EP1113878A1 - Catalyseur a support polymere comprenant un complexe de metal de transition soluble dans l'eau - Google Patents

Catalyseur a support polymere comprenant un complexe de metal de transition soluble dans l'eau

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Publication number
EP1113878A1
EP1113878A1 EP99946101A EP99946101A EP1113878A1 EP 1113878 A1 EP1113878 A1 EP 1113878A1 EP 99946101 A EP99946101 A EP 99946101A EP 99946101 A EP99946101 A EP 99946101A EP 1113878 A1 EP1113878 A1 EP 1113878A1
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European Patent Office
Prior art keywords
catalyst
water
transition metal
soluble
complex
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EP99946101A
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German (de)
English (en)
Inventor
Rocco Paciello
Edgar Zeller
Michael Röper
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/38—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitroso groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/068—Polyalkylene glycols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2702—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously
    • C07C5/2727—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously with hydrides or organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/52—Isomerisation reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/20—Carbonyls
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes

Definitions

  • the present invention relates to a catalyst comprising at least one water-soluble transition metal complex which is applied to a support, a process for the preparation of this catalyst and a process for hydroformylation and a process for reduction in the presence of such a catalyst.
  • Homogeneous catalyst systems are used in a large number of important industrial processes. This includes e.g. B. low-pressure hydroformylation for the production of aldehydes from olefins, carbon monoxide and hydrogen.
  • Co, Rh or Ru compounds or complexes are used as catalysts which can be modified with phosphine-containing ligands to influence the activity and / or selectivity.
  • Rhodium triphenylphosphine catalysts are particularly widespread.
  • a known problem when using homogeneous catalysts is their separation after the reaction catalyzed by them has ended.
  • the highest possible catalyst recirculation rates should be avoided using simple process measures, while avoiding product or catalyst losses, e.g. B. be achieved by decomposition as a result of the necessary separation measures.
  • So is the hydroformylation of higher olefins, i.e. generally with a number of 7 and more carbon atoms, in the presence of the rhodium / triphenylphosphine low-pressure catalysts mentioned above, technically very complex in order to avoid thermal decomposition of the catalyst when it is separated off.
  • DE-A-37 21 095 describes a process for the preparation of C 7 - to C ⁇ 7 -aldehydes by rhodium-catalyzed hydroformylation, the reaction medium obtained in the hydroformylation being subjected to a number of evaporation and (partial) condensation steps at exactly the same temperatures, Pressures and dwell times in the respective reactors.
  • This process is technically very complex, which has a negative impact on its economic implementation on an industrial scale.
  • EP-A-0 372 313 describes water-soluble complex compounds of elements of VII., VIII. And I. Subgroup of the periodic table, which have at least one P (C 6 H -m-S0 3 Na) 3 ligand. These are suitable for. B. for the hydroformylation of olefins, a heterogeneous reaction medium (two-phase system) consisting of an aqueous catalyst-containing phase and an organic olefin-containing or aldehyde-containing phase being used.
  • TPPTS Rh (CO) Cl
  • TPTS triphenylphospinetrisulfonate trisodium salt
  • a disadvantage of the two-phase systems described above is their limited technical uses.
  • a prerequisite for their use is always a certain solubility of the organic starting material in the aqueous phase.
  • Processes based on two-phase systems are therefore suitable, among other things. not for the hydroformylation of higher olefins, since these are essentially insoluble in the aqueous, catalyst-containing phase.
  • reagents that increase the solubility of the catalyst in the organic phase such as. B. phase transfer catalysts or emulsifiers or by appropriate modification of the ligands, such as. B. Introduction of long-chain alkylammonium groups, the separability of the catalyst is always deteriorated. The desired easy separability of the catalyst with high catalyst recirculation rates is therefore not achieved by the two-phase systems in a large number of reactions.
  • Supported water-phase catalysts (SAP, supported aqueous-phase) are described, where homogeneous transition metal catalysts on a support with a large surface area, such as. B. a large-pore glass substrate or a silica support.
  • SAP supported aqueous-phase
  • One disadvantage of these systems is their high sensitivity. Strict control of the water content of the catalyst particles is required to achieve sufficient catalytic activity. Since the loading of the catalyst particles is limited by the available surface, special highly porous supports must be used depending on the area of application. It is not possible to regenerate damaged catalysts. Because of the technical effort required, the production of such catalysts is generally expensive, so that their use in industrial processes is generally not economical.
  • hydrophilic tentacle polymers from an optionally crosslinked polystyrene core and grafted polyethylene glycol chains for protein synthesis is described.
  • the present invention has for its object to provide new catalysts based on water-soluble transition metal complexes. These should be manufactured using simple processes and should be easy to regenerate. They should preferably be readily separable from the reaction mixture after the catalyzed reaction has ended. Surprisingly, catalysts based on water-soluble transition metal complexes have now been found which have a hydrophobic polymer base with a hydrophilic matrix as a support.
  • An object of the present invention is thus a catalyst comprising at least one water-soluble transition metal complex which is applied to a support, the catalyst being characterized in that the support comprises a hydrophobic polymer base which is associated with a hydrophilic matrix, the hydrophilic matrix contains the transition metal complex.
  • the hydrophobic polymer base preferably contains at least one radically polymerizable, ⁇ , ⁇ -ethylenically unsaturated monomer, which is selected from vinyl aromatics, such as styrene, ⁇ -methylstyrene, o-chlorostyrene or vinyltoluenes, esters, ⁇ , ⁇ -ethylenically unsaturated C 3 - To C 6 -mono- and dicarboxylic acids with Ci- to C 2 o-alkanols, such as. B.
  • the hydrophobic polymer base preferably contains at least one of these monomers in an amount of generally about 50 to 99.95% by weight, preferably 60 to 99.9% by weight, in particular 70 to 99% by weight, based on the total amount of monomers to be polymerized.
  • the hydrophobic polymer base is preferably a crosslinked polymer. This then contains, in addition to the aforementioned monomers, at least one polymerized crosslinking monomer, which is selected from alkylene glycol diacrylates and alkylene dimethacrylates, such as, for. B.
  • the amount of these crosslinking monomers is preferably in a range from about 0.05 to 20% by weight, preferably 0.05 to 10% by weight, in particular 0.1 to 8 wt .-% and especially 0.2 to 5 wt .-% based on the total amount of the monomers to be polymerized.
  • the optionally crosslinked polymers forming the hydrophobic polymer base can additionally contain, in copolymerized form, at least one monomer which is selected from compounds which have at least one ⁇ -ethylenically unsaturated double bond and at least one active hydrogen atom per molecule.
  • these include e.g. B. the esters ⁇ , ß-ethylenically unsaturated mono- and dicarboxylic acids, such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid etc. with Ci to C 20 alkanediols, such as. B.
  • esters of the aforementioned acids with triols and polyols such as As glycerol, erythritol, pentaerythritol, sorbitol etc.
  • esters and amides of the aforementioned acids with C 2 - to C 2 amino alcohols which have a primary or secondary amino group.
  • aminoalkyl acrylates and aminoalkyl methacrylates and their N-monoalkyl derivatives which, for. B. wear an N-C ⁇ to Cs monoalkyl radical, such as aminomethyl acrylate, aminomethyl methacrylate, aminoethyl acrylate, N-methylaminomethylacrylate, etc.
  • vinyl aromatics which have at least one hydroxyl group, such as, for. B. 4-hydroxystyrene.
  • the monomers can be used individually or as mixtures. Their amount is generally 0 to 20% by weight, preferably 0.05 to 15% by weight, in particular 0.1 to 10% by weight, based on the total amount of the monomers to be polymerized. 4-hydroxystyrene is preferably used.
  • the optionally crosslinked polymer forming the hydrophobic polymer base is a polyvinyl alcohol which, for. B. via polymer-analogous reaction, such as partial or complete hydrolysis from a polyester of vinyl alcohol, preferably polyvinyl acetate, is available.
  • the amount of hydroxyl groups (degree of functionalization) is then preferably in a range from about 1 to 15 meq / g.
  • the polymer forming the hydrophobic polymer base is a polyhydroxystyrene homo- or copolymer.
  • Suitable comonomers are the aforementioned ⁇ , ⁇ -ethylenically unsaturated monomers and mixtures thereof, preference being given to using styrene. It is preferably a polymer based on polyhydroxystyrene with an amount of hydroxyl groups of about 0.05 to 0.7 meq / g.
  • the optionally crosslinked polymer forming the hydrophobic polymer base is a chloromethylated polystyrene crosslinked with divinylbenzene, which in a first functionalization reaction with a mono- or oligoalkylene glycol, such as, for. B. ethylene glycol, diethylene glycol, triethylene glycol and preferably tetraethylene glycol, is implemented.
  • Hydrophilic side chains which form the hydrophilic matrix of the catalysts according to the invention by swelling in the presence of a liquid, hydrophilic medium are preferably bound to the polymer base.
  • the carrier preferably has a swelling capacity in water of at least about 2 ml H 2 0 / g, in particular at least 3 ml H 2 0 / g and especially at least 3.5 ml H 2 0 / g.
  • the carriers used according to the invention are preferably a graft copolymer composed of a crosslinked polymer which forms the hydrophobic polymer base and has linear or branched polyether side chains.
  • they are linear polyether side chains.
  • the polymer particles used according to the invention as carriers are generally produced by reacting the crosslinked polymer which forms the hydrophobic polymer base with suitable monomers to form linear or branched polyether side chains or with suitable oligomers or polymers which contain linear or branched polyether groups.
  • the crosslinked polymers preferably have active hydrogen atoms, e.g. B. in the form of hydroxyl, primary and secondary amino and / or carboxyl groups, for the reaction with the monomers, oligomers or polymers forming the polyether side chains.
  • the groups containing the active hydrogen atoms are hydroxyl groups.
  • the active hydrogen atoms can be introduced into the base by using suitable initiators and / or monomers in the course of the polymerization or by subsequent functionalization.
  • the amount of active hydrogen atoms, e.g. B. on hydroxy groups (degree of functionalization) is generally in a range from about 0.02 to 25 meq / g polymer base, preferably 0.05 to 15 meq / g.
  • the linear polyether side chains forming the hydrophilic side chains of the support preferably have a number average molecular weight in the range from about 500 to 50,000, preferably 600 to 25,000, in particular 800 to 10,000, and especially 900 to 6,000.
  • the polymer base described above can be polyadditioned with at least one alkylene oxide, such as. B. ethylene oxide, propylene oxide, butylene oxide and mixtures thereof or with at least one cyclic ether, such as. B. tetrahydrofuran.
  • Suitable processes for the alkoxylation of compounds containing active hydrogen atoms, such as. B. have hydroxyl groups are known to those skilled in the art.
  • the linear polyether side chains obtained can have homopolymers of ethylene oxide, propylene oxide and n-butylene oxide, block copolymers of ethylene oxide, propylene oxide and / or n-butylene oxide or copolymers which contain the alkylene oxide units in a random distribution.
  • the aforementioned, preferably crosslinked, base polymers are reacted in a first reaction step with an oligoalkylene glycol, preferably an oligoethylene glycol of the general formula H- (OCHCH 2 ) n -OH, in which n is an integer from 2 to 20.
  • the reaction conditions correspond to the conditions known to the person skilled in the art for Williamson's ether synthesis.
  • this oligoalkylene glycol chain is then reacted further with at least one alkylene oxide to the desired chain length, as previously described.
  • This process is preferably suitable for the production of polystyrene-polyoxyethylene graft copolymers.
  • the carrier used according to the invention is preferably a graft copolymer with a crosslinked hydrophobic core, onto which the hydrophilic side chains are grafted.
  • an essentially monodisperse polymer is used as the crosslinked core polymer.
  • a process for producing crosslinked monodisperse polymers with a diameter in the range from about 0.5 to 50 .mu.m is described in DE-A-37 14 258, to which reference is hereby made in full.
  • Carriers and processes for their preparation which are suitable for use in the catalysts according to the invention are described in EP-A-0 187 391, to which reference is also hereby made in full. Suitable carriers are available under the name TentaGel® from Rapp Polymer, Tübingen.
  • TentaGel® S OH (particle size 90 ⁇ m, capacity 0.24 mmol / g, swelling capacity 3.5 to 4.5 ml H 2 0 / g) is particularly preferably used.
  • These polymer particles comprise a polystyrene core with linear polyethylene glycol side chains (approx. 68 ethylene oxide units).
  • polymer particles can be used as the carrier, which have a particle size in a range that enables their separation. In principle, there is no upper limit on the particle size.
  • the polymer particles used as carriers preferably have an average particle diameter in the range from approximately 10 to 500 ⁇ m, preferably 20 to 400 ⁇ m, in particular 20 to 300 ⁇ m, especially 20 to 200 ⁇ m.
  • the average particle diameter of the hydrophobic core is in a range from about 0.2 to 100 ⁇ m, preferably 0.5 to 50 ⁇ m, in particular 0.5 to 20 ⁇ m.
  • the crosslinked monomers have a narrow particle size distribution, i.e. they are essentially monodisperse.
  • the catalysts according to the invention comprise at least one water-soluble complex of a transition metal, the metal generally being a subgroup element, selected from the elements with atomic numbers 21 to 30 (Sc to Zn), 39 to 48 (Y to Cd), 57 to 80 (La to Hg) and mixtures thereof.
  • the transition metal is preferably selected from metals of subgroup VII, VIII, I or II, in particular from Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au or Zn and mixtures thereof.
  • the water-soluble transition metal complexes used in the catalysts according to the invention comprise at least one water-soluble ligand.
  • all ligands known to the person skilled in the art can be used which are essentially soluble in water without decomposition. Suitable water-soluble ligands and complexes are described by P. Kalck and F. Monteil in Adv. Organomet. Chem. 34, 1992, pp. 219-285, to which full reference is made here.
  • the water-soluble complexes preferably have at least one ligand which is selected from water-soluble phosphorus-containing ligands, preferably phosphines, phosphinites, phosphonites and phosphites, which additionally have at least one hydrophilic functional group.
  • Suitable hydrophilic functional groups are selected from carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, phosphoric acid groups, the alkali metal, alkaline earth metal and ammonium salts of these acid groups, primary, secondary and tertiary amino groups and quarterly ammonium groups.
  • the water-soluble, phosphorus-containing ligands are preferably a compound of the formula I.
  • R 1 , R 2 and R 3 independently of one another for C x - to C 25 -alkyl, C 5 - to Cg-cycloalkyl, aryl, aryl- (C ⁇ -C 4 ) -alkyl, Ci- to C 25 -alkyloxy, C 5 - to C 8 -cycloalkyloxy, aryloxy or aryl- (C ⁇ -C) alkyloxy, and at least one of the radicals R 1 , R 2 and / or R 3 at least one, for. B.
  • hydrophilic functional group which is selected from -C00X, -PO (OX) 2 , -OPO (OX) 2 , -S0 3 X, -NE 1 E 2 , -NE 1 E 2 E 3+ , where X is H, Li, Na, K or ammonium and E 1 , E 2 and E 3 independently of one another are hydrogen, Ci to C 25 alkyl, C 5 to Cg cycloalkyl or aryl stand.
  • alkyl encompasses straight-chain and branched alkyl groups.
  • these are straight-chain or branched Ci to C 25 alkyl, preferably Ci to C ⁇ o-alkyl and particularly preferably Ci to C ⁇ -alkyl groups.
  • alkyl groups are in particular methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec.-butyl, tert.-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1 , 2-dimethylpropyl, 1, 1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3 -Dimethylbutyl, 2,3-dimethylbutyl, 1, 1-dimethylbutyl, 2, 2-dimethylbutyl, 3, 3-dimethylbutyl, 1, 1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl , 2-ethylbutyl, 1-ethyl-2
  • the cycloalkyl group is preferably a Cs-Cg-cycloalkyl group, such as cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
  • Aryl preferably represents phenyl, tolyl, xylyl, mesityl, naphthyl, anthracenyl, phenanthrenyl, naphthacenyl and in particular phenyl or naphthyl.
  • Arylalkyl is preferably benzyl.
  • alkyl, cycloalkyl, arylalkyl and aryl radicals apply correspondingly to alkoxy, cycloalkyloxy, arylalkyloxy and aryloxy radicals.
  • radicals R 1 , R 2 and R 3 are preferably independently of one another C 5 - to C ⁇ -cycloalkyl or aryl, in particular cyclohexyl or phenyl, one, two or three of the radicals R 1 , R 2 and / or R 3 has one of the aforementioned hydrophilic functional groups.
  • the hydrophilic functional group is preferably a group of the formula -S0 3 X, where X is H, Li, Na, K or ammonium.
  • the water-soluble complex particularly preferably has at least one ligand which is selected from water-soluble, phosphorus-containing ligands, preferably phosphines, phosphinites, phosphonites and phosphites, which additionally have at least one hydrophilic functional group.
  • the water-soluble phosphorus-containing ligand is preferably selected from P (C 6 Hm-S0 3 M) 3 , P (C 6 H 5 ) P (C 6 H 4 -m-S0 3 M) 2 ,
  • the water-soluble complexes can have one or more of the water-soluble ligands described above.
  • they can also contain at least one further ligand, which is selected from cyanide, halides, amines, carboxylates, acetylacetonate, aryl or alkyl sulfonates, hydride, CO, olefins, dienes, cycloolefins, nitriles, N-containing heterocycles, aromatics and heteroaromatics, ethers, PF 3 and monodentate, bidentate and multidentate phosphine, phosphonite, phosphinite and phosphite ligands.
  • ligands can be monodentate, bidentate or multidentate and coordinate on the metal atom of the catalyst complex.
  • Suitable other phosphorus-containing ligands are z.
  • the water-soluble transition metal complexes used according to the invention are, for. B. to compounds of general formula II
  • M represents a transition metal, preferably Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au or Zn
  • L 1 stands for a water-soluble phosphorus-containing ligand as previously defined
  • L 2 and L 3 can be the same or different and represent one of the further ligands defined above, and
  • w, x, y and z are integers, depending on the valency and type of the metal and the binding of the ligands L 1 , L 2 and / or L 3 .
  • W is preferably an integer from 1 to 6.
  • y and z are each independently an integer from 0 to 7 w.
  • z is preferably an integer from 0 to 4 w.
  • the preparation of the water-soluble transition metal complexes can be carried out before or simultaneously with the preparation of the catalyst according to the invention, i.e. with the immobilization of the transition metal complex, or with the immobilization of compounds suitable for the formation of such a complex.
  • the water-soluble transition metal complexes are prepared by customary processes known to those skilled in the art. This includes :
  • a water-soluble salt is generally used to synthesize the water-soluble transition metal complexes from a transition metal compound.
  • halides preferably the chlorides and bromides, nitrates, sulfates, carboxylates, carboxylic acid salts, preferably formates, acetates and propionates, oxides etc.
  • a solvent for the transition metal compound z. B water or a mixture of water and at least one other water-miscible solvent, e.g. B. an alcohol, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, etc., can be used. Water is preferably used. If desired, the pH of the aqueous solution can be adjusted using a suitable buffer system. stem, e.g. B. acetic acid / acetate.
  • the molar ratio of transition metal to water-soluble phosphorus-containing ligand is generally selected as a function of the desired stoichiometry from central atom to ligand in the water-soluble complex.
  • the water-soluble phosphorus-containing ligand is then preferably used in the desired stoichiometric ratio or in an excess of about 0.05 to 0.5 mol% compared to the desired stoichiometric ratio.
  • a larger excess of the water-soluble ligand compared to the desired stoichiometry from central atom to ligand is generally used.
  • the water-soluble phosphorus-containing ligand is then preferably used in an excess of about 0.05 to 10 mol% compared to the desired stoichiometric ratio.
  • the reaction can be carried out in the presence of a reducing agent, such as. B. sodium borohydride or hydrazine hydrate.
  • a reducing agent such as. B. sodium borohydride or hydrazine hydrate.
  • the reaction is carried out under inert gas, such as. B. nitrogen or argon.
  • the temperature is generally in a range from about 0 to 50 ° C, preferably 10 to 40 ° C.
  • the water-soluble complexes can also be synthesized from a transition metal complex of the metal which forms the central atom of the water-soluble complex.
  • Suitable complex compounds of the transition metals are known in principle and are adequately described in the literature. These preferably include complexes of the transition metals based on the suitable additional ligands described above, which are then partially or completely exchanged for at least one water-soluble, phosphorus-containing ligand in a ligand exchange reaction.
  • Suitable solvents for the ligand exchange reaction are the aforementioned water-soluble solvents and preferably essentially water-immiscible organic solvents, such as aromatic hydrocarbons, e.g. B.
  • benzene, toluene, xylene, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, alcohols with 4 and more carbon atoms, such as n-butanol, isobutanol, tert-butanol, pentanol, octanol, alkanes and alkane mixtures etc.
  • two-phase systems e.g. B. from water and an incompletely water-miscible organic solvent.
  • the reaction is then preferably carried out with thorough mixing of the two phases, eg. B. by stirring.
  • the pH of the water phase can be adjusted using a suitable buffer, as described above.
  • the molar ratio of transition metal complex to water-soluble phosphorus-containing ligand is in turn dependent on the desired stoichiometry of the central atom to ligands in the water-soluble complexes.
  • the water-soluble phosphorus-containing ligand is used in the desired stoichiometric ratio or in an excess of about 0.05 to 0.5 mol% compared to the desired stoichiometric ratio for the synthesis of defined complexes, while in the " a larger excess can be used in situ "synthesis. In general, this corresponds to the desired excess ligand.
  • the ligand exchange reaction can, if desired, in the presence of a suitable activating agent, e.g. B. a Brönstedt acid, Lewis acid, such as. B. BF 3 , AICI 3 , ZnCl 2 or Lewis base.
  • a suitable activating agent e.g. B. a Brönstedt acid, Lewis acid, such as. B. BF 3 , AICI 3 , ZnCl 2 or Lewis base.
  • additional ligands can additionally be introduced into the complex compound or exchanged in a ligand exchange reaction. This is then done in a conventional manner known to those skilled in the art, e.g. B. by introducing CO or PF 3 , reaction with olefins, dienes, cycloolefins, nitriles, aromatics etc.
  • the actually catalytically active species are first formed from the catalysts or catalyst precursors used, eg. B. in the hydroformylation in the presence of synthesis gas (H 2 / CO) or in the hydrogenation in the presence of hydrogen.
  • the water-soluble transition metal complexes can be activated (preformed) under the conditions of the reaction to be catalyzed and, if appropriate, isolated and / or purified by customary processes to prepare the catalysts of the invention before they are immobilized on the polymer support.
  • the catalytically active species are preferably formed in situ in the reactor used for the catalyzed reaction.
  • Transition metal complexes based on triphenylposphintrisulfonate trisodium salt (TPPTS) which are suitable for the catalysts according to the invention are described in EP-A-0 372 313, to which reference is hereby made in full.
  • the invention further relates to a process for the preparation of a catalyst comprising at least one water-soluble complex of a transition metal as described above and a support as also described above.
  • the complex a) or the combination b) can be activated as described above before the support is soaked.
  • a non-pre-swollen carrier is preferably used for impregnation.
  • a water-soluble complex of a transition metal is used. Suitable processes for the preparation of these water-soluble complexes are those described above. If desired, the complex can be activated on the carrier before it is immobilized (so-called preforming). Suitable methods for activation depend on the reaction in which the catalyst according to the invention is to be used. In general, the catalytically active species are formed by treating the catalyst in the presence of at least some of the starting materials of the reaction to be catalyzed, such as, for example, B. by treating a hydroformylation catalyst with synthesis gas or a hydrogenation catalyst with hydrogen.
  • This treatment is generally carried out under the conditions which are also customary for the catalyzed reaction, ie, for example at elevated temperatures and / or elevated pressure.
  • the catalytically active species thus obtained can, if desired, be isolated and / or purified by customary methods before they are immobilized on the support.
  • a suitable cleaning method is e.g. B. gel chromatography.
  • the formation of the catalytically active species preferably takes place after the immobilization of the water-soluble transition metal complex on the support in situ immediately before or during the reaction catalyzed by the catalysts according to the invention.
  • the additional preforming step can then advantageously be dispensed with.
  • the water-soluble complex in water or in a mixture of water and a water-miscible solvent, for. B. one of the aforementioned alcohols, so that a highly concentrated solution is formed.
  • an additional amount of the water-soluble ligand used in each case can be added to the solution before the support is impregnated.
  • the molar ratio of added ligand to water-soluble complex is then generally in a range from about 0.1: 1 to 200: 1, preferably 0.5: 1 to 20: 1. This solution is then added to the polymer particles.
  • the polymer particles of the carrier can be degassed in a vacuum before soaking.
  • the mixture of transition metal complex and carrier can be impregnated by conventional methods, e.g. B. be mixed by stirring or ultrasound. After the impregnation, the catalyst is by conventional methods such. B. Decant the supernatant solvent and then dry in vacuo, dried. Drying is generally carried out at ambient temperature or a slightly elevated temperature up to about 40 ° C to constant weight. If desired, the aforementioned steps for catalyst preparation and the subsequent storage of the catalyst under inert gas, such as. B. under argon or nitrogen.
  • a combination of at least one transition metal compound or a complex, at least one water-soluble phosphorus-containing ligand and optionally at least one further ligand is used to produce the water-soluble complex of the transition metal in order to produce the catalyst according to the invention.
  • this combination can be converted into a water-soluble transition metal complex in situ before the catalyst is soaked.
  • this combination can also be preformed before it is immobilized on the carrier, as previously described, by be activated.
  • the additional step of preforming can also be delayed before the catalyst is impregnated when the catalyst is produced from a transition metal compound or a complex.
  • the molar ratio of water-soluble phosphorus-containing ligand to transition metal compound or complex is generally in a range from about 1: 1 to 150: 1, preferably 1.1: 1 to 100: 1, in particular 2: 1 to 75: 1.
  • the solvents and solvent mixtures mentioned above in the preparation of the water-soluble transition metal complexes can be used as solvents for impregnating and / or swelling the support. If a two-phase system is used, the impregnation is preferably carried out with intensive mixing. The impregnation conditions correspond to those previously described in the preparation of the catalyst from a water-soluble complex of the transition metal. If desired, the individual steps and the storage of the catalyst can take place under inert gas.
  • the catalysts according to the invention preferably have a water content in the range from 0.5 to 5.0 g per 100 g of carrier, preferably 0.7 to 2.5 g per 100 g of carrier, based on the weight of the dry i.e. unswollen, unladen carrier.
  • the catalysts according to the invention generally have a high reactivity and can be used successfully for a large number of reactions.
  • they can be followed by the reaction catalyzed in their presence by simple, conventional methods, such as. B. settling and decanting, or by filtration, such as nanofiltration, separate from the reaction mixture.
  • Suitable reactors for the use of the catalysts according to the invention are conventional reactors as are known to the person skilled in the art for solidly catalyzed liquid-phase and gas-liquid-phase reactions.
  • Reactors with a moving catalyst such as bubble columns, stirred tanks, stirred tank cascades, fluidized bed reactors, suspension bed reactors, tubular reactors, etc., are preferably used.
  • the catalyst can be separated off by the simple processes described above.
  • the catalysts according to the invention are also suitable for use in fixed bed reactors.
  • Substantially water-insoluble solvents and solvent mixtures are preferably used as solvents for the reaction to be catalyzed.
  • the water solubility is at generally at most 100 ppm (at 20 ° C.), preferably at most 50 ppm.
  • These include e.g. B. aliphatic hydrocarbons and hydrocarbon mixtures, such as pentane, hexane, heptane, petroleum ether, aromatic hydrocarbons, such as benzene, toluene, xylene, esters, such as butyl acetate, etc.
  • essentially water-insoluble starting materials and / or products of the respective catalyzed reaction used such.
  • the catalysts according to the invention generally show only very slight losses in the water-soluble transition metal complexes.
  • these are generally at most 1 ppm and are preferably below the detection limit.
  • the catalysts according to the invention have sufficient catalytic activity after they have been separated from the reaction mixture, so that they can be used again for catalysis, if appropriate after rinsing with one of the organic solvents or solvent mixtures described above.
  • An activation, e.g. B. by preforming as previously described is generally not required.
  • Catalyst regeneration is generally possible in a simple manner. You can do this e.g. B. rinse the catalyst with water, isolate the support by settling and decanting or filtering and work up the transition metal complex and / or ligand-containing rinsing solutions separately.
  • the support can generally be loaded with fresh catalyst immediately and used again without preforming.
  • the catalysts of the invention are suitable for reduction and in particular for hydrogenation, for. B. of carbon-carbon double bonds and triple bonds, of aldehydes and ketones to alcohols, of cycloalkanes to alkanes and in particular of nitriles and nitro compounds to amines.
  • the catalysts of the invention are also suitable for the catalysis of addition reactions on carbon-carbon double bonds.
  • This includes the hydroformylation of olefins by adding synthesis gas to the double bond.
  • This also includes the hydrocarbonylation of olefins, also in the presence of synthesis gas, to ketones, such as. B. the hydrocarbonylation from ethene to diethyl ketone.
  • This also includes the hydroacylation of alkenes by adding acyl halides to olefins, such as. B. the addition of benzoyl chloride to ethene to produce phenyl ethyl ketone.
  • the catalysts of the invention are also suitable for positional and double bond isomerization of olefins.
  • the process in which the catalyst according to the invention is used is hydroformylation.
  • the invention therefore furthermore relates to a process for the hydroformylation of compounds which contain at least one ethylenically unsaturated double bond by reaction with carbon monoxide and hydrogen in the presence of at least one hydroformylation catalyst, which is characterized in that one of the previously described hydroformylation catalysts is used Uses catalysts.
  • the transition metal of the water-soluble complex is then preferably cobalt, ruthenium, rhodium, palladium, platinum, osmium or iridium and in particular cobalt, ruthenium, rhodium and platinum.
  • P (C 6 H 4 -m-S0 3 Na) 3 , P (C 6 H 5 ) (C 6 H 4 -m-S0 3 Na) 2 or P (C 6 H 5 ) 2 are preferably used as the water-soluble phosphorus-containing ligand (C 6 H 4 -m-S0 3 Na) and mixtures thereof.
  • catalytically active species of the general formula H x M y (CO) z L q are formed from the catalysts or catalyst precursors used in each case under the hydroformylation conditions, where M is for the metal of subgroup VIII, L is a water-soluble phosphorus-containing ligand and x, y, z are integers, depending on the valency and type of the metal and the binding nature of the ligand L.
  • z and q are independently at least 1, such as. B. 1, 2 or 3.
  • the sum of z and q is preferably from 2 to 5.
  • the complexes can, if desired, additionally have at least one of the other ligands described above.
  • the catalytically active species (preforming) are formed in situ in the reactor used for the hydroformylation reaction. If desired, however, the preformed catalysts can, as described above, also be prepared separately and isolated by customary processes.
  • Suitable rhodium compounds or complexes for the preparation of the catalysts of the invention are e.g. B. rhodium (II) and rhodium (III) salts, such as rhodium (III) chloride, rhodium (III) nitrate, rhodium (III) sulfate, potassium rhodium sulfate, rhodium (II) - or Rhodium (III) carboxylate, rhodium (II) and rhodium (III) acetate, rhodium (III) oxide, salts of rhodium (III) acid, trisammonium hexachlororhodate (III) etc.
  • B. rhodium (II) and rhodium (III) salts such as rhodium (III) chloride, rhodium (III) nitrate, rhodium (III) sulfate, potassium
  • rhodium complexes such as rhodium biscarbonylacetylacetonate, acetylacetonatobisethylene rhodium (I) etc.
  • Rhodium biscarbonylacetylacetonate or rhodium acetate are preferably used.
  • Ruthenium salts or compounds are also suitable. Suitable ruthenium salts are, for example, ruthenium (III) chloride, ruthenium (IV) -, ruthenium (VI) - or ruthenium (VIII) oxide, alkali metal salts of ruthenium oxygen acids such as K 2 Ru0 4 or KRu0 4 or complex compounds of the general formula RuX 1 X 2 L 1 L 2 (L 3 ) n , in which L 1 , L 2 , L 3 and n have the meanings given above and X 1 , X 2 have the meanings given for X (see above), for. B.
  • RuHCl (CO) (PPh 3 ) 3 The metal carbonyls of ruthenium, such as trisruthenium dodecacarbonyl or hexaruthenium octadecacarbonyl, or mixed forms in which CO is partly replaced by ligands of the formula PR 3 , such as Ru (CO) 3 (PPh 3 ) 2 , can also be used in the process according to the invention.
  • Suitable cobalt compounds are, for example, cobalt (II) chloride, cobalt (II) sulfate, cobalt (II) carbonate, cobalt (II) nitrate, their amine or hydrate complexes, cobalt carboxylates, such as cobalt acetate, cobalt ethyl hexanoate, cobalt naphthanoate, and the cobalt caprolactamate -Complex.
  • the carbonyl complexes of cobalt such as dicobalt octacarbonyl, tetracobalt dodecacarbonyl and hexacobalt hexadecacarbonyl can be used.
  • Preferred solvents are the olefins used for the hydroformylation, the aldehydes which are formed in the hydroformylation of the respective olefins, the higher-boiling secondary reaction products, e.g. B. the products of aldol condensation, aromatic hydrocarbons such as benzene, toluene and xylenes, or mixtures thereof.
  • B. the products of aldol condensation
  • aromatic hydrocarbons such as benzene, toluene and xylenes
  • all compounds which contain one or more ethylenically unsaturated double bonds are suitable as substrates for the hydroformylation process according to the invention.
  • These include e.g. B. olefins, such as ⁇ -olefins, internal straight-chain and internal branched olefins.
  • Suitable ⁇ -olefins are e.g. B. ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonen, 1-decene, 1-undecene, 1-dodecene etc.
  • Suitable straight-chain internal olefins are preferably C - to C 2 o-olefins, such as 2-butene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, 2-octene, 3-octene, 4- Octene etc.
  • Suitable branched, internal olefins are preferably C to C 20 olefins, such as 2-methyl-2-butene, 2-methyl-2-pentene, 3-methyl-2-pentene, branched, internal heptene mixtures, branched , internal octene mixtures, branched, internal non-mixtures, branched, internal decene mixtures, branched, internal undecene mixtures, branched, internal dodecene mixtures etc.
  • Suitable olefins to be hydroformylated are furthermore C 5 -C 6 -cycloalkenes, such as cyclopentene, cyclohexene, cycloheptene, cyclooctene and their derivatives, such as, for. B. their Ci to C 2 o-alkyl derivatives with 1 to 5 alkyl substituents.
  • Suitable olefins to be hydroformylated are also vinyl aromatics, such as styrene, ⁇ -methylstyrene, 4-isobutylstyrene etc.
  • Suitable olefins to be hydroformylated are furthermore ⁇ , ⁇ -ethylenically unsaturated mono- and / or dicarboxylic acids, their esters, half-esters and amides, such as acrylic acid , Methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, 3-pentenoic acid methyl ester, 4-pentenoic acid methyl ester, oleic acid methyl ester, acrylic acid methyl ester, methacrylic acid methyl ester, unsaturated nitriles, such as 3-pentenenitrile, 4-pentenenitrile ether, acrylonitrile ether, acrylonitrile ether, acrylonitrile ether Vinyl ethyl ether, vinyl propyl ether etc., Ci to C 20 alkenols, alkylene diols and alkadienols, such as 2,7-octadienol-1.
  • Suitable substrates are further di- or polyenes with isolated or conjugated double bonds. These include e.g. B. 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, vinylcyclohexene, dicyclopentadiene, 1, 5, 9-cyclooctatriene and butadiene homo- and copolymers.
  • the catalysts according to the invention are therefore advantageously suitable for the hydroformylation of the aforementioned higher olefins having a carbon number of 7 or more and mixtures thereof, because they generally avoid the problems which occur when separating off conventional hydroformylation catalysts. In contrast to homogeneous catalysts, thermal separation, which can damage the catalyst, can be dispensed with. Also the A disadvantage of the two-phase systems, which results from the poor solubility of the higher olefins in the aqueous catalyst-containing phase, is generally advantageously avoided by the catalysts according to the invention.
  • the catalysts according to the invention generally allow better contact of the water-soluble transition metal complexes immobilized on the hydrophilic side chains of the support with the olefin than the conventional two-phase systems.
  • the loss of immobilized transition metal complex to the organic reaction solution is extremely low and is generally at most 1 ppm.
  • the catalysts of the invention can also be used advantageously over immobilized hydroformylation catalysts in which the active groups are bonded to the support via anchor groups and which tend to "bleed out" under the hydroformylation conditions.
  • the hydroformylation reaction can be carried out continuously, semi-continuously or batchwise.
  • Suitable reactors for the continuous reaction are known to the person skilled in the art and are described, for. B. in Ullmann's Encyclopedia of Industrial Chemistry, Vol. 1, 3rd Edition, 1951, p. 743 ff.
  • Suitable pressure-resistant reactors are also known to the person skilled in the art and are described, for. B. in Ullmann's Encyclopedia of Industrial Chemistry, Vol. 1, 3rd Edition, 1951, pp. 769 ff.
  • an autoclave is used for the method according to the invention, which can, if desired, be provided with a stirring device and an inner lining.
  • composition of the synthesis gas of carbon monoxide and hydrogen used in the process according to the invention can vary within wide ranges.
  • the molar ratio of carbon monoxide and hydrogen is usually about 5:95 to 70:30, preferably about 40:60 to 60:40.
  • a molar ratio of carbon monoxide and hydrogen in the range of approximately 1: 1 is particularly preferably used.
  • the temperature in the hydroformylation reaction is generally in the range from about 20 to 180 ° C., preferably about 50 to 150 ° C.
  • the reaction is usually carried out at the partial pressure of the reaction gas at the selected reaction temperature.
  • the pressure is in a range from about 1 to 700 bar, preferably 1 to 300 bar, in particular 1 to 100 bar and especially 1 to 30 bar.
  • the inventions Catalysts according to the invention a reaction in a range of low pressures, such as in the range of 1 to 100 bar.
  • the molar ratio of olefin to transition metal complex is generally in a range from about 100: 1 to 50,000: 1, preferably 1,000: 1 to 10,000: 1.
  • hydroformylation catalysts according to the invention can be prepared by customary processes known to those skilled in the art, such as settling and decanting or filtering, e.g. B. by nanofiltration, separate from the discharge of the hydroformylation reaction and can generally be used again for the hydroformylation.
  • the catalysts according to the invention advantageously have a high activity, so that the corresponding aldehydes are generally obtained in good yields. They also show good n / iso selectivity in the hydroformylation of ⁇ -olefins and of internal linear olefins.
  • the proportion of n-aldehyde (s) in the reaction product is generally at least 65% by weight, preferably at least 70% by weight.
  • the process in which the catalyst according to the invention is used is a reduction.
  • the compound used for the reduction is preferably a nitroaromatic.
  • Suitable nitroaromatics are compounds of the general formula III
  • R 1 and R 2 independently of one another are alkyl, cycloalkyl, aryl, hetaryl, arylalkyl, alkoxy, cycloalkoxy, aryloxy, acyl, nitro, cyano, carboxyl, alkoxycarbonyl or NE 1 E 2 , where E 1 and E 2 may be the same or different and represent alkyl, cycloalkyl or aryl.
  • alkyl preferably represents C ⁇ to Cg-alkyl, in particular Ci- to C -alkyl.
  • Suitable alkyl, cycloalkyl, aryl, arylalkyl, alkoxy, cycloalkyloxy, arylalkyloxy and aryloxy radicals are those mentioned above for the substituents of the formula I.
  • Suitable compounds of formula III are e.g. B. nitrobenzene, 2-chloronitrobenzene, 3-chloronitrobenzene, 4-chloronitrobenzene,
  • 2-alkoxynitrobenzenes, 3-alkoxynitrobenzenes and 4-alkoxynitrobenzenes such as 2-methoxynitrobenzene, 2-ethoxynitrobenzene, 3-methoxy-nitrobenzene, 3-ethoxynitrobenzene, 4-methoxynitrobenzene, 4-ethoxy-nitrobenzene, 4-ethoxy-nitrobenzene , 3-nitrobenzyl alcohol, 4-nitrobenzyl alcohol, 1-nitronaphthalene, 2-nitronaphthalene, 2-nitrophenol, 3-nitrophenol, 4-nitrophenol, 3-nitro-toluene etc.
  • the nitro compound to be reduced can also be two or more Contain nitro groups, which are then reduced to amino groups.
  • Rh (CO) Cl (TPPTS) 2 is preferably used as the water-soluble transition metal complex, where TPPTS stands for triphenylphosphine trisulfonate trisodium salt.
  • the molar ratio of water-soluble transition metal complex of the catalyst according to the invention to substrate is generally in a range from about 1: 100 to 1: 1,000,000, preferably 1: 1,000 to 1: 100,000.
  • the reaction temperature is generally in a range from about 10 to 150 ° C., preferably 20 to 130 ° C., in particular 50 to 110 ° C.
  • the hydrogen pressure is generally in a range from about 1 to 300 bar, preferably 2 to 150 bar, in particular 10 to 100 bar.
  • the catalyst according to the invention can be separated off from the reaction medium in a simple manner described above, for. B. by settling and decanting or filtering.
  • the catalyst can be used again for the catalytic reduction without a significant loss of activity.
  • a solvent can generally be dispensed with.
  • an organic solvent such as benzene, toluene, xylenes, cyclohexane, decalin, etc. or mixtures thereof.
  • TentaGel® S OH (product number S 30,900, particle size 90 ⁇ m, swelling capacity 3.5 to 4.5 ml H0 / g) from Rapp Polymer, Tübingen is used as a carrier for the catalysts. These particles consist of a cross-linked polystyrene core with grafted-on polyethylene glycol side chains (approx. 68 ethylene oxide units).
  • TPTS triphenylphosphine trisulfonate trisodium salt
  • the contents of the reactor are then stirred for a further 10 h at ambient temperature and a synthesis gas pressure of 3 bar.
  • the two-phase mixture obtained after relaxing and emptying the autoclave consisting of a bright yellow aqueous phase and a colorless organic phase, is transferred under argon protective gas into a Schlenk tube with 1 g of degassed TentaGel® S OH and stirred intensively for 1 hour with a magnetic stirrer.
  • the supernatant organic phase is then pipetted off and the remaining yellow gel is rinsed three times with 10 ml of toluene, the rinsing solutions also being pipetted off. Then it is dried for 5 hours at 50 ° C. and a pressure of 2 mbar.
  • Rhodium content 0.15 g / 100 g H 2 0 content: 1.1 g / 100 g
  • the yellow gel obtained is allowed to settle and the supernatant solution is removed by pipetting off.
  • the gel is rinsed three times with 10 ml of toluene, and the rinsing solutions are also pipetted off.
  • the solvent is then stripped off at 25 ° C. and 2 mbar, which results in a solid, intensely yellow product which, after comminution, is dried for a further 1.5 hours at ambient temperature and 2 mbar.
  • the steps described above for the production of the catalyst and its storage until use are carried out under an argon protective gas.
  • Rhodium content 0.11 g / 100 g H 2 0 content: 4.4 g / 100 g phosphorus content: 2.7 g / 100 g
  • the solvent is then removed at ambient temperature and a pressure of 2 mbar and the resulting residue is dried after comminution for a further 1.5 h at ambient temperature and 2 mbar. All of the steps described above for the production of the catalyst and its storage are carried out under argon protective gas.
  • Rhodium content 0.25 g / 100 g H 2 0 content: 1.1 g / 100 g phosphorus content: 1.4 g / 100 g
  • the contents of the autoclave are transferred into a 10 ml screw cap vessel under protective gas.
  • the supernatant solution is pipetted off and about 8 ml of absolute toluene are added to the catalyst three times, the mixture is stirred and allowed to settle, and the supernatant solution is then removed.
  • 1-dodecene and product aldehydes could no longer be detected.
  • the catalyst is then transferred to the stirred autoclave with about 1.5 ml of toluene and used for the hydroformylation under the conditions described above.
  • the space-time yield is defined as the total amount of aldehyde in mol per amount of rhodium of the catalyst in mol and reaction time in hours.

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Abstract

L'invention concerne un catalyseur comprenant au moins un complexe de métal de transition soluble dans l'eau et un support. Ledit catalyseur se caractérise en ce que le support utilisé consiste en particules polymères comportant un noyau hydrophobe et des chaînes latérales hydrophiles. Dans les exemples cités, les supports utilisés sont du tentagel, des particules polymères à base d'un noyau polystyrène avec des chaînes latérales polyéthylèneglycol. Le métal de transition est choisi parmi les métaux des groupes VIIB, VII, IB ou IIB de la classification périodique des éléments et leurs mélanges.
EP99946101A 1998-09-03 1999-09-02 Catalyseur a support polymere comprenant un complexe de metal de transition soluble dans l'eau Withdrawn EP1113878A1 (fr)

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DE19840255 1998-09-03
DE19840255A DE19840255A1 (de) 1998-09-03 1998-09-03 Katalysator umfassend einen wasserlöslichen Übergangsmetallkomplex
PCT/EP1999/006464 WO2000013794A1 (fr) 1998-09-03 1999-09-02 Catalyseur a support polymere comprenant un complexe de metal de transition soluble dans l'eau

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US8110519B2 (en) 2004-03-08 2012-02-07 Japan Science & Technology Agency Polymer-supported metal cluster composition
US7897817B2 (en) 2005-03-09 2011-03-01 Inter-University Research Institute Corporation National Institutes Of Natural Sciences Resin-platinum complex and resin-supported platinum cluster catalyst
JP5616586B2 (ja) * 2009-03-12 2014-10-29 地方独立行政法人 大阪市立工業研究所 カラムリアクター
KR102225041B1 (ko) 2012-04-17 2021-03-11 모멘티브 퍼포먼스 머티리얼즈 인크. 하이드로실릴화 반응을 위한 고 활성 촉매 및 그 제조방법
TWI793216B (zh) * 2017-12-07 2023-02-21 美商陶氏科技投資公司 氫甲醯化方法
JP7280596B2 (ja) * 2019-02-25 2023-05-24 大学共同利用機関法人自然科学研究機構 銀ナノ粒子樹脂複合体及び水素化触媒

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