WO2000013794A1 - Polymeric supported catalyst comprising a water-soluble transition metal complex - Google Patents

Abstract

The invention relates to a supported catalyst containing at least one water-soluble transition metal complex. The supported catalyst is characterized in that polymeric particles having a hydrophobic core and hydrophilic side-chains are utilized as a support. In the examples, tentagel, polymeric particles comprised of a cross-linked polystyrene core with polyethylene glycol side-chains grafted thereon are utilized as supports. The transition metal is selected from metals of groups VIIB, VII, IB or IIB of the periodic table and from mixtures thereof.

Description

 POLYMER SUPPORT CATALYST COMPRISING A WATER-SOLUBLE TRANSITION METAL COMPLEX

description

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. In this case, 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 Cχ 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.

DE-A-19 529 874 describes a process for the reduction of nitro compounds in the presence of a water-soluble rhodium catalyst of the formula Rh (CO) Cl (TPPTS) ₂ (TPPTS = triphenylphospinetrisulfonate trisodium salt) and optionally with the addition of an organic solvent. The exemplary embodiments only describe processes on a gram scale, the aqueous catalyst solution being separated off in a separating funnel.

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. By adding 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.

In Comprehensive Organometallic Chemistry, edited by G. Wilkinson, F.G.A. Stone and E.W. Abel, Pergamon Press, Oxford, 1982, Volume 8, page 553ff., Describe supported homogeneous transition metal catalysts in which the catalytically active component is covalently bound to a polymer support. A disadvantage of such immobilized homogeneous catalysts is that they often have a lower activity and / or different selectivity than the corresponding non-immobilized homogeneous systems. Bleeding of the transition metal is observed in particular in the case of hydroformylation catalysts. Such damaged catalysts cannot be regenerated.

In Chemtech 1992, 22, page 498ff., 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. 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.

In Angew. Chem. 1997, 109, page 1810ff., Describes an immobilization technique for homogeneous catalysts in which polyethers covalently bonded to silicate surfaces serve as solvents and / or ligands for polyoxometalates. These are suitable as oxidation catalysts.

In Beller et al., Journal of Molecular Catalysis A, 104 (1995), pages 17 to 85, various methods for immobilizing homogeneous catalyst systems are described in an overview (see in particular pages 34 to 37).

None of the references mentioned above describes immobilized catalysts in which a water-soluble transition metal complex is embedded in a hydrophilic outer layer of a solid, organic, hydrophobic polymer support.

In Angew. Chem. Int. Ed. Engl. 30, 1991, page 113ff., The use of hydrophilic tentacle polymers from an optionally crosslinked polystyrene core and grafted polyethylene glycol chains for protein synthesis is described. The use of these polymer particles as carriers for immobilizing water-soluble transition metal complexes is not 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, α, β-ethylenically unsaturated monomer, which is selected from vinyl aromatics, such as styrene, α-methylstyrene, o-chlorostyrene or vinyltoluenes, esters, α, β-ethylenically unsaturated C ₃ - To C ₆ -mono- and dicarboxylic acids with Ci- to C ₂ o-alkanols, such as. B. esters of acrylic acid and / or methacrylic acid with methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol or 2-ethylhexanol, maleic acid dimethyl ester or maleic acid n-butyl ester, α, ß-ethylenically unsaturated nitriles, such as . B. acrylonitrile and methacrylonitrile, esters of vinyl alcohol with Ci to C ₂ o-monocarboxylic acids, such as. B. vinyl formate, vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate, C ₂ - to C _δ monoolefins, such as. B. ethene, propene and butene, non-aromatic hydrocarbons with at least two olefinic double bonds, such as. B. butadiene, isoprene and chloroprene and mixtures thereof. 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. ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1, 3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, 1, 4-butylene glycol diacrylate, 1, 4-butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol, vinyl acrylate, vinyl acrylate, and vinyl methacrylate, vinyl methacrylate, vinyl acrylate, as well as vinyl acrylate, vinyl methacrylate, vinyl acrylate, as well as vinyl methylene acrylate, vinyl acrylate, as well as vinyl methylene acrylate, vinyl acrylate, as well as vinyl methylene acrylate, vinyl acrylate, as well as vinyl methylene acrylate, vinyl acrylate, as well as vinyl acrylate, vinyl acrylate, as well as - Lylacrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, methyl bisacrylamide, and mixtures thereof. 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 β-ethylenically unsaturated double bond and at least one active hydrogen atom per molecule. These include e.g. B. the esters α, 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. 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl ethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, etc. Also suitable are the esters of the aforementioned acids with triols and polyols, such as As glycerol, erythritol, pentaerythritol, sorbitol etc. Also suitable are the esters and amides of the aforementioned acids with C ₂ - to C ₂ amino alcohols which have a primary or secondary amino group. These include aminoalkyl acrylates and aminoalkyl methacrylates and their N-monoalkyl derivatives, which, for. B. wear an N-Cχ to Cs monoalkyl radical, such as aminomethyl acrylate, aminomethyl methacrylate, aminoethyl acrylate, N-methylaminomethylacrylate, etc. Also suitable are 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.

According to a preferred embodiment, 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.

According to a further preferred embodiment, the polymer forming the hydrophobic polymer base is a polyhydroxystyrene homo- or copolymer. Suitable comonomers are the aforementioned α, β-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. According to a particularly preferred embodiment, 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. In particular, 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. In particular, 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. To introduce the linear polyether side chains, 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.

Advantageously, 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. In a second step, 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.

According to a suitable embodiment, 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 μm, 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). In general, 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 μm, preferably 20 to 400 μm, in particular 20 to 300 μm, especially 20 to 200 μm.

The average particle diameter of the hydrophobic core is in a range from about 0.2 to 100 μm, preferably 0.5 to 50 μm, in particular 0.5 to 20 μm. Preferably 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. In general, 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. PR ^X R ² R ³ (I)

wherein

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- (Cι-C ₄ ) -alkyl, Ci- to C ₂₅ -alkyloxy, C ₅ - to C ₈ -cycloalkyloxy, aryloxy or aryl- (Cχ-C) alkyloxy, and at least one of the radicals R ¹ , R ² and / or R ³ at least one, for. B. has one, two or three, 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.

In the context of the present invention, the expression "alkyl" encompasses straight-chain and branched alkyl groups. In particular, these are straight-chain or branched Ci to C ₂₅ alkyl, preferably Ci to Cχo-alkyl and particularly preferably Ci to Cβ-alkyl groups. Examples of 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-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, 1-propylbutyl, octyl, nonyl, decyl, undecyl, dodecyl, etc.

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.

The above statements regarding alkyl, cycloalkyl, arylalkyl and aryl radicals apply correspondingly to alkoxy, cycloalkyloxy, arylalkyloxy and aryloxy radicals.

The radicals R ¹ , R ² and R ³ are preferably independently of one another C ₅ - to Cβ-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 ,

P (C ₆ H ₅ ) ₂ P (C ₆ H ₄ -m-S0 ₃ M) and mixtures thereof, where M is H, Li, Na, K or ammonium. M is preferably Na or K.

The water-soluble complexes can have one or more of the water-soluble ligands described above. In addition to 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. These further ligands can be monodentate, bidentate or multidentate and coordinate on the metal atom of the catalyst complex. Suitable other phosphorus-containing ligands are z. B. usual phosphine, phosphinite, phosphonite and phosphite ligands that have no hydrophilic polar groups.

The water-soluble transition metal complexes used according to the invention are, for. B. to compounds of general formula II

M _w Ll _χ L ² γL ³ _z (II)

wherein

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 :

- Reaction of a transition metal compound of the metal which forms the central atom of the water-soluble complex with at least one of the water-soluble ligands described above and optionally at least one further additional ligand;

Implementation of a transition metal complex with at least one of the water-soluble ligands described above and optionally a further additional ligand.

A water-soluble salt is generally used to synthesize the water-soluble transition metal complexes from a transition metal compound. Are suitable for. B. the halides, preferably the chlorides and bromides, nitrates, sulfates, carboxylates, carboxylic acid salts, preferably formates, acetates and propionates, oxides etc.

As 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. In the synthesis of defined water-soluble transition metal complexes, 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. In "in situ" synthesis, 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. If desired, the reaction can be carried out in the presence of a reducing agent, such as. B. sodium borohydride or hydrazine hydrate. If desired, 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. Preferably 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. If desired, 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. As in the synthesis from a transition metal compound, 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.

Both in the production of the water-soluble transition metal complexes from a transition metal compound used in the catalysts according to the invention and in the production from a transition metal complex, 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.

In many cases, under the reaction conditions of the reaction catalyzed by the catalysts according to the invention, 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.

As will be described below, 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. However, 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.

This process for the preparation of the catalyst is characterized in that the support

a) with the water-soluble complex of the transition metal or

b) with a combination of at least one transition metal compound or complex, suitable for forming complex a), at least one water-soluble ligand and optionally at least one further ligand,

soaks and then dries.

If necessary, 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.

According to a first suitable embodiment of the process according to the invention for producing the catalyst according to the invention, 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. However, 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.

To impregnate the carrier, 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. If desired, 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.

If desired, the polymer particles of the carrier can be degassed in a vacuum before soaking. In order to achieve better mixing, 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.

According to a second suitable embodiment of the process according to the invention, 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. If desired, this combination can be converted into a water-soluble transition metal complex in situ before the catalyst is soaked. If desired, this combination can also be preformed before it is immobilized on the carrier, as previously described, by be activated. According to a preferred embodiment, however, 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. Advantageously, 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. However, 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. Preferably, essentially water-insoluble starting materials and / or products of the respective catalyzed reaction used such. B. olefins, aldehydes etc.

Advantageously, the catalysts according to the invention generally show only very slight losses in the water-soluble transition metal complexes. When using the aforementioned essentially water-insoluble solvents and solvent mixtures, these are generally at most 1 ppm and are preferably below the detection limit. Under certain circumstances, it may be of advantage if an excess of water-soluble phosphorus-containing ligands is used in the preparation of the catalysts according to the invention.

In general, 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. These also include hydrocyanation by addition of hydrocyanic acid to olefins, hydroesterification by addition of carboxylic acids to olefins, hydroamination by addition of ammonia, primary and secondary amines to olefins, and hydroamidation by addition of car- bonsäureamiden on olefins. The catalysts of the invention are also suitable for positional and double bond isomerization of olefins.

According to a first preferred embodiment, 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.

In general, 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. Preferably, 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. According to a preferred embodiment, 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. Also suitable 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. Here too, 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. In principle, 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 α-olefins, internal straight-chain and internal branched olefins. Suitable α-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, α-methylstyrene, 4-isobutylstyrene etc. Suitable olefins to be hydroformylated are furthermore α, β-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. Thus, 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. Thus, 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. In general, 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.

The 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. In general, 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. In general, 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.

The 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 α-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.

According to a further preferred embodiment, the process in which the catalyst according to the invention is used is a reduction.

Another object of the invention is therefore a process for the reduction of compounds with non-aromatic C = C double and triple bonds, aldehydes, ketones, nitriles and nitro compounds by reaction with hydrogen in the presence of at least one hydrogenation catalyst, which is characterized in that uses one of the previously described catalysts according to the invention as the hydrogenation catalyst.

The compound used for the reduction is preferably a nitroaromatic. Suitable nitroaromatics are compounds of the general formula III

worin R¹ und R² unabhängig voneinander für Alkyl, Cycloalkyl, Aryl, Hetaryl, Arylalkyl, Alkoxy, Cycloalkoxy, Aryloxy, Acyl, Ni- tro, Cyano, Carboxyl, Alkoxycarbonyl oder NE¹E² stehen, wobei E¹ und E² gleich oder verschieden sein können und für Alkyl, Cycloal- kyl oder Aryl stehen.

wherein 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.

In formula III, 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. If desired, 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.

After the reaction has ended, 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. In general, the catalyst can be used again for the catalytic reduction without a significant loss of activity. If liquid nitroaromatics are used for the reduction, the addition of a solvent can generally be dispensed with. However, it is also possible to additionally use an organic solvent, such as benzene, toluene, xylenes, cyclohexane, decalin, etc. or mixtures thereof.

The invention is illustrated by the following, non-limiting examples. Examples

TentaGel® S OH (product number S 30,900, particle size 90 μm, 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).

example 1

Production of a catalyst based on triphenylphosphine trisulfonate trisodium salt (TPPTS) as ligand with preforming

4 ml of a buffer solution (40 g of H ₂ O, 190 mg of glacial acetic acid, 3.81 g of sodium acetate trihydrate) and 7 ml of toluene are introduced into an autoclave. Then 0.43 g (0.75 mmol) of TPPTS and 0.008 g (0.03 mmol) of Rh (CO) ₂ acac are added, the autoclave is closed and charged with three evacuations and subsequent gassing with a CO / H ₂ synthesis gas mixture (1: 1), whereby an initial pressure is set at an ambient temperature of 3 bar. The mixture is then heated to 120 ° C. for 45 minutes, the pressure rising to about 6 bar. 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.

1.41 g of a yellow catalyst are obtained, which is kept under an argon protective gas until it is used.

Rhodium content: 0.15 g / 100 g H ₂ 0 content: 1.1 g / 100 g

Example 2

Production of a catalyst based on TPPTS without preforming

In a Schlenk tube, 1.54 g (2.71 mmol) of TPPTS and 0.018 g (0.042 mmol) of Rh (CO) ₂ acac are mixed with 1 ml of the buffer solution described in Example 1 and 4 ml of H ₂ O under protective gas. Under Intensive stirring with a magnetic stirrer forms a deep yellow, slightly cloudy solution, which is mixed with 10 ml of toluene and then stirred at 70 ° C. for 15 minutes. After cooling, the resulting two-phase system is again placed under a protective argon gas in a Schlenk tube containing 1.0 g of degassed TentaGel® S OH and stirred vigorously for 1 hour. After the stirring has ended, 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

Example 3

Production of a catalyst based on triphenylphosphine monosulfonate monosodium salt (TPPMS) with preforming

1 ml of the buffer solution described in Example 1, 3 ml of H ₂ O and 10 ml of toluene are added to a stirred autoclave, and 0.285 g (0.74 mmol) of TPPMS and 0.0098 g (0.038 mmol) of Rh (CO) _{2 are then added} acac too. After the autoclave has been closed, it is evacuated three times and flushed with synthesis gas CO / H ₂ (1: 1). The synthesis gas pressure at ambient temperature is 3 bar. The mixture is then preformed at 120 ° C. for 45 minutes, the pressure rising to about 6 bar. After stirring for 10 hours at room temperature under a synthesis gas pressure of 3 bar, the light yellow suspension obtained is transferred under protective gas into a Schlenk tube which contains 1 g of degassed TentaGel® S OH. A magnetic stirrer is used for intensive stirring for 1 h, during which a gel-like phase forms. After stirring is complete, the mixture is allowed to settle and the supernatant solution is pipetted off. The remaining gel is rinsed three times with 8 ml of toluene. The solvent is then stripped off at 2 mbar and 20 ° C. and the catalyst is dried for a further 1.5 h at ambient temperature and 2 mbar. All steps of the catalyst production and its storage take place in a protective gas atmosphere. Rhodium content: 0.26 g / 100 g H ₂ 0 content: 1.3 g / 100 g

Phosphorus content: 1.3 g / 100 g

Example 4

Production of a catalyst based on TPPMS without preforming

In a Schlenk tube under argon protective gas, 0.450 g

(1.2 mmol) TPPMS and 0.0145 g (0.056 mmol) Rh (CO) ₂ acac with 1.5 ml of the buffer solution described in Example 1 and 6 ml of H ₂ 0 and stirred, a light yellow suspension being formed, to which you add 15 ml of toluene. After stirring for 1 hour at 80 ° C, after cooling, transfer to a Schlenk tube containing 1.5 g of degassed TentaGel® S OH. After the mixture has been stirred, phase separation occurs, whereupon the yellow gel obtained is allowed to settle and the supernatant clear solution is pipetted off. The gel-like phase obtained is rinsed three times with 10 ml of toluene each time and the solvent is pipetted off. 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

Example 5

Preparation of a catalyst based on Rh (CO) Cl (TPPTS) ₂ as ligand

30 mg Rh (CO) Cl (TPPTS) ₂ (23 μmol) are dissolved in 2.5 ml water and placed under argon protective gas in a Schlenk tube with 1 g degassed TentaGel® S OH. The resulting mass is stirred vigorously and then dried for 5 hours at ambient temperature and a pressure of 2 mbar. Examples 6 to 13

Discontinuous hydroformylation of 1-dodecene

In a 10 ml stirred autoclave, 1-dodecene, catalyst and toluene are introduced in an amount according to Table 1 under argon at room temperature and heated to the reaction temperature (see Table 1). Both preformed and nonformed catalysts from Examples 1 and 2 which have not yet been used and preformed and nonformed recycled catalysts are used as catalysts. The information about the catalyst used in each case can also be found in Table 1. After the reaction temperature has been reached, a pressure of 60 bar is set with synthesis gas C0 / H ₂ (1: 1) and kept constant for a reaction time of 4 h by pressing in synthesis gas via a pressure regulator. After the reaction is complete, the autoclave is cooled, decompressed and emptied. Any catalyst used for the recycle is handled under protective gas. The analysis of the reaction mixture was carried out by gas chromatography. The results are shown in Table 2.

GC analysis: Capillary GC 30 m UV-1 column with internal standard.

Catalyst recycle:

The contents of the autoclave are transferred into a 10 ml screw cap vessel under protective gas. After the catalyst has settled, 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. In a GC analysis of the third rinsing solution, 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.

3

3

4->

CD rt

3

O

Beispiele 14 bis 16

Examples 14 to 16

Hydroformylation with a catalyst based on TPPMS as ligand

In a 10 ml stirred autoclave, 1-dodecene, catalyst and toluene are introduced in an amount according to Table 3 under argon at room temperature and heated to the reaction temperature (see Table 3). Both preformed and nonformed catalysts from Examples 3 and 4 which have not yet been used and preformed and nonformed recycled catalysts are used as catalysts. The information on the catalyst used in each case can also be found in Table 3. After the reaction temperature has been reached, the reaction pressure, as indicated in Table 3, is set with synthesis gas CO / H ₂ (1: 1) and kept constant for a reaction time of 4 h by pressing in synthesis gas via a pressure regulator. After the reaction time, the autoclave is cooled, decompressed and emptied. The catalyst recycling and the analysis of the reaction mixture by means of gas chromatography were carried out as described in Examples 6 to 13.

0 2 ß) Φ

01

Tabelle 4

Table 4

Hydroformylation with TPPMS as a ligand

^e> Alle angegebenen Produkte wurden mittels Referenzgaschromatogrammen der entsprechenden Reinsubstanzen bzw. mittels GC-MS zugeordnet ^f) Anteil an n-Tridecanal bezogen auf Gesamtaldehydmenge

^e > All specified products were assigned to the corresponding pure substances by means of reference gas chromatograms or by means of GC-MS ^f ) Share of n-tridecanal based on the total amount of aldehyde

9) Total amount of aldehyde based on 1-dodecene used ^h ) 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.

Example 17

Hydrogenation of nitrobenzene with Rh (CO) C1 (TPPTS) ₂ as a water-soluble complex

4.83 g (39 mmol) of nitrobenzene and 110 mg of catalyst from Example 5 (corresponding to 3.3 mg (2.4 μm) Rh (CO) C1 (TPPTS) ₂ ) are added to a 10 ml stirred autoclave and the autoclave is flushed through repeated evacuation and gassing with hydrogen. A hydrogen pressure of 10 bar is then set and the autoclave is heated to 120 ° C. within 30 minutes. The pressure increases to about 20 bar. After a reaction time of 16 h, the autoclave was cooled and let down and the catalyst was separated from the reaction solution by filtration. The resulting reaction mixture was examined by gas chromatography.

The GC analysis was carried out as previously described.

Claims

claims 1. A catalyst comprising at least one water-soluble transition metal complex which is applied to a carrier, characterized in that the carrier comprises a hydrophobic polymer base which is associated with a hydrophilic matrix, the hydrophilic matrix containing the transition metal complex. 2. Catalyst according to claim 1, characterized in that hydrophilic side chains are bound to the polymer base, which in the presence of a liquid, hydrophilic medium, the hy

Form the hydrophilic matrix by swelling. 3. Catalyst according to one of the preceding claims, characterized in that the carrier is a graft copolymer with a

cross-linked hydrophobic core is on which the hydrophilic side chains are grafted. 4. Catalyst according to one of the preceding claims, characterized in that the hydrophilic side chains are linear or branched polyether side chains. 5. Catalyst according to one of the preceding claims, characterized in that the carrier in the form of polymer particles

with an average particle diameter in the range of about

10 to 500 μm is present. 6. Catalyst according to one of the preceding claims, characterized

characterized in that the transition metal is selected from the subgroup metals, preferably from metals of the VII., VIII., I. or II. subgroup of the periodic table and Mi 8. A method for producing a catalyst according to any one of claims 1 to 7, characterized in that the carrier a) with the water-soluble complex of the transition metal or b) with a combination of at least one transition metal compound or a complex, at least one water-soluble ligand and optionally at least one further ligand, which is suitable for forming the complex a) soaks and then dries. 9. 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, characterized in that a catalyst according to one of claims 1 to 7 is used as the hydroformylation catalyst. 10. A process for the reduction of compounds with non-aromatic carbon-carbon double and triple bonds, aldehydes, ketones, nitriles and nitro compounds by reaction with hydrogen in the presence of at least one hydrogenation catalyst, characterized in that a catalyst according to one of the claims is used as the hydrogenation catalyst 1 to 7. 11. Use of a catalyst according to one of claims 1 to 7 for carrying out reduction reactions, in particular for hydrogenation, hydroformylation, hydrocarbonylation, hydroacylation, hydrocyanation, hydroesterification, hydroamination, hydroamidation and for positional and double bond isomerization of olefins.