: June 22, 2001
    Publication date: January 24, 2002
    Applicant: Kao Corporation
    Inventors: Jun Kaita, Taku Mimura, Noriaki Fukuoka, Yasuyuki Hattori
  • Patent number: 6323362
    Abstract: A process for the continuous and simultaneous manufacture of at least two different acetates by at least two simultaneous transesterification reactions comprising continuously bringing into contact in the presence of a catalyst in a reaction zone: (i) an acetate of the formula CH3COOR in which R is an alkyl radical, with (ii) at least two alcohols of formulae R1OH and R2OH in which R1 and R2, are different, and are alkyl radicals with a linear or branched chain, or radicals of formula R3(OCH2CR4R5)m— in which R3 is an alkyl radical, R4 and R5, being identical or different, are a hydrogen atom or an alkyl radical, and m is an integer of from 1 to 4 to form a reaction mixture having a homogeneous liquid phase and produce in the reaction zone by at least two simultaneous transesterification reactions of (i) with (ii) at least two acetates of formulae CH3COOR1 and CH3COOR2 and continuously drawing off from the reaction zone the at least two acetates and continuously separating the at least two acetates from
    Type: Grant
    Filed: April 24, 2000
    Date of Patent: November 27, 2001
    Assignee: BP Chemicals Limited
    Inventors: Philippe Lalanne-Magne, Bruno Grenouiller, Daniel Brun-Buisson
  • Patent number: 6316664
    Abstract: Formic ester is transesterified with a hydroxyl-containing compound in the presence of a tertiary amine as transesterification catalyst to form a formic ester which differs from the formic ester used as reactant, and of a hydroxyl-containing compound which is different from the hydroxyl-containing compound used as reactant.
    Type: Grant
    Filed: May 8, 1998
    Date of Patent: November 13, 2001
    Assignee: BASF Aktiengesellschaft
    Inventors: Detlef Kratz, Christoph Sigwart
  • Patent number: 6215019
    Abstract: The present invention relates to syntheses of 5-decenyl acetate, the major component in Peach Twig Borer pheromone, and other pheromone components. The syntheses entails few reaction steps, use commercially available starting materials, and have relatively short process times. A preferred embodiment of the syntheses involves self-metathesizing 1-hexene in the presence of Grubbs' catalyst, [(PCy3)2Cl2]Ru═CHPh. The resulting 5-decene is then reacted with an alcohol or acetate protected hexene under vacuum to yield 5-decenyl acetate. These syntheses produce good yields without the need for expensive or sophisticated equipment.
    Type: Grant
    Filed: September 1, 1999
    Date of Patent: April 10, 2001
    Assignee: TillieChem, Inc.
    Inventors: Richard L. Pederson, Robert H. Grubbs
  • Patent number: 6130191
    Abstract: A process for the preparation of a mixture of trimethylolpropane caprylate and trimethylolpropane caprate comprising the steps ofA) purifying a less than pure mixture of methyl caprylate and methyl caprate;B) reacting the purified mixture from step A) with trimethylolpropane to transesterify the purified mixture to produce a reaction mixture containing trimethylolpropane caprylate and trimethylolpropane caprate; andC) removing methanol and unreacted methyl caprylate and methyl caprate from the reaction mixture.
    Type: Grant
    Filed: September 10, 1999
    Date of Patent: October 10, 2000
    Assignee: Henkel Corporation
    Inventors: Robert P. Ribelin, Stephen W. Turner
  • Patent number: 6018074
    Abstract: A process for the preparation of polyalcohols comprises the stages:(a) Reaction of an alkanal or ketone with formaldehyde in aqueous solution in the presence of a tertiary amine, to form a formates containing polyalcohol product mixture,(b) removal of water, excess tertiary amine, excess formaldehyde(c) heating of remaining mixture from (b) with removal of further formaldehyde and tertiary amine with formation of the formates of the polyalcohol,(d) transfer of tertiary amine removed from stage (b) and/or from stage (c), to synthesis stage (a) and/or to the subsequent transesterification stage (e),(e) transesterification of the resulting formates of the polyalcohol from stage (c) with an alcohol of the formula ROH in the presence of a transesterification catalyst to give polyalcohols and formates of the formula ##STR1## where R is a hydrocarbon radical, preferably alkyl of 1-6, particularly preferably 1-2, carbon atoms, and(f) isolation of the polyalcohols.
    Type: Grant
    Filed: October 5, 1998
    Date of Patent: January 25, 2000
    Assignee: BASF Aktiengesellshcaft
    Inventors: Detlef Kratz, Achim Stammer, Tom Witzel, Martin Brudermuller
  • Patent number: 6008404
    Abstract: The present invention relates to a process to prepare alkyl (meth)acrylate esters from corresponding alkyl/methacrylate esters using an alkali metal alkoxide as an ester interchange catalyst to produce an alkyl (meth)acrylate ester monomer product C ##STR1## The present invention further relates to the use of bromide and iodide salts as free radical polymerization inhibitors. The present invention further relates to the use of a noninterfering alcohol or polyol that prevents anionic polymerization reactions of reactant ester B and/or alkyl (meth)acrylate product C. The present invention further relates to a process for inhibiting polymerization of (meth)acrylates being synthesized in a transesterification or ester-ester interchange reaction system.
    Type: Grant
    Filed: August 11, 1998
    Date of Patent: December 28, 1999
    Assignee: Ciba Specialty Chemicals Corporation
    Inventors: Timothy M. Miller, Narayanan Pondicherry, Louis E. Trapasso, Aaron van de Sande
  • Patent number: 5973214
    Abstract: Both enantiomers of optically active 2-alkanol are produced by transesterification reaction of racemic 2-alkanol and aliphatic acid 2,2,2-trichloroethylester in the presence of enzyme derived from Candida antarctica.Both enantiomers of optically active 2-alkanol, which are useful as starting materials of liquid crystal materials and have optical purity of 99% or more, can be efficiently produced.
    Type: Grant
    Filed: September 16, 1998
    Date of Patent: October 26, 1999
    Assignee: Chisso Corporation
    Inventors: Naoyuki Yoshida, Hitoshi Yano
  • Patent number: 5847239
    Abstract: Dihydromyrcene is reacted with a carboxylic acid, eg acetic acid, to produce an ester which is then reacted with an alcohol in a transesterification reaction to produce (dihydro)myrcenol and another ester. The preferred alcohol is 4-tertiarybutylcyclohexanol. Myrcenol can be produced in a similar way.
    Type: Grant
    Filed: January 15, 1997
    Date of Patent: December 8, 1998
    Assignee: Quest International B.V.
    Inventors: Paul Nicolas Davey, Clive Derek Richardson, Christopher Paul Newman, Barrie R. Hart
  • Patent number: 5817844
    Abstract: A method of manufacturing a fatty acid ester of polyoxyalkylene alkyl ether wherein a fatty acid ester of polyoxyalkylene alkyl ether represented by the following formula (I) is produced through a reaction between a fatty acid alkyl ester with an alkylene oxide in the presence of a composite metal-oxide catalyst whose surface is modified with a metal hydroxide or a metal alkoxide: ##STR1## wherein each of R.sub.1 and R.sub.3 independently represents an alkyl group or an alkenyl group, R.sub.2 represents an alkylene group, and n is a positive number.
    Type: Grant
    Filed: April 8, 1996
    Date of Patent: October 6, 1998
    Assignee: Lion Corporation
    Inventors: Ituo Hama, Takahiro Okamoto, Hisashi Sasamoto, Hirofumi Nakamura
  • Patent number: 5723639
    Abstract: A low temperature method for esterifying ammonium- and amine-containing salts is provided whereby the salt is reacted with an alcohol in the presence of heat and a catalyst and then subjected to a dehydration and deamination process using pervaporation.The invention also provides for a method for producing esters of fermentation derived, organic acid salt comprising first cleaving the salt into its cationic part and anionic part, mixing the anionic part with an alcohol to create a mixture; heating the mixture in the presence of a catalyst to create an ester; dehydrating the now heated mixture; and separating the ester from the now-dehydrated mixture.
    Type: Grant
    Filed: October 16, 1995
    Date of Patent: March 3, 1998
    Assignee: University of Chicago
    Inventors: Rathin Datta, Shih-Perng Tsai
  • Patent number: 5543560
    Abstract: A method for the hydrogenolytic reduction of peroxidic ozonolysis products to the corresponding carbonyl compounds in the presence of an inert organic diluting agent and in the presence of a monolith catalyst at hydrogen pressures of 0.01 to 2.0 MPa and at temperatures of -10.degree. to 150.degree. C., and a device for the catalytic hydrogenolysis of chemical compounds which yield uniform, new products by means of hydrogenolysis with hydrogen.
    Type: Grant
    Filed: March 11, 1994
    Date of Patent: August 6, 1996
    Assignee: Chemie Linz Gesellschaft m.b.H.
    Inventors: Stefan Pollhammer, Josef Scaller, Willibald Winetzhammer
  • Patent number: 5516776
    Abstract: A process and intermediates for the enantioselective synthesis of 5,10-dideaza-5,6,7,8-tetrahydrofolic acid are disclosed.
    Type: Grant
    Filed: September 12, 1994
    Date of Patent: May 14, 1996
    Assignee: Eli Lilly and Company
    Inventors: Charles J. Barnett, Thomas M. Wilson
  • Patent number: 5481029
    Abstract: A process for preparing ketones, for example CF.sub.3 C(O)CH.sub.3, CF.sub.3 C(O)CH.sub.2 C(O)CF.sub.3 and CF.sub.3 C(O)CF.sub.2 H, in which .beta.-ketoesters are transesterified and decarboxylated using a carboxylic acid, for example trifluoroacetic acid, in the presence of a catalyst, particularly an "onium" salt of a carboxylic acid or an effective amount of a proton-donating acid, preferably a sulfonic acid such as alkyl- or arylsulfonic acids, or a mineral acid. The process is advantageously carried out in the absence of water, so that no formation of acetals or hydrates occurs, and no dehydrating step is needed. The process is simple to carry out, and if transesterification is carried out with a sufficiently active carboxylic acid, for example with trifluoroacetic acid, the presence of an additional catalyst is unnecessary.
    Type: Grant
    Filed: April 26, 1994
    Date of Patent: January 2, 1996
    Assignee: Solvay Fluor und Derivate GmbH
    Inventors: Max Braun, Johannes Eicher, Werner Rudolph, Kerstin Eichholz