DE19840255A1 - 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

The present invention relates to a catalyst comprising at least one water-soluble transition metal complex based on a carrier is applied, a method for producing the ses catalyst and a process for hydroformylation and a process for reduction in the presence of such a catalyst tors.

In a large number of important large-scale processes, ho mogeneous catalyst systems used. This includes e.g. B. the never derdruck hydroformylation for the production of aldehydes from oils finen, carbon monoxide and hydrogen. As catalysts Co, Rh or Ru compounds or complexes used for Influencing activity and / or selectivity with phosphinhal term ligands can be modified. Rho in particular dium triphenylphosphine catalysts widely used.

A known problem when using homogeneous catalysts is their separation after the end of the catalyzed Re action. It should preferably be done with simple procedural measures Avoid high catalyst recycling rates of product or catalyst losses, e.g. B. by a decomposition tion as a result of the necessary separation measures. So is the hydroformylation of higher olefins, i.e. H. in general with a number of 7 and more carbon atoms, in the presence the aforementioned rhodium / triphenylphosphine low-pressure catalyst technically very expensive to thermal decomposition to avoid the catalyst when it is separated.

DE-A-37 21 095 describes a process for the preparation of C ₇ to C ₁₇ aldehydes by rhodium-catalyzed hydroformylation, the reaction medium obtained in the hydroformylation being reacted with a number of evaporation and (partial) condensation steps at exactly 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 Periodensy stems, which have at least one P (C ₆ H ₄ -m-SO ₃ Na) ₃ ligand. These are suitable for. B. for the hydroformylation of olefins, wherein a heterogeneous reaction medium (two-phase system) from egg ner aqueous catalyst-containing phase and an organic olefin-containing or aldehyde product-containing phase is used.

DE-A-195 29 874 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 = triphenylphosphinetrisulfonate 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.

The two-phase systems described above are disadvantageous their limited technical uses. requirement there is always a certain solubility of the organi for their use educt in the aqueous phase. Process based on Two-phase systems are therefore u. a. not for hydroformy lation of higher olefins, since these in the aqueous, cataly sator phase are essentially insoluble. By the Zu set of reagents that test the solubility of the catalyst in the increase organic phase such. B. phase transfer catalysts or emulsifiers or by appropriate modification of the Li ganden, such as B. Introduction of long chain alkyl ammonium group pen, the separability of the catalyst is always ver worsened. The desired easy separability of the catalytic converter tors with high catalyst recirculation rates with through the two-phase systems in a variety of implementations not reached.

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

In Chemtech 1992, 22, page 498ff., Supported water pha lower catalysts (SAP, supported aqueous-phase) described where with homogeneous transition metal catalysts on a support a large surface such as B. a large-pore glass substrate  or a silica support. Disadvantageous on the one hand, these systems are highly sensitive. So is to achieve sufficient catalytic activity strict control of the water content of the catalyst particles required. Since the loading of the catalyst particles by the available surface must be limited depending on special highly porous supports are used in each area of application become. A regeneration of damaged catalysts is not possible. Due to the required technical effort the production of such catalysts is generally expensive, so their use in industrial processes in general is not economical.

In Angew. Chem. 1997, 109, page 1810ff., Becomes an immobilization tion technology for homogeneous catalysts described in which Silicate surfaces covalently bound polyethers as solvents and / or serve as a ligand for polyoxometalates. These are suitable as oxidation catalysts.

In Beller et al., Journal of Molecular Catalysis A, 104 (1995), Pages 17 to 85, various procedures are summarized described for the immobilization of homogeneous catalyst systems (see in particular pages 34 to 37).

None of the previously mentioned references describes immobili based catalysts, in which a water-soluble transition measurement tall complex in a hydrophilic outer layer of a solid, orga African, hydrophobic polymer carrier is stored.

In Angew. Chem. Int. Ed. Engl. 30, 1991, page 113ff., The Use of hydrophilic tentacle polymers from one, if necessary cross-linked polystyrene core and grafted polyethylene described glycol chains for protein synthesis. A stake this polymer particle as a carrier for immobilization water-soluble Licher transition metal complexes is not described.

The present invention has for its object new kata analyzers based on water-soluble transition metal complexes to provide. According to simple ver Establish driving and have it regenerated easily. Preferably they should look good after the catalyzed reaction has ended let it separate from the reaction mixture.  

Surprisingly, catalysts based on what are now ser soluble transition metal complexes found as carriers a hydrophobic polymer base with a hydrophilic matrix sen.

An object of the present invention is thus a catalytic converter gate comprising at least one water soluble transition metal complex, which is applied to a support, the Kataly sator is characterized in that the carrier is a hydrophobic Includes polymer base associated with a hydrophilic matrix is, wherein the hydrophilic matrix ent the transition metal complex holds.

The hydrophobic polymer base preferably contains at least one radically polymerizable, α, β-ethylenically unsaturated monomer, which is selected from vinylaromatics such as styrene, α-methylstyrene, o-chlorostyrene or vinyltoluenes, esters, α, β-ethylenically unsaturated C ₃ - To C ₆ mono- and dicarboxylic acids with C ₁ - to C ₂₀ 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, β-ethylenically unsaturated nitriles, such as. As acrylonitrile and methacrylonitrile, esters of vinyl alcohol with C ₁ - to C ₂₀ monocarboxylic acids, such as. B. Vinylfor miat, vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate, C ₂ - to C ₆ 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, copolymerized.

The hydrophobic polymer base is preferably a cross-linked polymer. This then includes ge in addition to those previously called monomers at least one crosslinking monomer rized, which is selected from Alkylengylkoldiacrylaten and Alkylene dimethacrylates, such as. B. ethylene glycol diacrylate, ethyl lenglycol dimethacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol diacrylate, 1,4-butylene gly koldimethacrylate, propylene glycol diacrylate, propylene glycol dimeth acrylate, as well as divinylbenzene, vinyl acrylate, vinyl methacrylate, Al lylacrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, Me thylbisacrylamide, and mixtures thereof. The amount of these networks zenden monomers is preferably in a range of about 0.05 to 20 wt .-%, preferably 0.05 to 10 wt .-%, in particular 0.1 to  8 wt .-% and especially 0.2 to 5 wt .-% based on the total amount of monomers to be polymerized.

The optionally crosslinked polymers forming the hydrophobic polymer base can additionally contain at least one copolymerized polymer which is selected from compounds which have at least one α, β-ethylenically unsaturated double bond and at least one active hydrogen atom per molecule. These include e.g. B. the esters α, β-ethylenically unsaturated mono- and dicarboxylic acids, such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid etc. with C ₁ - 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 ₁₂ amino alcohols which have a primary or secondary amino group. These include aminoalkyl acrylates and aminoalkyl methacrylates and their N-monoal kylderivate, the z. B. wear an NC ₁ - to C ₈ -monoalkyl radical, such as aminomethyl acrylate, aminomethyl methacrylate, aminoethyl acrylate, N-methylaminomethylacrylate, etc. Also suitable are vinylates 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 the possibly cross-linked polymer forming the hydrophobic polymer base a polyvinyl alcohol, e.g. B. via polymer-analogous reaction, such as partial or complete hydrolysis from a polyester of Vinyl alcohol, preferably polyvinyl acetate, is available. The The amount of hydroxyl groups (degree of functionalization) is then available preferably in a range from about 1 to 15 meq / g.

According to a further preferred embodiment, it is in the polymer forming the hydrophilic polymer base around a Po lyhydroxystyrene homo- or copolymer. Suitable comonomers are the aforementioned α, β-ethylenically unsaturated monomers and Mixtures thereof, styrene being preferably used. Before it is preferably a polymer based on polyhydro xystyrene with an amount of hydroxyl groups from about 0.05 to 0.7 meq / g.  

According to a particularly preferred embodiment, it is in which, if necessary, cross-linking forms the hydrophobic polymer base Polymer around a chloromethylated crosslinked with divinylbenzene Polystyrene, which is used in a first functionalization reaction with a mono- or oligoalkylene glycol, such as. B. ethylene glycol, Diethylene glycol, triethylene glycol and preferably tetraethylene glycol, is implemented.

Hydrophilic side chains are preferably bound to the polymer base, which form the hydrophilic matrix of the catalysts of the invention by swelling in the presence of a liquid, hydrophilic medium. The carrier preferably has a swelling capacity in water of at least about 2 ml H ₂ O / g, in particular at least 3 ml H ₂ O / g and especially at least 3.5 ml H ₂ O / g.

These are preferably those used according to the invention Carriers around a graft copolymer from a cross-linked, the hydro Phobic polymer-based polymer with linear or branched polyether side chains. In particular, it is li linear polyether side chains.

The production of the poly used according to the invention as a carrier Merparticles are generally made by implementing the network The polymer forming the hydrophobic polymer base with suitable ten monomers to form linear or branched Po side chains or with suitable oligomers or polyme ren, which contain linear or branched polyether groups. Before preferably the crosslinked polymers 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 polyether chain-forming monomers, oligomers or polymers. In particular, it is the active hydrogen atoms having groups around hydroxyl groups. The active hydrogen Atoms can be created by using suitable initiators and / or mono mers in the course of the polymerization or by subsequent radio nationalization. The amount of acti ven hydrogen atoms, e.g. B. on hydroxyl groups (functionality degree) is generally in the range of about 0.02 to 25 meq / g polymer base, preferably 0.05 to 15 meq / g.

The linear ones forming the hydrophilic side chains of the support Polyether side chains preferably have a number-average Mo molecular weight in the range from about 500 to 50,000, preferably 600 up to 25,000, in particular 800 to 10,000, and especially 900 to 6,000 on.  

For the introduction of linear polyether side chains, the previously described polymer base in a polyaddition with at least an alkylene oxide such as e.g. B. ethylene oxide, propylene oxide, butyleno xid and mixtures thereof or with at least one cyclic Ethers such as B. tetrahydrofuran. Suitable Process for alkoxylation of compounds containing active water atoms of matter, such as B. have hydroxyl groups are the subject man known. The linear polyether side chains obtained can NEN 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 which contain statistically distributed alkylene oxide units.

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- (OCH ₂ CH 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 further reacted 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.

It is preferably the one used according to the invention Carrier around a graft copolymer with a cross-linked hydrophobic Core on which the hydrophilic side chains are grafted.

According to a suitable embodiment, an essentially monodisperse polymer is used as the crosslinked Kernpo polymer. A process for producing crosslinked monodisperse polymers with a diameter in the range from about 0.5 to 50 μm is described in DE-A-37 14 258, to which reference is hereby made in full. Carriers and processes for their production which are suitable for use in the catalysts according to the invention are described in EP-A-0 187 391, to which reference is hereby also 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 O / 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 carriers those that have a particle size in a range that their Separation enabled. In principle, the particle size is included no upper limit. Preferably, they have as a carrier used polymer particles have an average particle diameter in the range of about 10 to 500 microns, preferably 20 to 400 microns, esp especially 20 to 300 µm, especially 20 to 200 µm.

The average particle diameter of the hydrophobic core is there at in a range of about 0.2 to 100 microns, preferably 0.5 to 50 µm, especially 0.5 to 20 µm. Preferably, the networked Monomers have a narrow particle size distribution, i.e. H. they are essentially monodisperse.

The catalysts of the invention include at least one water-soluble complex of a transition metal, where it is the metal generally around a sub-group element among 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, acts. The transition metal is preferably selected from Me tallen the VII., VIII., I. or II. subgroup, especially un ter Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au or Zn and mixtures thereof.

The water used in the catalysts of the invention soluble transition metal complexes include at least one what ser soluble ligands. In general, everyone can do the subject known ligands are used in water in We are substantially soluble 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, whereupon here is fully referred to.

The water-soluble complexes preferably have at least one Ligand, which is selected from water-soluble phosphorus containing ligands, preferably phosphines, phosphinites, phosphoni ten and phosphites, which additionally have at least one hydrophilic have 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 this acid group pen, primary, secondary and tertiary amino groups and quarter nary ammonium groups.

The water-soluble, phosphorus-containing ligands are preferably a compound of the formula I.

PR ¹ R ² R ³ (I)

wherein
R ¹ , R2 and R ³ independently of one another for C ₁ - to C ₂₅ -alkyl, C ₅ - to C ₈ -cycloalkyl, aryl, aryl- (C ₁ -C ₄ ) -alkyl, C ₁ - to C ₂₅ -alkyloxy , C ₅ - to C ₈ -cycloalkyloxy, aryloxy or aryl- (C ₁ -C ₄ ) 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 -COOX, -PO (OX) ₂ , -OPO (OX) ₂ , -SO 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, C ₁ to C ₂₅ alkyl, C ₅ to C ₈ cycloalkyl or Aryl stand.

In the context of the present invention, the term “alkyl” encompasses straight-chain and branched alkyl groups. In particular, these are straight-chain or branched C ₁ -C ₂₅ -alkyl, preferably C ₁ -C ₁₀ -alkyl and particularly preferably C ₁ -C ₈ -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-hep tyl, 2-ethylpentyl, 1-propylbutyl, octyl, nonyl, decyl, undecyl, dodecyl, etc.

The cycloalkyl group is preferably a C ₅ -C ₈ cycloalkyl group, such as cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

Aryl is preferably phenyl, tolyl, xylyl, mesityl, naph thyl, anthracenyl, phenanthrenyl, naphthacenyl and in particular for phenyl or naphthyl.

Arylalkyl is preferably benzyl.

The above comments on alkyl, cycloalkyl, arylalkyl and Aryl radicals apply accordingly to alkoxy, cycloalkyloxy, aryl alkyloxy and aryloxy radicals.

The radicals R ¹ , R ² and R ³ preferably independently of one another are C ₅ -C ₈ -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 -SO ₃ X, where X is H, Li, Na, K or ammonium.

The water-soluble complex particularly preferably has little least one ligand selected from water-soluble Chen, phosphorus-containing ligands, preferably phosphines, phosphini ten, phosphonites and phosphites, which additionally at least one have hydrophilic functional group.

The water-soluble phosphorus-containing ligand is preferably selected from P (C ₆ H ₄ -m-SO ₃ M) ₃ , P (C ₆ H ₅ ) P (C ₆ H ₄ -m-SO ₃ M) ₂ , P (C ₆ H ₅ ) ₂ P (C ₆ H ₄ -m-SO 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 have 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 heteroaromas, 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 Wei tere phosphorus-containing ligands are such. B. usual phosphine, phosphite, phosphonite and phosphite ligands that have no hydrophilic polar groups.

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

M _W L ¹ _X L ² _Y L 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 independently for 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 before or simultaneously with the production of the invention Catalyst, d. H. with immobilizing the transition metal com plexes, or with the immobilization of to form a sol Chen complex suitable compounds.

The water-soluble transition metal complexes are prepared by customary processes known to those skilled in the art. These include:

• - Implementation of a transition metal compound of the metal that forms the central atom of the water-soluble complex, with we at least one of the previously described water-soluble ligan that and optionally at least one additional one chen ligands;
• - Implementation of a transition metal complex with at least one of the previously described water-soluble ligands and against if necessary, another additional ligand.

For the synthesis of water-soluble transition metal complexes from egg A transition metal compound is generally assumed to be one water-soluble salt. Are suitable for. B. the halogen nides, preferably the chlorides and bromides, nitrates, sulfates, car boxylates, carboxylic acid salts, preferably formates, acetates and pro pionates, 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 solvents, e.g. B. an alcohol such as metha nol, ethanol, n-propanol, isopropanol, n-butanol etc. are used become. Water is preferably used. If desired, can the pH of the aqueous solution through a suitable buffer system  stem, e.g. B. acetic acid / acetate. With the syn these defined water-soluble transition metal complexes the molar ratio of transition metal to water-soluble phosphorus ligand generally depending on the desired stoichiometry from central atom to ligand in what complex soluble. The water-soluble is preferred then ligand containing phosphorus in the desired stoichiometric Ratio or in excess of about 0.05 to 0.5 mol%, compared to the desired stoichiometric ratio puts. In "in situ" synthesis there is generally a size excess of the water-soluble ligand over the target stoichiometry from central atom to ligand. Be the water-soluble phosphorus-containing ligand is then preferred in an excess of about 0.05 to 10 mol% over the target th stoichiometric ratio used. The implementation can, if desired, in the presence of a reducing agent, such as e.g. B. sodium borohydride or hydrazine hydrate. Desired if the reaction takes place 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 synthesis of the water-soluble complexes can also start from a transition metal complex of the metal, which is the central atom of the forms water-soluble complex. Suitable complex ver Bonds of the transition metals are known in principle and in the Literature adequately described. These preferably include com plexes of the transition metals based on the previously described ge suitable additional ligands, which are then partially or completely dig in a ligand exchange reaction against at least one water-soluble, phosphorus-containing ligands are exchanged. Suitable solvents for the ligand exchange reaction are the aforementioned water-soluble solvents and preferred essentially water-immiscible organic solutions medium, such as aromatic hydrocarbons, e.g. B. benzene, toluene, Xylene, halogenated hydrocarbons, such as dichloromethane, Chlo roform, carbon tetrachloride, 1,2-dichloroethane, alcohols with 4 and more carbon atoms such as n-butanol, isobutanol, tert-Bu tanol, pentanol, octanol, alkanes and alkane mixtures etc. preferred two-phase systems such. B. from water and not one completely water-miscible organic solvents be set. The reaction is then preferably carried out under good conditions Mixing of the two phases, e.g. B. by stirring. Desired if the pH of the water phase can be adjusted by a suitable Buffers can be set as previously described.  

The molar ratio of transition metal complex to water-soluble Lich phosphorus-containing ligand is in turn dependent on the ge wanted stoichiometry from central atom to ligand in what complexes soluble in water. As with the synthesis from a transition metal compound becomes the synthesis of defined complexes of what Serous phosphorus-containing ligand in the desired stoichioma trical ratio or in an excess of about 0.05 to 0.5 mol% compared to the desired stoichiometric ratio used, while in the "in situ" synthesis a larger excess shot can be used. Generally this corresponds then 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 , AlCl ₃ , ZnCl ₂ or Lewis base.

Both in the production of the water-soluble transition metal complexes used in the catalysts according to the invention from a transition metal compound 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 übli cher, the person skilled in the art, for. B. by introducing CO or PF ₃ , reaction with olefins, dienes, cycloolefins, Ni trilen, aromatics etc.

In many cases, the actually catalytically active species are only formed under the reaction conditions of the reaction catalyzed by the catalysts according to the invention from the catalysts or catalyst precursors used in each case, e.g. B. in the hydroformylation in the presence of synthesis gas (H ₂ / CO) or in the hydrogenation in the presence of hydrogen.

As described below, it can be used to manufacture the Catalysts according to the invention the water-soluble transition me tall complexes before they are immobilized on the polymer support already acti under the conditions of the reaction to be catalyzed fourth (preformed) and, if necessary, by customary methods be isolated and / or cleaned. Education is preferred of the catalytically active species, however, in situ in the for each because catalyzed reaction used reactor.  

Transition measurements suitable for the catalysts of the invention tall complexes based on triphenylphosphine trisulfonate trina trium salt (TPPTS) are described in EP-A-0 372 313, to which reference is hereby made in full.

Another object of the invention is a process for the manufacture position of a catalyst comprising at least one water soluble complex of a transition metal as previously described and a carrier, as also previously described.

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 suitable for forming complex a) from at least one transition metal compound or one complex, at least one water-soluble ligand and counter optionally at least one further ligand,

soaks and then dries.

If necessary, complex a) or combination b) activate as described above before soaking the wearer.

An impregnated carrier is preferably used for impregnation used.

According to a first suitable embodiment of the invention essen process for the preparation of the catalyst according to the invention you put a water-soluble complex of a transition metal on. Suitable processes for the preparation of these water-soluble Complexes are those previously described. If desired, the Complex to be activated on the support prior to its immobilization (so-called preforming). Appropriate activation procedures depend on the reaction in which the Ka Talysator is to be used. In general, bil formation of the catalytically active species by treating the cataly sators in the presence of at least part of the educts of the ka talizing reaction, e.g. B. by treating a hydrofor mylation catalyst with synthesis gas or a hydrogenation catalyst sators with hydrogen. This treatment is generally done under the usual conditions for the catalyzed reaction gen, d. H. e.g. B. at elevated temperatures and / or elevated Print.  

The catalytically active species thus obtained can be desired if prior to their immobilization on the carrier according to usual Ver drive isolated and / or cleaned. A suitable Reini delivery process is such. B. gel chromatography. He prefers However, the formation of the catalytically active species follows after Immobilization of the water-soluble transition metal complex the wearer in situ immediately before or during which he Catalysts according to the invention catalyzed reaction. Advantageous You can then click on the additional preforming step dispense.

To water the carrier, the water-soluble complex becomes water or in a mixture of water and a water-miscible solution means, e.g. B. one of the aforementioned alcohols, dissolved that a highly concentrated solution is created. Desire If necessary, the solution can be an additional one before the wearer is soaked Liche amount of the water-soluble ligand used be set. The molar ratio of ligand added to water-soluble complex is then generally in a Be range from about 0.1: 1 to 200: 1, preferably 0.5: 1 to 20: 1 Solution is then added to the polymer particles.

The polymer particles of the carrier can, if desired, before Potions are degassed in a vacuum. For better mixing to achieve, the mixture of transition metal complex and Trä ger during the soaking by conventional methods, e.g. B. by Stirring or ultrasound. After soaking the catalyst is by conventional methods such. B. Abdekan animals of the supernatant solvent and subsequent drying NEN in vacuum, dried. Drying is generally done at ambient temperature or a slightly elevated temperature up to about 40 ° C to constant weight. If desired, the previously mentioned steps for catalyst preparation as well as the closing storage of the catalyst under inert gas, such as e.g. B. under argon or nitrogen.

According to a second suitable embodiment of the invention essen process is used to produce the invention Catalyst to form the water-soluble complex of Transition metal suitable combination of at least one over gang metal compound or a complex, at least one what serially soluble phosphorus-containing ligands and possibly little at least one other ligand. If desired, this can Combination in situ before soaking the catalyst water-soluble transition metal complex can be implemented. Ge if desired, this combination can continue before your property lization to the carrier, as previously described, by preforming  be activated. According to a preferred embodiment however, also in the manufacture of the catalyst from an over gear metal compound or a complex on the additional Verforming step before soaking the catalyst to be waived. The molar ratio of water soluble phosphorus-containing ligand to transition metal compound or -kom plex is generally in the range of about 1: 1 to 150: 1, preferably 1.1: 1 to 100: 1, in particular 2: 1 to 75: 1.

Can be used as a solvent for soaking and / or swelling of the carrier the previously in the manufacture of the water-soluble transition me tallcomplex called solvents and solvent mixtures be used. If a two-phase system is used, he says the impregnation follows preferably with intensive mixing. The conditions for soaking correspond to those for the Her position of the catalyst from a water-soluble complex of Transition metal described. If desired, the one steps and storing the catalyst under inert gas.

The catalysts of the invention preferably have one Water content in the range of 0.5 to 5.0 g per 100 g carrier, be preferably 0.7 to 2.5 g per 100 g carrier, based on the weight the dry d. H. unswollen, unladen carrier.

The catalysts of the invention generally have one high reactivity and can be used for a variety of reactions successfully used. They can be advantageously following the reaction catalyzed in their presence by simple, common procedures such. B. Weaning and Dean animals, or by filtration, such as nanofiltration, from the reaction separate mixture.

Suitable reactors for the use of the Kataly according to the invention Sators are conventional reactors, as they are known to those skilled in the art for solid bealyzed liquid-phase and gas-liquid-phase reactions are known. Reactors with a moving catalyst are preferred, such as bubble columns, stirred kettles, stirred kettle cascades, fluid bed reactors gates, suspension bed reactors, tubular reactors etc. are used. The removal of the catalyst can be according to the previously written simple procedures. The invention However, catalysts are also suitable for use in solid bed reactors.

As a solvent for the reaction to be catalyzed be preferably essentially water-insoluble solvents and solvents mixed solvents used. The water solubility is there  at generally at most 100 ppm (at 20 ° C.), preferably at most at least 50 ppm. These include e.g. B. aliphatic hydrocarbons and hydrocarbon mixtures such as pentane, hexane, heptane, petro ether, aromatic hydrocarbons, such as benzene, toluene, Xy lols, esters, such as butyl acetate, etc. As a solvent before preferably essentially water-insoluble starting materials and / or pro products of the catalyzed reaction used, such as. B. Olefins, aldehydes etc.

The catalysts of the invention advantageously show in Generally only very small losses of the water-soluble Transition metal complexes. These are when using the previous ones mentioned essentially water-insoluble solvent and Lö Mixtures of solvents generally at most 1 ppm and lie preferably below the detection limit. It can be under Circumstances may be advantageous if the inventions Catalysts according to the invention an excess of water-soluble phosphorus-containing ligand is used.

In general, the catalysts of the invention detect their separation from the reaction mixture sufficient catalytic cal activity so that, if necessary, after rinsing with one of the organic solvents or solvents described above mixtures of solvents, can be used again for catalysis nen. An activation, e.g. B. by preforming as before is generally not required.

Catalyst regeneration is generally easier Way possible. You can do this e.g. B. the catalyst with water rinse the carrier by settling and decanting or filtering isolate and the transition metal complex and / or ligand containing Process rinse solutions separately. The carrier can generally immediately load with fresh catalyst and without preforming it be used again.

The catalysts of the invention are suitable for reduction and especially for hydrogenation, e.g. B. of carbon-carbon Double bonds and triple bonds, of aldehydes and ketones to alcohols, from cycloalkanes to alkanes and in particular from Nitriles and nitro compounds to amines.

The catalysts of the invention are also suitable for Ka Analysis of addition reactions on carbon-carbon double bonds. This includes the hydroformylation of olefins by Addition of synthesis gas to the double bond. This also counts towards the hydrocarbonylation of olefins, also in the presence from synthesis gas to ketones such as e.g. B. the hydrocarbonylation  from ethene to diethyl ketone. This still includes the hydroacyly alkenes by adding acyl halides to olefins, such as B. the addition of benzoyl chloride to ethene to manufacture phenyl ethyl ketone. This also includes the hydrocyanie tion by adding hydrocyanic acid to olefins, the hydroesterifi ornamentation by adding carboxylic acids to olefins, the hydroami nation by adding ammonia, primary and secondary ami olefins and hydroamidation by adding Car bonsäureamiden on olefins. The catalysts of the invention are also suitable for positional and double bond isomers sation of olefins.

According to a first preferred embodiment, it is the process in which the catalyst according to the invention is used to hydroformylation. Another subject of the He The invention is therefore a process for the hydroformylation of verbin that contain at least one ethylenically unsaturated double bond contained by reaction with carbon monoxide and hydrogen in the presence of at least one hydroformylation catalyst, that is characterized in that one is called hydroformylation catalyst one of the previously described Kata invention uses analyzers.

The transition metal of the water-soluble complex is then preferably cobalt, ruthenium, rhodium, palladium, Platinum, osmium or iridium and especially around cobalt, ruthe nium, rhodium and platinum.

P (C ₆ H ₄ -m-SO ₃ Na) ₃ , P (C ₆ H ₅ ) (C ₆ H ₄ -m-SO 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-SO ₃ Na) and mixtures thereof.

In general, catalytically active species of the general formula H _x M _y (CO) _z L _q ge 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 q , x, y, z stand for integers, depending on the valency and type of the metal as well as the binding 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 preferably represents a value from 2 to 5. The complexes can, if desired, additionally have at least one of the further ligands described above.

According to a preferred embodiment, the formation of the catalytically active species (preforming) in situ, in the for the reactor used the hydroformylation reaction. Desired however, if the preformed catalysts can also, such as described before, manufactured separately and by conventional methods be isolated.

Suitable rhodium compounds or complexes for the preparation of the Catalysts according to the invention are, for. B. Rhodium (II) - and Rho dium (III) salts, such as rhodium (III) chloride, rhodium (III) nitrate, Rhodium (III) sulfate, potassium rhodium sulfate, rhodium (II) - or Rho dium (III) carboxylate, rhodium (II) and rhodium (III) acetate, Rho dium (III) oxide, salts of rhodium (III) acid, trisammonium hexa chlororhodate (III) etc. Rhodium complexes such as Rhodium biscarbonylacetylacetonate, acetylacetonatobisethylene rho dium (I) etc. Rhodium biscarbonylacetylacetonate are preferred or rhodium acetate 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 salts of ruthenium oxygen acids such as K ₂ RuO ₄ or KRuO 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 example RuHCl (CO) (PPh _{3) 3.} also, the metal carbonyls of ruthenium such as dodecacarbonyltriruthenium or Hexarutheniumoctadecacarbo nyl, or mixed forms can, in which CO has been partly replaced by ligands of the formula PR _3, such as Ru (CO) ₃ (PPh _{3) 2,} used in the inventive method.

Suitable cobalt compounds are, for example, cobalt (II) chloro rid, cobalt (II) sulfate, cobalt (II) carbonate, cobalt (II) nitrate, de ren amine or hydrate complexes, cobalt carboxylates, such as cobalt tat, cobalt ethyl hexanoate, cobalt naphthanoate, and the cobalt Caprolactamate complex. The carbonyl complexes of the Cobalt such as dicobalt octacarbonyl, tetracobalt dodecacarbonyl and Hexacobalthexadecacarbonyl can be used.

Preferred solvents are those for hydroformylation used olefins, the aldehydes, which are used in the hydroformylation of the respective olefins arise, their higher-boiling secondary reaction tion products, e.g. B. the products of aldol condensation, aromati hydrocarbons such as benzene, toluene and xylenes, or Mi uses of it.  

As substrates for the hydroformylation process according to the invention In principle, all connections are considered, which one or contain several ethylenically unsaturated double bonds. 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-non, 1-decene, 1-undecene, 1-dodecene etc.

Suitable straight-chain internal olefins are preferably C ₄ to C ₂₀ 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 ₄ - 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 - to C ₈ -cycloalkenes, such as cyclopentene, cyclohexene, cycloheptene, cyclooctene and their derivatives, such as, for. B. whose C ₁ - to C ₂₀ 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, vinyl, such as vinyl nitrile ether, vinyl, such as vinyl nitrile ether, vinyl ether, vinyl nitrile ether, vinyl nitrile ether, vinyl nitrile ether, vinyl nitrile ether, vinyl nitrile ether, vinyl nitrile ether propyl ether, etc., C ₁ -C ₂₀ -alkenols, -alkenediols and -alkadienols, such as 2,7-octadienol-1. Suitable substrates are further di- or polyenes with isolated or conjugated Doppelbindun gene. 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 of the invention are therefore advantageous fortunately for the hydroformylation of the aforementioned higher ones Olefins with a carbon number of 7 or more and mixtures of it because with them the problems associated with the separation of previously common hydroformylation catalysts occur in Generally avoided. In contrast to homogeneous Catalysts on a thermal separation leading to a Schä damage to the catalyst can be dispensed with. Also the  Disadvantage of two-phase systems, due to the lack of solubility ity of the higher olefins in the aqueous catalyst-containing Resulting phase is by the catalysts of the invention generally avoided advantageously. So allow the invention modern catalysts generally better contact the what was immobilized on the hydrophilic side chains of the carrier Serious transition metal complexes with the olefin as the usual Chen two-phase systems. Here is the loss of immobilized Extremely transition metal complex to the organic reaction solution low and is generally at most 1 ppm. So leave the catalysts of the invention are also advantageous use over immobilized hydroformylation catalysts, in which the active groups via anchor groups on the carrier ge are bound and under the hydroformylation conditions to "Bleeding" tend.

The hydroformylation reaction can be continuous, semi-continuous done nuously or discontinuously.

Suitable reactors for the continuous reaction are Known expert and z. B. in Ullmann's encyclopedia of technical chemistry, vol. 1, 3rd ed., 1951, pp. 743ff. described ben.

Suitable pressure-resistant reactors are also known to the person skilled in the art knows and z. B. in Ullmann's Encyclopedia of Technical Chemistry, Vol. 1, 3rd edition, 1951, pp. 769ff. described. In space An autoclave is common for the method according to the invention used, if desired with a stirrer and egg ner inner lining can be provided.

The composition of the used in the inventive method th synthesis gas from carbon monoxide and hydrogen can be in white ranges vary. The molar ratio of carbon monoxide and hydrogen is typically about 5:95 to 70:30 before approx. 40:60 to 60:40. A mola is particularly preferred res ratio of carbon monoxide and hydrogen in the range of used about 1: 1.

The temperature in the hydroformylation reaction is generally mean in a range of about 20 to 180 ° C, preferably about 50 up to 150 ° C. The reaction is usually at the partial pressure of the reaction gas at the selected reaction temperature leads. Generally the pressure is in the range of about 1 up to 700 bar, preferably 1 to 300 bar, in particular 1 to 100 bar and especially 1 to 30 bar. Generally they allow inventions  Catalysts according to the invention never implement in one area third pressures, such as in the range from 1 to 100 bar.

The molar ratio of olefin to transition metal complex is generally in the range of about 100: 1 to 50,000: 1, preferably 1,000: 1 to 10,000: 1.

The hydroformylation catalysts according to the invention can be by customary methods known to those skilled in the art, such as settling and Decant or filter, e.g. B. by nanofiltration, from the out remove the hydroformylation reaction and can in space generally used again for the hydroformylation.

The catalysts according to the invention advantageously show high activity, so that the corresponding Al dehydes can be obtained in good yields. With hydroformyly tion of α-olefins and of internal, linear olefins they also show good n / iso selectivity. So is the type part of n-aldehyde (s) in the reaction product in general min at least 65% by weight, preferably at least 70% by weight.

According to a further preferred embodiment, it is in the process in which the catalyst according to the invention is turned on is set to a reduction.

Another object of the invention is therefore a method for Reduction of compounds with non-aromatic C = C double and Triple bonds, aldehydes, ketones, nitriles and nitroverbin at least by reaction with hydrogen in the presence of a hydrogenation catalyst, which is characterized in that one of the inventions described above is invented as the hydrogenation catalyst uses catalysts according to the invention.

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

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 are} identical or can be different and stand for alkyl, cycloal kyl or aryl.

In formula III, alkyl preferably represents C ₁ -C ₈ -alkyl, in particular C ₁ -C ₄ -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-alkoxynitrobenes zoles, such as 2-methoxynitrobenzene, 2-ethoxynitrobenzene, 3-methoxy nitrobenzene, 3-ethoxynitrobenzene, 4-methoxynitrobenzene, 4-ethoxy nitrobenzene, 3-nitrobenzonitrile, 2-nitrobenzyl alcohol, 3-nitro benzyl alcohol, 4-nitrobenzyl alcohol, 1-nitronaphthalene, 2-nitro naphthalene, 2-nitrophenol, 3-nitrophenol, 4-nitrophenol, 3-nitro toluene etc. The nitro compound to be reduced can be desired if also contain two or more nitro groups, which then to Amino groups are reduced.

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 com plex of the catalyst of the invention to substrate is in space common in a range from about 1: 100 to 1: 1,000,000 before increases 1: 1,000 to 1: 100,000. The reaction temperature is in space generally in a range from about 10 to 150 W, preferably 20 to 130 ° C, especially 50 to 110 ° C. The hydrogen pressure is in Generally in a range from about 1 to 300 bar, preferably 2 up to 150 bar, in particular 10 to 100 bar.

After the reaction has ended, the catalyst according to the invention can tion in a simple, previously described manner from the reaction medium be separated, e.g. B. by settling and decanting or fil wear. In general, the catalyst can be used without essential loss of activity again for catalytic reduction Zen. If liquid nitroaromatics are used for the reduction, so can generally do without the addition of a solvent be tested. However, it is also possible to add an organic chemical solvent such as benzene, toluene, xylenes, cyclohexane, De calin, etc. or mixtures thereof.

The invention is illustrated by the following, not restrictive Examples explained in more detail.  

Examples

TentaGel® S OH (product number S 30,900, particle size 90 µm, swelling capacity 3.5 to 4.5 ml H ₂ O / g) from Rapp Polymer, Tübingen is used as a support for the catalysts. These particles consist of a cross-linked polystyrene core with grafted 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 add 0.43 g (0.75 mmol) of TPPTS and 0.008 g (0.03 mmol) of Rh (CO) ₂ acac, close the autoclave and charge it by evacuating three times and then gassing it with a CO / H synthesis gas mixture ₂ (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. Then the reactor contents are 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 with a magnetic stirrer for 1 h. The supernatant organic phase is then pipetted off under protective gas and the remaining yellow gel is rinsed three times with 10 ml of toluene, the rinsing solutions also being pipetted off in each case. 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 O content: 1.1 g / 100 g

Example 2 Production of a catalyst based on TPPTS without prefor lubrication

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. With intensive stirring with a magnetic stirrer, a deep yellow, slightly cloudy solution forms, which is mixed with 10 ml of toluene and then stirred at 70 ° C. for 15 minutes. After cooling, the two-phase system obtained is again placed under argon protective gas in a Schlenk tube which contains 1.0 g of degassed TentaGel® S OH and is 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, after which a solid, intensely yellow product results, which, after comminution, is dried for a further 1.5 hours at ambient temperature and 2 mbar. The previously described steps for catalyst production and its storage until use are carried out under argon protective gas.

Rhodium content: 0.11 g / 100 g
H ₂ O content: 4.4 g / 100 g
Phosphorus content: 2.7 g / 100 g

Example 3 Production of a catalyst based on triphenylphosphine mo nosulfonate 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 acac too. After closing the autoclave, evacuation is carried out three times and flushing 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 containing 1 g of degassed TentaGel® S OH. With a magnetic stirrer, the mixture is stirred intensively for 1 h, a gel-like phase being formed. After stirring is complete, the mixture is allowed to sit 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 O content: 1.3 g / 100 g
Phosphorus content: 1.3 g / 100 g

Example 4 Production of a catalyst based on TPPMS without prefor lubrication

In a Schlenk tube, 0.450 g (1.2 mmol) of TPPMS and 0.0145 g (0.056 mmol) of Rh (CO) ₂ acac are mixed with 1.5 ml of the buffer solution described in Example 1 and 6 ml of H ₂ O under argon protective gas and stirred, forming a light yellow suspension to which 15 ml of toluene are added. After stirring for 1 hour at 80 ° C., after cooling, it is transferred to a Schlenk tube which contains 1.5 g of degassed Tenta-Gel® S OH. After stirring the mixture, a phase separation occurs, whereupon the yellow gel obtained is allowed to settle and the clear solution above is pipetted off. The gel-like phase obtained is rinsed three times with 10 ml of toluene 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 previously described steps for catalyst production and its storage take place under argon protective gas.

Rhodium content: 0.25 g / 100 g
H ₂ O 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 under argon protective gas in a Schlenk tube with 1 g degassed TentaGel® S OH given. The resulting mass is intensely ge stirred and then 5 h at ambient temperature and one Pressure of 2 mbar dried.  

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). The catalysts used here are both not yet used preformed and nonformed catalysts from Examples 1 and 2, and preformed and nonformed recycled 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 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 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 left to sit, 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.

Examples 14 to 16 Hydroformylation with a catalyst based on TPPMS as Ligands

In a 10 ml stirred autoclave, 1-dodecene, catalyst and toluene are initially introduced in an amount according to Table 3 under argon at room temperature and heated to the reaction temperature (see Table 3). As catalysts, not yet used preformed and non-preformed catalysts from Examples 3 and 4 as well as preformed and not preformed recycled catalysts are used. The information on the catalyst used in each case can also be found in Table 3. After reaching the reaction temperature with synthesis gas CO / H ₂ (1: 1), the reaction pressure, as shown in Table 3, is set and kept constant for a reaction time of 4 h by pressing synthesis gas through 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 was carried out as described in Examples 6 to 13.

Example 17 Hydrogenation of nitrobenzene with Rh (CO) Cl (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) Cl (TPPTS) ₂ ) are added to a 10 ml stirred autoclave and the mixture is rinsed Autoclave through multiple 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 (11)

1. A catalyst comprising at least one water-soluble transition metal complex which is applied to a support, characterized in that the support 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 the polymer base is bound to hydrophilic side chains, wel che in the presence of a liquid, hydrophilic medium Form the hydrophilic matrix by swelling. 3. Catalyst according to one of the preceding claims, characterized characterized in that the carrier is a graft copolymer with a cross-linked hydrophobic core is what the hydrophilic be chains are grafted on. 4. Catalyst according to one of the preceding claims, characterized characterized that the hydrophilic side chains are linear or are branched polyether side chains. 5. Catalyst according to one of the preceding claims, characterized characterized in that the carrier is 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 VII., VIII., I. or II. Subgroup of the periodic table and Mi made of it. 7. Catalyst according to one of the preceding claims, characterized characterized that the water-soluble transition metal com plex at least one water-soluble, phosphorus-containing Li existed with at least one hydrophilic functional group having.   8. A method for producing a catalyst according to any one of claims 1 to 7, characterized in that the carrier ger

• 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 suitable for forming the complex a), at least one water-soluble ligand and optionally at least one further ligand,

soaks and then dries. 9. Process for hydroformylation of compounds that have little contain at least one ethylenically unsaturated double bond, by reaction with carbon monoxide and hydrogen in counter were at least one hydroformylation catalyst, thereby characterized in that as a hydroformylation catalyst uses a catalyst according to any one of claims 1 to 7. 10. Process for reducing compounds with non-aromatic carbon-carbon double and triple bonds, Aldehydes, ketones, nitriles and nitro compounds by Um settlement with hydrogen in the presence of at least one Hy drier catalyst, characterized in that as Hy Third catalyst a catalyst according to one of claims 1 up 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, hydroacy lation, hydrocyanation, hydroesterification, hydroamine tion, hydroamidation and for position and double bond isomerization of olefins.