JP2003510167A - Polymer-supported catalyst having water-soluble transition metal complex - Google Patents

Abstract

  (57) [Summary] The present invention relates to a supported catalyst containing at least one water-soluble transition metal complex, wherein the supported catalyst is characterized by using polymer particles having a hydrophobic core and hydrophilic side chains as a support. . In the examples, tentagel, polymer particles consisting of cross-linked polystyrene nuclei and grafted polyethylene glycol side chains are used as carriers. The transition metal is selected from metals of group VIIB, VII, IB or IIB of the periodic table and mixtures thereof.

Description

Detailed Description of the Invention

The present invention relates to a catalyst having at least one water-soluble transition metal complex coated on a support, a process for the preparation of this catalyst, and a hydroformylation and reduction process in the presence of such a catalyst.

For many important industrial processes, homogeneous catalyst systems are used. This includes low pressure hydroformylation, for example to produce aldehydes from olefins, carbon monoxide and hydrogen. The catalysts may be Co compounds or Co complexes, Rh compounds or Rh complexes or Ru compounds or Ru, which may be modified with phosphine-containing ligands due to activity and / or selectivity effects.
Complexes are used. In this case, especially rhodium-triphenylphosphine-catalysts are widespread.

A known problem when using homogeneous catalysts is the separation of the catalyst after completion of the catalytic reaction with the homogeneous catalyst. In this case, it should be possible to obtain as high a catalyst return rate as possible while avoiding product losses or catalyst losses, preferably by means of simple treatment methods, for example by the required separation treatment and subsequent cracking. Thus, to avoid thermal decomposition of the catalyst during separation, the hydroformylation of higher olefins, i.e. generally olefins having 7 or more carbon atoms, in the presence of the aforementioned rhodium / triphenylphosphine-low pressure-catalysts, It is extremely expensive industrially.

DE-A 37 210 95 describes a process for the preparation of C ₇ -C ₁₇ -aldehydes by rhodium-catalyzed hydroformylation, which is obtained during the hydroformylation. The reaction medium is subjected to a plurality of evaporation steps and (partial) condensation steps in each reactor at the temperature, pressure and residence time to be kept exactly. This method is industrially very expensive, which adversely affects the economic conversion rate on a large industrial scale.

EP-A-0 372 313 discloses that there is at least one P (C ₆ H ₄ -m-SO ₃ Na) ₃ -ligand, the VII subgroup of the Periodic Table, VI
Water-soluble complex compounds of elements from group II and group I are described. The compounds are suitable, for example, for the hydroformylation of olefins, in which case a heterogeneous reaction medium (two-phase system) consisting of a water-soluble catalyst-containing phase and an organic olefin educt-containing phase or an aldehyde product-containing phase is used. It

The German patent application DE 195 29 874 discloses the formula: Rh (
A method for reducing nitro compounds in the presence of a water soluble rhodium catalyst of CO) Cl (TPPTS) ₂ (TPPTS = triphenylphosphine trisulfonate-trisodium salt), and optionally addition of an organic solvent, is described. There is. In this case, the examples only describe the method on a gram scale, in which case the aqueous catalyst solution is separated in a separating funnel.

A drawback of the above-mentioned two-phase system is its limited industrial applicability. A prerequisite for the use of biphasic systems is the constant and constant solubility of organic educts in the aqueous phase. Therefore, processes based on two-phase systems are particularly unsuitable for hydroformylation of higher olefins, since the two-phase system is essentially insoluble in the aqueous catalyst-containing phase. Always by addition of reagents which increase the solubility of the catalyst in the organic phase, for example by adding phase transfer catalysts or emulsifiers, or by corresponding modification of the ligands, for example by introducing long-chain alkylammonium groups. ,
The separability of the catalyst is also deteriorated. Thus, the simple separability of the intended catalysts, together with high catalyst return rates, is not achieved by the two-phase system in the case of a large number of reactions.

Comprehensive Organometallic Chemistry, G. Wilkinson, F. G. A. Stone
And E. W. Abel, Pergamon Press, Oxford, 1982, Vol. 8, p. 553 et seq., Describes supported homogeneous transition metal catalysts, where the catalytically active component is shared with the polymer carrier. Are connected. A disadvantage of immobilized homogeneous catalysts of this kind is that they often have less activity and / or other selectivities than the corresponding nonimmobilized homogeneous systems. Bleeding of transition metals is observed, especially in the case of hydroformylation catalysts. Damaged catalysts of this kind cannot be reused.

Since Chemtech 1992, pages 22, 498, supported aqueous phase catalysts (SAP, supp
orted aqueous-phase), in which the homogeneous transition metal catalyst is immobilized on a support using a large surface area, for example a macrosporig glass support or a silicon dioxide support. The disadvantage of these systems is in part their high sensitivity. That is, 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 area, special highly porous supports have to be used, depending on the respective use area. Reuse of damaged catalyst is not possible. Due to the industrial costs required, the production of such catalysts is generally expensive, so that the use of said catalysts in industrial processes is generally uneconomical.

Angew. Chem. 1997, 109, 1810 et seq. Describe immobilization techniques for homogeneous catalysts, where the polyether covalently bound to the silicate surface is a solvent and / or polyoxometallate. Used as a rank. It is suitable as an oxidation catalyst.

Beller et al., Journal of Molecular Catalysis A, 104 (1995), pp. 17-85, describe various methods for immobilizing generally homogeneous catalytic forms (especially 3
See pages 4-37).

[0012] In the literature cited above, no immobilized catalyst is described, in this case
The water-soluble transition metal complex accumulates in the hydrophilic outer layer of the solid organic hydrophobic polymer carrier.

Angew. Chem. Int. For the protein synthesis of hydrophilic tentacle-type polymers (Tentakelpolymer) consisting of a polystyrene core that is optionally crosslinked and a polyethyleneglycol chain grafted onto it, from English edition, 30, 1991, pages 113 onwards. The use of is described. The use of this polymer particle as a carrier for immobilizing water-soluble transition metal complexes is not described.

The present invention is based on the problem of providing new catalysts based on water-soluble transition metal complexes. The catalyst can be produced in a simple manner and can be easily recycled. Advantageously, the catalyst can be separated well from the reaction mixture after the end of the catalytic reaction.

Now, surprisingly, catalysts based on water-soluble transition metal complexes have been found, which have a hydrophobic polymer substrate with a hydrophilic matrix as carrier.

The subject of the present invention is therefore a catalyst which contains at least one water-soluble transition metal complex coated on a carrier, in which case the catalyst is a hydrophobic catalyst in which the carrier is associated with a hydrophilic matrix. It has a polymeric substrate, in which case the hydrophilic matrix is characterized by containing a transition metal complex.

Preferably the hydrophobic polymer substrate is at least one radically polymerizable α,
A β-ethylenically unsaturated monomer is polymerized and contained, and this monomer is a vinyl aromatic compound such as styrene, α-methylstyrene, o-chlorostyrene or vinyltoluol, α, β-ethylenically unsaturated monomer. C ₃ -C ₆ - monocarboxylic acids and _C 3 -C ₆ - dicarboxylic acids with _C 1 _{-C 20} - esters of alkanols, such as acrylic acid and / or methacrylic acid with methanol, ethanol, n- propanol, isopropanol, n Esters of butanol, isobutanol or 2-ethylhexanol, maleic acid dimethyl ester or maleic acid-n-butyl ester, α, β-ethylenically unsaturated nitriles such as acrylonitrile and methacrylonitrile, vinyl alcohol and C _1- . C ₂₀ - monocarboxylic Esters with acids such as vinyl formate, vinyl acetate, vinyl propionate, vinyl-n-butyrate, vinyl laurate and vinyl stearate, C ₂ -C ₆ -monoolefins such as ethene, propene and butene, at least 2 Of non-aromatic hydrocarbons having olefinic double bonds, such as butadiene, isoprene and chloroprene, and mixtures thereof. Advantageously, the hydrophobic polymer substrate comprises at least one of these monomers, generally about 50 to 99.95% by weight, preferably 6% by weight, based on the total amount of the monomers to be polymerized.
It is polymerized and contained in an amount of 0 to 99.9% by mass, particularly 70 to 99% by mass.

Preferably the hydrophobic polymer substrate is a crosslinked polymer. In this case, the polymer substrate contains, in addition to the above-mentioned monomers, at least one crosslinkable monomer which is polymerized and introduced, and the monomers include alkylene glycol diacrylate and alkylene glycol dimethacrylate, for example 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 dimethacrylate, as well as divinyl benzene, vinyl acrylate, vinyl methacrylate, allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, methylbis Selected from acrylamide, and mixtures thereof. The amount of these crosslinkable monomers is preferably about 0.05 to 20% by weight, preferably 0.05 to 10% by weight, in particular 0, based on the total amount of monomers to be polymerized.
． It is in the range of 1 to 8% by weight and especially 0.2 to 5% by weight.

The optionally crosslinked polymer forming the hydrophobic polymer substrate may additionally contain at least one monomer polymerized in, which monomer comprises at least one monomer per molecule. It has been selected among compounds having an α, β-ethylenically unsaturated double bond and at least one active hydrogen atom. This monomer includes, for example, α, β-ethylenically unsaturated monocarboxylic acid and α, β-ethylenically unsaturated dicarboxylic acid such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, and the like, C ₁ -C ₂₀ - alkanediol, for example 2
-Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-
Hydroxyethyl ethacrylate, 2-hydroxypropyl acrylate, 2-
Hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3
Examples thereof include esters with hydroxypropyl methacrylate and the like. Furthermore, esters of the above-mentioned acids with triols and polyols, such as glycerin, erythritol, pentaerythritol, sorbit, etc. are suitable. Furthermore, it said acid, C ₂ -C 12 having a first amino group or secondary amino group _- esters and amides of amino alcohols are suitable. The compounds include aminoalkyl acrylates and aminoalkyl methacrylates and their N-monoalkyl derivatives, such as derivatives having N—C ₁ -C ₈ -monoalkyl groups, such as aminomethyl acrylate, aminomethyl methacrylate, aminoethyl acrylate,
Examples thereof include N-methylaminomethyl acrylate. Also suitable are vinyl aromatic compounds having at least one hydroxyl group, for example 4-hydroxystyrene. The monomers may be used alone or as a mixture. The amount of these monomers 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 monomers to be polymerized. Preferably 4-hydroxystyrene is used.

According to a preferred embodiment, the optionally crosslinked polymer forming the hydrophobic polymer substrate is polyvinyl alcohol, said compound being eg a polymer-like reaction, eg a polyester of vinyl alcohol, preferably Is obtained by partial or complete hydrolysis from polyvinyl acetate. In this case, the amount of hydroxy groups (degree of functionalization) is preferably in the range of about 1 to 15 meq / g.

According to another preferred embodiment, the polymer forming the hydrophobic polymer substrate is a polyhydroxystyrene homopolymer or polyhydroxystyrene copolymer. Suitable comonomers are the abovementioned α, β-ethylenically unsaturated monomers and mixtures thereof, preferably styrene is used. Preference is given to polyhydroxystyrene-based polymers having hydroxyl groups in an amount of about 0.05 to 0.7 meq / g.

According to a particularly preferred embodiment, the optionally cross-linked polymer forming the hydrophobic polymer substrate is a chloromethylated polystyrol cross-linked with divinyl benzene and the compound is a first functional group. During the conversion reaction, it is reacted with monoalkylene glycols or oligoalkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol and preferably tetraethylene glycol.

Preferably attached to the polymer substrate are hydrophilic side chains, which form by swelling the hydrophilic matrix of the catalyst according to the invention in the presence of a liquid hydrophilic medium. Preferably the carrier is at least about 2 ml H ₂ O / g in water, especially at least 3 ml.
It has a swelling capacity of H ₂ O / g and especially at least 3.5 ml H ₂ O / g.

[0024] Preferably the carrier used according to the invention is a graft copolymer consisting of a crosslinked polymer forming a hydrophobic polymer substrate and linear or branched polyether side chains. Especially, it is a linear polyether side chain.

The production of polymer particles for use as a carrier according to the invention generally involves the cross-linking of the polymer forming the hydrophobic polymer matrix and a suitable monomer to form a linear or branched polyether side chain. It is carried out either by reacting with the formation of chains or by reacting with suitable oligomers or polymers containing linear or branched polyether groups. Advantageously crosslinked polymers have active hydrogen atoms in the form of hydroxyl groups, primary amino groups and secondary amino groups and / or carboxyl groups, for example for reaction with polyether side chain-forming monomers, oligomers or polymers. Have. A group having an active hydrogen atom is a hydroxyl group. Active hydrogen atoms can be introduced into the substrate during the course of the polymerization by using suitable initiators and / or monomers or by subsequent functionalization. The amount of active hydrogen atoms such as hydroxy groups (degree of functionalization) is generally about 0.
Within the range of 02 to 25 meq / g of polymer base material, preferably 0.05 to 15 meq /
It is g.

The linear polyether side chains forming the hydrophilic side chains of the carrier are preferably about 500-5.
It has a number average molecular weight in the range of 0000, preferably 600 to 25000, especially 800 to 10000 and especially 900 to 6000.

Due to the introduction of linear polyether side chains, the polymer bases mentioned in the case of polyaddition have at least one alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide and mixtures thereof, or at least one. Can be reacted with cyclic ethers such as tetrahydrofuran. Suitable methods for alkoxylating compounds having active hydrogen atoms, eg hydroxyl groups, are known to the person skilled in the art. In this case, the linear polyether side chains obtained are homopolymers of ethylene oxide, propylene oxide and n-butylene oxide, block copolymers of ethylene oxide, propylene oxide and / or n-butylene oxide, and thus alkylene oxide units. May have a copolymer containing and statistically distributed.

Advantageously, said, preferably crosslinked, base polymer is an oligoalkylene glycol in the first reaction step, preferably of the general formula: H- (OCH ₂ CH ₂ ) _n —OH, in which case , N is an integer of 2 to 20). In this case, the reaction conditions correspond to those of the Williamson ether synthesis known to those skilled in the art. Then, in the second step, the oligoalkylene glycol chain is reacted with at least one alkylene oxide, as described above, to the desired chain length. This method is preferably suitable for the production of polystyrene-polyoxyethylene-graft copolymers.

The carrier used according to the invention is preferably a graft copolymer having a crosslinked hydrophobic core on which hydrophilic side chains are grafted.

According to a suitable embodiment, essentially monodisperse polymers are used as crosslinked core polymers. A process for the production of crosslinked monodisperse polymers having a diameter in the range of about 0.5 to 50 μm is described in DE-A 371425.
No. 8, which is incorporated herein by reference in its entirety. Suitable carriers for use in the catalysts according to the invention and the process for their preparation are described in EP-A-0187391, which is likewise incorporated herein by reference in its entirety. ing. Suitable carriers include Wrap Polymers (Firma Rap
p Polymere), Tübingen, under the name (TentaGel®). Particularly preferred is TentaGel® S OH (particle size 90 μm, capacity 0.24 mmol / g, swelling capacity 3.5-4.5 ml H ₂ O /
g) is used. The polymer particles include polystyrene cores with linear polyethylene glycol side chains (ethylene oxide units of about 68).

In general, as the carrier, polymer particles having a particle size within a range that allows separation may be used. In this case, the upper limit of the grain size is not set in principle. The polymer particles which are advantageously used as carriers are about 10 to 500 μm, preferably 20 to 4 μm.
It has an average particle size in the range of 00 μm, in particular 20 to 300 μm, in particular 20 to 200 μm.

In this case, the average particle size of the hydrophobic core is about 0.2 to 100 μm, preferably 0.
It is in the range of 5 to 50 μm, especially 0.5 to 20 μm. Preferably the crosslinked monomers have a narrow particle size distribution, ie the monomers are essentially monodisperse.

The catalyst according to the invention contains at least one water-soluble complex of a transition metal, in which case the metal generally has atomic numbers 21-30 (Sc-Zn), 39-48 (Y-Cd).
), 57-80 (La-Hg), and subgroup elements selected from the mixture thereof. Preferably, a metal of Group VII, Group VIII, Group I or Group II, especially Mn, Fe, Ru, Os, Co, Rh, Ir, N.
It is a transition metal selected from i, Pd, Pt, Cu, Ag, Au or Zn and mixtures thereof.

The water-soluble transition metal complex used in the catalyst according to the invention has at least one water-soluble ligand. In this case, all ligands known to the person skilled in the art which are generally soluble in water without substantial decomposition may be used. Suitable water-soluble ligands and complexes are described in P. Kalck and F. By Monteil, Adv. Organomet. Chem.
34, 1992, pp 219-285, which is incorporated herein by reference in its entirety.

The water-soluble complex is preferably a water-soluble phosphorus-containing ligand additionally having at least one hydrophilic functional group, preferably at least one selected from phosphines, phosphinites, phosphonites and phosphites. Has one ligand. Suitable hydrophilic functional groups include carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, phosphoric acid groups, alkali metal salts, alkaline earth metal salts and ammonium salts of these acid groups, primary amino groups, secondary amino groups. A group and a tertiary amino group and a quaternary ammonium group.

[0036]   Advantageously, the water-soluble phosphorus-containing ligand has the formula I:       PR¹R^TwoR^Three              (I) [In the formula, R¹, R^TwoAnd R^ThreeC independently of each other₁~ C₂₅-Alkyl, C₅ ~ C₈-Cycloalkyl, aryl, aryl- (C₁~ C_Four) -Alkyl, C ₁ ~ C₂₅-Alkyloxy, C₅~ C₈-Cycloalkyloxy, aryl
Xy or aryl- (C₁~ C_Four) -Alkyloxy and the radical R¹ , R^TwoAnd / or R^ThreeAt least one of at least one, for example one,
It has two or three hydrophilic functional groups, and these hydrophilic functional groups are -COOX, -PO.
(OX)_Two, -OPO (OX)_Two, -SO_ThreeX, -NE¹E^Two, -NE¹E^TwoE ³⁺ , (Where X represents H, Li, Na, K or ammonium, and
E¹, E^TwoAnd E^ThreeIndependently of each other hydrogen, C₁~ C₂₅-Alkyl, C₅~
C₈-Representing cycloalkyl or aryl)]
Is a compound.

Within the scope of the present invention, the term “alkyl” includes straight-chain alkyl groups and branched-chain alkyl groups. In particular, they are straight-chain or branched C ₁ -C ₂₅ -alkyl radicals, preferably C ₁ -C ₁₀ -alkyl radicals and particularly preferably C ₁ -C ₈ -alkyl radicals. Examples of alkyl radicals are in particular methyl, ethyl, propyl, isopropyl, n-butyl,
2-butyl, s-butyl, t-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 and the like.

Cycloalkyl groups are preferably C ₅ -C ₈ -cycloalkyl groups, for example cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

Aryl preferably represents phenyl, tolyl, xylyl, mesityl, naphthyl, anthracenyl, phenanthrenyl, naphthacenyl and especially phenyl or naphthyl.

[0040]   Arylalkyl preferably represents benzyl.

The above-mentioned embodiments for alkyl groups, cycloalkyl groups, arylalkyl groups and aryl groups apply correspondingly to alkoxy groups, cycloalkyloxy groups, arylalkyloxy groups and aryloxy groups.

Preferably, the radicals R ¹ , R ² and R ³ independently of one another represent C ₅ -C ₈ -cycloalkyl or aryl, in particular cyclohexyl or phenyl, in which case the radicals R ¹ , R ² and / or One, two or three of R ³ have one of the hydrophilic functional groups mentioned above.

Preferably, the hydrophilic functional group has the formula —SO ₃ X, where X is H, Li, Na, K.
Or represents ammonium).

Particularly preferably, the water-soluble complex is selected from water-soluble phosphorus-containing ligands, preferably phosphines, phosphinites, phosphonites and phosphites, and additionally at least one hydrophilic functional group. Having at least one ligand having

Preferably, 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 a water-soluble phosphorus-containing ligand selected from these mixtures, in this case, M
Represents H, Li, Na, K or ammonium. Advantageously M is Na or K
Represents

The water-soluble complex may have one or more of the above water-soluble complexes. The water-soluble complex is, in addition to the above-mentioned water-soluble ligand, cyanide, halide, amine, carboxylate, acetylacetonate, aryl sulfonate or alkyl sulfonate, hydride, CO, olefin, diene, cycloolefin,
Nitriles, N-containing heterocyclic compounds, aromatic and heteroaromatic compounds, ethers, PF ₃ and mono-, bidentate and polydentate phosphine ligands, phosphonites, phosphinites and phosphites It may have at least one other ligand selected from the ligands. These other ligands are monodentate, 2
It may be bidentate and polydentate, and may be coordinated to the metal atom of the catalyst complex. Suitable other phosphorus-containing ligands include, for example, conventional phosphine ligands, phosphinite ligands,
Phosphonite and phosphite ligands, which have no hydrophilic polar groups.

The water-soluble transition metal complex used according to the present invention has, for example, the general formula II: M _w L ¹ _x L ² _y L ³ _z (II) [wherein M is a transition metal, preferably Mn, Fe] , Ru, Os, Co, Rh, Ir, Ni,
Represents Pd, Pt, Cu, Ag, Au or Zn, L ¹ represents a water-soluble phosphorus-containing ligand as defined above, L ² and L ³ may be the same or different, and Represents one of the other ligands defined above, and w, x, y and z are dependent on the valence and type of the metal and the valency of the ligands L ¹ , L ² and / or L ^3. And, depending on the value, represents an integer].

Preferably w is an integer from 1 to 6. y and z are 0 independently of each other
Represents an integer of ~ 7w. z is preferably an integer from 0 to 4w.

The production of the water-soluble transition metal complex may be carried out before or simultaneously with the production of the catalyst according to the invention, ie the immobilization of the transition metal complex or the immobilization of the compounds suitable for the formation of such a complex. .

The water-soluble transition metal complex may be produced by a conventional method known to those skilled in the art. This includes in particular: a transition metal compound of the metal forming the central atom of the water-soluble complex, and at least one water-soluble ligand as described above, and optionally at least one additional ligand. A reaction of a transition metal complex with at least one water-soluble ligand as described above, and optionally at least one additional ligand.

To synthesize a water-soluble transition metal complex from a transition metal compound, one generally starts with a water-soluble salt. In this case, for example, halides, preferably chlorides and bromides, nitrates, sulfates, carboxylates, carboxylates, preferably formates, acetates and propionates, oxides and the like are suitable.

The solvent of the transition metal compound is, for example, water or at least one other water-miscible solvent such as alcohol, for example, methanol, ethanol, n.
Mixtures of propanol, isopropanol, n-butanol and the like may be used. Water is preferably used. If desired, the pH value of the aqueous solution is
It can be adjusted by a suitable buffer system, for example acetic acid / acetate. When synthesizing a defined water-soluble transition metal complex, the molar ratio of transition metal to water-soluble phosphorus-containing ligand generally depends on the desired stoichiometry of the central atom and the ligand in the water-soluble complex. To be selected. In this case, preferably the water-soluble phosphorus-containing ligand is in the desired stoichiometric ratio or in excess of about 0.05 to 0.5 mol% with respect to the desired stoichiometric ratio. used. "In situ" -in the case of synthesis, a large excess of water-soluble ligand is generally used relative to the desired stoichiometry of the central atom and the ligand.
Preferably, in this case, the water-soluble phosphorus-containing ligand is used in an excess amount of about 0.05 to 10 mol% with respect to the aimed stoichiometric ratio. The reaction may be carried out in the presence of a reducing agent such as sodium borohydride or hydrazine hydrate if desired. If desired, the reaction may be carried out under an inert gas such as nitrogen or argon. The temperature is generally in the range of about 0-50 ° C, preferably 10-40 ° C.

The synthesis of the water-soluble complex may be carried out starting from a transition metal complex of the metal forming the central atom of the water-soluble complex. Suitable transition metal complex compounds are known in principle,
And it is well described in the literature. Said compounds preferably include transition metal complexes based on said suitable additional ligands, which then undergo at least one water-soluble phosphorus-containing coordination during the ligand exchange reaction. Partially or completely exchanged with child. Suitable solvents for the ligand exchange reaction are the water-soluble solvents mentioned above, as well as organic solvents which are preferably essentially immiscible with water, for example aromatic hydrocarbons such as benzene, toluene, xylol, halogenated hydrocarbons. Examples thereof include dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, alcohols having 4 or more carbon atoms, such as n-butanol, isobutanol, t-butanol, pentanol, octanol, alkanes and alkane mixtures. Advantageously, a two-phase system consisting of, for example, water and an organic solvent which is not completely miscible with water is used. In this case, the reaction is preferably carried out with good mixing of the two phases, for example by stirring. If desired, the pH value of the aqueous phase can be adjusted by suitable buffering agents as described above.

The molar ratio of transition metal complex to water-soluble phosphorus-containing ligand also depends on the desired stoichiometry of the central atom and the ligand in the water-soluble complex. As in the case of synthesizing a transition metal compound, a water-soluble phosphorus-containing ligand is used to synthesize a defined complex in a stoichiometric proportion of interest, or in a stoichiometric proportion of interest. About 0.05
An excess of ˜0.5 mol% is used, while in the case of “in situ” synthesis, larger excesses may be used. In this case, this generally corresponds to an excess of the desired ligand.

The ligand exchange reaction may, if desired, be carried out in the presence of a suitable activator such as a Bronsted acid, a Lewis acid such as BF ₃ , AlCl ₃ , ZnCl ₂ or a Lewis base.

When the water-soluble transition metal complex used in the catalyst according to the invention is produced from a transition metal compound, as well as from one transition metal complex, additionally another ligand is present in the complex compound. It may be introduced or exchanged during the ligand exchange reaction. In this case, the ligand exchange reaction is a conventional method known to those skilled in the art, such as CO or P.
It is carried out by introducing F ₃ , and reacting with an olefin, a diene, a cycloolefin, a nitrile, an aromatic compound or the like.

Often, under the reaction conditions catalyzed by the catalysts according to the invention, the catalysts or catalyst precursors used in each case are converted into native catalytically active species, for example in the presence of synthesis gas (H ₂ / CO). It is only formed when hydroformylating or when hydrogenating in the presence of hydrogen.

As will be described below, for the preparation of the catalyst according to the invention, the water-soluble transition metal complex is activated (preliminary) under the conditions of the catalytic reaction to be carried out before it is immobilized on the polymer support. Formed) and optionally isolated by conventional methods, and / or
Or it may be purified. However, preferably, the formation of the catalytically active species is carried out in situ in the reactor used for the respective catalytic reaction.

Suitable transition metal complexes based on triphenylphosphine trisulphonate-trisodium salt (TPPTS) for the catalysts according to the invention are disclosed in EP-A-0.
No. 372313, which is incorporated herein by reference in its entirety.

Another subject of the invention is a process for the preparation of a catalyst having at least one water-soluble complex of a transition metal as described above and also one support as also described above.

This process for the preparation of the catalyst comprises the steps of: a) at least one transition metal compound or transition metal complex, at least one transition metal compound, suitable for forming a) a water-soluble complex of a transition metal, or b) a complex a). It is characterized by impregnating with a water-soluble ligand and optionally a combination of at least one other ligand, followed by drying.

Optionally, the complex a) or the combination b) may be activated as described above before impregnation of the support.

[0063]   Advantageously, a carrier which has not been preswelled for impregnation is used.

According to a first suitable embodiment of the process according to the invention for producing the catalyst according to the invention, water-soluble complexes of transition metals are used. Suitable methods for preparing this water-soluble complex have been described above. If desired, the complex may be activated (so-called preformed) before being immobilized on the support. The appropriate method for activation depends on the reaction in which the catalyst according to the invention is to be used. Generally, the formation of catalytically active species involves treating the catalyst in the presence of an educt of at least part of the catalytic reaction to be carried out, for example treating the hydroformylation catalyst with syngas or using hydrogen. By treating the hydrogenation catalyst. This treatment is generally carried out under the conditions which are also usual for catalytic reactions, ie at elevated temperature and / or elevated pressure.

The catalytically active species thus obtained may, if desired, be isolated and / or purified by conventional methods before being immobilized on a support. A suitable purification method is eg gel chromatography. However, preferably the formation of the catalytically active species is carried out in situ after immobilization of the water-soluble transition metal complex on the support, immediately before or during the catalytic reaction with the catalyst according to the invention. In this case, an additional preforming step may advantageously be dispensed with.

For impregnation of the carrier, the water-soluble complex is dissolved in water or in a mixture of water and a water-miscible solvent, for example one of the alcohols mentioned, so that a solution which is as highly concentrated as possible is prepared. Occurs. If desired, additional amounts of the water-soluble ligands used in each case can be added to the solution before impregnation of the support. In this case, the molar ratio of the added ligand to the water-soluble complex is generally about 0.1: 1 to 200: 1.
, Preferably in the range of 0.5: 1 to 20: 1. In this case, this solution is added to the polymer particles.

The polymeric particles of the carrier may be degassed in a vacuum before impregnation if desired.
In order to obtain a good admixture, the mixture consisting of the transition metal complex and the support may be admixed during impregnation by conventional methods, for example by stirring or sonication. After impregnation, the catalyst is dried in a customary manner, for example by decanting off excess solvent and subsequently drying in a vacuum. Drying is generally at ambient temperature or about 40 to constant weight.
It is carried out at lightly elevated temperatures up to ° C. If desired, the above steps for catalyst preparation, as well as the subsequent storage of the catalyst, may be carried out under an inert gas, for example under argon or nitrogen.

According to a second suitable embodiment of the process according to the invention, for the preparation of the catalyst according to the invention, at least one transition metal compound or transition metal complex, at least one water-soluble phosphorus-containing coordination Suitable combinations for the water-soluble complexing of transition metals are used, which consist of a child and optionally at least one other ligand. If desired, this combination may be converted in situ to the water-soluble transition metal complex prior to impregnation of the catalyst. If desired, the combination may further be activated by preforming, as described above, prior to immobilization with the support. However, according to a preferred embodiment, the additional step of preforming before impregnation of the catalyst may also be dispensed with when producing the catalyst from a transition metal compound or transition metal complex. The molar ratio of water-soluble phosphorus-containing ligand to transition metal compound or transition metal complex is generally about 1: 1 to 150: 1,
It is preferably in the range of 1.1: 1 to 100: 1, especially 2: 1 to 75: 1.

As solvents for impregnating and / or swelling the support, the solvents and solvent mixtures already mentioned in the preparation of the water-soluble transition metal complexes can be used. If a two-phase system is used, the impregnation is preferably carried out under intensive mixing. The conditions for impregnation are
It corresponds to the conditions already described when preparing the catalyst from the water-soluble complex of the transition metal. If desired, each step and storage of the catalyst may be carried out under an inert gas.

The catalyst according to the invention is advantageously 0.5 to 5.0 g, preferably 0. 0 g / 100 g carrier, based on the mass of the carrier which is dry, ie not swollen and unloaded.
It has a water content in the range of 7 to 2.5 g.

The catalysts according to the invention are generally highly reactive and can be used effectively for a large number of reactions. Advantageously, the catalyst can be separated from the reaction mixture following catalytic reactions carried out in the presence of the catalyst, by simple conventional methods, such as precipitation and decanting, or by filtration, for example nanofiltration. .

Suitable reactors for the use of the catalysts according to the invention are the customary reactors as are known to the person skilled in the art for fixed-catalysed liquid-phase-reactions and gas-liquid-phase-reactions. is there. Preference is given to using reactors with the catalyst to be transferred, such as bubble columns, stirred tanks, stirred tank cascades, fluidized bed reactors, suspended bed reactors, tubular reactors and the like. In this case, the catalyst may be separated by the simple method described above. However, the catalyst according to the invention is also suitable for use in fixed bed reactors.

Solvents and solvent mixtures which are essentially water-insoluble are preferably used as solvents for the catalytic reaction. At that time, the water solubility is generally 100 ppm (20 ppm maximum).
(In ° C), preferably up to 50 ppm. Solvents include, for example, aliphatic hydrocarbons and hydrocarbon mixtures such as pentane, hexane, heptane, petroleum ether,
Aromatic hydrocarbons such as benzol, toluene, xylol, esters such as butyl acetate, and the like. The solvent used is preferably an essentially water-insoluble educt and / or the respective catalytic reaction products, such as olefins, aldehydes and the like.

Advantageously, the catalysts according to the invention generally show only a very slight loss of water-soluble transition metal catalyst. This loss is generally at most 1 ppm and is preferably below the detection limit when using the abovementioned essentially water-insoluble solvents and solvent mixtures. In that case, it may be advantageous in some circumstances if an excess of water-soluble phosphorus-containing ligand is used in the preparation of the catalyst according to the invention.

In general, the catalysts according to the invention have sufficient catalytic activity after separation from the reaction mixture, so that after the catalyst has been optionally washed with the organic solvents or solvent mixtures mentioned above, It can be used again for catalytic reactions. In this case, activation, eg by preforming as described above, is generally unnecessary.

Regeneration of the catalyst can generally be carried out by a simple method. Thus, for example, the catalyst may be washed with water, the support may be isolated by precipitation and decanting or filtering, and the washing solution containing the transition metal complex and / or the ligand may be separately worked up. You may The support may generally be immediately loaded with fresh catalyst and used fresh without preformation.

The catalysts according to the invention are for example reducing carbon-carbon-double and triple bonds, aldehydes and ketones to alcohols, cycloalkanes to alkanes, and in particular nitrites and nitro compounds to amines and in particular Suitable for hydrogenation.

Furthermore, the catalysts according to the invention are suitable for catalyzing addition reactions on carbon-carbon-double bonds. This includes hydroformylation of olefins by adding syngas to the double bond. Further this includes hydrocarbonylation of olefins to ketones, also in the presence of syngas, such as ethene to diethyl ketone. Further this includes hydroacylation of alkenes by addition of acyl halides to olefins, for example addition of benzoyl chloride to ethene to produce phenylethylketone. It further includes hydrocyanation by adding hydrocyanic acid to olefins, hydroesterification by adding carboxylic acids to olefins, hydroamination by adding ammonia, primary amines and secondary amines to olefins, and olefins. Hydroamidation by adding a carboxylic acid amide to Furthermore, the catalysts according to the invention are suitable for regioisomerization and double bond isomerization of olefins.

According to a first preferred embodiment, the method in which the catalyst according to the invention is used is hydroformylation. Therefore, another subject of the invention is the hydroformylation of compounds having at least one ethylenically unsaturated double bond by reacting them with carbon monoxide and hydrogen in the presence of at least one hydroformylation catalyst. A process, in which case it is characterized by using as the hydroformylation catalyst one of the catalysts according to the invention described above.

In this case, the transition metal of the water-soluble complex is preferably cobalt, ruthenium, rhodium, palladium, platinum, osmium or iridium, in particular cobalt, ruthenium, rhodium and platinum.

[0081]   As the water-soluble phosphorus-containing ligand, P (C₆H_Four-M-SO_ThreeNa)_Three , P (C₆H₅) (C₆H_Four-M-SO_ThreeNa)_TwoOr P (C₆H₅)_Two(C ₆ H_Four-M-SO_ThreeNa) and mixtures of these are used.

[0082] In general, the hydroformylation conditions, the catalysts or catalyst precursors used in each case, the general _{formula: H x M y (CO)} z L q, ( wherein, M represents a group VIII metal , L represents a water-soluble phosphorus-containing ligand, and q, x, y, z represent an integer depending on the valence and type of the metal and the valency of the ligand L). Active species are formed. Preferably z and q are independently of one another a numerical value of at least 1, for example 1, 2 or 3. The sum of z and q is preferably 2 to
It is a numerical value of 5. In this case, the complex additionally has at least one more if desired.
It may have one of the other ligands mentioned above.

According to a preferred embodiment, the formation of the catalytically active species (pre-formation) is carried out in situ in the reactor used for the hydroformylation reaction. However, if desired, the preformed catalyst may be separately prepared and isolated by conventional methods, as described above.

Suitable rhodium compounds or rhodium complexes for the preparation of the catalysts according to the invention are eg rhodium (II) -salts and rhodium (III) -salts such as rhodium chloride (
III), rhodium (III) nitrate, rhodium (III) sulfate, rhodium sulfate-
Potassium, rhodium (II) -carboxylate or rhodium (III)-
Carboxylates, rhodium (II) acetate and rhodium (III) acetate, rhodium (III) oxide, rhodium (III) -acid salts, trisammonium hexachlororhodium acid (III) and the like. Further, rhodium complexes such as rhodium biscarbonylacetylacetonate and acetylacetonatobisethylenerhodium (I) are suitable. Preference is given to using rhodium biscarbonylacetylacetonate or rhodium acetate.

[0085]   Similarly, ruthenium salts or compounds are suitable. A suitable ruthenium salt is
For example, ruthenium (III) chloride, ruthenium (IV) oxide, ruthenium oxide (VI
), Or ruthenium (VIII) oxide, an alkali metal salt of ruthenium oxyacid,
For example K_TwoRuO_FourOr KRuO_FourOr general formula: RuX¹X^TwoL¹L^Two(L ^Three )_n, (Where L¹, L^Two, L^ThreeAnd n have the meanings given above, and X¹ , X^TwoRepresents the meaning given to X (see above)), for example
RuHCl (CO) (PPh_Three)_Three,. In addition, ruthenium metal carbon
Such as trisultenium dodecacarbonyl or hexaruthenium octade
Cacarbonyl, or CO is partly represented by the formula: PR_ThreeReplaced by the ligand
Mixed type, eg Ru (CO)_Three(PPh_Three)_TwoAlso used in the method according to the invention.
Can be used.

Suitable cobalt compounds are, for example, cobalt (II) chloride, cobalt sulfate (II)
), Cobalt (II) carbonate, cobalt (II) nitrate, their amine or hydrate complexes, cobalt carboxylates such as cobalt acetate, cobalt ethylhexanoate, cobalt naphthanoate, and cobalt caprolactamate- It is a complex. Again, carbonyl complexes of cobalt, such as dicobalt octacarbonyl, tetracobalt dodecacarbonyl and hexacobalt hexadecacarbonyl may be used.

Solvents preferably used are olefins used for hydroformylation, aldehydes which are formed in the hydroformylation of the respective olefins, their high-boiling subsequent reaction products, for example the products of aldol condensations, aromatic hydrocarbons. , For example benzol, toluene and xylol, or mixtures thereof.

Substrates for the hydroformylation process according to the invention include in principle all compounds having one or more ethylenically unsaturated double bonds. This compound includes, for example, olefins such as α-olefins, intramolecular linear olefins and intramolecular branched olefins. Suitable α-olefins are, for example, ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene and the like. .

Suitable linear intramolecular olefins are preferably C ₄ -C ₂₀ -olefins such as 2-butene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, 3
-Heptene, 2-octene, 3-octene, 4-octene and the like.

Suitable branched chain internal olefins are preferably C ₄ -C ₂₀ -olefins, for example 2-methyl-2-butene, 2-methyl-2-pentene, 3-methyl-2-pentene, Branched internal heptene mixture, branched intramolecular octene mixture, branched intramolecular nonene mixture, branched intramolecular decene mixture, branched intramolecular undecene mixture, branched Chain intramolecular dodecene mixture, etc.

Suitable olefins to be hydroformylated are furthermore C ₅ -C ₈ -cycloalkenes, such as cyclopentene, cyclohexene, cycloheptene, cyclooctene and their derivatives, such as those C ₁ -with alkyl substituents 1-5. alkyl derivatives - C _20. Suitable olefins to be hydroformylated are further vinylaromatic compounds such as styrene, α-methylstyrene, 4-
Isobutyl styrene and the like. Suitable olefins to be hydroformylated are:
Furthermore, α, β-ethylenically unsaturated monocarboxylic acids and / or α, β-ethylenically unsaturated 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 nitrile, for example 3-pentenenitrile, 4-pentenenitrile, acrylonitrile, vinyl ether, for example Vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether and the like, C ₁ -C ₂₀ -alkenols, C ₁ -C ₂₀ -alkene diols and C ₁ -C ₂₀ -alkadienols, for example 2,7-octadienol-1. Is. Suitable substrates are dienes or polyenes additionally having isolated double bonds or conjugated double bonds. Examples of the compound include 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,
7-octadiene, vinylcyclohexene, dicyclopentadiene, 1,5,9
-Cyclooctatriene, and butadiene homopolymers and butadiene copolymers.

The catalysts according to the invention are therefore suitable for the hydroformylation of the abovementioned higher olefins having 7 or more carbon atoms and their mixtures, since these compounds allow the conventional hydroformylation. This is because problems that occur when separating the catalyst are generally avoided. That is, unlike a homogeneous catalyst,
Thermal separation, which can lead to catalyst damage, can be avoided. Also, the disadvantages of the two-phase system that occur in the aqueous catalyst-containing phase due to the lack of solubility of the higher olefins are generally advantageously avoided by the catalyst according to the invention. That is, the catalysts according to the invention generally allow better contact with olefins with water-soluble transition metal complexes fixed to the hydrophilic side chains of the support than with conventional two-phase systems. In this case, the loss of immobilized transition metal complex to the organic reaction solution is very low, generally up to 1 ppm. The catalysts according to the invention are therefore advantageous even when compared with immobilized hydroformylation catalysts whose active groups are bound to the support via anchor groups and which tend to "bleed" under hydroformylation conditions. Can be used.

[0093]   The hydroformylation reaction may be carried out continuously, semi-continuously or intermittently.

Suitable reactors for the continuous reaction are known to the person skilled in the art and are eg described by Ullmanns Enzy.
klopaedie der technischen Chemie, Vol. 1, 3rd edition, 1951, pages 743 et seq.

Suitable pressure-resistant reactors are likewise known to the person skilled in the art and are, for example, Ullmanns Enzy.
klopaedie der technischen Chemie, Vol. 1, 3rd edition, 1951, p. 769 and subsequent pages. In general, the process according to the invention uses an autoclave which may be equipped with a stirrer and an internal lining if desired.

The composition of the synthesis gas consisting of carbon monoxide and hydrogen used in the process according to the invention may vary within wide limits. The molar ratio of carbon monoxide to hydrogen is generally about 5:95 to 70:30, preferably about 40:60 to 60:40. Most preferably, the molar ratio of carbon monoxide to hydrogen is used in the range of about 1: 1.

The temperature for the hydroformylation reaction is generally in the range of about 20 to 180 ° C, preferably about 50 to 150 ° C. The reaction is generally carried out at the partial pressure of the reaction gas at the reaction temperature selected. Generally the pressure is about 1 to 700 bar, preferably 1
In the range from to 300 bar, in particular from 1 to 100 bar, and especially from 1 to 30 bar. In general, the catalysts according to the invention allow reactions at relatively low pressures, for example in the range 1-100 bar.

The molar ratio of olefin to transition metal complex is generally about 100: 1 to 50,000.
:, Preferably in the range of 1000: 1 to 10000: 1.

The hydroformylation catalysts according to the invention can be separated from the hydroformylation reaction effluent by conventional methods known to the person skilled in the art, such as precipitation and decanting or filtration, eg nanofiltration, and are generally It can be used again for hydroformylation.

Advantageously, the catalysts according to the invention show a high activity, so that the corresponding aldehydes are generally obtained in good yields. Moreover, in the hydroformylation of α-olefins as well as internal linear olefins, the catalysts show good n / iso-selectivity. That is, the n-aldehyde content of the reaction product is generally at least 65% by weight, preferably at least 70% by weight.

According to another preferred embodiment, the method in which the catalyst according to the invention is used is reduction.

Therefore, another subject of the invention is the non-aromatic C═C-double bond and
A method of reducing a compound having a triple bond, an aldehyde, a ketone, a nitrile and a nitro compound by reacting with hydrogen in the presence of at least one hydrogenation catalyst, in which case the invention described above as a hydrogenation catalyst. Is characterized by the use of the catalyst according to.

The compound preferably used for the reduction is a nitroaromatic compound. Suitable nitroaromatic compounds have the general formula III:

[0104]

[Chemical 1]

Wherein R ¹ and R ² are independently of each other alkyl, cycloalkyl, aryl, hetaryl, arylalkyl, alkoxy, cycloalkoxy, aryloxy, acyl, nitro, cyano, carboxyl, alkoxycarbonyl or N
Represents E ¹ E ² , wherein E ¹ and E ² may be the same or different,
And represents alkyl, cycloalkyl or aryl].

Alkyl in formula III preferably represents C ₁ -C ₈ -alkyl, in particular C ₁ -C ₄ -alkyl. Suitable alkyl, cycloalkyl, aryl, arylalkyl, alkoxy, cycloalkyloxy, arylalkyloxy and aryloxy groups are those mentioned above for the substituents of formula I. .

Suitable compounds of formula III are, for example, nitrobenzene, 2-chloronitrobenzol, 3-chloronitrobenzol, 4-chloronitrobenzol, 2-alkoxynitrobenzols, 3-alkoxynitrobenzols and 4-alkoxynitrobenzols. , 2-methoxynitrobenzol, 2-ethoxynitrobenzol, 3-methoxynitrobenzol, 3-ethoxynitrobenzol, 4-methoxynitrobenzol, 4-ethoxynitrobenzol, 3-nitrobenzonitrile, 2-nitrobenzyl alcohol, 3-nitrobenzyl alcohol, 4-nitrobenzyl alcohol, 1-nitronaphthalene, 2-nitronaphthalene, 2-nitrophenol, 3-nitrophenol, 4-nitrophenol,
3-nitrotoluol and the like. The nitro compound to be reduced can be 2 if desired.
It may contain one or more nitro groups, which are then reduced to amino groups.

As water-soluble transition metal complex preferably Rh (CO) Cl (TPPTS) ₂ is used, where TPPTS stands for triphenylphosphine trisulfonate-trisodium salt.

The molar ratio of water-soluble transition metal complex to substrate of the catalyst according to the invention is generally about 1:
It is in the range of 100 to 1: 1,000,000, preferably 1: 1000 to 1: 100,000. The reaction temperature is generally about 10 to 150 ° C, preferably 20 to 130 ° C.
In particular, it is in the range of 50 to 110 ° C. The hydrogen pressure is generally in the range of about 1 to 300 bar, preferably 2 to 150 bar, in particular 10 to 100 bar.

The catalyst according to the invention may be separated from the reaction medium in a simple, above-mentioned manner after the end of the reaction, for example by precipitation and decanting or filtration. In general, the catalyst can be freshly used for catalytic reduction without loss of essential activity. If liquid nitroaromatic compounds are used for the reduction, the addition of solvents may generally be dispensed with. However, it is also possible to additionally use organic solvents such as benzene, toluene, xylol, cyclohexane, decalin, etc., or mixtures thereof.

[0111]   The invention is illustrated in greater detail by the following non-limiting examples.

Example As a catalyst carrier, Rapp Polymere, Tübingen,
Tentagel® S OH (product number S 30900, particle size 90 μm, swelling capacity 3.5-4.5 ml H 2 O / g). This particle is
It consists of a cross-linked polystyrene core with grafted polyethylene glycol side chains (about 68 ethylene oxide units).

[0113] Example 1 Triphenylphosphine trisulfonate-trisodium salt (TP) as a ligand
Preparation of PTS-based catalysts with preforming   In the autoclave, add the buffer solution (H_TwoO 40g, glacial acetic acid 190mg, sodium acetate
Add 4 ml of thorium trihydrate (3.81 g) and 7 ml of toluene. Then T
0.43 g (0.75 mmol) PPTS and Rh (CO)_Twoacac 0.
Add 008 g (0.03 mmol), seal the autoclave, and discharge 3 times.
Gas and subsequent gas treatment, the synthesis gas mixture CO / H is added to the autoclave. _Two (1: 1) is added, in which case the starting pressure at ambient temperature of 3 bar is adjusted.
It is subsequently heated to 120 ° C. for 45 minutes, in which case the pressure rises to about 6 bar.
Subsequently, the reactor contents are further heated at ambient temperature and a synthesis gas pressure of 3 bar for another 10 hours.
Stir for a while. Pale yellow water phase obtained after depressurizing and emptying the autoclave
The two-phase mixture consisting of the organic phase and the colorless organic phase was degassed under argon protective gas.
Transferred into a Schlenk tube containing 1 g of S. OH.
Stir vigorously for 1 hour. Continue to pipette the supernatant organic phase under protective gas.
Remove and wash the remaining yellow gel 3 times with 10 ml of toluene each.
In this case, the wash solution was likewise pipetted out each time. Next, 50 ℃
And dried at a pressure of 2 mbar for 5 hours.

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

Rhodium content: 0.15 g / 100 g H ₂ O-content: 1.1 g / 100 g Example 2 Preparation of TPPTS-based catalysts without preforming TPPTS 1. under protective gas in a Schlenk tube. To 54 g (2.71 mmol) and 0.018 g (0.042 mmol) of Rh (CO) ₂ acac are added 1 ml of the buffer solution described in Example 1 and 4 ml of H ₂ O. Under vigorous stirring using a magnetic stirrer, a dark yellow, slightly cloudy solution is formed, which
10 ml of toluene are added and subsequently stirred at 70 ° C. for 15 minutes. The obtained two-phase system was cooled and then again degassed under argon protective gas to obtain the degassed TENTAGEL (registered trademark) S.
Place in a Schlenk tube with 1.0 g of OH and stir vigorously for 1 hour.
After stirring, the yellow gel obtained is precipitated and the supernatant solution is removed by pipetting. The gel is washed 3 times with 10 ml of toluene each time, in which case the washing solution is likewise pipetted off. The solvent is subsequently removed at 25 ° C. and 2 mbar, after which a solid, dark yellow product forms, which after grinding is further dried at ambient temperature and 2 mbar for 1.5 hours. The steps of catalyst production and storage up to use are carried out under an 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 of catalyst based on triphenylphosphine monosulfonate-monosodium salt (TPPMS) Preparation with preform 1 ml of the buffer solution described in Example 1, H ₂ O 3 in a stirred autoclave.
ml and 10 ml of toluene were added, followed by 0.285 g of TPPMS (0
． 74 mmol) and 0.0098 g of Rh (CO) ₂ acac (0.038
Mmol) is added. After sealing the autoclave, it is evacuated 3 times and washed with synthesis gas CO / H ₂ (1: 1). The synthesis gas pressure at ambient temperature is 3 bar. It is subsequently preformed at 120 ° C. for 45 minutes, the pressure rising to about 6 bar. After stirring for 10 hours at room temperature under a synthetic gas pressure of 3 bar, the resulting bright yellow suspension is degassed under protective gas (TentaGel®).
Transfer into a Schlenk tube with 1 g of S OH. Stir vigorously for 1 hour using a magnetic stirrer, in which case a gel-like phase is formed. After stirring, it can be allowed to settle and the supernatant solution is pipetted out. Remaining gel with toluene 8 ml each
Wash 3 times with. The solvent is subsequently removed at 2 mbar and 20 ° C. and the catalyst is dried at ambient temperature and 2 mbar for a further 1.5 hours. The whole process of catalyst production and its storage are carried out under 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 Preparation of TPPMS-based catalysts without preforming in Schlenk tubes. , TPPMS 0.450 g (1.2
To 0.145 g of Rh (CO) ₂ acac (0.056 mmol) and 1.5 ml of the buffer solution described in Example 1 and 6 ml of H ₂ O,
And with stirring, in this case a light yellow suspension is formed, which is toluol 15
Add ml. After stirring at 80 ° C for 1 hour, cooling and then degassing the tentagel
Transfer to a Schlenk tube with 1.5 g of ((TentaGel) ®) S OH. After stirring the mixture, phase separation occurs, in which the yellow gel obtained can be precipitated,
And withdraw the clear supernatant solution with a pipette. The gel phase obtained is washed 3 times with 10 ml of toluene each time and the solvent is pipetted off each time. The solvent is subsequently removed at ambient temperature and a pressure of 2 mbar, and the resulting residue is ground and then dried at ambient temperature and 2 mbar for 1.5 hours. All the steps of catalyst production and storage described above are carried out 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 Catalysts based on Rh (CO) Cl (TPPTS) ₂ as ligand Preparation of Rh (CO) Cl (TPPTS) ₂ 30 mg (23 μmol) in water 2
． Dissolve in 5 ml and place under a protective gas of argon in a Schlenk tube with 1 g of degassed Tentagel® S OH. The resulting material is vigorously stirred and subsequently dried at ambient temperature and a pressure of 2 mbar.

Examples 6 to 13 Discontinuous hydroformylation of 1-dodecene In a stirred autoclave for 10 ml, under argon, at room temperature, the amounts of 1-dodecene, catalyst and toluol according to Table 1 are charged and the reaction temperature is (Refer to Table 1)
Heat to. In this case, the fresh preformed catalysts and fresh nonpreformed catalysts obtained from Examples 1 and 2 as well as the preformed returned catalyst and the nonpreformed returned catalyst are used as catalysts. use. Descriptions of the catalysts used in each case are likewise quoted from Table 1. After reaching the reaction temperature, the pressure of 60 bar was adjusted with syngas CO / H ₂ (1: 1) and the syngas was repressurized by the pressure regulator to a constant reaction time of 4 hours. Keep on. After the reaction is complete, the autoclave is cooled, depressurized and emptied. The catalyst, which is optionally used for return, is handled under protective gas. Analysis of the reaction mixture was performed using gas chromatography. The results are summarized in Table 2.

GC-analysis: Capillary GC 30m UV-1-column catalyst with internal standard Return: The autoclave contents are transferred under protective gas into a 10 ml screw-capped vessel. After the catalyst has settled, the supernatant solution is pipetted off, and about 8 ml of anhydrous toluene are added to the catalyst 3 times, stirred and precipitated, and subsequently the supernatant solution is removed. Three
No further 1-dodecene and product aldehydes were detected when GC analysis of the second wash solution. The catalyst is then transferred into a stirred autoclave with about 1.5 ml of toluene and used under the above conditions for hydroformylation.

[0121]

[Table 1]

[0122]

[Table 2]

Examples 14 to 16 Hydroformylation with TPPMS-based catalysts as ligands A 10 ml stirred autoclave was charged under argon at room temperature with the amounts of 1-dodecene, catalyst and toluol according to Table 3. And the reaction temperature (see Table 3)
Heat to. The catalysts used are the fresh, preformed catalysts and fresh, nonpreformed catalysts obtained from Examples 3 and 4, as well as the preformed and recycled catalysts and the nonpreformed recycled catalysts. Descriptions of the catalysts used in each case are likewise quoted from Table 3. After reaching the reaction temperature, by adjusting the reaction pressure as described in Table 3 with syngas CO / H ₂ (1: 1) and repressurizing the syngas with a pressure regulator. Keep constant with a reaction time of 4 hours. Following the reaction time, the autoclave is cooled, depressurized and emptied. Analysis of the reaction mixture using catalyst recycle and gas chromatography was performed as described in Examples 6-13.

[0124]

[Table 3]

[0125]

[Table 4]

Example 17 Hydrogenation of Nitrobenzol with Rh (CO) Cl (TPPTS) ₂ as Water-Soluble Complex In a stirred autoclave for 10 ml, 4.83 g (39 mmol) of nitrobenzene and 110 mg of catalyst obtained from Example 5 ( Rh (CO) Cl (TPPTS
) ₂ 3.3 mg (2.4 μm)) and placed in the autoclave.
Wash with several exhausts and gassing with hydrogen. The hydrogen pressure is subsequently adjusted to 10 bar and the autoclave is heated to 120 ° C. for 30 minutes. In this case, the pressure rises to about 20 bar. After a reaction time of 16 hours, the autoclave was cooled and depressurized, and the catalyst was separated from the reaction solution by filtration. The resulting reaction mixture was tested by gas chromatography method.

[0127]   GC-analysis was performed as described above.

[Procedure for Amendment] Submission for translation of Article 34 Amendment of Patent Cooperation Treaty

[Submission date] September 30, 2000 (2000.9.30)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Contents of correction]

[Claims]

─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Michael Laper             Federal Republic of Germany Wachenheimpe             Gauer Strasse 10 F-term (reference) 4G069 AA03 AA08 BA21B BA22A                       BA27A BA27B BC01A BC02B                       BC18A BC29A BC61A BC65A                       BC69A BC71B BE22B BE25A                       BE26B CB02 CB59 DA05                       EA02Y EB18X FA01 FA02                       FB14 FB23                 4H006 AA02 AC45 BA24 BA48 BA81                       BA82                 4H039 CA62 CF10

Claims (11)

[Claims] 1. A catalyst containing at least one water-soluble transition metal complex coated on a carrier, wherein the carrier comprises a hydrophobic polymer substrate associated with a hydrophilic matrix, wherein the hydrophilic matrix is hydrophilic. A catalyst, wherein the matrix contains a transition metal complex. 2. The catalyst according to claim 1, wherein a hydrophilic side chain forming a hydrophilic matrix by swelling in the presence of a liquid hydrophilic medium is bound to the polymer substrate. 3. The catalyst according to claim 1, wherein the carrier is a graft copolymer having a crosslinked hydrophobic core on which hydrophilic side chains are grafted. 4. The catalyst according to claim 1, wherein the hydrophilic side chain is a linear or branched polyether side chain. 5. The catalyst according to claim 1, wherein the support is present in the form of polymer particles having an average particle size in the range of about 10 to 500 μm. 6. The transition metal is selected from a subgroup of metals, preferably a metal of Group VII, Group VIII, Group I or Group II of the Periodic Table and mixtures thereof. The catalyst according to any one of claims 1 to 5, wherein 7. The catalyst according to claim 1, wherein the water-soluble transition metal complex has at least one water-soluble phosphorus-containing ligand having at least one hydrophilic functional group. 8. A process for producing a catalyst according to any one of claims 1 to 7, in which at least a suitable water-soluble complex of a transition metal or b) a) is formed on the support. Impregnation with one transition metal compound or transition metal complex, a combination of at least one water-soluble ligand and optionally at least one other ligand, followed by drying. Any 1 from 1 to 7
A method for producing the catalyst according to the item. 9. A method for hydroformylating a compound having at least one ethylenically unsaturated double bond by reacting it with carbon monoxide and hydrogen in the presence of at least one hydroformylation catalyst. A hydroformylation process, characterized in that the catalyst according to any one of claims 1 to 7 is used as a catalyst. 10. A compound having a non-aromatic carbon-carbon-double bond and a non-aromatic carbon-carbon-triple bond, an aldehyde, a ketone, a nitrile and a nitro compound are hydrogenated in the presence of at least one hydrogenation catalyst. In the method of reducing by reacting with, the reduction method characterized by using the catalyst according to any one of claims 1 to 7 as a hydrogenation catalyst. 11. To carry out the reduction reaction, in particular for hydrogenation, hydroformylation, hydrocarbonylation, hydracylation, hydrocyanation, hydroesterification, hydroamination, hydroamidation and for the regioisomerization and double olefinization. Use of a catalyst according to any one of claims 1 to 7 for bond isomerization.