EP2147007A1 - Précurseur stable de catalyseurs à base de complexes de rh - Google Patents

Précurseur stable de catalyseurs à base de complexes de rh

Info

Publication number
EP2147007A1
EP2147007A1 EP08717985A EP08717985A EP2147007A1 EP 2147007 A1 EP2147007 A1 EP 2147007A1 EP 08717985 A EP08717985 A EP 08717985A EP 08717985 A EP08717985 A EP 08717985A EP 2147007 A1 EP2147007 A1 EP 2147007A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
hydroformylation
catalyst precursor
alkyl
ligands
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Withdrawn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
EP08717985A
Other languages
German (de)
English (en)
Inventor
Detlef Selent
Dr. Armin BÖRNER
Klaus-Diether Wiese
Dieter Hess
Dirk Fridag
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.)
Evonik Operations GmbH
Original Assignee
Evonik Oxeno GmbH and Co KG
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
Application filed by Evonik Oxeno GmbH and Co KG filed Critical Evonik Oxeno GmbH and Co KG
Publication of EP2147007A1 publication Critical patent/EP2147007A1/fr
Withdrawn legal-status Critical Current

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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
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0073—Rhodium compounds

Definitions

  • the present invention relates to the preparation and use of catalyst precursors of rhodium complex catalysts.
  • the active catalyst is not brought into the process in pure form for cost reasons and / or because of its difficult handling, but is produced in the hydroformylation reactor under the reaction conditions of hydroformylation from one or more suitable precursors.
  • the suitability of a potential catalyst precursor depends on various factors. These factors include: commercial availability and price, storage stability, suitability for transport and entry into the reactor, compatibility with cocatalysts, solubility in the desired reaction medium, rapid catalyst formation or fast reaction start with minimal induction period, and absence of negative effects of catalyst formation By-products on the production plant or the yield of the reaction.
  • Phosphite compounds as cocatalysts too. Phosphites are generally prone to reactions with proton-active compounds. In the context of the hydroformylation reaction, the compounds used as cocatalysts are also referred to as ligands.
  • precursor salts representing organic Brönsted acids are often present in the wrong oxidation state of rhodium so that rhodium must first be reduced during preformation.
  • rhodium harmful compounds may already arise for the cocatalyst.
  • catalyst precursors which do not contain anions which react with Hydrogen or may result in the catalyst formation generally harmful protic acids.
  • the precursors for rhodium complex catalysts are very stable and therefore easy to handle if they have the structure I.
  • These compounds are very suitable catalyst precursors because they do not form protic acids or other undesired by-products in the catalyst formation, have good solubilities and the ligands in compounds of structure I are easily displaced by ligands of the desired catalyst system.
  • the present invention therefore relates to a catalyst precursor comprising a rhodium complex according to the formula I.
  • R 1 to R 6 H, C 1 to C 4 alkyl or C 1 to C 4 alkoxy radical or
  • R 1, R 2, R 4 and R 6 H, C r to C 4 -alkyl or C 1 to C 4 -alkoxy radical and
  • a mixture comprising a catalyst precursor according to the invention and at least one organophosphorus ligand,
  • the present invention is the use of a catalyst precursor according to the invention for the preparation of a catalyst for the hydrocyanation, the hydroacylation, the hydroamidation, the hydrocarboxyalkylation, the aminolysis, the alcoholysis, the carbonylation, the isomerization or for a hydrogen transfer process and a method for the hydroformylation of olefins, which is characterized in that a catalyst is used which is obtained from a catalyst precursor according to the invention.
  • the catalyst precursors according to the invention have the advantage that they are very storage-stable.
  • the catalyst precursors have a relatively high stability to thermal stress, oxidation or hydrolysis.
  • the catalyst precursors according to the invention are outstandingly suitable for being kept ready as a catalyst precursor for processes in which metal-organophosphorus ligands should or must be used.
  • the corresponding metal-organophosphorus ligand complex catalysts can be very easily generated from the catalyst precursors according to the invention by addition of the desired ligands and synthesis gas.
  • a particular advantage results from the fact that no harmful protic acids are formed from the catalyst precursors according to structure I in the catalyst formation under synthesis gas, but instead the rhodium
  • R1, R2, R4 and R6 H alkyl-, C r to C 4 -alkyl or d- to C 4 alkoxy radical and
  • all radicals R 1 to R 6 are a C 1 to C 4 alkyl radical. It may be advantageous if at least one of the radicals R 1 to R 6 is a tert-butyl radical. Most preferably, all radicals R 1 to R 6 are a tert-butyl radical.
  • the catalyst precursor according to the invention is very particularly preferably a complex according to formula II
  • the preparation of the catalyst precursor of the general formula I is carried out by known per se reaction of a cyclooctadiene-rhodium complex, preferably allyl (cyclooctadiene-1, 5) rhodium, with a phosphite of the general formula IM.
  • the catalyst precursors according to the invention can be used as pure substances or as a mixture.
  • the mixtures according to the invention which comprise the catalyst precursors according to the invention may, in particular, comprise one or more solvents in addition to the catalyst precursor.
  • solvents may be solvents that are inert with respect to the reaction for which the catalyst precursor is to be used after conversion to the catalyst. Is used in the reactions as a solvent of one of the reactants, so It may be advantageous to provide one of these starting materials used as solvent in the reaction as a solvent in the mixture according to the invention.
  • the catalyst precursor be used, for example, to form the catalyst for a hydroformylation reaction, it may be advantageous to use the olefin used in the hydroformylation, such as.
  • the mixtures according to the invention may comprise further ligands, in particular organophosphorus ligands.
  • the catalyst precursor of the present invention can be used as a precursor for the preparation of a catalyst for hydrocyanation, hydroacylation, hydroamidation, hydrocarboxyalkylation, aminolysis, alcoholysis, carbonylation, isomerization, or a hydrogen transfer process.
  • a catalyst for hydrocyanation, hydroacylation, hydroamidation, hydrocarboxyalkylation, aminolysis, alcoholysis, carbonylation, isomerization, or a hydrogen transfer process To prepare the actual catalyst, it has proven expedient to react the catalyst precursor under reaction conditions in the presence of the ligand provided for the metal complex catalyst, with complete or at least partial ligand exchange taking place.
  • olefins having 2 to 25 carbon atoms, particularly preferably 6 to 12 and very particularly preferably 8, 9, 10, 11 or 12 carbon atoms.
  • the free and ligands bound in the complex catalysts are selected from the phosphines, phosphites, phosphinites, phosphonites.
  • the ligands may have one or more phosphine, phosphite, phosphonite or phosphinite groups. It is also possible that the ligands have two or more different groups selected from the phosphine, phosphite, phosphonite or phosphinite groups.
  • the ligands may be bisphosphites, bisphosphines, bisphosphonites, bisphosphinites, phosphine phosphites, phosphine phosphonites, phosphine phosphinites, phosphite phosphonites, phosphite phosphinites or phosphonite phosphinites.
  • the ligands of the complex catalyst and the free ligands may be the same or different.
  • the organophosphorus ligands of the complex catalyst and the free ligands are the same.
  • Examples of complex catalysts or ligands that can be used and their preparation and use in the hydroformylation can be, for example, EP 0 213 639, EP 0 214 622, EP 0 155 508, EP 0 781 166, EP 1209164, EP 1201675, DE 10114868, DE 10140083, DE 10140086, DE 10210918 are taken.
  • phosphines triphenylphosphine, tris (p-tolyl) phosphine, Ths (m-tolyl) phosphine, tris (o-tolyl) phosphine, tris (p-methoxyphenyl) phosphine, tris (p-dimethylaminophenyl) phosphine, Tris (cyclohexyl) phosphine, tris (cyclopentyl) phosphine, triethylphosphine, tris (1-naphthyl) phosphine, tribenzylphosphine, tri-n-butylphosphine, tri-t-butylphosphine.
  • Phosphites trimethyl phosphite, triethyl phosphite, tri-n-propyl phosphite, tri-i-propyl phosphite, tri-n-butyl phosphite, tri-i-butyl phosphite, tri-t-butyl phosphite, tris (2-ethylhexyl) phosphite, triphenyl phosphite, tris (2, 4-di-t-butylphenyl) phosphite, tris (2-t-butyl-4-methoxyphenyl) phosphite, tris (2-t-butyl-4-methylphenyl) phosphite, tris (p-cresyl) phosphite.
  • Phosphonites methyldiethoxyphosphine, phenyldimethoxyphosphine, Phenyldiphenoxyphosphine, 2-phenoxy-2H-dibenz [c, e] [1, 2] oxaphosphorin and its derivatives in which the hydrogen atoms are wholly or partly replaced by alkyl and / or aryl radicals or halogen atoms.
  • Common phosphinite ligands are diphenyl (phenoxy) phosphine and its derivatives diphenyl (methoxy) phosphine and diphenyl (ethoxy) phosphine.
  • Complex catalysts containing a mixed anhydride of the phosphorous acid and an aryl or hydroxyarylcarboxylic acid are particularly preferably used in the process according to the invention for the hydroformylation.
  • Acyl phosphites or acyl phosphite-containing ligands, their preparation and their use in the hydroformylation are described for example in DE 100 53 272, which is to be part of the disclosure of the present invention.
  • Heteroacyl phosphites and heteroacyl phosphite-containing ligands, their preparation and their use in the hydroformylation are described for example in DE 10 2004 013 514.
  • acyl phosphites described in DE 100 53 272 are particularly preferred organophosphorus ligands which may be present in a hydroformylation process according to the invention as a catalyst complex ligand and / or as a free ligand.
  • heteroacyl phosphites described in DE 10 2004 013 514 according to the general formula (1) can be used as ligands in a further preferred embodiment.
  • the hydroformylation process according to the invention is preferably carried out such that 1 to 500 mol, preferably 1 to 200 mol and more preferably 2 to 50 mol of organophosphorus ligands per mol of rhodium are used.
  • Fresh organophosphorus ligands may be added at any time to the hydroformylation reaction to reduce the concentration of free heteroacyl phosphite, i. H. not coordinated to the metal, to keep constant.
  • the concentration of the metal in the hydroformylation mixture is preferably in the range from 1 ppm by mass to 1000 ppm by mass, preferably in the range from 5 ppm by mass to 300 ppm by mass, based on the total mass of the hydroformylation mixture.
  • the hydroformylation reactions carried out with the organophosphorus ligands or the corresponding metal complexes can be carried out according to known rules, such as. As described in J. FALBE, "New Syntheses with Carbon Monoxide", Springer Verlag, Berlin, Heidelberg, New York, page 95 et seq., (1980).
  • the olefin compound (s) is (are) in the presence of the catalyst with a mixture of CO and H 2 (synthesis gas) to the aldehydes richer to a C atom implemented.
  • the reaction temperatures are preferably from 40 ° C. to 180 ° C., and preferably from 75 ° C. to 140 ° C.
  • the pressures at which the hydroformylation proceeds are preferably from 0.1 to 30 MPa of synthesis gas and preferably from 1 to 6.4 MPa.
  • the molar ratio between hydrogen and carbon monoxide (H 2 / CO) in the synthesis gas is preferably from 10/1 to 1/10, and preferably from 1/1 to 2/1.
  • the catalyst or ligand is present in the hydroformylation mixture, consisting of educts (olefins and synthesis gas) and products (aldehydes, alcohols, high boilers formed in the process), preferably homogeneously dissolved.
  • a solvent may be present, which solvent may also be selected from the educts (olefins) or products (aldehydes) of the reaction.
  • Other possible solvents are organic compounds which do not interfere with the hydroformylation reaction and preferably easily, e.g. B. by distillation or extraction, can be separated again. Such solvents may, for. B. hydrocarbons, such as. B. be toluene.
  • Preferred starting materials are in particular ⁇ -olefins such as propene, 1-butene, 2-butene, 1-hexene, 1-octene and oligomers of butene (isomer mixtures), in particular di-n-butene and tri-n-butene.
  • the hydroformylation can be carried out continuously or batchwise.
  • Examples of technical versions are stirred tanks, bubble columns, jet nozzle reactors, tube reactors, or loop reactors, which may be partly cascaded and / or provided with internals.
  • the reaction can take place continuously or in several stages.
  • the workup of the hydroformylation mixture can be carried out on various, in The prior art known ways done.
  • the workup is preferably carried out in such a way that initially all gaseous constituents are separated off from the hydroformylation mixture. This is usually followed by separation of the hydroformylation products and possibly unreacted feed olefins. This separation can z. B. be achieved by the use of flash or falling film evaporators or distillation columns.
  • the residue which can be obtained is a fraction which essentially comprises the catalyst and any high boilers formed as by-products. This fraction can be attributed to the hydroformylation.
  • Mono-toluene adduct in the form of bright orange-red crystals Mono-toluene adduct in the form of bright orange-red crystals.
  • the complex II is a very good precursor for the hydroformylation. With 2 equivalents of Ligand 6-a complete conversion and 62.8% selectivity are obtained for the n-octenes at 120 0 C, 20 bar, 100 ppm Rh, toluene.
  • the gas consumption curve is analogous to that of [acacRh (COD)] as a precursor, indicating a rapid formation of a rhodium hydride with hydrogenolysis of the Rh-aryl bond.
  • Test conditions 120 0 C, 20 bar, 8 h, 100 ppm Rh, 10.7 g dibutene and 35.2 g of toluene,
  • Rh / ligand ratio was set as follows, assuming complete hydrogenolysis of the metallated precursor II:
  • the catalyst precursor is easy to handle in terms of transport and entry into the reactor, easy to convert to the active catalyst, and does not form materials that reduce catalyst stability and / or reactivity and / or selectivity.
  • the cyclooctadiene is hydroformylated during the preformation of the catalyst to Cyclooctencarbaldehyd and the second double bond is then hydrogenated, so that after the preformation thereof for the catalyst harmless cyclooctanecarbaldehyde formed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne la production et l'utilisation de précurseurs stables de catalyseurs à base de complexes de rhodium.
EP08717985A 2007-05-18 2008-03-19 Précurseur stable de catalyseurs à base de complexes de rh Withdrawn EP2147007A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007023514A DE102007023514A1 (de) 2007-05-18 2007-05-18 Stabile Katalysatorvorstufe von Rh-Komplexkatalysatoren
PCT/EP2008/053254 WO2008141853A1 (fr) 2007-05-18 2008-03-19 Précurseur stable de catalyseurs à base de complexes de rh

Publications (1)

Publication Number Publication Date
EP2147007A1 true EP2147007A1 (fr) 2010-01-27

Family

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Family Applications (1)

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EP08717985A Withdrawn EP2147007A1 (fr) 2007-05-18 2008-03-19 Précurseur stable de catalyseurs à base de complexes de rh

Country Status (5)

Country Link
US (1) US20100137623A1 (fr)
EP (1) EP2147007A1 (fr)
CN (1) CN101306387A (fr)
DE (1) DE102007023514A1 (fr)
WO (1) WO2008141853A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008043582A1 (de) * 2008-11-07 2010-05-12 Evonik Oxeno Gmbh Verfahren zur Herstellung von 6-Chlorodibenzo(d,f) (1,3,2)-dioxaphosphepin
DE102008043584A1 (de) 2008-11-07 2010-05-12 Evonik Oxeno Gmbh Verfahren zur Herstellung von 6-Chlorodibenzo(d,f) (1,3,2)-dioxaphosphepin
DE102009029050A1 (de) 2009-08-31 2011-03-03 Evonik Oxeno Gmbh Organophosphorverbindungen basierend auf Tetraphenol(TP)-substituierten Strukturen
DE102011085883A1 (de) 2011-11-08 2013-05-08 Evonik Oxeno Gmbh Neue Organophosphorverbindungen auf Basis von Anthracentriol

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4599206A (en) 1984-02-17 1986-07-08 Union Carbide Corporation Transition metal complex catalyzed reactions
US4748261A (en) 1985-09-05 1988-05-31 Union Carbide Corporation Bis-phosphite compounds
US4668651A (en) 1985-09-05 1987-05-26 Union Carbide Corporation Transition metal complex catalyzed processes
KR970703805A (ko) 1995-05-01 1997-08-09 유니온 카바이드 케미칼즈 앤드 플라스틱스 테크놀러지 코포레이션 막 분리방법(Membrane Separation)
DE19954721A1 (de) * 1999-11-12 2001-05-17 Oxeno Olefinchemie Gmbh Verfahren zur Herstellung von Aldehyden aus Olefinen durch Hydroformylierung
DE19954510A1 (de) * 1999-11-12 2001-05-17 Oxeno Olefinchemie Gmbh Verfahren zur katalytischen Herstellung von Aldehyden aus Olefinen unter Einsatz von Ligandenmischungen
DE19957528A1 (de) * 1999-11-30 2001-05-31 Oxeno Olefinchemie Gmbh Verfahren zur Hydroformylierung von Olefinen
DE10031493A1 (de) * 2000-06-28 2002-01-10 Oxeno Olefinchemie Gmbh Neue Bisphosphitverbindungen und deren Metallkomplexe
DE10053272A1 (de) 2000-10-27 2002-05-08 Oxeno Olefinchemie Gmbh Neue Bisphosphitverbindungen und deren Metallkomplexe
DE10058383A1 (de) 2000-11-24 2002-05-29 Oxeno Olefinchemie Gmbh Neue Phosphininverbindungen und deren Metallkomplexe
DE10114868C1 (de) * 2001-03-26 2002-10-31 Oxeno Olefinchemie Gmbh Verfahren zur Herstellung von Diphosphinen und deren Verwendung
EP1249441A1 (fr) 2001-04-13 2002-10-16 Dsm N.V. Procédé continu d'hydroformylation
DE10140083A1 (de) * 2001-08-16 2003-02-27 Oxeno Olefinchemie Gmbh Neue Phosphitverbindungen und deren Metallkomplexe
DE10140086A1 (de) 2001-08-16 2003-02-27 Oxeno Olefinchemie Gmbh Neue Phosphitverbindungen und neue Phosphitmetallkomplexe
DE10210918B4 (de) 2002-03-13 2004-06-03 Oxeno Olefinchemie Gmbh Verfahren zur Herstellung von Bisphosphiten
CA2481037A1 (fr) * 2002-04-04 2003-10-16 Degussa Ag Bisphosphines utilisees en tant que ligands bidentates
DE10223593A1 (de) * 2002-05-27 2003-12-11 Degussa Hydroxydiphosphine und deren Verwendung in der Katalyse
DE10353831A1 (de) * 2003-11-18 2005-06-23 Degussa Ag Verfahren zur Herstellung von Bisphospholanliganden
DE10360772A1 (de) * 2003-12-23 2005-07-28 Oxeno Olefinchemie Gmbh Verfahren zur Herstellung von Organoacylphosphiten
DE10360771A1 (de) * 2003-12-23 2005-07-28 Oxeno Olefinchemie Gmbh Verfahren zur Herstellung von dreiwertigen Organophosphor-Verbindungen
DE102004013514A1 (de) 2004-03-19 2005-10-06 Oxeno Olefinchemie Gmbh Verfahren zur Hydroformylierung von Olefinen in Anwesenheit von neuen phosphororganischen Verbindungen
DE102004051456A1 (de) * 2004-10-22 2006-04-27 Degussa Ag Neue Bisphosphankatalysatoren
DE102005014055A1 (de) * 2005-03-23 2006-09-28 Degussa Ag Unsymmetrisch substituierte Phospholankatalysatoren

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008141853A1 *

Also Published As

Publication number Publication date
DE102007023514A1 (de) 2008-11-20
WO2008141853A1 (fr) 2008-11-27
CN101306387A (zh) 2008-11-19
US20100137623A1 (en) 2010-06-03

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