Preparing By Catalytic Alkylation Patents (Class 568/785)
  • Patent number: 9434668
    Abstract: The present invention relates to an improved process for the selective alkylation of phenols by reacting it with methyl tertiary butyl ether (MTBE) using polymer supported carbon composite acidic catalyst under mild to moderate conditions at atmospheric pressure. The process is economically viable since the catalyst regenerated after the initial reaction on further use gives the para tertiary butyl phenol (PTBP) in high yield.
    Type: Grant
    Filed: December 1, 2015
    Date of Patent: September 6, 2016
    Assignee: Council of Scientific and Industrial Research
    Inventors: Praveen Kumar Khatri, Suman Lata Jain, Indrajit Kumar Ghosh
  • Patent number: 9012697
    Abstract: A process is proposed for preparing hydroxyaromatics by heterogeneous catalytic reaction of hydroxyaromatics with C1-C4-alkanols in a microreactor (10), comprising the steps of: a) introducing the hydroxyaromatic and at least one compound selected from the group consisting of C1-C4-alkanols as reactants into at least one inlet orifice (22) of the microreactor (10) comprising at least one microreactor unit (18), b) passing the reactants through at least one microreactor unit (18) of the microreactor (10), said unit comprising a multitude of microchannels (28), said microchannels (28) having a lateral extent of less than 1 mm, and a heterogeneous catalyst being incorporated in the microchannels (28) for conversion of the reactants, c) passing the hydroxyaromatics prepared out through at least one outlet orifice (24) of the microreactor (10).
    Type: Grant
    Filed: March 7, 2012
    Date of Patent: April 21, 2015
    Assignee: Elantas GmbH
    Inventors: Oliver Bleifuβ, Simon Rost, Klaus-Wilhelm Lienert, Hans-Ulrich Moritz
  • Patent number: 8207380
    Abstract: An alkylated hydroxyaromatic compound prepared by reacting at least one hydroxyaromatic compound with a branched olefinic oligomer having from about 20 to about 80 carbon atoms in the presence of a acid catalyst. The alkylated hydroxyaromatic compound has been determined to be substantially free of endocrine disruptive chemicals when the effects were quantified on pubertal development and thyroid function in the intact juvenile female rat.
    Type: Grant
    Filed: April 27, 2007
    Date of Patent: June 26, 2012
    Assignee: Chevron Oronite LLC
    Inventors: Curt B. Campbell, James J. Harrison
  • Patent number: 7705191
    Abstract: Substituted hydrofluoroalkylphenol compounds and methods of using the compounds, e.g., for anesthetizing a subject, are disclosed.
    Type: Grant
    Filed: July 13, 2007
    Date of Patent: April 27, 2010
    Assignee: University of Iowa Research Foundation
    Inventor: Max T. Baker
  • Patent number: 7692047
    Abstract: The present invention relates to an improved process for the selective alkylation of phenols using heteropolyacid catalyst supported onto zirconia under mild conditions. The process is economically viable since the catalyst regenerated after the initial reaction on further use gives the product in high yield.
    Type: Grant
    Filed: September 26, 2007
    Date of Patent: April 6, 2010
    Assignee: Secretary, Department of Science & Technology
    Inventors: Anjali Uday Patel, Nikunj Bhagwatiprasad Bhatt
  • Patent number: 7288683
    Abstract: An alkylation method comprises reacting a hydroxy aromatic compound with an alkyl alcohol in the presence of an alkylation catalyst comprising a metal oxide wherein the alkylation catalyst, has a surface area to volume ratio of about 950 to about 4,000 m2/m3, an aspect ratio of about 0.7 to about 1.0 or a combination of the foregoing.
    Type: Grant
    Filed: June 16, 2006
    Date of Patent: October 30, 2007
    Assignee: General Electric Company
    Inventors: Hugo G. E. Ingelbrecht, David Parrillo, Mukund Parthasarathy, Gert-Jan Schoenmakers, Geuch Zijlma
  • Patent number: 6670513
    Abstract: An alkylated hydroxyl-containing aromatic compound is produced by isomerizing a normal alpha-olefin having from about 16 to about 30 carbon atoms in the presence of a first solid, acidic catalyst capable of inducing both olefin isomerization and skeletal isomerization to produce a mixture of isomerized olefin, then alkylating an hydroxyl-containing aromatic compound with the mixture of isomerized olefins in the presence of a second solid, acidic catalyst. The first solid, acidic catalyst can be SM-3, MAPO-11, SAPO-11, SSZ-32, ZSM-23, MAPO-39, SAPO-39, ZSM-22, SSZ-20, ZSM-35, SUZ-4, NU-23, NU-87, natural ferrierite or synthetic ferrierite. The second solid, acidic catalyst can be a sulfonic acid anionic ion exchange resin catalyst or an acidic clay.
    Type: Grant
    Filed: December 3, 1999
    Date of Patent: December 30, 2003
    Assignees: Chevron Oronite Company, LLC, Chevron Oronite S.A.
    Inventors: Curtis Bay Campbell, Jean Louis Le Coënt
  • Patent number: 6617476
    Abstract: A process for producing an aromatic ring alkylated phenols, wherein said process comprises reacting phenols represented by the general formula (1): wherein, each of R1, R2, R3, R4 and R5 independently represents a hydrogen atom, or a linear or branched alkyl group having 1 to 10 carbon atoms; with monohydric or dihydric alcohol in the presence of a hydroxide of a metal, an alkoxide of a metal, or a hydroxide of a metal and an alkoxide of a metal under a supercritical state of the alcohol.
    Type: Grant
    Filed: December 13, 2000
    Date of Patent: September 9, 2003
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Tomoyuki Suzuki, Fumisato Goto, Kozo Tanaka
  • Patent number: 6232485
    Abstract: A process for the production of liquid meta-rich triaryl phosphate esters having low triphenyl phosphate content and low viscosity comprises (a) an alkylation stage wherein a phenol is reacted with an olefin having 2 to 12 carbon atoms in the presence of a strong acid catalyst to give a reaction product comprising a mixture of meta and para alkylated phenols; and (b) a transalkylation stage wherein the mixture of alkylated phenols from the alkylation stage is heated in the presence of a strong acid catalyst to increase the meta isomer content of the mixture to at least 25% whilst maintaining a phenol level below 22%; and (c) a phosphorylation stage wherein the mixture of alkylated phenols from the transalkylation stage is reacted with a phosphorylating agent; and wherein the strong acid catalyst used in stages (a) and (b) is a Bronsted acid having an acid strength of less than zero. Preferred catalysts are activated clays such as bentonite, montmorillonite or Fullers Earth clay.
    Type: Grant
    Filed: November 26, 1999
    Date of Patent: May 15, 2001
    Assignee: Great Lakes Chemical Corporation
    Inventors: Tracy Anne Derbyshire, Hazel May Farrow, Jonathan Simon Hill
  • Patent number: 6049015
    Abstract: A method for C-alkylating a hydroxylated aromatic compound having at least one hydrogen atom in the ortho or para position relative to the hydroxyl grouping, wherein the aromatic compound is exposed to a proton acid and a compound causing the formation of a carbo-cation in the presence of the acid, and the reaction is performed in the presence of a solvent consisting of a water-alcohol pair.
    Type: Grant
    Filed: August 31, 1998
    Date of Patent: April 11, 2000
    Assignee: Rhodia Chimie
    Inventors: Cecile Serrano, Michel Dury, Jean-Roger Desmurs, Paul Cruciani
  • Patent number: 5399786
    Abstract: The present invention has as purpose a process for the manufacture of tert-butylphenols, mainly of tertbutyl-4-phenols from a phenol and an alkyltert-butylether. The improvement consists in separating in at least two steps, the reaction of phenol alkylation and transalkylation/isomerization of undesirable alkyltert-butylphenols, enabling the flexibilization of the type and quality of end product, and easily adapt to the demands of the market, plus the fact that the total yield improved as well as this improvement has good industrial hygiene properties.Tert-butylphenols are useful intermediate products is the manufacture of phenolic resins or antioxydizing agents for rubber and for several plastic substances.
    Type: Grant
    Filed: July 13, 1993
    Date of Patent: March 21, 1995
    Assignee: Rhodia S/A
    Inventors: Antonio U. B. Queiroz, Lumi T. Aikawa, deceased
  • Patent number: 5356976
    Abstract: Compounds of formula I ##STR1## wherein R.sub.1 is C.sub.1 -C.sub.4 n-alkyl, isopropyl, s-butyl, cyclopentyl, cyclohexyl or .alpha.-methylbenzyl, R.sub.2 is C.sub.4 -C.sub.18 tert-alkyl or .alpha.,.alpha.-dimethylbenzyl, R.sub.3 is C.sub.1 -C.sub.28 alkyl, and R.sub.4 s methyl or ethyl, with the proviso that the --CHR.sub.3 R.sub.4 group contains at least 4 carbon atoms, are suitable for stabilizing organic material which is susceptible to degradation induced by heat, oxidation or actinic light.
    Type: Grant
    Filed: July 12, 1993
    Date of Patent: October 18, 1994
    Assignee: Ciba-Geigy Corporation
    Inventors: Paul Dubs, Rita Pitteloud
  • Patent number: 5345002
    Abstract: The present invention is directed to oil-soluble lubricating oil additives comprising Mannich Base condensates of an alkyl substituted hydroxy aromatic compound with formaldehyde and an amine, wherein the alkyl-moiety of the aromatic compounds is derived from at least one ethylene alpha-olefin copolymer of 300 to 20,000 number average molecular weight, wherein at least about 30% of the polymer's chains contain terminal ethenylidene unsaturation. The Mannich Base condensates of this invention are useful as dispersants.
    Type: Grant
    Filed: October 9, 1992
    Date of Patent: September 6, 1994
    Assignee: Exxon Chemical Patents Inc.
    Inventors: Won R. Song, Robert D. Lundberg, Antonio Gutierrez, Robert A. Kleist
  • Patent number: 5344997
    Abstract: A fluorided silica-alumina catalyst, particularly one with a silica:alumina ratio in the range of 1:1-9:1 containing from 1 to 6 weight percent fluoride, is particularly effective in the liquid phase alkylation of benzene by linear olefins to produce linear alkyl benzenes at temperatures no greater than 140.degree. C. These catalysts also are effective in the liquid phase alkylation of alkylatable aromatics generally with a variety of alkylating agents, including olefins, alcohols, and alkyl halides.
    Type: Grant
    Filed: December 14, 1992
    Date of Patent: September 6, 1994
    Assignee: UOP
    Inventor: Joseph A. Kocal
  • Patent number: 5302732
    Abstract: Silica-aluminas having a sodium content less than about 0.1 weight percent show increased stability when used as a catalyst for the alkylation of aromatic compounds. Where such silica-aluminas are used as the catalyst in detergent alkylation their increased stability permits continuous alkylation to be performed at lower temperatures, as a result of which the detergent alkylate product shows an incrementally higher linearity. Fluorided silica-aluminas having a sodium content of under 0.05 weight percent are particularly advantageous.
    Type: Grant
    Filed: September 14, 1992
    Date of Patent: April 12, 1994
    Assignee: UOP
    Inventors: Karl Z. Steigleder, Christine M. Conway, David M. Baldwin, Diane C. Dierking
  • Patent number: 5288927
    Abstract: There is provided a process for reacting phenol with butene or butanol over fairly large-pore zeolites to give butylphenol with high para-selectivity. Particular zeolites for use in this reaction include ZSM-12 and zeolite beta. A particular butene or butanol reactant is isobutanol. The product of this reaction may have a high content of the mono-alkylated, tert-butyl product.
    Type: Grant
    Filed: February 1, 1993
    Date of Patent: February 22, 1994
    Assignee: Mobil Oil Corp.
    Inventors: Clarence D. Chang, Stuart D. Hellring
  • Patent number: 5274174
    Abstract: A method for producing 4-acetoxystyrene by heating 4-acetoxyphenylmethylcarbinol, with an acid catalyst, at a temperature of from about 85.degree. C. to about 300.degree. C. under a pressure of from about 0.1 mm HgA to about 760 mm HgA for from about 0.2 minutes to about 10 minutes. The process also provides for the solventless (neat) hydrogenation of 4-acetoxyacetophenone to produce 4-acetoxyphenylmethylcarbinol. The reaction proceeds by heating at 54.degree. C. to 120.degree. C. with an excess of hydrogen in the presence of a Pd/C or activated nickel such as Raney Nickel catalyst in the absence of a solvent. The 4-acetoxyphenylmethylcarbinol may then be dehydrated to 4-acetoxystyrene. The later may be polymerized to poly(4-acetoxystyrene) and hydrolyzed to poly(4-hydroxystyrene).
    Type: Grant
    Filed: June 10, 1993
    Date of Patent: December 28, 1993
    Assignee: Hoechst Celanese Corporation
    Inventors: Bakulesh N. Shah, Dung Q. Tran, Donna L. Keene
  • Patent number: 5091594
    Abstract: For producing 2,6-di-tert-butylphenol and products therefrom, utilizing small quantities of aluminum tris-(2-tert-butylphenolate as a catalyst by reaction of 2-tert-butylphenol with isobutene in the liquid phase, the reaction is performed in the presence of diluents such as liquid saturated aliphatic or cycloaliphatic hydrocarbons, C.sub.5 -C.sub.16 alkenes of formula R.sub.1 --CH.dbd.CH.sub.2 or R.sub.2 --CH.dbd.CH--R.sub.3, C.sub.5 to C.sub.12 cycloalkenes, which contain no branching on the C.dbd.C-bond, excess isobutene or mixtures thereof, at temperatures of 0.degree. C. to 80.degree. C., pressures of 0.1 to 11 bars and catalyst amounts of 0.005 to 5 mol %, based on 2-tert-butylphenol. High conversions are obtained with few undesirable trialkylated products.
    Type: Grant
    Filed: December 11, 1990
    Date of Patent: February 25, 1992
    Assignee: Huels Aktiengesellschaft
    Inventors: Friedrich-Wilhelm Kupper, Wolfgang H. E. Muller, Alfred Oberholz
  • Patent number: 5087772
    Abstract: A method for preparing 4-hydroxystyrene is disclosed. The method comprises reacting 4-acetoxystyrene with a suitable alcohol in the presence of a catalytic amount of a suitable base.
    Type: Grant
    Filed: November 16, 1990
    Date of Patent: February 11, 1992
    Assignee: Hoechst Celanese Corporation
    Inventors: Michael T. Sheehan, Lan Shen
  • Patent number: 4950810
    Abstract: A selective process for preparing a 2,4- or 3,6-di-substituted phenol compound which comprises reacting an olefin compound of the formula: ##STR1## wherein R.sup.1 is hydrogen, halogen, alkyl, halogen substituted alkyl, aryl, halogen substituted-aryl or alkyl substituted-aryl; and R.sup.2, R.sup.3 and R.sup.4 are the same or different and each is hydrogen, halogen, alkyl, halogen substituted-alkyl or aralkyl; with a phenol compound of the formula: ##STR2## wherein R.sup.5 is hydrogen, hydroxy, halogen, alkyl, halogen substituted-alkyl, alkoxy or --C(R.sup.6)(R.sup.7)CH(R.sup.8)(R.sup.9) (wherein R.sup.6 is hydrogen, halogen, alkyl, halogen substituted-alkyl, aryl, halogen substituted-aryl or alkyl substituted-aryl; and R.sup.7, R.sup.8 and R.sup.9 are the same or different and each is hydrogen, halogen, alkyl, halogen substituted-alkyl or aralkyl), in the presence of a phosphorus compound and a carboxylic acid compound as catalysts.
    Type: Grant
    Filed: March 29, 1989
    Date of Patent: August 21, 1990
    Assignee: Yoshitomi Pharmaceutical Industries, Ltd.
    Inventors: Ryoichi Kinishi, Shuichi Wakamatsu, Tetsuji Ike
  • Patent number: 4631349
    Abstract: A process using heterogeneous resin-bonded aluminum phenoxide catalyst to alkylate phenols, the catalyst per se, and a process for making the catalyst. The inventive alkylation process uses ortho-tert-butylphenoxide bonded to a phenolformaldehyde condensation resin heterogeneous catalyst to prepare 2,6-di-tert-butylphenol from isobutylene and ortho-tert-butylphenol.
    Type: Grant
    Filed: June 25, 1985
    Date of Patent: December 23, 1986
    Assignee: Ethyl Corporation
    Inventors: Dixie E. Goins, Silas W. Holmes, Edward A. Burt
  • Patent number: 4628127
    Abstract: A process for producing 2,4-di-substituted phenols wherein an olefin is reacted with phenol in the presence of a heterogeneous catalyst comprising an aluminum phenoxide bonded to an acidic solid polymeric resin to preferably form 2,4-di-substituted phenol. A process for preparing a heterogeneous catalyst and a heterogeneous catalyst having the structure(Resin --A--).sub.m Al(--OC.sub.6 R.sub.5).sub.n (11)wherein Resin is a solid polymeric resin having acidic functional groups A, m is 1 or 2, n is 2 or 3 and the R are independently selected from H, alkyl, cycloalkyl, and aralkyl. Preferably, a styrene-divinylbenzene polymeric resin of a macroreticular structure is used for the alkylation process and A is --SO.sub.3 --.
    Type: Grant
    Filed: June 25, 1985
    Date of Patent: December 9, 1986
    Assignee: Ethyl Corporation
    Inventors: Silas W. Holmes, Edward A. Burt, Dixie E. Goins
  • Patent number: 4568778
    Abstract: A process for producing tert-amylphenols is described, comprising reacting isoamylene with phenols in the presence of an inorganic solid acid catalyst or an acidic ion exchange resin catalyst. This process permits efficient production of tert-amylphenols, i.e., 2,4-di-tert-amylphenol and p-tert-amylphenol. These tert-amylphenols are useful as starting materials for preparation of color formers for color photography, additives for resins, oil-soluble dyes, additives for lubricating oils, etc.
    Type: Grant
    Filed: February 7, 1985
    Date of Patent: February 4, 1986
    Assignee: Mitsubishi Petrochemical Co., Ltd.
    Inventors: Makoto Imanari, Hiroshi Iwane, Takahiro Sugawara, Tadashi Ayusawa, Tadamichi Aoki
  • Patent number: 4560809
    Abstract: A process for the production of a 2,6-dialkylphenol in high yield wherein the alkyl groups are secondary or tertiary with a reduced overall production of 4-alkylphenol by-products by the aluminum phenoxide catalyzed pressure reaction of isobutylene with phenol and a mixture of 2,4-dialkylphenol and 2,4,6-trialkylphenol which may be obtained, in a cyclic process, as a bottom stream from the distillation of the reaction mixture to obtain the 2,6-dialkylphenol product.
    Type: Grant
    Filed: October 9, 1984
    Date of Patent: December 24, 1985
    Assignee: Ethyl Corporation
    Inventors: Dixie E. Goins, Harold V. Huggins, Edward A. Burt, Silas W. Holmes
  • Patent number: 4540831
    Abstract: A process is disclosed for performing an exothermic reaction such as the etherification of isobutylene with methanol. The feed is charged to a vertical reaction zone containing a solid catalyst. Heat released by the exothermic reaction partially vaporizes the reactants, with the vapors traveling upward to a condensing zone. All of the condensable vapors entering the condensing zone are condensed and returned downward to the catalyst bed. A single effluent stream made up of the product, excess reactants and any unreactive compounds present in the feed streams is removed from the bottom of the reaction zone. This total reflux reaction zone allows temperature control within a catalyst bed without the use of indirect heat exchangers located within the reaction zone.
    Type: Grant
    Filed: May 17, 1984
    Date of Patent: September 10, 1985
    Assignee: UOP Inc.
    Inventor: Bruce A. Briggs
  • Patent number: 4461916
    Abstract: p-tert-octyl phenol is produced by reaction of phenol with diisobutene in the presence of an acidic ion exchanger and water, in a first stage, in a solid-bed reactor at temperatures of 110.degree.-140.degree. C. and under an excess pressure of up to 5 bar. The resultant dioctyl phenol formed as a by-product is alkylated in a second stage in a further solid-bed reactor with phenol in the presence of an acidic ion exchanger, and water at temperatures of 110.degree.-140.degree. C. and under an excess pressure of up to 5 bar to obtain additional p-tert-octyl phenol.
    Type: Grant
    Filed: December 29, 1982
    Date of Patent: July 24, 1984
    Assignee: Chemische Werke Huels A.G.
    Inventors: Helmut Alfs, Werner Boexkes, Erwin Vangermain
  • Patent number: 4370506
    Abstract: Hydroxyaromatic compounds, especially phenols, are reacted with an alkyl tert.butyl ether in the presence of an acidic catalyst and the as formed light alcoholic fractions are removed by flashing.
    Type: Grant
    Filed: July 24, 1981
    Date of Patent: January 25, 1983
    Assignee: Anic S.p.A.
    Inventors: Francesco Ancillotti, Giuseppe Terzoni, Lidio Micucci, Paolo Maggioni, Pietro Panseri
  • Patent number: 4366331
    Abstract: There is disclosed a process for the production of 2,6-di-tert-alkyl-4-alkenyl phenols wherein the improvement comprises the reaction of a 2,6-di-tert-alkyl phenol with an allyl halide to yield the 2,6-di-tert-alkyl-4-alkenyl phenol through the use of a triphase or polymer bound catalyst.
    Type: Grant
    Filed: December 14, 1981
    Date of Patent: December 28, 1982
    Assignee: The Goodyear Tire & Rubber Company
    Inventor: Dane K. Parker
  • Patent number: 4323713
    Abstract: Hydroquinone is subjected to an alkylation reaction utilizing isobutylene or t-butyl alcohol as the alkylating agent to obtain t-butyl hydroquinone. The alkylation reaction is effected in the presence of an acidic catalyst such as phosphoric acid at temperatures ranging from about 75.degree. to about 200.degree. C. and a pressure in the range of from about atmospheric to about 100 atmospheres. By employing a mixture of a nonpolar hydrocarbon solvent such as xylene and an aliphatic ketone such as 2-heptanone, it is possible to obtain a greater ratio of mono-alkylated product to di-alkylated product.
    Type: Grant
    Filed: November 20, 1980
    Date of Patent: April 6, 1982
    Assignee: UOP Inc.
    Inventor: Dusan J. Engel
  • Patent number: 4316996
    Abstract: Detrimental color change of phenolic antioxidants during production, storage and use in rubbers is inhibited by adding during the synthesis of the phenolic antioxidant a disubstituted hydroxylamine to the catalyst neutralization solution and a substituted oxime together with a disubstituted hydroxylamine to the reaction mixture prior to filtration.
    Type: Grant
    Filed: November 17, 1980
    Date of Patent: February 23, 1982
    Assignee: The Goodyear Tire & Rubber Company
    Inventors: Jacques H. Collonge, Hans Widmer
  • Patent number: 4092367
    Abstract: A process of preparing an alkylated phenol which is substantially monoalkylated and para oriented which comprises reacting phenol with a C.sub.4 -C.sub.9 olefin and wherein said olefin is utilized in about 5-10% stoichiometric excess. The broad reaction temperature utilized is about 60.degree.-105.degree. C and the time of reaction is at least 30 minutes. The catalyst utilized is anhydrous H.sub.3 PO.sub.4 which is used in a value of at least 8% based upon the weight of reactant phenol. The preferred products are p-t-amylphenol and p-t-butylphenol, and in the process of preparing these preferred phenols, the olefin may be reacted in 5-8% stoichiometric excess and the reaction temperature utilized may be 95.degree.-115.degree. C. An additional preferred product is p-nonylphenol derived from a branched propylene trimer.
    Type: Grant
    Filed: September 3, 1976
    Date of Patent: May 30, 1978
    Assignee: Nalco Chemical Co.
    Inventors: Billy W. Bridwell, Carl E. Johnson