EP1805190A1 - Production d'organosilanes en presence de catalyseurs de type iridium et de cocatalyseurs - Google Patents

Production d'organosilanes en presence de catalyseurs de type iridium et de cocatalyseurs

Info

Publication number
EP1805190A1
EP1805190A1 EP05802325A EP05802325A EP1805190A1 EP 1805190 A1 EP1805190 A1 EP 1805190A1 EP 05802325 A EP05802325 A EP 05802325A EP 05802325 A EP05802325 A EP 05802325A EP 1805190 A1 EP1805190 A1 EP 1805190A1
Authority
EP
European Patent Office
Prior art keywords
general formula
cyclohexanedione
iii
cocatalysts
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05802325A
Other languages
German (de)
English (en)
Inventor
Frank Baumann
Marco Hofmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wacker Chemie AG
Original Assignee
Wacker Chemie AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE200410052424 external-priority patent/DE102004052424A1/de
Priority claimed from DE200510030581 external-priority patent/DE102005030581A1/de
Application filed by Wacker Chemie AG filed Critical Wacker Chemie AG
Publication of EP1805190A1 publication Critical patent/EP1805190A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
    • 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
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
    • C07F7/0827—Syntheses with formation of a Si-C bond
    • C07F7/0829—Hydrosilylation reactions
    • 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
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/12—Organo silicon halides
    • C07F7/14—Preparation thereof from optionally substituted halogenated silanes and hydrocarbons hydrosilylation reactions

Definitions

  • the invention relates to a process for the preparation of organosilanes by hydrosilylation of Si-bonded
  • Substituted alkyl silanes are of tremendous commercial interest in a variety of fields. They are used z. As adhesion promoters, as crosslinkers or as precursors for further chemical reactions, such as hydrolysis or nucleophilic substitution reactions.
  • the platinum- or rhodium-catalyzed hydrosilylation of unsaturated, halogen-substituted compounds has been widely studied.
  • the product yields are often very low at 20 to 45%, which is due to significant side reactions.
  • a major side reaction which occurs here is the exchange of a hydrogen atom for a halogen atom on the silicon.
  • Diene ligand iridium catalysts are used in the hydrosilylation of allyl compounds with alkoxy-substituted silanes according to US-A-4,658,050.
  • the invention relates to a process for the preparation of silanes of the general formula I.
  • iridium compounds as catalysts and in the presence of cocatalysts selected from the group of inorganic oxidizing agents selected from the group of oxygen, chlorine, bromine, iodine, peracids, peroxides, bromate,
  • Potassium hexacyanoferrate (III) organometallic oxidants selected from the group of ferricinium, [Ru (bipyridine) 3 ] 3+ and [Fe (phenanthroline) 3 ] 3+ ; and organic oxidants selected from the group of
  • Phosphine oxides Phosphine oxides, sulfones, tritylium salts and tropylium salts,
  • cocatalysts in amounts of 0.5 wt .-% to 5.0 wt .-%, based on the total weight of the used
  • R 4 , R5, R6 is a hydrogen atom, a monovalent optionally substituted by F, Cl, OR, NR2, CN or NCO Ci-Ci8 ⁇ ⁇ ° l enements toff-, chlorine, fluorine or C ] _-C ⁇ 8 ⁇ A lkoxyrest , where in each case 2 radicals of R ⁇ , R ⁇ , R ⁇ together with the carbon atoms to which they are attached can form a cyclic radical, or wherein R 4 and R 1 together may represent a bond between the carbon atoms to which they are attached, and
  • R is a hydrogen atom or a monovalent C ⁇ -C] _8-
  • X is a halogen atom, such as chlorine, bromine or iodine, or a
  • R ⁇ -, R ⁇ , R3 are preferably alkyl, alkenyl, cycloalkyl or aryl radicals.
  • R 1, R 2, R 3 have at most 10, in particular at most 6
  • R - * -, R ⁇ , R3 are straight-chain or branched Ci-Cg-alkyl radicals or Ci-Cg-alkoxy radicals.
  • halogen substituents are fluorine and chlorine.
  • Particularly preferred as R ⁇ , R ⁇ , R3 are the radicals methyl, ethyl, methoxy, ethoxy, chlorine, phenyl and vinyl.
  • silanes of the formula II are chlorosilanes, dimethylchlorosilane being particularly preferred.
  • Hydrocarbon radicals R 4 , R ⁇ , R ⁇ are preferably alkyl, alkenyl, cycloalkyl or aryl radicals.
  • at most one of the hydrocarbon radicals R 4 , R ⁇ , R ⁇ is an alkoxy radical.
  • R 1, R 2 have at most 10, in particular at most 6, carbon atoms.
  • R5, R6 are straight-chain or branched C ⁇ -Cg-alkyl radicals, chlorine-substituted C] _Cg-alkyl radicals or Ci-Cg-alkoxy radicals.
  • R ⁇ , R ⁇ are the radicals hydrogen, methyl, ethyl, chlorine, phenyl and chloromethyl.
  • hydrocarbon radical R 4 has at most 6, in particular at most 2 carbon atoms.
  • Particularly preferred as R 4 are the radicals hydrogen, methyl, ethyl.
  • hydrocarbon radical R has at most ⁇ , in particular at most 2 carbon atoms.
  • alkene of formula III is allyl chloride.
  • an alkene instead of an alkene, an alkyne can be used, which is not preferred.
  • Formula (I) in which the two radicals R 4 and R ⁇ then together also represent a bond between the two carbon atoms to which they are attached.
  • the dienes Preferably, the dienes have 6 to 12 carbon atoms. Preference is given to mono- or bicyclic dienes. preferred
  • dienes examples include butadiene, 1, 3-hexadiene, 1, 4-hexadiene, 1,5-hexadiene, isoprene, 1, 3-cyclohexadiene, 1,3-cyclooctadiene, 1, 4-cyclooctadiene, 1, 5-cyclooctadiene and norbornadiene.
  • the catalyst of the general formula IV used is [(cycloocta-1c, 5c-diene) IrCl] 2.
  • aldehydes as cocatalysts are benzaldehyde,
  • Acetaldehyde and cinnamaldehyde are 1, 5-diphenyl
  • Triphenylphosphine oxide and trimethylphosphine oxide Triphenylphosphine oxide and trimethylphosphine oxide.
  • sulfones as cocatalysts are dimethylsulfone and diphenylsulfone.
  • Preferred cocatalysts are organic oxidizing agents such as aldehydes, acetone, methyl isobutyl ketone, acetylacetone, 1,4-cyclohexanedione, 1,3-cyclohexanedione, 1,2-cyclohexanedione, 1,9-cyclohexanedicarband, benzil, naphthoquinone and organic peroxides and inorganic peroxides.
  • organic oxidizing agents such as aldehydes, acetone, methyl isobutyl ketone, acetylacetone, 1,4-cyclohexanedione, 1,3-cyclohexanedione, 1,2-cyclohexanedione, 1,9-cyclohexanedicarband, benzil, naphthoquinone and organic peroxides and inorganic peroxides.
  • the alkene of the general formula III is preferably in excess of 0.01 to 100 mol%, particularly preferably 0.1 to 25 mol%, based on the silane component of the general formula II implemented.
  • the iridium compound used as the catalyst is preferably calculated in amounts of 3 to 10,000 ppm by weight, preferably 20 to 1000 ppm by weight, particularly preferably 50 to 500 ppm by weight, in each case as elemental iridium and based on the total weight of the present in the reaction mixture components of the formula II and III used.
  • the oxidative cocatalyst is preferably used in amounts of from 0.5 to 2.5% by weight, preferably 1.0 to 2.0% by weight, based in each case on the total weight of the components of the formulas II and III present in the reaction mixture, used.
  • the process according to the invention can be carried out in the presence or in the absence of aprotic solvents. If aprotic solvents are used, preference is given to solvents or solvent mixtures having a boiling point or boiling range of up to 120 ° C. at 0.1 MPa.
  • solvents examples include chlorinated hydrocarbons, such as dichloromethane, trichloromethane, carbon tetrachloride, 1, 2-dichloroethane, trichlorethylene; Hydrocarbons, such as pentane, n-hexane, hexane isomer mixtures, heptane, octane, benzine, petroleum ether, benzene, toluene, xylenes; Esters such as ethyl acetate, butyl acetate, propyl propionate, ethyl butyrate, ethyl isobutyrate; Carbon disulfide and nitrobenzene, or mixtures of these solvents.
  • chlorinated hydrocarbons such as dichloromethane, trichloromethane, carbon tetrachloride, 1, 2-dichloroethane, trichlorethylene
  • Hydrocarbons such as pentane, n-hexane
  • aprotic solvent used in the process according to the invention also the target product of the general formula I, ie the reacted reaction mixture can also serve as a solvent.
  • the advantage here is that no further substances are entered into the reaction system.
  • reaction component of the general formula III are presented together with iridium catalyst of the general formula IV and optionally the oxidative cocatalyst and the reaction component of the general formula
  • the inventive method is preferably performed at a temperature from 0 to 200 0 C, preferably at 20 to 100 0 C, particularly preferably 25 to 4O 0 C is performed.
  • the process according to the invention can be carried out at the pressure of the surrounding atmosphere, ie at about 0.10 MPa, or else at higher or lower pressures. If the process according to the invention is carried out at higher pressures, a pressure of from 2 to 20 bar, more preferably from 6 to 12 bar, is preferably used.
  • the process according to the invention can be carried out batchwise, semicontinuously or fully continuously or as a reactive distillation.
  • a preferred embodiment is a continuous process for the preparation of silanes of the general formula I.
  • cocatalysts in amounts of from 0.5% by weight to 5.0% by weight, based on the total weight of the components of the general formula (II) and (III) used,
  • reaction temperature is 0 0 C to 4O 0 C, preferably 20 0 C to 40 ° C, and the temperature of the reaction mixture at these temperatures, is held.
  • a preferred method is the start of the reaction at 35 0 C to 40 0 C and the lowering of the reaction temperature to 2O 0 C to 30 ° C after the exothermic start of the hydrosilylation reaction.
  • the continuous process is preferably carried out at the pressure of the surrounding atmosphere, that is about 0.10 MPa, but it can also be carried out at higher or lower pressures.
  • the reaction pressure may therefore preferably be 0.10 to 50 MPa, preferably 0.10 to 2.0 MPa.
  • the continuous process gives the silane of the general formula (I) in high yields and excellent purity.
  • the target products of general formula (I) are obtained when using very small amounts of catalyst in yields of preferably 90% to 99%, based on the silane used, preferably chlorosilane, of the formula (II).
  • the excess of allyl chloride may preferably be significantly reduced.
  • the formation of the corresponding silane by-products by hydrogen-chlorine exchange can be significantly reduced.
  • the process is easy to control and perform safely.
  • all conventional reactors for continuous reaction z. B. tube and loop reactors and continuously operated stirred reactors or combinations of these reactor types, such as loop-tube reactor, tube-loop tube reactor, tubular stirred tank reactor, continuous stirred cell reactor, continuous reactive distillation in vacuo at low temperatures etc., wherein the tube reactors may have static and / or dynamic stirring units.
  • microreactors with channel sizes from 1 micron to several millimeters.
  • the various reactors must have a suitable cooling device to withstand the heat generated during the exothermic reaction dissipate quantitatively and thus keep the reactor or reaction temperature less than 4O 0 C.
  • Suitable cooling units are, for example, internal cooling coils, tube or plate heat exchangers in the loop circuit, etc.
  • a reactant or all starting materials in the continuous process can be precooled by suitable heat exchangers, preferably at temperatures from -20 0 C to 30 0 C, preferably 0 0 C to 15 0 C.
  • suitable heat exchangers again plate or tube heat exchangers, etc., and micro heat exchanger with a channel cross-section of 1 micron to 10 millimeters.
  • the iridium catalyst is not in an environment of excess silane of formula (II) over the alkene of formula (III), as the iridium catalyst may otherwise exhibit deactivation.
  • Another possibility is an optionally tempered premix of all components in a continuous active or static mixing unit, such as static mixer, Pentax or planetary mixer or micromixing with subsequent transfer of this reaction mixture in a downstream reaction path, which in turn is designed to be continuous, z. B. as tubular reactor, loop reactor, etc.
  • the temperature is preferably lowered from initially 35 0 C continuously up to 3O 0 C.
  • the target product of the formula (I) or an aprotic solvent is introduced together with the iridium catalyst and the cocatalyst at 35 ° C.
  • reaction mixture is cooled to 25 0 C.
  • the silane of the general formula (I) formed after the reaction is continuously discharged from the reactor.
  • the average residence times of the reactor contents are preferably 0.5 to 60 minutes and are dependent on the particular reaction temperature.
  • MIBK methyl isobuthyl ketone

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de production de silanes de formule générale (I) : R6R5CH-R4CH-SiR1R2R3. Ce procédé consiste à faire réagir un silane de formule générale (II) : HSiR1R2R3 avec des alcènes ou des alcynes de formule générale (III) : R6R5C=CHR4 en présence de composés iridium en tant que catalyseurs, et en présence de cocatalyseurs selon la première revendication, la quantité de cocatalyseurs étant comprise entre 0,5 % en poids et 5,0 % en poids par rapport au poids total des composants employés. Selon l'invention, R1, R2, R3, R4, R5, R6 et R sont tels que définis dans la première revendication.
EP05802325A 2004-10-28 2005-10-20 Production d'organosilanes en presence de catalyseurs de type iridium et de cocatalyseurs Withdrawn EP1805190A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE200410052424 DE102004052424A1 (de) 2004-10-28 2004-10-28 Herstellung von Organosilanen in Gegenwart von Iridium-Katalysatoren und Cokatalysatoren
DE200510030581 DE102005030581A1 (de) 2005-06-30 2005-06-30 Kontinuierliche Herstellung von Organosilanen in Gegenwart von Iridium-Katalysatoren und Cokatalysatoren
PCT/EP2005/011300 WO2006045533A1 (fr) 2004-10-28 2005-10-20 Production d'organosilanes en presence de catalyseurs de type iridium et de cocatalyseurs

Publications (1)

Publication Number Publication Date
EP1805190A1 true EP1805190A1 (fr) 2007-07-11

Family

ID=35517185

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05802325A Withdrawn EP1805190A1 (fr) 2004-10-28 2005-10-20 Production d'organosilanes en presence de catalyseurs de type iridium et de cocatalyseurs

Country Status (3)

Country Link
US (1) US20090036702A1 (fr)
EP (1) EP1805190A1 (fr)
WO (1) WO2006045533A1 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007023762A1 (de) * 2006-08-10 2008-02-14 Evonik Degussa Gmbh Anlage und Verfahren zur kontinuierlichen industriellen Herstellung von 3-Glycidyloxypropylalkoxysilanen
DE102007023759A1 (de) * 2006-08-10 2008-02-14 Evonik Degussa Gmbh Anlage und Verfahren zur kontinuierlichen industriellen Herstellung von Fluoralkylchlorsilan
DE102007023760A1 (de) * 2006-08-10 2008-02-14 Evonik Degussa Gmbh Anlage, Reaktor und Verfahren zur kontinuierlichen industriellen Herstellung von 3-Methacryloxypropylalkoxysilanen
DE102007023764A1 (de) * 2006-08-10 2008-02-14 Evonik Degussa Gmbh Anlage und Vorrichtung zur kontinuierlichen industriellen Herstellung von 3-Chlorpropylchlorsilanen
DE102007023763A1 (de) * 2006-08-10 2008-02-14 Evonik Degussa Gmbh Anlage, Reaktor und Verfahren zur kontinuierlichen industriellen Herstellung von Polyetheralkylalkoxysilanen
DE102007023757A1 (de) * 2006-08-10 2008-02-14 Evonik Degussa Gmbh Anlage und Verfahen zur kontinuierlichen industriellen Herstellung von Organosilanen
DE102007023756A1 (de) * 2006-08-10 2008-02-14 Evonik Degussa Gmbh Anlage und Verfahren zur kontinuierlichen industriellen Herstellung von Alkylalkoxysilanen
DE102007011158A1 (de) 2007-03-07 2008-09-11 Wacker Chemie Ag Iridiumkatalysiertes Herstellungsverfahren für siliciumorganische Verbindungen
EP2262817B1 (fr) * 2008-03-06 2012-07-25 Dow Corning Corporation Procédé de préparation d'haloalkylalcoxysilanes et d'haloalkylhalosilanes
US9556208B2 (en) * 2012-10-12 2017-01-31 Momentive Performance Materials Inc. Hydrosilylation synthesis of haloalkylorganosilanes using peroxide promoters
CN110252411B (zh) * 2019-06-26 2022-02-08 江西蓝星星火有机硅有限公司 一种端环氧硅油生产用络合型铂催化剂及其制备方法和用途
JP2021178786A (ja) * 2020-05-13 2021-11-18 信越化学工業株式会社 ジメチルクロロシラン化合物の製造方法

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US4658050A (en) * 1986-03-31 1987-04-14 Union Carbide Corporation Novel process for the preparation of halopropyltrialkoxysilanes and halopropylalkylalkoxysilanes
JP3856081B2 (ja) * 2000-05-15 2006-12-13 信越化学工業株式会社 ハロプロピルジメチルクロロシラン化合物の製造方法
DE10053037C1 (de) * 2000-10-26 2002-01-17 Consortium Elektrochem Ind Herstellung von Organosilanen
DE10232663C1 (de) * 2002-07-18 2003-10-16 Wacker Chemie Gmbh Kontinuierliche Herstellung von Organosilanen

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Also Published As

Publication number Publication date
US20090036702A1 (en) 2009-02-05
WO2006045533A1 (fr) 2006-05-04

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