US3730857A - Production of alkoxides - Google Patents

Production of alkoxides Download PDF

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Publication number
US3730857A
US3730857A US00137613A US3730857DA US3730857A US 3730857 A US3730857 A US 3730857A US 00137613 A US00137613 A US 00137613A US 3730857D A US3730857D A US 3730857DA US 3730857 A US3730857 A US 3730857A
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percent
liquid medium
alkoxides
process according
solution
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US00137613A
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English (en)
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T Tripp
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Monsanto Chemicals Ltd
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Monsanto Chemicals Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/04—Esters of silicic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds

Definitions

  • ammonium and quaternary ammonium salts can function as supporting electrolytes in such a process, and that when these salts are used, the process can be applied to the production of alkoxides of other elements in addition to silicon alkoxides.
  • the process of the present invention is one for the production of an alkoxide of an element in Group IV or Va of the Periodic Table according to Mendeleeff, and which has an atomic number of from 14 to 82, or of a transition element in the fourth period, and in Group Ib, IIb, III a, VIa, VIIa or VIII of the Periodic Table ac- -cording 'to Mendeleeff, which comprises passing an electric current through a substantially anhydrous liquid medium comprising a solution, in a monohydric alkanol having from one to four carbon atoms per molecule, of an ammonium or a quarternary ammonium salt that is ionized to a sufficient extent and is present in sufficient amount to function as a supporting electrolyte, using an anode comprising the element in contact with the liquid medium.
  • the process of the invention is particularly useful for the preparation of alkoxides, for example the methoxides, ethoxides and isopropoxides, of silicon, germanium, zirconium, titanium, chromium, iron, zinc and tantalum.
  • the alkoxides of such elements have a variety of uses.
  • silicon alkoxides (alkyl silicates) are useful as binders in the production of refractory articles such as moulds for metal casting.
  • the alkoxides of zirconium, titanium and tantalum can be used as binders in the production of moulds for casting metals having melting points higher than silica, or for metals which react with silica at their casting temperatures.
  • Titanium and zirconium alkoxides are useful as gelling, curing and drying agents for naturaland epoxy resins, and as components of heabresistant paints, water-repellant compositions, and anti-fouling compositions.
  • Alkoxides of titanium, zirconium, chromium and iron are useful in the production of catalyst compositions containing these metals. Hitherto known methods of making these alkoxides have often involved several stages of synthesis, but by the present process they are produced directly from the element.
  • the monohydric alkanol employed in the process can be for example methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol or a mixture of these alkanols.
  • Alkanols containing from one to three carbon atoms per molecule are preferred, and particularly good results are obtained with ethanol.
  • ammonium and quarternary ammonium salts useful in the process include ammonium chloride, ammonium nitrate, quaternary ammonium salts of the formula where R R R and R are each alkyl, aryl, cycloalkyl or aralkyl, or R and R or R,, R and R together with the nitrogen atom represent a heterocyclic ring, and X is chloride, bromide, iodide or half a sulphate, such as tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, dimethylpiperidinium bromide, methylpyridinium chloride, ethylpyridinium chloride, trimethylphenylammonium chloride, tetramethylammonium sulphate, benzyltrimethylammonium iodide.
  • Tetramethylammonium chloride is the preferred quaternary ammonium salt.
  • the ammonium salt or the quaternary ammonium salt must be anhydrous and must have sufficient solubility and ionization in the liquid medium to produce a solution which has sufficient conductivity to act as a current carrier.
  • the amount of such a salt which needs to be dissolved in the liquid medium to give a practical conductivity obviously depends on a number of factors. However, a practical lower limit for the specific conductivity of the liquid is about 2.4 X 10 ohm". At lower conductivities the process is unduly prolonged.
  • the liquid medium has a specific conductivity of at least 3.0 X 10"", for example a conductivity within the range 10' to 10 ohm cm such as for instance from 3 X 10" to 5 X 10" ohm" cm.
  • the anode employed may consist of the substantially pure element but the presence of small amounts of'impurity is not deleterious to the process, and alloys are sometimes preferred for economic reasons. Also, in some instances, the conductivity of the pure element is impractically low. Thus in general, the resistivity of the anode material should not exceed 10 ohm-cm.
  • ferrosilicons In the case of silicon, a compound or alloy of silicon rather than a semiconductor grade of the element is preferably used. Ferrosilicons have been found to be especially suitable.
  • the silicon content of the ferrosilicon can, for example, be within the range 60 to 99 percent or to 77 percent by weight, and in typical instances may be within the ranges 70 80 percent, 90 95 percent or 97 99 percent by weight.
  • titanium, zirconium, germanium and tantalum pieces of scrap metal or compressed scrap metal with or without undergoing a preliminary cleaning procedure, can be used.
  • any inert conductive material can serve as the cathode.
  • Graphite is a useful cathodic material having a considerable advantage in terms of cost over other functionally suitable materials such as platinum or silver.
  • the electric current used in the process of the invention can be a simple direct current or rectified A.C. with or without smoothing.
  • the current density at the anode may typically be within the range of from 7 to 200 milliamps per square centimeter, although operation at current densities over a wider range than this is possible.
  • the voltage applied in excess of the decomposition voltage of the system should be kept as low as possible. In practice, the operating voltage is determined by factors such as cell design and electrolyte concentration, and wide variations are possible.
  • the temperature at which the electrolysis is conducted is not critical.
  • the generally most convenient manner of operating is to provide the electrolysis cell with a reflux condenser and to carry out the process at the boiling point of the liquid medium. Often the resistive heating by the current is sufficient to maintain the liquid medium at its boiling point.
  • the process can be conducted at lower temperatures, however, for example from 10 C. up to the boiling point of the liquid medium, but it is then generally necessary to provide cooling means.
  • the liquid medium may contain an inert organic liquid miscible with the liquid medium, e.g., a ketone, an ether or an ester as a liquid diluent.
  • an inert organic liquid miscible with the liquid medium e.g., a ketone, an ether or an ester as a liquid diluent.
  • the liquid medium can contain inert solvents up to percent based on the weight of the liquid medium, i.e., acetone.
  • solvents include ketones, higher alcohols ethers and esters, for example 2-ethylhexanol, hexanol or pentanol, glycols such as ethylene glycol or propylene glycol, or glycol ethers, such as ethylene glycol monoethyl ether or diethylene glycol monoethyl ether.
  • Alkoxides containing these solvents are preferably prepared by gradual addition of the solvent to the medium from which the alcohol containing one to three carbon atoms per molecule is being evaporated.
  • Alkoxides such as zirconium ethoxide which are solid at room temperature can be purified by recrystallization from anhydrous solvents or by distillation.
  • the invention is illustrated by the following examples.
  • the ethanol used in the examples was dried over molecular sieves.
  • the yields quoted in the following examples are calculated from the weight of oxide obtained when a sample of known volume is taken from the solution obtained after the electrolysis and hydrolyzed and the precipitate is filtered off and ignited.
  • a hot saturated solution of ammonium chloride in anhydrous ethanol was electrolyzed under an atmosphere of nitrogen in a flask fitted with a graphite cathode, a germanium anode and a reflux condenser.
  • a direct current of 2 amps was passed through the cell which maintained the electrolyte at its boiling point by resistive heating. Towards the end of the run the current had fallen to 0.7 amps.
  • the applied voltage was 40-60 volts and a total of 32 amp. hours was supplied to the cell during the run.
  • the resultant solution was found to contain 61 g. of germanium ethoxide which represents a current efficiency of 78 percent.
  • a hot saturated solution of ammonium chloride in anhydrous ethanol was electrolyzed under an atmosphere of nitrogen in a flask fitted with a graphite cathode, a tantalum anode and a reflux condenser.
  • a direct current of between 0.4 and 0.25 amps was maintained throughout the run after reversing the polarity of the electrodes for 20 minutes.
  • the applied voltage was 50 volts and a total of 6 amp. hours was supplied to the cell during the run.
  • the resultant solution was found to contain 17.6 g. of tantalum ethoxide which represents a current efficiency of 97 percent. Evaporation of the ethanol from an aliquot of this solution and distillation of the residue at 1 mm. Hg. gave tantalum ethoxide.
  • the alkoxide had a Ta,O content of 54 percent by weight compared with the theoretical content of 55 EXAMPLE 3
  • a hot saturated solution of ammonium chloride in anhydrous ethanol was electrolyzed under an atmosphere of nitrogen in a flask fitted with a graphite cathode, a titanium anode and a reflux condenser.
  • a direct current of 2 amps at 55-65 volts was passed which fell after 2 hours to 0.15 amps at 80 volts.
  • the electrolyte contained titanium ethoxide and gave a soft gel when mixed with water.
  • a hot saturated solution of ammonium chloride in anhydrous ethanol was electrolyzed under an atmosphere of nitrogen in a flask fitted with a graphite cathode, a zirconium anode and a reflux condenser.
  • a direct current of 0.5 amps was passed which slowly fell to 0.3 amps.
  • the electrolysis was continued until the ZrO content of the electrolyte rose to about 10 percent by weight.
  • the resultant solution was found to contain 12.9 g. of zirconium ethoxide which represents a current efficiency of 82 percent.
  • Evaporation of the ethanol from an aliquot of the solution and distillation of the residue gave zirconium ethoxide b.p. 150-200 C./1 mm. Hg. as a waxy solid which had a ZrO content of 45.3 percent compared with the theoretic value 45.4 percent.
  • EXAMPLE 5 The ethanol was evaporated from an aliquot of the solution and distillation under reduced pressure gave silicon ethoxide b.p. 60-80/25 mm. of Hg. having a SiO content of 25 percent by weight compared with the theoretical value for Si(OEt) of 28.8 percent.
  • This material had a TiO content of 33.3 percent compared with the theoretical value of 35.1 percent.
  • the current efficiency of the process was 91 percent based on the TiO content of the crude reaction product at theend of the run and was 109 percent based on the loss in weight of the anode.
  • EXAMPLE 7 The preparation of silicon ethoxide.
  • liquid medium is a solution having a specific conductivity of at least 3.0 X 10" ohm cm at the operating temperature.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
US00137613A 1970-05-05 1971-04-26 Production of alkoxides Expired - Lifetime US3730857A (en)

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GB2164470 1970-05-05

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DE (1) DE2121732B2 (enrdf_load_stackoverflow)
FR (1) FR2091229A6 (enrdf_load_stackoverflow)
GB (1) GB1307581A (enrdf_load_stackoverflow)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3964983A (en) * 1972-10-05 1976-06-22 Studiengesellschaft Kohle M.B.H. Process for the electrochemical synthesis of organic metal compounds
US4104140A (en) * 1972-10-05 1978-08-01 Studiengesellschaft Kohle Mbh Process for the electrochemical synthesis of organic metal compounds
US4217184A (en) * 1979-03-26 1980-08-12 Stauffer Chemical Company Continuous process for preparing metal alkoxides
US4250000A (en) * 1979-03-26 1981-02-10 Stauffer Chemical Company Electrochemical process for metal alkoxides
US4337125A (en) * 1980-12-08 1982-06-29 Stauffer Chemical Company Electrochemical synthesis of organophosphorus compounds from the element
US4338166A (en) * 1980-12-08 1982-07-06 Stauffer Chemical Company Electrochemical synthesis of organophosphorus compounds
US5711783A (en) * 1994-02-15 1998-01-27 H.C. Starck, Gmbh & Co., Kg Preparation from metal alkoxides of high purity metal powder
US20050177008A1 (en) * 2003-12-11 2005-08-11 Shekar Balagopal Electrolytic method to make alkali alcoholates using ceramic ion conducting solid membranes
US20060226022A1 (en) * 2003-12-11 2006-10-12 Ceramatec, Inc. Electrolytic method to make alkali alcoholates using ceramic ion conducting solid membranes
US20070138020A1 (en) * 2005-12-20 2007-06-21 Shekar Balagopal Electrolytic process to produce sodium hypochlorite using sodium ion conductive ceramic membranes
US20070158205A1 (en) * 2006-01-11 2007-07-12 Shekar Balagopal Synthesis of Biodiesel Using Alkali Ion Conductive Ceramic Membranes
US20080142373A1 (en) * 2003-12-11 2008-06-19 Joshi Ashok V Electrolytic method to make alkali alcoholates using ion conducting alkali electrolyte/seperator
US20080173551A1 (en) * 2003-12-11 2008-07-24 Joshi Ashok V Electrolytic Method to Make Alkali Alcoholates
US20080173540A1 (en) * 2003-12-11 2008-07-24 Joshi Ashok V Electrolytic Cell for Producing Alkali Alcoholates
US20080245671A1 (en) * 2007-04-03 2008-10-09 Shekar Balagopal Electrochemical Process to Recycle Aqueous Alkali Chemicals Using Ceramic Ion Conducting Solid Membranes
RU2371428C2 (ru) * 2007-11-30 2009-10-27 Федеральное государственное унитарное предприятие "Государственный научно-исследовательский институт органической химии и технологии" (ФГУП "ГосНИИОХТ" Способ получения метилата ниобия

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4439041C2 (de) * 1994-11-02 1998-08-13 Starck H C Gmbh Co Kg Verfahren zum Aufschluß und Rückgewinnung der metallischen Bestandteile aus rheniumhaltigen Superlegierungen

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3394059A (en) * 1964-06-19 1968-07-23 Union Oil Co Electrolytic preparation of olefin oxides
GB1136016A (en) * 1966-04-21 1968-12-11 Monsanto Chemicals Production of sols
US3511762A (en) * 1967-11-02 1970-05-12 Phillips Petroleum Co Electrochemical conversion

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3394059A (en) * 1964-06-19 1968-07-23 Union Oil Co Electrolytic preparation of olefin oxides
GB1136016A (en) * 1966-04-21 1968-12-11 Monsanto Chemicals Production of sols
US3511762A (en) * 1967-11-02 1970-05-12 Phillips Petroleum Co Electrochemical conversion

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3964983A (en) * 1972-10-05 1976-06-22 Studiengesellschaft Kohle M.B.H. Process for the electrochemical synthesis of organic metal compounds
US4104140A (en) * 1972-10-05 1978-08-01 Studiengesellschaft Kohle Mbh Process for the electrochemical synthesis of organic metal compounds
US4217184A (en) * 1979-03-26 1980-08-12 Stauffer Chemical Company Continuous process for preparing metal alkoxides
US4250000A (en) * 1979-03-26 1981-02-10 Stauffer Chemical Company Electrochemical process for metal alkoxides
US4337125A (en) * 1980-12-08 1982-06-29 Stauffer Chemical Company Electrochemical synthesis of organophosphorus compounds from the element
US4338166A (en) * 1980-12-08 1982-07-06 Stauffer Chemical Company Electrochemical synthesis of organophosphorus compounds
US5711783A (en) * 1994-02-15 1998-01-27 H.C. Starck, Gmbh & Co., Kg Preparation from metal alkoxides of high purity metal powder
US20060169594A1 (en) * 2003-12-11 2006-08-03 Shekar Balagopal Electrolytic method to make alkali alcoholates using ceramic ion conducting solid membranes
US7918986B2 (en) 2003-12-11 2011-04-05 Ceramatec, Inc. Electrolytic method to make alkali alcoholates using ceramic ion conducting solid membranes
US20060226022A1 (en) * 2003-12-11 2006-10-12 Ceramatec, Inc. Electrolytic method to make alkali alcoholates using ceramic ion conducting solid membranes
US20050177008A1 (en) * 2003-12-11 2005-08-11 Shekar Balagopal Electrolytic method to make alkali alcoholates using ceramic ion conducting solid membranes
US8506790B2 (en) 2003-12-11 2013-08-13 Shekar Balagopal Electrolytic cell for making alkali alcoholates using ceramic ion conducting solid membranes
US20080142373A1 (en) * 2003-12-11 2008-06-19 Joshi Ashok V Electrolytic method to make alkali alcoholates using ion conducting alkali electrolyte/seperator
US20080173551A1 (en) * 2003-12-11 2008-07-24 Joshi Ashok V Electrolytic Method to Make Alkali Alcoholates
US20080173540A1 (en) * 2003-12-11 2008-07-24 Joshi Ashok V Electrolytic Cell for Producing Alkali Alcoholates
US8075758B2 (en) 2003-12-11 2011-12-13 Ceramatec, Inc. Electrolytic method to make alkali alcoholates using ion conducting alkali electrolyte/separator
US7959784B2 (en) 2003-12-11 2011-06-14 Ceramatec, Inc. Electrolytic method to make alkali alcoholates using ceramic ion conducting solid membranes
US7824536B2 (en) 2003-12-11 2010-11-02 Ceramatec, Inc. Electrolytic method to make alkali alcoholates using ceramic ion conducting solid membranes
US20070138020A1 (en) * 2005-12-20 2007-06-21 Shekar Balagopal Electrolytic process to produce sodium hypochlorite using sodium ion conductive ceramic membranes
US8268159B2 (en) 2005-12-20 2012-09-18 Ceramatec, Inc. Electrolytic process to produce sodium hypochlorite using sodium ion conductive ceramic membranes
US20070158205A1 (en) * 2006-01-11 2007-07-12 Shekar Balagopal Synthesis of Biodiesel Using Alkali Ion Conductive Ceramic Membranes
US20080245671A1 (en) * 2007-04-03 2008-10-09 Shekar Balagopal Electrochemical Process to Recycle Aqueous Alkali Chemicals Using Ceramic Ion Conducting Solid Membranes
RU2371428C2 (ru) * 2007-11-30 2009-10-27 Федеральное государственное унитарное предприятие "Государственный научно-исследовательский институт органической химии и технологии" (ФГУП "ГосНИИОХТ" Способ получения метилата ниобия

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DE2121732B2 (de) 1976-05-13
DE2121732A1 (de) 1972-03-02
GB1307581A (en) 1973-02-21
FR2091229A6 (enrdf_load_stackoverflow) 1972-01-14

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