DE10163400A1 - Catalyst comprising a complex of a metal of subgroup VIII based on a heterophosphacyclohexane ligand - Google Patents

Abstract

The invention relates to a catalyst, comprising at least one complex of a platinate metal of the VIII. sub-group with at least one heterophosphacyclohexane ligand, a method for hydroformylation in the presence of such a catalyst and the use thereof.

Description

The present invention relates to a catalyst which at least one complex of a platinum metal from subgroup VIII comprises at least one heterophosphacyclohexane ligand Process for hydroformylation in the presence of such Catalyst and its use.

Hydroformylation or oxo synthesis is an important one industrial process and is used for the production of aldehydes Olefins, carbon monoxide and hydrogen. These aldehydes can optionally with hydrogen in the same operation corresponding oxo alcohols are hydrogenated. The reaction itself is highly exothermic and generally runs under increased pressure and at elevated temperatures in the presence of catalysts from.

Cobalt catalysts were initially found for industrial processes Application. In the meantime, too Rhodium catalysts established in technology. Such systems show generally higher selectivities than systems containing cobalt. To one Stabilization of the rhodium-containing catalysts in the To cause reaction and decomposition during processing Avoiding deposition of metallic rhodium are used in the General phosphorus-containing ligands used. Make this possible in addition, the reaction with even lower synthesis gas pressures sufficient activity.

For the hydroformylation of lower α-olefins in particular the use of triphenylphosphine and other triarylphosphines Proven as cocatalysts. A disadvantage of these cocatalysts is that higher olefins, especially those with internal and internal branched double bonds only very slowly be hydroformylated. Furthermore, the distillative Processing of reaction mixtures for the hydroformylation of higher olefins Ligand is also lost, which must be constantly added. It is also generally known that triarylphosphines are present of rhodium and olefins can be broken down, resulting in a Deactivation of the catalyst leads.

It is known to hydroformylate specifically from low-boiling olefins phosphite-modified rhodium catalysts see M. Beller, B. Cornils, C. D. Frohning, C. W. Kohlpaintner, J. Mol. Catal. A, 104, 17-85 (1995). Both α-olefins as well as short chain internal olefins can work well with Rhodium-containing, chelate-phosphite-modified catalysts hydroformylated become. However, this catalyst system is for long chain internal olefins with more than 7 carbon atoms and internal branched olefins are unsuitable. For these olefins monodentate, sterically hindered monophosphites experimentally proven. However, phosphites generally have the disadvantage of Sensitivity to hydrolysis and the tendency towards degradation reactions (especially at higher temperatures), making their technical Use is hindered.

In contrast to triarylphosphines and phosphites they have far more basic trialkylphosphine the benefit less Degrade reactions. However, these catalysts have Compared to triarylphosphines a lower activity, which increased by increased pressure and / or elevated temperature must become. Rhodium catalysts with sterically demanding Trialkylphosphanes such as tricyclohexylphosphine at higher temperatures in the medium pressure range also able hydroformylating internal olefins, but are for the Hydroformylation of internal branched olefins due to their low Activity unsuitable. The advantages of trialkylphosphines as cocatalysts in the hydroformylation essential in thermal stability. However, the disadvantage is low activity of the resulting catalyst systems, which only insufficient by increasing the oxogas pressure and by Temperature increase can be compensated.

The unpublished international application PCT / EP 01/07219 describes phosphacyclohexanes and their use as ligands in Hydroformylation.

US 3,420,898 describes a one-stage Hydroformylation process for the production of primary alcohols using a cobalt catalyst based on a Monophosphabicycloalkans as ligands.

B. Fell and H. Bahrman describe in the Journal of Molecular Catalysis, 2, pp. 211-218 (1977) the use of am Phosphorus-substituted phospholanes as cocatalysts in the Rhodium-catalyzed hydroformylation of dienes.

None of the aforementioned documents describes the use of unbridged heterophosphacyclohexanes as ligands in Hydroformylation catalysts.

DE-PS 17 68 441 describes a process for the production of Aldehydes and alcohols by oxo synthesis in the presence of a Cobalt hydroformylation catalyst based on a 1,4-oxaphosphacyclohexane as ligands. DE-OS 19 00 706 has one comparable disclosure content.

DE-OS 22 42 646 describes a process for the production of Aldehydes and / or alcohols in the presence of a Catalyst system consisting of cobalt and a tri-substituted tertiary phosphine, in which the phosphorus atom is attached to at least one alkoxymethyl group is bound. This can be, for example Trade 1-isopropyl-1-phospha-3-oxacyclohexane.

The present invention has for its object new Catalyst systems for the hydroformylation of unsaturated To provide connections that are characterized by high Stability and higher activity compared to before known systems. The selectivity should the hydrogenation product should be as low as possible.

Surprisingly, it has now been found that this task is accomplished by the use of special compounds with at least one unbridged heterophosphacyclohexane structural element as Ligands in complexes of platinum metals of subgroup VIII Periodic table of the elements is solved.

The present invention therefore relates to a catalyst comprising at least one complex of a platinum metal of VIII. Subgroup with at least one ligand with at least one unbridged heterophosphacyclohexane structural element, the Heterocycle in addition to the phosphorus atom at least one further heteroatom and / or a heteroatom-containing group in the 6-ring which are not adjacent to the phosphorus atom and wherein at least one of those adjacent to the phosphorus atom Ring carbon atoms have a substituent other than hydrogen having.

Not to the "unbridged" structural elements in the sense of this Invention count ring systems in which two are not adjacent Ring atoms of the heterophosphacyclohexane ring are part of another are common rings.

A catalyst based on a ligand which is selected from heterophosphacyclohexanes of the general formula I is preferred


wherein
A ¹ , A ² and A ³ independently of one another represent O, S, SO ₂ , NR ^a , SiR ^b R ^c or CR ^d R ^e , with the proviso that at least one of the radicals A ¹ , A ² or A ^{3 is} not stands for CR ^d R ^e , where
R ^a , R ^b , R ^c , R ^d and R ^e independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy or hetaryloxy,
R ¹ for hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, WCOO ^- M ⁺ , WSO ₃ ^- M ⁺ , WPO ₃ ^2- M ⁺ ₂ , W (NE ¹ E ² E ³ ) ⁺ X ^- , WOR ^f , WNE ¹ E ² , WCOOR ^f , W (SO ₃ ) R ^f , WPO ₃ R ^f R ^g , WSR ^f , W-polyoxyalkylene, W-polyalkyleneimine or WCOR ^f ,
R ² to R ⁵ independently of one another are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, WCOO ^- M ⁺ , WSO ₃ ^- M ⁺ , WPO ₃ ^2- M ⁺ ₂ , W (NE ¹ E ² E ³ ) ⁺ X ^- , WOR ^f , WNE ¹ E ² , WCOOR ^f , W (SO ₃ ) R ^f , WPO ₃ R ^f R ^g , WSR ^f , W-polyoxyalkylene, W-polyalkyleneimine, W-halogen, WNO ₂ , WCOR ^f or WCN stand in what
W represents a single bond or a divalent bridging group with 1 to 20 bridge atoms,
R ^f , R ^g , E ¹ , E ² and E ³ independently of one another represent hydrogen, alkyl, carbonylalkyl, cycloalkyl or aryl,
M ^{+ stands} for a cation equivalent,
X ^{- represents} an anion equivalent,
with the proviso that at least one of the radicals R ² to R ^{5 is} different from hydrogen,
where in each case two of the geminal radicals (R ² , R ³ ), (R ⁴ , R ⁵ ) and / or (R ^d , R ^e ) can also form an oxo group or together with the carbon atom to which they are attached, can stand for a 3- to 8-membered carbo- or heterocycle, which is optionally additionally fused one, two or three times with cycloalkyl, heterocycloalkyl, aryl and / or hetaryl,
where one or more of the radicals R ¹ to R ⁵ and R ^a to R ^{e can have} an additional trivalent phosphorus or nitrogen group capable of coordination,
where two adjacent atoms of the heterophosphacyclohexane ring can also be part of a non-aromatic condensed ring system with 1, 2 or 3 further rings,
where at least one of the radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^a , R ^b , R ^c , R ^d or R ^{e can} also represent a divalent or polyvalent bridging group Y, the at least two covalently connects identical or different heterophosphacyclohexane structural elements to one another,
wherein at least one of the radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^a , R ^b , R ^c , R ^d or R ^e or, if present, the group Y also for one of the previous definitions for these residues can be different polymer residues with a number average molecular weight in the range from 500 to 50,000.

In the context of the present invention, the term “alkyl” includes straight-chain and branched alkyl groups. These are preferably straight-chain or branched C ₁ -C ₂₀ alkyl, preferably C ₁ -C ₁₂ alkyl, particularly preferably C ₁ -C ₈ alkyl and very particularly preferably C ₁ -C ₄ alkyl groups. Examples of alkyl groups are in particular methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,2 -Dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl , 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1 -Ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, 1-propylbutyl, octyl, nonyl, decyl, dodecyl.

The term alkyl also includes substituted alkyl groups. Substituted alkyl radicals preferably have 1, 2, 3, 4 or 5, in particular 1, 2 or 3, preferably selected from cycloalkyl, aryl, hetaryl, halogen, NE ¹ E ² , (NE ¹ E ² E ³ ) ⁺ , carboxyl, Carboxylate, -SO ₃ H and sulfonate.

The term cycloalkyl includes unsubstituted and substituted cycloalkyl groups. The cycloalkyl group is preferably a C ₅ -C ₇ cycloalkyl group, such as cyclopentyl, cyclohexyl or cycloheptyl.

When the cycloalkyl group is substituted, it has preferably 1, 2, 3, 4 or 5, in particular 1, 2 or 3 substituents, preferably selected from alkyl, alkoxy or halogen.

The term heterocycloalkyl for the purposes of the present invention encompasses saturated, cycloaliphatic groups with generally 4 to 7, preferably 5 or 6 ring atoms, in which 1 or 2 of the ring carbon atoms are replaced by heteroatoms selected from the elements oxygen, nitrogen and sulfur, and the may optionally be substituted, but in the case of substitution, these heterocycloaliphatic groups 1, 2 or 3, preferably 1 or 2, particularly preferably 1, selected from alkyl, aryl, COOR ^a , COO ^- M ⁺ and NE ¹ E ² , preferred Alkyl, can wear. Examples of such heterocycloaliphatic groups are pyrrolidinyl, piperidinyl, 2,2,6,6-tetramethyl-piperidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl-, tetrahydrothiophenyl, tetrahydroflanyl, tetrahydroflanyl, tetrahydroflanyl, tetrahydroflanyl, tetrahydroflanyl, tetrahydroflanyl, tetrahydroflanyl, tetrahydroflanyl, tetrahydroflanyl, tetrahydroflanyl, tetrahydroflanyl, tetrahydroflanyl, tetrahydroflanyl, tetrahydroflanyl, tetrahydroflanyl, tetrahydroflanyl, tetrahydroflanyl, and tetrahydroflanyl, called tetrahydroflanyl, tetrahydroflanyl, and tetrahydrothiophenyl, tetrahydroflanyl.

Aryl preferably represents phenyl, tolyl, xylyl, mesityl, Naphthyl, anthracenyl, phenanthrenyl, naphthacenyl and in particular for phenyl, tolyl, xylyl or mesityl.

Substituted aryl radicals preferably have 1, 2, 3, 4 or 5, in particular 1, 2 or 3, substituents selected from alkyl, alkoxy, carboxyl, carboxylate, trifluoromethyl, -SO ₃ H, sulfonate, NE ¹ E ² , alkylene-NE ¹ E ² , nitro, cyano or halogen.

Hetaryl preferably represents pyrrolyl, pyrazolyl, imidazolyl, Indolyl, carbazolyl, pyridyl, quinolinyl, acridinyl, pyridazinyl, Pyrimidinyl or pyrazinyl.

Substituted hetaryl radicals preferably have 1, 2 or 3 substituents selected from alkyl, alkoxy, carboxyl, carboxylate, -SO ₃ H, sulfonate, NE ¹ E ² , alkylene-NE ¹ E ² , trifluoromethyl or halogen.

The above statements on alkyl, cycloalkyl and aryl radicals apply accordingly to alkoxy, cycloalkyloxy, Heterocycloalkoxy, aryloxy and hetaryloxy.

The residues NE ¹ E ² and NE ⁴ E ⁵ preferably represent N, N-dimethyl, N, N-diethyl, N, N-dipropyl, N, N-diisopropyl, N, N-di-n-butyl, N, N-di-tert-butyl, N, N-dicyclohexyl or N, N-diphenyl.

Halogen stands for fluorine, chlorine, bromine and iodine, preferably for Fluorine, chlorine and bromine.

In the context of this invention, carboxylate and sulfonate preferably represent a derivative of a carboxylic acid function or a sulfonic acid function, in particular a metal carboxylate or sulfonate, a carboxylic acid or sulfonic acid ester function or a carboxylic acid or sulfonic acid amide function. These include e.g. B. the esters with C ₁ -C ₄ alkanols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and tert-butanol.

M ⁺ stands for a cation equivalent, ie for a monovalent cation or the portion of a multivalent cation corresponding to a positive single charge. M ⁺ is preferably an alkali metal cation, such as. B. Li ⁺ , Na ⁺ or K ⁺ or for an alkaline earth metal cation, for NH ₄ ⁺ or a quaternary ammonium compound, as can be obtained by protonation or quaternization of amines. Alkali metal cations are preferred, in particular sodium or potassium ions.

X ^- stands for an anion equivalent, ie for a monovalent anion or the proportion of a multivalent anion corresponding to a negative single charge. X ^- preferably represents a carbonate, carboxylate or halide, particularly preferably Cl ^- and Br ^- .

Condensed ring systems can be linked by annealing (condensed) aromatic, hydroaromatic and cyclic Connections. Condensed ring systems consist of two, three or more than three rings. Depending on the type of link a distinction is made in condensed ring systems between an ortho- Annulation, d. H. each ring has with each neighboring ring one edge, or two atoms together, and one peri annulation in which a carbon atom belongs to more than two rings. Are preferred among the condensed ring systems ortho-condensed ring systems.

Polyoxyalkylene preferably represents compounds with repeating units which are selected from (CH ₂ O), (CH ₂ CH ₂ O), (CH ₂ -CH (CH ₃ ) O), (CH ₂ -CH (C ₂ H ₅ ) O) ) and ((CH ₂ ) ₄ O). The number of repeating units is preferably in a range from 1 to 1000, preferably 1 to 240, in particular 2 to 100. Low molecular weight polyoxyalkylenes have, for example, 1 to 20, such as. B. 2 to 10 repetition units. In polyoxyalkylenes which have two or three different types of repeat units, the order is arbitrary, ie it can be randomly distributed, alternating or block-like repeat units. The statements made above for the polyoxyalkylenes apply analogously to polyalkyleneimines, the oxygen atom being replaced in each case by a group NR ⁱ , in which R ^{i is} hydrogen or C ₁ -C ₄ -alkyl. Suitable polyoxyalkylenes are derived, for. B. from formaldehyde (polyoxymethylene), cyclic ethers such as tetrahydrofuran, alkylene oxides with 2 to 4 carbon atoms in the alkyl radical and combinations thereof. Suitable alkylene oxides are, for example, ethylene oxide, 1,2-propylene oxide, epichlorohydrin, 1,2- and 2,3-butylene oxide. Suitable polyalkyleneimines are derived, for. B. of aziridines (alkyleneimines) of the formula


from where R ^{α is} hydrogen or alkyl. The number average molecular weight of higher molecular weight polyoxyalkylene or polyalkyleneimine residues is preferably in a range from about 400 to 50,000, particularly preferably 800 to 20,000, especially 1,000 to 10,000.

In addition to the phosphorus atom, the heterophosphacyclohexanes used in the catalysts according to the invention have up to three additional heteroatoms or groups containing heteroatoms in the 6-ring. In the 2- and 6-position (in the adjacent position) to the phosphorus atom, the 6-ring has carbon atoms as ring atoms. Heterophosphacyclohexanes which have the phosphorus atom and a further heteroatom or a further heteroatom-containing group in the 1,3-position are preferred. Also preferred are heterophosphacyclohexanes which have the phosphorus atom and an SO ₂ group in the 1,4-position. Also preferred are heterophosphacyclohexanes which have the phosphorus atom and two further heteroatoms or groups containing heteroatoms in the 1,3,5-position. Also preferred are heterophosphacyclohexanes which have a group of the formula -O-Si (R ^b R ^c ) -O- in the 3 to 5 position to the phosphorus atom, in which R ^b and R ^{c have} the meanings given above.

The radicals A ¹ , A ² and A ³ , which represent heteroatoms or groups containing heteroatoms ^{, are} preferably selected from O and NR ^a , where R ^a preferably represents alkyl or cycloalkyl. R ^a is preferably a C ₁ -C ₁₀ -alkyl radical, in particular methyl, propyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl or octyl. R ^a preferably furthermore represents a C ₅ -C ₈ cycloalkyl radical, in particular cyclohexyl.

A ^{1 is} particularly preferably O or NR ^a and A ² and A ^{3 are the} same or different groups CR ^d R ^e , where R ^d and R ^{e have} the meanings given above. R ^d and R ^e are preferably independently of one another hydrogen, C ₁ -C ₁₀ alkyl and C ₅ -C ₈ cycloalkyl. R ^d and R ^e are preferably both hydrogen.

A ¹ and A ³ are particularly preferably selected from O and NR ^a and A ^{2 represents} a group CR ^d R ^e , where R ^a , R ^d and R ^{e have} the meanings given above. A ¹ and A ³ then preferably both represent groups NR ^a , both radicals R ^{a representing} C ₁ -C ₁₀ -alkyl radicals, in particular propyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, Are heptyl or octyl.

The radical R ¹ is preferably selected from alkyl, cycloalkyl and aryl radicals. Preferred alkyl radicals are C ₁ -C ₁₂ alkyl radicals, which may be linear or branched alkyl radicals which are also not directly linked to P-bonded oxygen atoms and / or groups NR ^α with R ^α = hydrogen, alkyl, cycloalkyl or aryl the chain may contain, e.g. B. in the form of alkylene oxide, especially ethylene oxide units, which may be terminally alkylated.

The R ¹ radical is preferably a C ₂ -C ₁₄ -alkyl radical, in particular propyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, decyl or dodecyl.

The radical R ¹ preferably furthermore represents a C ₅ -C ₈ cycloalkyl radical, in particular cyclohexyl.

In the radical R ^1, the carbon atom bound to the phosphorus atom is preferably not sp ² hybridized.

The radical R ¹ preferably furthermore represents a polyoxyalkylene or polyalkyleneimine radical. The number average molecular weight of the polyoxyalkylene or polyalkyleneimine radicals is preferably in a range from about 400 to 50,000, particularly preferably 800 to 20,000, especially 1,000 to 10,000.

The structures of the formula I can be heterophosphacyclohexanones, provided that two geminal residues selected from (R ² , R ³ ), (R ⁴ , R ⁵ ) and / or (R ^d , R ^e ) stand for = O. Ligands of the formula are preferred


wherein R ^{1 has} the meanings given above.

According to the invention, in the heterophosphacyclohexanes of the formula I at least one of the radicals R ² to R ^{5 is} different from hydrogen. When used in hydroformylation, catalyst systems based on these ligands advantageously have a higher activity than those based on correspondingly unsubstituted heterophosphacyclohexanes.

At least one of the radicals R ² to R ⁵ is preferably alkyl or aryl, in particular C ₁ -C ₁₂ alkyl radicals, C ₇ -C ₁₃ aralkyl radicals, C ₇ -C ₁₃ alkaryl radicals and / or C ₆ -C ₁₂ aryl radicals , The alkyl radicals can contain cyclic structures. The aryl groups of the aralkyl radicals, alkaryl radicals and aryl radicals are preferably derived from benzene or naphthalene. If the aryl groups are substituted, they preferably have one, two or three alkyl substituents, which are in particular methyl or ethyl radicals. For example, the aryl groups can be phenyl, tolyl, xylyl or naphthyl radicals.

If R ¹ and / or one or more of the radicals R ² to R ⁵ and / or one or more of the radicals R ^a to R ^{e represent} alkyl and aryl radicals, these can be fluorinated or perfluorinated. Preferred fluorinated alkyl radicals are trifluoromethyl and pentafluorophenyl.

In a suitable embodiment of the invention, in the compounds of the general formula I at least one of the radicals R ¹ , R ² to R ⁵ , R ^a to R ^{e represents} a polar (hydrophilic) group, which generally results in water-soluble catalysts. The polar groups are preferably selected from WCOO ^- M ⁺ , WSO ₃ ^- M ⁺ , WPO ₃ ^2- M ⁺ ₂ , W (NE ¹ E ² E ³ ) ⁺ X ^- , WOR ^f , WNE ¹ E ² , WCOOR ^f , W (SO ₃ ) R ^f , WPO ₃ R ^f R ^g , WSR ^f , W-polyoxyalkylene, W-polyalkyleneimine, W-halogen, WNO ₂ , WCOR ^f or WCN, where W, M ⁺ , X ^- , E ¹ , E ² , E ³ , R ^f and R ^{g have} the meanings given above.

At least one of the substituents R ¹ to R ⁵ and R ^a to R ^e can have an additional, trivalent phosphorus or nitrogen group capable of coordination, which results in a bidentate or multidentate ligand. Phosphane, phosphinite, phosphonite, phosphoramidite and phosphite groups and η ⁵ -phospholyl complexes or phosphabenzene groups are particularly preferred.

The radicals R ² to R ^{5 are} preferably hydrocarbon radicals which have no further heteroatoms.

In a preferred embodiment, the bridges W are single bonds or bridges with 1 to 6 carbon atoms, which can be part of a cyclic or aromatic group. It can be single bonds, as well as lower alkylene groups, such as. B. C ₁ -C ₁₀ alkylene.

According to a preferred embodiment, the invention heterophosphacyclohexanes used at least one divalent bridging group Y on, the same or different Ligands of formula I covalently linked together.

The divalent bridging group Y preferably represents a C ₁ -C ₂₀ alkylene bridge which has one, two, three or four double bonds and / or one, two, three or four substituents which are selected from alkyl, alkoxy, halogen, Nitro, cyano, carboxyl, carboxylate, cycloalkyl and aryl may have, wherein the aryl substituent may additionally carry one, two or three substituents which are selected from alkyl, alkoxy, halogen, trifluoromethyl, nitro, alkoxycarbonyl or cyano, and / or the alkylene bridge Y can be interrupted by up to twenty non-adjacent, optionally substituted heteroatoms, and / or the alkylene bridge Y can be fused one, two or three times with aryl and / or hetaryl, the fused aryl and hetaryl groups each having one, two or three substituents which are selected from alkyl, cycloalkyl, aryl, alkoxy, cycloalkoxy, aryloxy, acyl, halogen, trifluoromethyl, nitro, cyano, carboxyl, alkoxycarbonyl or NE ¹ E ² , tr agen, where E ¹ and E ^{2 may be the} same or different and represent alkyl, cycloalkyl or aryl.

Y is preferably a C ₁ -C ₂₀ alkylene bridge which can be interrupted by up to twenty, in particular up to ten, non-adjacent, optionally substituted heteroatoms. The optionally substituted heteroatoms are preferably selected from O, S, NR ^α or SiR ^β R ^γ , the radicals R ^α , R ^β and R ^γ independently of one another representing hydrogen, alkyl, cycloalkyl, aryl or hetaryl. The bridging groups Y are then preferably C ₁ -C ₁₀ -, particularly preferably C ₂ -C ₆ -alkylene bridges which are neither substituted nor interrupted by heteroatoms. The bridging groups Y are furthermore preferably oligomeric polyoxyalkylene or polyalkyleneimine bridges. These preferably have 1 to 20, particularly preferably 2 to 10, of the repeat units described above.

The bridging group Y is preferably also selected from groups of the formulas II.1 to II.7


R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ independently of one another for hydrogen, alkyl, cycloalkyl, aryl, alkoxy, halogen, SO ₃ H, sulfonate, NE ⁴ E ⁵ , alkylene -NE ⁴ E ⁵ , trifluoromethyl, nitro, alkoxycarbonyl, carboxyl or cyano, in which E ⁴ and E ⁵ each represent the same or different radicals selected from hydrogen, alkyl, cycloalkyl and aryl,
Z represents O, S, NR ²⁵ or SiR ²⁵ R ²⁶ ,
where R ²⁵ and R ²⁶ independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
or Z represents a C ₁ -C ₃ alkylene bridge which can have a double bond and / or an alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl substituent,
or Z represents a C ₂ -C ₃ alkylene bridge which is interrupted by O, S or NR ²⁵ or SiR ²⁵ R ²⁶ ,
B ¹ and B ² independently of one another are O, S, SiR ²⁵ R ²⁶ , NR ²⁵ or CR ²⁷ R ²⁸ , where
R ²⁷ and R ²⁸ independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
D a two-gang bridge group selected from the groups


is where
R ²⁹ and R ³⁰ independently of one another represent hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, carboxyl, carboxylate or cyano or are connected to one another to form a C ₃ -C ₄ -alkylene bridge, and
R ³¹ , R ³² , R ³³ and R ³⁴ independently of one another for hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, COOH, carboxylate, cyano, alkoxy, SO ₃ H, sulfonate, NE ⁴ E ⁵ , alkylene-NE ⁴ E ⁵ E ⁶⁺ X ^- , acyl or nitro, where X ^{- stands} for an anion equivalent.

The group of the formula II.6 is preferably a xanthendiyl group of the formula


in which R ¹⁷ , R ¹⁸ , R ¹⁹ and R ^{20 have} the abovementioned meaning and R ²⁷ and R ²⁸ independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.

Furthermore, the group of the formula II.7 preferably represents a triptycendiyl group of the formula


or the formula


is in which R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²⁹ , R ³⁰ , R ³¹ and R ^{32 have} the meanings mentioned above.

Y is preferably a bridging group of the formula II.2, in which R ¹⁷ , R ¹⁸ , R ¹⁹ and R ^{20 are} hydrogen.

The bridging group Y preferably also represents one High molecular weight polyoxyalkylene or polyalkyleneimine bridge with at least 21 carbon atoms. The number average Molecular weight of the polyoxyalkylene or polyalkyleneimine is preferably in a range from about 400 to 50,000, especially preferably 800 to 20,000 and especially 1,000 to 10,000. Particularly it is preferably polyethylene oxides, copolymers of Ethylene oxide and 1,2-propylene oxide, in which the alkylene oxides in in any order, alternating or in the form of blocks can be installed as well as polyethyleneimines.

In a special embodiment, the bridging group Y or one of the radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^a , R ^b , R ^c , R ^d or R ^{e represents} a polymer radical other than polyoxyalkylenes and polyalkyleneimines with a number average molecular weight in the range of 500 to 50,000.

The repeating units of these polymer residues are preferably formally derived from monomers selected from mono- and diolefins, vinyl aromatics, esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C ₁ -C ₃₀ -alkanols, N-vinylamides, N-vinyllactams , ring-polymerizable heterocyclic compounds and mixtures thereof.

The polymer residues preferably have a number average Molecular weight in the range from 800 to 20,000, particularly preferably 2,000 up to 10,000.

Preferred monoolefins as monomers are C ₂ -C ₈ monoolefins, such as ethene, propene, n-butene, isobutene and aromatic-substituted monoolefins, such as 1,1-diphenylethylene, 1,2-diphenylethylene and mixtures of the aforementioned monoolefins. Diolefins preferred as monomers are conjugated dienes, such as butadiene, isoprene, 2,3-dimethylbutadiene, piperylene (1,3-pentadiene) and mixtures thereof. The esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids are preferably selected from the esters of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and crotonic acid. The esters with C ₁ -C ₂₀ alkanols are preferred. These include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, ethylhexyl ( meth) acrylate, etc. Vinylaromatics suitable as monomers are, for example, styrene, α-methylstyrene, o-chlorostyrene, vinyltoluenes and mixtures thereof. Suitable N-vinylamides are, for example, N-vinylformamide, N-vinylacetamide, N-vinylpropionamide and mixtures thereof. Suitable N-vinyl lactams are, for example, N-vinyl pyrrolidine, N-vinyl piperidone, N-vinyl caprolactam and mixtures thereof. Suitable monomers for ring opening polymerization are e.g. B. cyclic ethers such as ethylene oxide and propylene oxide, cyclic amines, cyclic sulfides (ethylene sulfide, thietane), lactones and lactams. 6-caprolactone and ε-caprolactam are preferred.

The aforementioned monomers can be used individually, in the form of Mixtures from the respective monomer class and generally as Mixtures are used.

The polymers suitable as residues are produced after usual polymerization processes known to the person skilled in the art. In Depending on the monomers to be polymerized, this includes radical, cationic and anionic polymerization, including the cationic and anionic Ring-opening polymerization.

The polymer residues are produced by anionic ones Polymerization, for example by the corresponding one below described reaction variant for the production of heterophosphacyclohexanes according to the invention are preferred as monomers Acceptor-activated ethylenically unsaturated compounds and Ethen used.

If in the compounds of the formula I one of the radicals R ¹ to R ⁵ , R ^a , R ^b , R ^c , R ^d , R ^e or a group Y is a polymer radical, it is preferably a polyolefin radical (polyalkene radical) , These polyolefins have repeat units which are derived from polymerized monomers, which are preferably selected from C ₂ -C ₆ -alkenes, such as ethene, propene, n-butene, isobutene, olefins with two double bonds, such as butadiene, isoprene, 1,3 -Pentadiene and mixtures thereof. Polyolefins, which contain conjugated dienes incorporated, can essentially only have the 1,2- and 1,4-polymerization products as well as mixed forms with any 1,2- and 1,4-proportions. Methods for adjusting the 1,2- and 1,4-proportions conjugated dienes during the polymerization are known to the person skilled in the art. This includes, for example in anionic polymerization, the addition of donor solvents, e.g. B. ethers, such as THF, or amines. Polyolefins with repeating units of 1,2-addition products of conjugated dienes have pendant ethylenically unsaturated groups. Polyolefins with repeating units of 1,4-addition products have ethylenically unsaturated groups in the main chain. If desired, these can be partially or completely hydrogenated. However, it is also possible to use heterophosphacyclohexanes with polyolefin residues with ethylenically unsaturated side chains as ligands in transition metal complexes for the hydroformylation. Under hydroformylation conditions, at least some of the ethylenically unsaturated side chains are usually converted into alcohol groups, ie ligands with polar side chains result.

If one of the radicals R ¹ to R ⁵ , R ^a to R ^e or a group Y in the compounds of the formula I is a polyolefin radical, it is preferably a polyethylene or polybutadiene radical.

The bridged used according to the invention Heterophosphacyclohexanes preferably have 1, 2 or 3 bridging groups Y on. Bridged heterophosphacyclohexanes are preferred, the one have bridging group Y. The group Y is preferably on the phosphorus atom or the one adjacent to the phosphorus atom Carbon atom of the heterophosphacyclohexane ring bound.

Bridged ligands are preferably selected from compounds of the general formula I.1


wherein
A ¹ , A ² , A ³ , R ² , R ³ and Y have the meanings given above,
where the atoms of the heterophosphacyclohexane rings not bonded to the bridge Y can be substituted as previously defined for R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^a , R ^b , R ^c , R ^d or R ^e .

Another special embodiment are catalysts Basis of at least one heterophosphacyclohexane ligand, the one has bridging group Y which stands for a polymer radical, on the at least three heterophosphacyclohexane structural elements are bound.

3 to 20, in particular 4 to, of the polymer radical Y are preferred 12 heterophosphacyclohexane structural elements bound.

The connection of the heterophosphacyclohexane groups to the Polymer residue can be functional complementary by reaction Groups take place, for example in an addition or Condensation reaction. The connection can continue via complementary groups capable of electrostatic interaction respectively.

In the context of the present invention, “complementary functional groups” is understood to mean a pair of functional groups which can react with one another to form a covalent bond. "Complementary compounds" are pairs of compounds which have functional groups which are complementary to one another. The heterophosphacyclohexanes can have such functional groups in the form of appropriately functionalized radicals R ² to R ⁵ or R ^a to R ^e . It is preferably R ² to R ⁵ , in which the functional group via one of the aforementioned bridging groups W, z. B. a C ₁ -C ₄ alkylene group, is bound to the phosphacyclohexane ring. The heterophosphacyclohexanes can also have suitable groups capable of binding to a correspondingly complementarily functionalized polymer in the form of the radical R ¹ on the ring phosphorus atom. Then the functional groups are usually a bridging group W, z. B. a C ₁ -C ₄ alkylene group, bound to the phosphorus atom.

Preferred complementary functional groups are selected from the complementary functional groups in the overview below. Overview of examples of complementary functional groups

According to a first suitable embodiment, the polymer radical is derived from a polymer obtainable by free-radical polymerization of suitable α, β-ethylenically unsaturated monomers which contains groups which are capable of reacting with corresponding complementary groups of the heterophosphacyclohexanes. Suitable are, for example, polymers which 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 methacrylate, 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-monoalkyl derivatives, which, for. B. wear an NC ₁ - to C ₈ -monoalkyl radical, such as aminomethyl acrylate, aminomethyl methacrylate, aminoethyl acrylate, N-methylaminomethylacrylate, etc. Also suitable are vinyl aromatics which have at least one hydroxyl group, such as, for. B. 4-hydroxystyrene. The monomers can be used individually or as mixtures. Their amount is generally 0.001 to 100% by weight, preferably 0.05 to 50% by weight, in particular 0.1 to 20% by weight, based on the total amount of the monomers to be polymerized.

The polymer radical 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 -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, dimethyl maleate or n-butyl maleate, α, β-ethylenically unsaturated nitriles, such as, for. As acrylonitrile and methacrylonitrile, esters of vinyl alcohol with C ₁ - to C ₂₀ monocarboxylic acids, such as. B. vinyl formate, 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 polymer base preferably contains at least one of these monomers in an amount of generally about 0 to 99.999% by weight, preferably 80 to 99.95% by weight, in particular 50 to 99.9% by weight, based on the total amount of monomers to be polymerized.

According to a further suitable embodiment, the Polymer residue from one more suitable by anionic polymerization Monomers available polymer from.

H. L. Hsieh and R. P. Quirk describe in anionic polymerization, Principles and Practical Applications, Marcel Dekker-Verlag (1996), 5, pp. 93-127 suitable monomers, initiators and general aspects of anionic polymerization. In Chapter III, Pp. 131-258 the polymerization of styrene-butadiene, in Chapter IV, pp. 261-368 the production of block copolymers, in Chapter V, 22, pp. 621-638 become Telechele and in Chapter VI, 23, Pp. 641-684 describe (meth) acrylates. Chapters VI, 24, Pp. 685-710 describes the ring-opening anionic polymerization. Reference is made to the references mentioned.

Suitable ethylenically unsaturated compounds for anionic polymerization are ethene and preferably acceptor-substituted ethylenically unsaturated compounds. These include, for example, vinyl aromatics such as styrene, aromatic-substituted monoolefins such as 1,1-diphenylethylene, 1,2-diphenylethylene and mixtures thereof. Conjugated dienes such as butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene and mixtures thereof are also suitable. Suitable anionically polymerizable monomers are also the aforementioned esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C _1-30 alkanols. Suitable anionically polymerizable monomers are furthermore heterocyclic compounds polymerizable with ring opening. These preferably include the aforementioned alkylene oxides, such as ethylene oxide and 1,2-propylene oxide, aziridines, lactones, such as ε-caprolactone and lactams, such as ε-caprolactam. If less reactive monomers are used, the polymerization can take place in the presence of at least one ether or amine, in particular an amine which does not contain any amine hydrogens. Amines which have two or more amino groups and which do not carry any amine hydrogens are preferred. For example, tetramethylethylenediamine (TMEDA) is preferred.

When using di- or polyfunctional initiators or Functionalized initiators for anionic polymerization are obtained Polymers that have 3 or more metal atoms on the chain ends exhibit. Such initiators are described by H. L. Hsieh and R. P. Quirk (loc. cit.), pp. 110-114 and the literature cited there described, to which reference is made here in full. So are used, for example, when using functionalized and suitably derivatized alkyl lithium initiators star-shaped Get polymers (e.g. polyisoprene). Appropriate protected Functionalized initiators are, for example 6-lithium hexylacetaldehyde acetal, 4-bis (trimethylsilyl) aminophenyllithium, 6- (tert-butyldimethylsiloxy) hexyllithium and 3- (tert-butyldimethylsilyloxy) propyllithium.

For linking the heterophosphacyclohexane groups to anionic Polymers that still have free metal residues can be used for example halogenated or halogenated alkylated on the phosphorus atom Use heterophosphacyclohexanes.

The polymer radical is preferably also derived from previously mentioned residues of various star polymers or dendritic polymers. Star-shaped polymers are understood to mean those in which from a center 3 and more unbranched Run out of chains. Dendritic polymers are understood to mean those which have branched side chains. The production of suitable star polymers are described by H. L. Hsieh and R. P. Quirk (loc. cit.), pp. 333-368 and the literature cited there described what is referred to here.

Suitable star polymers can be prepared by radical polymerization of monomers with suitable polyfunctional initiators. With regard to suitable α, β-ethylenically unsaturated monomers and the attachment of the heterophosphacyclohexane groups, reference is made to the previous statements on radical polymerization. Suitable initiators are, for example, aromatic acylium ions of the formula:

The production of suitable star polymers can continue through Polyaddition of epoxides to trihydric and higher alcohols respectively. Suitable triols are, for example, glycerol or Trimethylolpropane. Suitable higher alcohols are, for example Erythritol, pentaerythritol and sorbitol. Such star polymers generally have hydroxyl groups as end groups. The Attachment of heterophosphacyclohexane groups can then, as before described, by reaction with halogenated, preferably halogenated alkyl heterophosphacyclohexanes.

Heterophosphacyclohexanes which are selected from compounds of the general formulas Ia to Im are particularly preferably used as ligands




wherein
A ¹ , A ^{1 '} , A ² , A ³ and A ^3' independently of one another are O or NR ^a , where R ^{a is} hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
R ¹ and R ^{1 '} independently of one another are C _1-20 -alkyl, C ₅ -C ₈ -cycloalkyl, C _6-12 -aryl, W-polyoxyalkylene, W-polyakyleneimine or a polymer residue with a number average molecular weight in the range from 500 to 50,000, which is composed of ethylene and / or butadiene, where W is a single bond or C _1-4 alkylene,
R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ^{6 '} , R ^7' , R ^{8 '} , R ^9' , R ^{10 '} and R ^11' independently of one another for hydrogen, alkyl, alkoxy, Carboxyl, carboxylate, trifluoromethyl, -SO ₃ H, sulfonate, NE ¹ E ² or alkylene-NE ¹ E ² , where E ¹ and E ² independently of one another are hydrogen, alkyl or cycloalkyl, and
R ^b , R ^c , R ^d and R ^e independently of one another are C ₁ -C ₁₀ alkyl, C ₅ -C ₈ cycloalkyl or phenyl.

In the compounds of the formulas Ia to If and Ii to Il, the radicals A ¹ , A ¹ , A ² , A ³ and A ^{3 'are} preferably, independently of one another, O or NR ^a , where R ^{a is} hydrogen or C ₁ -C ₁₀ Alkyl, preferably methyl, ethyl, isopropyl, tert-butyl and octyl.

In the compounds of the formulas Ia to Ih, the radicals R ¹ and in the compound Ik the radicals R ¹ and R ^{1 '} independently of one another are preferably C ₁ -C ₁₀ -alkyl, preferably methyl, ethyl, isopropyl, tert-butyl, Octyl and dodecyl, and C ₅ -C ₆ cycloalkyl, in particular cyclohexyl.

In the compounds of the formulas Ib, Id, Ie, Ih and Ii, the radicals R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ^{11 are} preferably, independently of one another, hydrogen, C ₁ -C ₄ -alkyl, preferably methyl , Ethyl, isopropyl, tert-butyl, and C ₁ -C ₄ alkoxy, preferably methoxy.

The following heterophosphacyclohexanes are examples of preferred compounds:

For the production of the used according to the invention Various known processes are available for heterophosphacyclohexanes Available. The following methods are mentioned as examples, to which in full reference is made.

K. Issleib et al. describe in Chem. Ber. 101, pp. 4032-4035 (1968) the preparation of 1,3-azaphosphacyclohexanes by cyclizing condensation of 3-aminopropylphosphines with Carbonyl compounds.

A. W. Frank and G. L. Drake describe in J. Org. Chem. 37, S. 2752-2755 (1972) the synthesis of 1,3,5-diazaphosphacyclohexanes from tetrakis (hydroxymethyl) phosphonium chlorides.

K. Issleib et al. describe in Syn. Inorg. Metalorg. Chem. 2 (3), pp. 223-229 (1972) the synthesis of 1,3-oxaphosphacyclohexanes by acid catalyzed cyclocondensation of 3-hydroxypropylphenylphosphines with aldehydes and ketones.

H. H. Karsch et al. describe in Chem. Ber./Recueil 130, S. 11777-1785 (1997) the synthesis of 1,3,5-diazaphosphacyclohexanes by nucleophilic aminomethylation of dichlorophosphines.

B. A. Trofimov et al. describe in Russ. Chem. Rev. 68 (3), p. 215-227 (1999) and the literature cited therein the synthesis of 1,4-oxaphosphacyclohexanes and 1,3,5-dioxaphosphacyclohexanes.

DE-OS 19 00 706 describes a process for the production of 1,4-oxaphosphacyclohexanes from divinyl ether and Hydrogen phosphide or a monosubstituted phosphine.

US 3,005,020 describes a process for the synthesis of 1,3-dioxa-5-phosphacyclohexanes from bis (1-hydroxyalkyl) phosphanes and an aldehyde.

US 3,116,314 describes a process for the synthesis of 1,3-dioxa-5-phosphacyclohexanes from alkylphosphines and Aldehydes.

SU 652 184 describes the synthesis of 1,3- Dioxa-2-sila-5-phosphorinanen.

D. M. Schubert et al. describe in Phosphorus, Sulfur and Silicon, 123, pp. 141-160 (1997) including 4-silaphosphorinanes and Derivatives thereof.

R. Thamm and E. Fluck describe in Z. Naturforsch., 37B (8), S. 965-974 (1982) the synthesis of 1,3-oxophosphorinan-2-ones.

H. Oehme and E. Leißring describe in Z. Chem. 13, pp. 291-292 (1973) the synthesis of PH-functional 1,3-oxaphosphacyclohexanes.

S. A. Buckler et al. describe in J. Am. Chem. Soc. 83 Pp. 168-173 (1961) the synthesis of corresponding PH-functional 1,3,5-Dioxaphosphacyclohexane.

• a) das P-H-funktionelle Heterophosphacyclohexan mit wenigstens einer ethylenisch ungesättigten Verbindung umsetzt, wobei der Reaktionsschritt i)
  • - in Gegenwart wenigstens eines Radikalbildners erfolgt, oder
  • - in Gegenwart wenigstens einer Säure oder wenigstens einer Base oder wenigstens einer Übergangsmetallverbindung erfolgt, oder
  • - bei einer erhöhten Temperatur im Bereich von 100 bis 250°C erfolgt,
  oder
• b) das P-H-funktionelle Heterophosphacyclohexan mit wenigstens einer Verbindung der Formel R¹-X¹ oder X¹-Y-X² umsetzt, wobei X¹ und X² für nucleophil verdrängbare Gruppen stehen und R¹ und Y die zuvor angegebenen Bedeutungen, ausgenommen R¹ für Wasserstoff, besitzen.

One can introduce a radical R ¹ on the phosphorus atom other than hydrogen into PH-functional heterophosphacyclohexanes

• a) reacting the PH-functional heterophosphacyclohexane with at least one ethylenically unsaturated compound, reaction step i)
  • - Is carried out in the presence of at least one radical generator, or
  • - in the presence of at least one acid or at least one base or at least one transition metal compound, or
  • - takes place at an elevated temperature in the range from 100 to 250 ° C,
  or
• b) the PH-functional heterophosphacyclohexane is reacted with at least one compound of the formula R ¹ -X ¹ or X ¹ -YX ² , where X ¹ and X ^{2 represent} nucleophilically displaceable groups and R ¹ and Y have the meanings given above, except R ¹ for hydrogen.

Step i)

• A) in Gegenwart wenigstens eines Radikalbildners,
• B) in Gegenwart wenigstens einer Säure oder wenigstens einer Base oder wenigstens einer Übergangsmetallverbindung,
• C) bei einer erhöhten Temperatur im Bereich von 100 bis 250°C.

A first embodiment of the process for the preparation of heterophosphacyclohexanes substituted in the 1-position comprises the reaction according to one of the following three reaction variants:

• A) in the presence of at least one radical generator,
• B) in the presence of at least one acid or at least one base or at least one transition metal compound,
• C) at an elevated temperature in the range of 100 to 250 ° C.

In principle, are suitable for the reaction in reaction step i) all compounds that have one or more ethylenic contain unsaturated double bonds. These include e.g. B. olefins, such as α-olefins, internal straight-chain and internal branched olefins, functionalized olefins, oligomeric and polymeric compounds, the at least one ethylenically unsaturated double bond exhibit etc.

If desired, reaction step i) can be carried out in the presence of a Solvent. These include aromatics such as benzene and toluene and xylenes, cycloalkanes, such as cyclohexane, aliphatic Hydrocarbons, etc. According to a suitable embodiment, the Reaction in the olefin used for the reaction as Solvent, which is generally in a large molar Excess over the heterophosphacyclohexane is used.

Variant I)

According to a preferred embodiment, the Reaction step i) in the presence of at least one radical generator.

Suitable radical formers are the usual ones known to the person skilled in the art known polymerization initiators, such as those for radical polymerization can be used. examples for such compounds are organic peroxides, e.g. B. Perester of carboxylic acids, such as tert-amyl perpivalate, tert-butyl perpivalate, tert-butyl perneohexanoate, tert-butyl perisobutyrate, tert-butyl per-2-ethylhexanoate, tert-butyl perisononanoate, tert-butyl permaleate, tert-butyl perbenzoate, percarbonates, such as Di- (2-ethylhexyl) peroxodicarbonate, dicyclohexylperoxodicarbonate, Di- (4-tert-butylcyclohexyl) peroxodicarbonate, ketone peroxides, such as Acetylacetone peroxide, methyl ethyl ketone peroxide, hydroperoxides such as tert-butyl hydroperoxide and cumene hydroperoxide and Azo initiators, such as 2,2'-azobis (amidinopropane) dihydrochloride, 2,2'-azobis (N, N'-dimethylene) isobutyramidindihydrochlorid, 2- (carbamoylazo) isobutyronitrile, 2,2-azobisisobutyronitrile, 2,2-azobisisovaleronitrile, or 4,4'-azobis (4-cyanovaleric acid). These include e.g. B. the Vazo® brands from Du Pont, such as Vazo 52, 67 and 88, whereby the Number denotes the temperature at which the initiator is one Has half-life of 10 hours. To be favoured Azo initiators used.

The radical generator is preferably used in an amount of 0.001 to 10 wt .-%, particularly preferably 0.01 to 5 wt .-%, based on the Total amount of ethylenically unsaturated compounds, used.

If the reaction step i) in the presence of at least one Free radical generator takes place, the reaction temperature is preferably 20 to 200 ° C, particularly preferably 50 to 150 ° C. The The person skilled in the art selects the suitable reaction temperature on the basis of the Decay temperature, d. H. the corresponding half life of Initiator at this temperature.

Variant II)

According to a further suitable embodiment, the Step i) in the presence of at least one acid or at least a base or at least one transition metal compound. Suitable acids are, for example, mineral acids, such as hydrochloric acid and sulfuric acid. Carboxylic acids, such as. B. Acetic acid. Suitable bases are alkali metal bases, such as Sodium hydroxide solution, potassium hydroxide solution, soda, sodium hydrogen carbonate, Potassium carbonate or potassium hydrogen carbonate and alkaline earth metal bases, such as Calcium hydroxide, calcium oxide, magnesium hydroxide or Magnesium carbonate as well as ammonia and amines. Preferably amines such as Trimethylamine, triethylamine, triisopropylamine, etc. are used. Rhodium compounds and complexes are preferred. Latter generally advantageously enable in situ production the ligands according to the invention and used according to the invention and the hydroformylation catalysts based on them.

Variant III

According to a further preferred embodiment, the Reaction step i) at a temperature in a range of about 100 to 250 ° C. So in general it is also a purely thermal one Implementation of the heterophosphacyclohexanes with ethylenic unsaturated compounds possible.

Step ii)

A second embodiment of the process according to the invention for the preparation of heterophosphacyclohexanes substituted in the 1-position comprises the reaction of the PH-functional heterophosphacyclohexanes with at least one compound of the formula R ¹ -X ¹ or X ¹ -YX ² , where X ¹ and X ^{2 are} nucleophilic displaceable group (leaving group) and R ¹ and Y have the meanings given above.

The nucleophilically displaceable groups (leaving groups) X ¹ and X ^{2 of} the compounds of the formulas R ¹ -X ¹ or X ¹ -YX ² are the usual leaving groups known to the person skilled in the art from nucleophilic substitution. The anions of strong acids, such as the halides, e.g. B. -Cl, -Br and -I or groups such as OH, p-CH ₃ C ₆ H ₄ -SO ₃ - (tosylates), p-BrC ₆ H ₄ SO ₃ - (brosylates) and F ₃ C-SO ₃ - (triflates).

The groups R ¹ and Y can generally have all of the meanings mentioned above.

This process variant is advantageously suitable for the preparation of heterophosphacyclohexanes which are substituted in the 1-position and which are not or only inadequately accessible through the addition of ethylenically unsaturated compounds described above. The use of compounds of the formula X ¹ -YX ² results in dinuclear, each in the 1-position bridged heterophosphacyclohexanes, bridges with any number of carbon atoms being accessible. Thus, this process also enables the production of dinuclear compounds with bridges with odd-numbered bridge atoms.

According to a suitable embodiment, the PH-functional heterophosphacyclohexanes are first metalated on the phosphorus atom before the reaction with at least one compound R ¹ -X ¹ or X ¹ -YX ² . "Metallization" means the formal exchange of the hydrogen atom for a metal atom. Suitable reagents for the metalation are generally strong bases, e.g. B. alkali metal and alkaline earth metal hydrides and Li, Mg, Al, Sn and Zn organic compounds. Organolithium compounds are preferred. These include, for example, n-butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium, etc. Suitable reagents for the metalation are also lithium-2,2,6,6-tetramethylpiperidine, lithium-hexamethyldisilazane, lithium-dicyclohexylamide and lithium-diisopropylamide ,

The catalysts of the invention can additionally at least one further ligand selected from halides, amines, carboxylates, acetylacetonate, aryl or alkyl sulfonates, hydride, CO, olefins, dienes, cycloolefins, nitriles, N-containing heterocycles, aromatics and heteroaromatics, ethers, PF ₃ , Have phospholes, phosphabenzenes and monodentate, bidentate and multidentate phosphine, phosphinite, phosphonite, phosphoramidite and phosphite ligands.

The group of platinum metals includes ruthenium, rhodium, Palladium, osmium, iridium and platinum. Preferably include the catalysts of the invention at least one complex of rhodium or the palladium, especially the rhodium.

The catalysts active in the hydroformylation are generally transition metal complexes of the general formula ML _n (CO) _m , in which M is an element of subgroup VIII of the periodic table, L is at least one monodentate or polydentate heterophosphacyclohexane ligand capable of complex formation, and n and m whole Represent numbers between 1 and 3. The transition metal complex can also contain further radicals such as hydrido, alkyl or acyl radicals as ligands. The use of rhodium as the transition metal is particularly preferred.

The active carbonyl complex is usually made in situ from one Transition metal salt, preferably a rhodium salt, or one Transition metal complex compound, preferably one Rhodium complex compound, the ligand, hydrogen and carbon monoxide formed; but it can also be manufactured and used separately.

If the complex catalysts are generated in situ, one sets particularly preferred precursor complexes such as rhodium dicarbonyl acetonate, Rhodium (2-ethylhexanoate) or rhodium acetate in the presence of the corresponding phosphacyclohexane ligands.

The composition of the synthesis gas CO / H ₂ used in the hydroformylation process according to the invention can be varied within wide limits. For example, synthesis gas can with CO / H ₂ molar ratios of 5: are successfully used 10, synthesis gas is preferably with CO / H ₂ ratios from 40: to 90 95 60 to 70: 30, particularly preferably a CO / H ₂ - Ratio of about 1: 1 applied.

The hydroformylation is carried out in a manner known per se Temperatures from 50 to 250 ° C, preferably at 70 to 180 ° C and at pressures from 5 to 600 bar, preferably at 10 to 100 bar. However, the optimal temperature and pressure are in the Essentially depending on the olefin used.

Because of their higher reactivity, α-olefins are special preferably at temperatures from 80 to 120 ° C and pressures from 10 to 40 bar hydroformylated. 1-alkenes are preferably used in Temperatures from 80 to 120 ° C hydroformylated. The pressure is there preferably in a range from 10 to 40 bar. Olefins with vinylidene Double bonds are preferably at 100 to 150 ° C. hydroformylated. Here, too, the pressure is preferably 10 to 40 bar. A Carrying out the reaction at higher temperatures and higher Pressing than the one specified above is not excluded.

Due to their lower reactivity, internal and internal, olefins branched on the double bond are particularly preferred Temperatures from 120 to 180 ° C and pressures from 40 to 100 bar hydroformylated.

The hydroformylation is usually carried out in the presence of a 1- up to 1000 times molar excess, preferably a 2- to 100-fold excess of the ligand, based on the one used Amount of transition metal.

In principle, all compounds which contain one or more ethylenically unsaturated double bonds are suitable as substrates for the hydroformylation process according to the invention. These include olefins such as α-olefins, internal straight-chain olefins or internal branched olefins with any number of C atoms, but especially those with 2 to 14 C atoms and those with internal and internal branched double bonds. The following olefins are mentioned by way of example: ethene, propene, 1-butene, 1-hexene, 1-octene, α-C _5-20 olefins, 2-butene, linear internal C _5-20 olefins and isobutene.

Suitable branched, internal olefins are preferably C _4-20 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 _5-8 -cycloalkenes, such as cyclopentene, cyclohexene, cycloheptene, cyclooctene and their derivatives, such as, for. B. their C _1-20 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 also ethylenically unsaturated polypropene and polyisobutene.

Functional groups are also tolerated. Be exemplary called the following olefins: 3-pentenenitrile, 4-pentenenitrile, 3-pentenoate, 4-pentenoate, (meth) acrylic acid ester, Vinyl glycol diacetate, 2,5-dihydrofuran and butenediol diacetate. Likewise suitable substrates are di- and polyenes with isolated or conjugated double bonds. The following olefins are examples called: 1,3-butadiene, 1,5-hexadiene, vinylcyclohexene, Dicyclopentadiene, 1,5,9-cyclooctatriene, butadiene homo- and copolymers.

The unsaturated compound used for the hydroformylation is preferably selected from internal linear olefins and olefin mixtures which contain at least one internal linear olefin. Suitable linear (straight-chain) internal olefins are preferably C _4-20 olefins, such as 2-butene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, 2-octene, 3-octene, 4 -Octen etc. and mixtures thereof.

• - thermisches Cracken (Steamcracken),
• - katalytisches Dehydrieren und
• - chemisches Dehydrieren durch Chlorieren und Dehydrochlorieren.

Preferably, an industrially accessible olefin mixture is used in the hydroformylation process according to the invention, which contains in particular at least one internal linear olefin. These include e.g. B. the Ziegler olefins obtained by targeted ethene oligomerization in the presence of alkyl aluminum catalysts. These are essentially unbranched olefins with a terminal double bond and an even number of carbon atoms. These also include the olefins obtained by ethene oligomerization in the presence of various catalyst systems, e.g. B. the predominantly linear α-olefins obtained in the presence of alkyl aluminum chloride / titanium tetrachloride catalysts and the α-olefins obtained in the presence of nickel-phosphine complex catalysts according to the Shell Higher Olefin Process (SHOP). Suitable technically accessible olefin mixtures are still used in the paraffin dehydrogenation of corresponding petroleum fractions, e.g. B. the so-called petroleum or diesel oil fractions obtained. Essentially three processes are used to convert paraffins, primarily n-paraffins to olefins:

• - thermal cracking (steam cracking),
• - catalytic dehydration and
• - chemical dehydration by chlorination and dehydrochlorination.

Thermal cracking mainly leads to α-olefins, while the other variants give olefin mixtures which are in the Generally also larger proportions of olefins with internal Have double bond. Suitable olefin mixtures are also those olefins obtained in metathesis or telomerization reactions. These include e.g. B. the olefins from the Phillips triolefin process, a modified SHOP process from ethylene oligomerization, Double bond isomerization and subsequent metathesis (Ethenolysis).

Suitable in the hydroformylation process according to the invention usable technical olefin mixtures are still selected among dibutenes, tributes, tetrabutenes, dipropenes, Tripropenes, tetrapropenes, mixtures of butene isomers, in particular Raffinate II, dihexenes, dimers and oligomers from the Dimersol® IFP process, Hüls Octolprocess®, polygas process etc.

Also preferred are 1-butene-containing hydrocarbon mixtures such as Raffinate II. Suitable 1-butene-containing hydrocarbon mixtures can have a proportion of saturated hydrocarbons.

The reaction can be carried out in the presence of a solvent. For example, those which are selected from the group of ethers, supercritical CO ₂ , fluorocarbons or alkylaromatics, such as toluene and xylene, are suitable. The solvent can also be a polar solvent. For example, those which are selected from the group of alcohols, dimethylacetamide, dimethylformamide or N-methylpyrrolidone are suitable. It is also possible to carry out the reaction in the presence of a high-boiling condensation product, e.g. B. an oligomeric aldehyde, especially in the presence of an oligomer of the aldehyde to be produced, which also functions as a solvent here. It is also possible to carry out the reaction in a two-phase mixture.

Since the catalysts used in the invention besides theirs Hydroformylation activity also often has some activity in the hydrogenation of aldehydes, in addition to the aldehydes also the alcohols corresponding to the aldehydes as valuable products arise.

• a) die wenigstens eine ethylenisch ungesättigte Doppelbindung enthaltende(n) Verbindung(en) in einer Reaktionszone in Gegenwart von Kohlenmonoxid, Wasserstoff und des Katalysators umsetzt,
• b) aus der Reaktionszone einen Austrag entnimmt und diesen einer Trennung in eine produktangereicherte Fraktion und eine an Katalysatorsystem angereicherte Fraktion unterzieht,
• c) gegebenenfalls die in Schritt ii) enthaltene an Katalysatorsystem angereicherte Fraktion einer Aufarbeitung unterzieht und
• d) die, gegebenenfalls aufgearbeitete, an Katalysatorsystem angereicherte Fraktion zumindest teilweise in die Reaktionszone zurückführt.

The reaction discharge can in principle be worked up by known processes. A method is preferred in which

• a) reacting the compound (s) containing at least one ethylenically unsaturated double bond in a reaction zone in the presence of carbon monoxide, hydrogen and the catalyst,
• b) withdrawing a discharge from the reaction zone and subjecting it to a separation into a product-enriched fraction and a catalyst system-enriched fraction,
• c) optionally subjecting the fraction enriched in catalyst system contained in step ii) to a workup and
• d) the fraction, optionally worked up, enriched in the catalyst system is at least partially returned to the reaction zone.

The reaction discharge in step ii) can be separated for example by distillation, extraction, ultrafiltration or a combination of these measures can be done. After a suitable one Embodiment is a catalyst for hydroformylation used with at least one polymeric ligand Heterophosphacyclohexan structural element and in which the separation in Step ii) and / or working up in step iii) Includes ultrafiltration.

In the following, the distillative processing of the Reaction discharge described. The discharge of the The hydroformylation stage is usually carried out before it is worked up by distillation relaxed. Unreacted synthesis gas is released, that can be recycled in the hydroformylation. The same applies to the relaxation in the gas phase passed, unreacted olefin, which, if appropriate after separation of the inert contained therein by distillation Hydrocarbons, also be returned to the hydroformylation can. The distillation of the relaxed Hydroformylation output is generally at pressures from 0.1 to 1000 mbar absolute, preferably at 1 to 500 mbar and particularly preferably from 10 to 400 mbar carried out.

The temperature and pressure set in the distillation depend on the type of Hydroformylation product and the distillation apparatus used. For the Methods according to the invention can generally be any Distillation apparatus can be used. However, are preferred Apparatus used that cause low investment costs and, especially for higher olefins, the lowest possible Allow distillation temperature, like thin film evaporators, Wiper blade evaporator or falling film evaporator, since with higher Temperature of the aldehydes formed in the reaction discharge how aldol condensation can enter. Since this distillation in Essentially the separation of the hydroformylation products Aldehyde and alcohol and any low boilers still present, such as unreacted olefin and inert, from high-boiling Condensation products of aldehydes, so-called high boilers, and serves the catalyst and excess ligand, it can be expedient, the separated hydroformylation products and optionally olefins and inerts, another distillative Cleaning that can be done in a conventional manner undergo. In particular, there should still be an increase in level contained high boilers can be avoided.

• a) der Destillationssumpf, der den Katalysator und überschüssigen Ligand enthält, insgesamt zurückgeführt werden, oder
• b) der Katalysator und überschüssiger Ligand mit einem Lösungsmittel, in dem der Katalysator und der überschüssige Ligand unlöslich oder nahezu unlöslich sind, ausgefällt und nur das Fällungsprodukt zurückgeführt werden, oder
• c) die im Destillationssumpf enthaltenen Hochsieder mittels Wasserdampfdestillation vom Katalysator und überschüssigem Liganden abgetrennt werden und nur der nach der Wasserdampfdestillation erhaltene Katalysator und überschüssige Liganden enthaltene Destillationssumpf in die Hydroformylierungsreaktion zurückgeführt werden, oder
• d) der Katalysator und überschüssiger Ligand durch Ultrafiltration des Destillationssumpfs gewonnen und das Retentat zurückgeführt werden, oder
• e) der Katalysator und überschüssiger Ligand durch Extraktion des Destillationssumpfs gewonnen werden,

wobei z. B. zur Vermeidung einer Anreicherung von Hochsiedern im Kreislauf eine Kombination wenigstens zweier der Methoden a) bis e) möglich ist. An advantage of the process according to the invention is the possibility of recycling the complex catalyst and the excess ligand from the distillation residue of the reaction mixture. You can either

• (a) the distillation bottoms containing the catalyst and excess ligand are all recycled, or
• b) the catalyst and excess ligand are precipitated with a solvent in which the catalyst and the excess ligand are insoluble or almost insoluble and only the precipitate is returned, or
• c) the high boilers contained in the distillation bottoms are separated by steam distillation from the catalyst and excess ligand and only the distillation bottoms obtained after the steam distillation and excess ligands are returned to the hydroformylation reaction, or
• d) the catalyst and excess ligand are obtained by ultrafiltration of the distillation bottoms and the retentate is recycled, or
• e) the catalyst and excess ligand are obtained by extraction of the distillation bottoms,

where z. B. to avoid enrichment of high boilers in the circuit, a combination of at least two of the methods a) to e) is possible.

Alternatively, in order to avoid an accumulation of High boilers in the reaction mixture of the hydroformylation also part of the Distillation bottoms from the process from time to time be removed and further processing for recovery the transition metal of subgroup VIII of the periodic table and, if desired, the ligand used become. When doing this, one of the amount of transition metal of subgroup VIII of the Periodic table and ligand corresponding amount of this compound by feeding these compounds into the Hydroformylation reaction are supplemented.

Method a)

Preferred ligands according to the invention are those which are so have high boiling point that when distilling the Reaction discharge the entire ligand-transition metal complex and all or at least most of it is not for complex formation required ligand remain in the bottom of the distillation and the bottom from this distillation together with fresh olefin into the Reaction can be attributed.

This method surprisingly leads to excellent ones Results in hydroformylation with distillative Working up the reaction discharge, since the ligands to be used are very good stabilizers for the thermolabile catalyst are and themselves have high thermal stability. Losses of Ligands and the transition metal component of the catalyst can be largely avoided, even if a very Inexpensive distillation with a low number of theoretical Soils such as B. thin film evaporator or falling film evaporator is used.

Since in this variant of the process all high-boiling By-products get back into the reaction, a certain occurs Leveling up the high boilers and it may be necessary a continuous or batch removal of To carry out high boilers. This can e.g. B. done by one at least according to variants b) or c) described in more detail below at times a separation of the catalyst complex and the excess ligand from the distillation sump and the mainly ejecting the rest containing high boilers.

Method b)

Advantageous for this method of precipitation Catalyst complex and the excess ligand is a solvent that with the organic components of the distillation bottoms of the Reaction discharge is miscible in a wide range in which however, the catalyst complex and the ligand are insoluble or nearly are insoluble so that it becomes possible by choosing the type and Amount of solvent, the catalyst complex and the ligand precipitate after separation by decantation or Filtration can be returned to the hydroformylation.

A large number of polar solvents are used Solvents, especially hydroxy, carbonyl, carboxamide or Have ether groups, i.e. alcohols, ketones, amides or ethers and mixtures of these solvents or mixtures of these Consider solvents with water.

The type and amount of the solvent to be used can Determine the specialist in a few manual tests in detail. in the In general, the amount of solvent becomes as low as possible kept so that the recovery effort is as low as possible. Accordingly, usually, based on the volume of the Distillation bottoms, 1 to 50 times, preferably 3 to 15 times Amount needed.

Method c)

Another method of removing high-boiling Condensation products of the aldehydes consist of these from the Bottom of the distillation using steam distillation separate. Steam distillation of the distillation bottoms can discontinuously, i.e. batchwise, or continuously take place, the steam distillation in the Distillation apparatus itself or a separate device for Steam distillation can be made. For example, in the discontinuous design of the process of Distillation bottoms before being returned to the hydroformylation Passing water vapor in whole or in part from high-boiling Condensation products are released, or the Depending on the amount of high boiler, distillation bottoms can from time to time in one separate apparatus subjected to steam distillation become.

The continuous design of the method can e.g. B. like this done that the distillation bottoms or part of the Distillation bottoms before being returned to the hydroformylation continuously fed to a steam distillation apparatus and it is wholly or partially freed from high boilers. As well it is possible to work up the distillative Hydroformylation discharge continuously in the presence of Water vapor to operate with the aldehyde and the Alcohol also the high boilers from the catalyst and the remove excess ligand. It goes without saying that at such a procedure in a subsequent fractionation and distillation device the valuable products of high boilers and may need to be divorced from water.

Steam distillation generally takes place on conventional way by introducing water vapor into the high boiler containing distillation bottoms and subsequent condensation of the Steam distillate. The water vapor is advantageous in this way passed through the distillation sump that it is not in the Distillation bottoms condensed. This can be done by choosing the print and / or Temperature conditions under which steam distillation is carried out. This can both decrease Pressure can be applied or overheated when used Water vapor also increased pressure. Generally the Steam distillation at a temperature of 80 to 200 ° C and at a Pressure from 1 mbar to 10 bar, preferably from 5 mbar to 5 bar, performed. The water vapor is relative to that in the swamp contained high-boiling condensation products of the aldehydes (High boilers) generally in a weight ratio Steam: high boilers from 10: 1 to 1:10 through the distillation sump directed. After the steam distillation has ended, the so catalyst completely and partially freed from high boilers and distillation bottoms containing excess ligand into the Hydroformylation are recycled.

As already mentioned above, it may be appropriate to Methods a) and b) or a) and c) to combine.

Method d)

Due to the difference in molecular weights of the Catalyst complexes and excess ligands on the one hand and the im High boilers remaining on the other hand it is distillation bottoms also possible through catalyst complexes and ligands To separate ultrafiltration from the high boilers. The mean is Molecular weight of the ligand preferably more than 500 daltons, more preferably more than 1000 daltons.

The process can be continuous or discontinuous operate. Refinements of such methods are in the WO 99/36382, to which reference is made here.

After a suitable continuous operation, the Educts in the presence of the catalyst and ligands in one Reactor implemented. The reactor discharge is in one Distillation apparatus into a distillate stream containing the oxo products, and separated into a residue. The catalyst-containing residue is continuously fed to a membrane filtration. there the residue, the high boiler (or a mixture of high boilers, Educts and oxo products), catalyst and ligands, worked up. The high boilers (and possibly educts and Oxo products) permeate through the membrane. The high boiler (and depleted in educts and oxo products if necessary) and Catalyst and ligand enriched retentate stream is in the Hydroformylation recycled.

After a suitable discontinuous procedure, the Educts in the presence of the catalyst and ligands in one Reactor implemented. At the end of the reaction, the reactor discharge is in a distillation apparatus in a distillate stream, which the Contains oxo products, and separated into a residue stream. This Catalyst-containing residue from the distillation is in a Refurbished membrane filtration. The high boiler (and depleted in educts and oxo products if necessary) and Catalyst and ligand enriched distillation residue is on End of ultrafiltration in the reactor for the next batch the hydroformylation.

Ultrafiltration can be single-stage or multi-stage (preferably two-stage). At every stage the feed solution z. B. brought to filtration pressure by means of a pressure pump; the Overflow, d. H. Wetting, the membrane can then pass through Recycling part of the retentate stream in a second pump be ensured. For a notable top layer construction to avoid the catalyst on the membrane surface (Concentration polarization), which leads to a decrease in the permeate flow can lead between the membrane and the catalyst-containing Solution preferably a relative speed in the range of 0.1 to 10 m / s observed. Further suitable measures for Avoiding a top layer structure are e.g. B. mechanical movement the membrane or the use of stirring units between the Membranes. In the multi-stage variant, the permeate stream becomes one Stage passed to the downstream stage and the retentate stream forwarded to this downstream stage of the previous stage. This working up of the permeate is a better one Retention of the catalyst and ligand achievable.

In the case of multi-stage ultrafiltration, the different stages with the same or with different membranes be equipped.

The optimal transmembrane pressures between retentate and permeate are essentially dependent on the diameter of the membrane pores and the mechanical stability of the membrane in the Operating temperature and, depending on the membrane type, between 0.5 and 100 bar, preferably 10 to 60 bar and at a temperature up to 200 ° C. Higher transmembrane pressures and higher temperatures lead to higher permeate flows. The overflow rate in the Module is usually 1 to 10, preferably 1 to 4 m / s.

All membranes that are stable in the reaction system are suitable for ultrafiltration. The separation limit of the membranes is about 200 to 20,000 daltons, especially 500 to 5000 daltons. The separating layers can consist of organic polymers, ceramics, metal or carbon and must be stable in the reaction medium and at the process temperature. For mechanical reasons, the separating layers are generally applied to a single-layer or multilayer porous substructure made of the same or also several different materials as the separating layer. Examples are:

The membranes can be in flat, tubular, multi-channel element, Capillary or winding geometry can be used for corresponding pressure housing, which is a separation between retentate (containing catalyst) and the permeate (catalyst-free filtrate) allow are available.

Examples of such membranes are compiled in the following tables.

Method e)

As a further variant, a distillative can also be used initially Separation of the aldehydes / alcohols are carried out, whereupon the Catalyst-containing sump with a polar extractant such as z. B. water is treated. The catalyst enters the polar phase over, while high boilers in the organic phase remain. Are preferred according to this variant Catalysts with water-soluble (hydrophilic) ligands or with ligands, which can be converted into a water-soluble form used. The catalyst can be re-extracted be recovered or returned directly as such. Alternatively, the catalyst can be a non-polar solvent are extracted, whereupon the high boilers are separated off.

As an alternative to a work-up process by distillation, the reaction product can also be worked up by extraction. For this purpose, depending on the type of catalyst used, a polar or non-polar solvent is added to the reaction discharge which is essentially immiscible with the reaction discharge or with at least one of the solvents which may be present in the reaction discharge. If desired, a two-phase mixture of at least one polar and at least one non-polar solvent can also be added to the reaction discharge for extraction. In the case of a two-phase reaction procedure, the addition of a further solvent can generally be dispensed with. The extraction can take place continuously or discontinuously. A suitable continuous extraction is countercurrent extraction. After phase separation in a suitable apparatus, a phase is obtained which contains the hydroformylation products and higher-boiling condensation products, and a phase which contains the catalyst. Particularly suitable polar phases are water and ionic liquids, ie salts, which have a low melting point. In such a hydroformylation process, preference is given to using heterophosphacyclohexane ligands containing ionic or polar groups, so that a high solubility of the catalyst in the polar phase results and "leaching" of the catalyst into the organic phase is prevented or at least largely prevented. Suitable substituents are, for example, W'COO ^- M ⁺ , W'SO ₃ ^- M ⁺ , W'PO ₃ ^2- M ²⁺ , W'NR ' ₃ ⁺ X ^- , W'OR', WNR ' ₂ , W'COOR ', W'SR', W '(CHR'CH ₂ O) _x R', W '(CH ₂ NR') _x R 'and W' (CH ₂ CH ₂ NR ') _x R', where X ^- , M ⁺ , R ', W' and x have the meanings mentioned above.

Heterophosphacyclohexanes with non-polar residues can also with an apolar solvent can be removed by phase separation. Heterophosphacyclohexanes with lipophilic are particularly suitable Residues. In this way you can "leach" the catalyst at least largely prevent.

In a preferred embodiment, the workup of the Reaction mixture also take place directly via an ultrafiltration. It is used to separate the catalyst and obtain a catalyst-free product or high-boiling stream of Synthesis discharge, as described above, under pressure with a membrane contacted and permeate (filtrate) on the back of the Membrane at a lower pressure than on the feed side deducted. A catalyst concentrate (retentate) and a practically catalyst-free permeate.

If the synthesis is directly the membrane process with the Synthesizing pressure is supplied, the transmembrane pressure can Raising the permeate pressure can be set.

The essentially catalyst-free permeate obtained can by customary processes known to those skilled in the art, such as distillation or crystallization, further into products and high boilers be separated.

When using α-olefins as feed can Comparison of hydroformylation processes used according to the invention to a corresponding rhodium / triphenylphosphine-catalyzed Hydroformylation process higher isoaldehyde levels in the Aldehyde mixture are formed. This is beneficial for certain Applications, e.g. B. for the production of neopentyl glycol.

The catalysts used according to the invention show in the Hydroformylation a high selectivity to aldehydes and Alcohols. The formation of paraffin by hydrogenation of educt alkenes is in the Comparison to a rhodium / triphenylphosphine catalyzed Hydroformylation process significantly lower.

In addition to hydroformylation, the catalyst is also in others suitable implementations. Examples are Hydroacylation, hydrocyanation, hydroamidation, hydroesterification, Aminolysis, alcoholysis, hydrocarbonylation, hydroxycarbonylation, Carbonylation, isomerization or transfer hydrogenation.

Another area of application for catalysts based on Heterophosphacyclohexane ligands represent the hydrocyanation of Olefins. The hydrocyanation catalysts of the invention include complexes of nickel. The metal is usually in the inventive metal complex before zero. The production the metal complexes can, as already for use as Hydroformylation catalysts described above take place. The same applies to the in situ production of the invention Hydrocyanation.

A suitable one for producing a hydrocyanation catalyst Nickel complex is e.g. B. Bis (1,5-cyclooctadiene) nickel (0).

The invention therefore furthermore relates to a process for the hydrocyanation of compounds which contain at least one ethylenically unsaturated double bond by reaction with hydrogen cyanide in the presence of a catalyst comprising at least one complex of nickel with at least one ligand as defined above. Suitable olefins for hydrocyanation are generally the olefins previously mentioned as starting materials for hydroformylation. A special embodiment of the process according to the invention relates to the preparation of mixtures of monoolefinic C ₅ mononitriles with non-conjugated C = C and C CN bonds by catalytic hydrocyanation of 1,3-butadiene or 1,3-butadiene-containing hydrocarbon mixtures and the isomerization / Further reaction to saturated C ₄ dinitriles, preferably adiponitrile in the presence of at least one catalyst according to the invention. When using hydrocarbon mixtures for the production of monoolefinic C ₅ -mononitriles by the process according to the invention, a hydrocarbon mixture is preferably used which has a 1,3-butadiene content of at least 10% by volume, preferably at least 25% by volume, in particular at least 40% by volume .-%, having.

Hydrocarbon mixtures containing 1,3-butadiene are available on an industrial scale. So z. B. in the processing of petroleum by steam cracking of naphtha as a C _{4 cut} hydrocarbon mixture with a high total olefin content, with about 40% to 1,3-butadiene and the rest to monoolefins and polyunsaturated hydrocarbons and alkanes. These streams always contain small amounts of generally up to 5% of alkynes, 1,2-dienes and vinyl acetylene.

Pure 1,3-butadiene can e.g. B. by extractive distillation technically available hydrocarbon mixtures isolated become.

The catalysts of the invention can be used advantageously Hydrocyanation of such olefin-containing, in particular Use hydrocarbon mixtures containing 1,3-butadiene, as a rule even without prior purification of the Hydrocarbon mixture. Possibly included, the effectiveness of Catalyst-affecting olefins, such as. B. alkynes or Cumulenes can, if necessary, undergo hydrocyanation selective hydrogenation removed from the hydrocarbon mixture become. Suitable processes for selective hydrogenation are Known specialist.

The hydrocyanation according to the invention can be carried out continuously, semi-continuously or discontinuously. suitable Reactors for the continuous reaction are known to the person skilled in the art and z. B. in Ullmann's Encyclopedia of Chemical Engineering, Volume 1, 3rd edition, 1951, p. 743 ff. Preferably is for the continuous variant of the invention Process used a cascade of stirred tanks or a tubular reactor. Suitable, optionally pressure-resistant reactors for the semi-continuous or continuous execution are the expert known and z. B. in Ullmann's Encyclopedia of Technical Chemistry, Volume 1, 3rd edition, 1951, pp. 769 ff. in the In general, an autoclave is used for the method according to the invention used, if desired with a stirrer and can be provided with an inner lining.

The hydrocyanation catalysts according to the invention can be by conventional methods known to those skilled in the art of discharging the Separate hydrocyanation reaction and can in general be used again for the hydrocyanation.

The invention is illustrated below with the aid of examples explains:

Examples General description of the experiment discontinuous hydroformylation attempts

Catalyst precursor, heterophosphacyclohexane ligand and solvent were mixed in a Schlenk tube under nitrogen inert gas. The solution obtained was transferred to a 70 ml or 100 ml autoclave flushed with CO / H ₂ (1: 1). At room temperature, 2-5 bar CO / H ₂ (1: 1) were injected. The reaction mixture was heated to the desired temperature within 30 min with vigorous stirring using a gassing stirrer. The olefin used was then pressed into the autoclave with CO / H ₂ overpressure via a lock. The desired reaction pressure was then immediately set using CO / H ₂ (1: 1). During the reaction, the pressure in the reactor was kept at the pressure level by injecting synthesis gas through a pressure regulator. After the reaction time, the autoclave was cooled, decompressed and emptied. Analysis of the reaction mixture was performed by gas chromatography (GC) using correction factors.

example 1 Low pressure hydroformylation of 1-octene

Starting from 1.8 mg (0.007 mmol) Rhodium dicarbonylacetylacetonate, 24 mg (0.06 mmol) 1,3,5-trioctyl-3,5-diaza-1-phosphacyclohexane, 6.3 g (56 mmol) 1-octene (purity: 95%, residual amount: n-octenes with internal double bond) and 6.0 g of toluene were obtained 4-hour hydroformylation at 90 ° C and 10 bar Synthesis gas pressure according to the general test procedure a turnover of 1-octene of 92%. The yield of nonanals was 89% Selectivity to n-nonanal (n content) was 69%, and the Selectivity to n-nonanal and 2-methyloctanal (α content) was 100%.

Example 2 Low pressure hydroformylation of 1-octene

Starting from 7.5 mg (0.029 mmol) Rhodium dicarbonylacetylacetonate, 64 mg (0.23 mmol) 3-cyclohexyl-1-methyl-2-phenyl-1,3-azaphosphacyclohexane, 25.0 g (223 mmol) 1-octene (purity: 95%, Remaining amount: n-octenes with internal double bond) and 25.0 g toluene was obtained after 4 hours of hydroformylation at 90 ° C. and 10 bar synthesis gas pressure according to the general Experimental implementation a conversion of 1-octene of 100%. The yield at Nonanal was 85%, the selectivity to n-nonanal (n portion) was 63%, and the selectivity to n-nonanal (n portion) and 2-Methyloctanal (α content) was 99%.

Example 3 Low pressure hydroformylation of 1-octene

Starting from 3.2 mg (0.012 mmol) Rhodium dicarbonylacetylacetonate, 28 mg (0.10 mmol) 3-cyclohexyl-1-methyl-2-phenyl-1,3-azaphosphacyclohexane, 10.1 g (90 mmol) 1-octene (purity: 95%, Remaining amount: n-octenes with internal double bond) and 10.0 g toluene was obtained after 4 hours of hydroformylation at 90 ° C. and 10 bar synthesis gas pressure according to the general Experimental implementation a conversion of 1-octene of 100%. The yield at Nonanal was 83%, the selectivity to n-nonanal (n portion) was 45% and the selectivity to n-nonanal and 2-methyloctanal (α portion) was 83%.

Example 4 Low pressure hydroformylation of 2-octene

Starting from 4.4 mg (0.017 mmol) Rhodium dicarbonylacetylacetonate, 37 mg (0.14 mmol) 3-Cyclohexyl-1-methyl-2-phenyl-1,3-azaphosphacyclohexane, 15.2 g (135 mmol) 2-octene (ratio cis: trans = 80:20) and 15.0 g of toluene were obtained after 4 hours Hydroformylation at 90 ° C and 10 bar synthesis gas pressure according to the general experimentation a turnover of 2-octene of 68%. The yield of nonanals was 65% and the selectivity to n-nonanal and 2-methyloctanal (α content) was 56%.

Comparative Example 1 Low pressure hydroformylation of 2-octene

Starting from 3.9 mg (0.015 mmol) Rhodium dicarbonylacetylacetonate, 75 mg (0.29 mmol) triphenylphosphine, 12.1 g (108 mmol) 2-octene (ratio cis: trans = 80:20) and 12.0 g of toluene after hydroformylation for 4 hours at 90 ° C. and 10 bar Synthesis gas pressure according to the general experimental procedure 2-octene conversion of 62%. The yield of nonanals was 57%, the selectivity to n-nonanal (n component) was 5% and that Selectivity to n-nonanal and 2-methyloctanal (α portion) was 71%.

Example 5 Medium pressure hydroformylation of dimerbutene

Starting from 6.0 mg (0.023 mmol) of rhodium dicarbonylacetylacetonate, 50 mg (0.18 mmol) of 3-cyclohexyl-1-methyl-2-phenyl-1,3-azaphosphacyclohexane, 19.7 g (176 mmol) of dimerbutene (obtained from Nickel-catalyzed dimerization of n-butene, degree of branching 1.06) and 20.1 g of Texanol® (2,2,4-trimethyl-1,3-pentanediol monobutyrate from Eastman) were obtained at 140 ° C., 80 bar CO / H ₂ according to the general experimental procedure, a conversion of dimerbutene of 82% after 4 h and 95% after 24 h. The yield of nonanals was 79% after 4 h and 72% after 24 h. The yield of nonanols was 3% after 4 h and 24% after 24 h.

Comparative Example 2 Medium pressure hydroformylation of dimerbutene

Starting from 6.1 mg (0.024 mmol) of rhodium dicarbonylacetylacetonate, 60 mg (0.228 mmol) of triphenylphosphine, 20.3 g (181 mmol) of dimerbutene (obtained by nickel-catalyzed dimerization of n-butenes, degree of branching 1.06) and 19.8 g Texanol® was obtained at 140 ° C, 80 bar CO / H ₂ according to the general experimental procedure, a conversion of dimerbutene of 9% after 4 h and 30% after 24 h. The yield of nonanals was 6% after 4 h and 24% after 24 h.

Comparative Example 3 Medium pressure hydroformylation of dimerbutene

Starting from 6.3 mg (0.024 mmol) of rhodium dicarbonylacetylacetonate, 50 mg (0.178 mmol) of tricyclohexylphosphine, 20.3 g (181 mmol) of dimerbutene (obtained by nickel-catalyzed dimerization of n-butenes, degree of branching 1.06) and 20.0 g Texanol® was obtained at 140 ° C, 80 bar CO / H ₂ according to the general experimental procedure, a conversion of dimerbutene of 52% after 4 h and 82% after 24 h. The yield of nonanals was 51% after 4 h and 77% after 24 h. The yield of nonanols was 1% after 4 h and 5% after 24 h.

Example 6 Low pressure hydroformylation of 1-octene

Starting from 3.1 mg (0.012 mmol) Rhodium dicarbonylacetylacetonate, 31 mg (0.10 mmol) 3-cyclohexyl-2-mesityl-1-methyl-1,3-azaphosphacyclohexane, 9.9 g (88 mmol) 1-octene (purity: 95%, Remaining amount: n-octenes with an internal double bond) and 10.1 g of toluene was obtained after 4 hours of hydroformylation at 90 ° C and according the general test procedure a conversion of 1-octene of 99%. The yield of nonanols was 69% and the selectivity increased n-Nonanal (n content) was 67% and the selectivity increased n-Nonanal and 2-methyloctanal (α content) was 99%.

Example 7 Low pressure hydroformylation of 1-octene

Starting from 3.0 mg (0.012 mmol) Rhodium dicarbonylacetylacetonate, 24 mg (0.09 mmol) 3-cyclohexyl-2-phenyl-1,3-oxaphosphacyclohexane, 10.1 g (90 mmol) 1-octene (purity: 95%, residual amount: n- Octenes with an internal double bond) and 10.2 g of toluene were obtained after 4 hours of hydroformylation at 90 ° C and according to general experimentation a conversion of 1-octene of 100%. The yield of nonanols was 87% and the selectivity increased n-Nonanal (n content) was 63% and the selectivity to n-nonanal and 2-methyloctanal (α content) was 98%.

Example 8 Low pressure hydroformylation of 2-octene

Starting from 3.0 mg (0.012 mmol) Rhodium dicarbonylacetylacetonate, 26 mg (0.10 mmol) 3-cyclohexyl-3-phenyl-1,3-oxaphosphacyclohexane, 10.1 g (90 mmol) 2-octene (ratio cis: trans = 80:20) and 10.0 g of toluene were obtained after 4 hours of hydroformylation at 90 ° C and 10 bar synthesis gas pressure according to the general Test implementation a conversion of 2-octene of 54%. The yield on nonanals was 50%, the selectivity to n-nonanal (n content) was 3%, and the selectivity to n-nonanal and 2-methyloctanate (α content) was 59%.

Example 9 Medium pressure hydroformylation of dimerbutene

Starting from 7.5 mg (0.029 mmol) of rhodium dicarbonyl acetylacetonate, 90 mg (0.25 mmol) of 3-cyclohexyl-2-diphenylmethyl-1-methyl-1,3-azaphosphacyclohexane, 25.0 g (223 mmol) of dimerbutene (obtained from Nickel-catalyzed dimerization of n-butene, degree of branching 1.06) and 25.0 g of Texanol® gave a conversion of dimerbutene of 84% after 4 h and 97 at 140 ° C, 80 bar CO / H ₂ according to the general test procedure % after 24 h. The yield of nonanals was 75% after 4 h and 65% after 24 h. The yield of nonanols was 9% after 4 hours and 32% after 24 hours.

Claims (12)

1. A catalyst comprising at least one complex of a Platinum metal of subgroup VIII with at least one ligand with at least one unbridged heterophosphacyclohexane Structural element, the heterocycle in addition to Phosphorus atom at least one further heteroatom and / or one Has heteroatom-containing group in the 6-ring, the / the Phosphorus atom are not adjacent and at least one of the ring carbon atoms adjacent to the phosphorus atom has substituents other than hydrogen. 2. Catalyst according to claim 1, wherein the ligand is selected from heterophosphacyclohexanes of the general formula I.


wherein
A ¹ , A ² and A ³ independently of one another represent O, S, SO ₂ , NR ^a , SiR ^b R ^c or CR ^d R ^e , with the proviso that at least one of the radicals A ¹ , A ² or A ^{3 is} not stands for CR ^d R ^e , where
R ^a , R ^b , R ^c , R ^d and R ^e independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy or hetaryloxy,
R ¹ for hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, WCOO ^- M ⁺ , WSO ₃ ^- M ⁺ , WPO ₃ ^2- M ⁺ ₂ , W (NE ¹ E ² E ³ ) ⁺ X ^- , WOR ^f , WNE ¹ E ² , WCOOR ^f , W (SO ₃ ) R ^f , WPO ₃ R ^f R ^g , WSR ^f , W-polyoxyalkylene, W-polyalkyleneimine or WCOR ^f ,
R ² to R ⁵ independently of one another are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, WCOO ^- M ⁺ , WSO ₃ ^- M ⁺ , WPO ₃ ^2- M ⁺ ₂ , W (NE ¹ E ² E ³ ) ⁺ X ^- , WOR ^f , WNE ¹ E ² , WCOOR ^f , W (SO ₃ ) R ^f , WPO ₃ R ^f R ^g , WSR ^f , W-polyoxyalkylene, W-polyalkyleneimine, W-halogen, WNO ₂ , WCOR ^f or WCN stand in what
W represents a single bond or a divalent bridging group with 1 to 20 bridge atoms,
R ^f , R ^g , E ¹ , E ² and E ³ independently of one another represent hydrogen, alkyl, carbonylalkyl, cycloalkyl or aryl,
M ^{+ stands} for a cation equivalent,
X ^{- represents} an anion equivalent,
with the proviso that at least one of the radicals R ² to R ^{5 is} different from hydrogen,
where in each case two of the geminal radicals (R ² , R ³ ), (R ⁴ , R ⁵ ) and / or (R ^d , R ^e ) can also form an oxo group or together with the carbon atom to which they are attached, can stand for a 3- to 8-membered carbo- or heterocycle, which is optionally additionally fused one, two or three times with cycloalkyl, heterocycloalkyl, aryl and / or hetaryl,
where one or more of the radicals R ¹ to R ⁵ and R ^a to R ^{e can have} an additional trivalent phosphorus or nitrogen group capable of coordination,
where two adjacent atoms of the heterophosphacyclohexane ring can also be part of a non-aromatic condensed ring system with 1, 2 or 3 further rings,
where at least one of the radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^a , R ^b , R ^c , R ^d or R ^{e can} also represent a divalent or polyvalent bridging group Y, the at least two covalently connects identical or different heterophosphacyclohexane structural elements to one another,
wherein at least one of the radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^a , R ^b , R ^c , R ^d or R ^e or, if present, the group Y also for one of the previous definitions for these residues can be different polymer residues with a number average molecular weight in the range from 500 to 50,000. 3. A catalyst according to claim 2, wherein in the ligand of the formula I at least one of the radicals R ¹ to R ⁵ , R ^a to R ^e or the group Y is a polymer radical which is composed of repeating units which are derived from monomers, which are selected from mono- and diolefins, vinyl aromatics, esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C ₁ -C ₃₀ -alkanols, N-vinylamides, N-vinyl lactams, ring-polymerizable heterocyclic compounds and mixtures thereof. 4. Catalyst according to one of claims 2 or 3, wherein the Ligand of formula I has a group Y which is for a Stands for polymer to which at least 3 heterophosphacyclohexane Structural elements are bound. 5. A catalyst according to claim 2, wherein the compound of formula I comprises at least one divalent bridging group Y, which is selected from groups of formulas II.1 to II.7


wherein
R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ independently of one another for hydrogen, alkyl, cycloalkyl, aryl, alkoxy, halogen, SO ₃ H, sulfonate, NE ⁴ E ⁵ , alkylene -NE ⁴ E ⁵ , trifluoromethyl, nitro, alkoxycarbonyl, carboxyl or cyano, in which E ⁴ and E ⁵ each represent the same or different radicals selected from hydrogen, alkyl, cycloalkyl and aryl,
Z represents O, S, NR ²⁵ or SiR ²⁵ R ²⁶ ,
where R ²⁵ and R ²⁶ independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
or Z represents a C ₁ -C ₃ alkylene bridge which can have a double bond and / or an alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl substituent,
or Z represents a C ₂ -C ₃ alkylene bridge which is interrupted by O, S or NR ²⁵ or SiR ²⁵ R ²⁶ ,
B ¹ and B ² independently of one another are O, S, SiR ²⁵ R ²⁶ , NR ²⁵ or CR ²⁷ R ²⁸ , where
R ²⁷ and R ²⁸ independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl or the group R ²⁷ together with another group R ²⁷ or the group R ²⁸ together with another group R ^{28 form} an intramolecular bridge group D,
D a two-gang bridge group selected from the groups


is where
R ²⁹ and R ³⁰ independently of one another represent hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, carboxyl, carboxylate or cyano or are connected to one another to form a C ₃ -C ₄ -alkylene bridge,
R ³¹ , R ³² , R ³³ and R ³⁴ independently of one another for hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, COOH, carboxylate, cyano, alkoxy, SO ₃ H, sulfonate, NE ⁴ E ⁵ , alkylene-NE ⁴ E ⁵ E ⁶⁺ X ^- , acyl or nitro, where X ^{- stands} for an anion equivalent, and
c is 0 or 1. 6. Catalyst according to one of claims 2 to 5, wherein the compound of formula I is selected from compounds of general forms Ia-Im




wherein
A ¹ , A ^{1 '} , A ² , A ³ and A ^3' independently of one another are O or NR ^a , where R ^{a is} hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
R ¹ and R ^{1 '} independently of one another are C _1-20 -alkyl, C ₅ -C ₈ -cycloalkyl, C _6-12 -aryl, W-polyoxyalkylene, W-polyakyleneimine or a polymer residue with a number average molecular weight in the range from 500 to 50,000, which is composed of ethylene and / or butadiene, where W is a single bond or C _1-4 alkylene,
R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ^{6 '} , R ^7' , R ^{8 '} , R ^9' , R ^{10 '} and R ^11' independently of one another for hydrogen, alkyl, alkoxy, Carboxyl, carboxylate, trifluoromethyl, -SO ₃ H, sulfonate, NE ¹ E ² or alkylene-NE ¹ E ² , where E ¹ and E ² independently of one another are hydrogen, alkyl or cycloalkyl, and
R ^b , R ^c , R ^d and R ^e independently of one another are C ₁ -C ₁₀ alkyl, C ₅ -C ₈ cycloalkyl or phenyl. 7. Catalyst according to one of the preceding claims, wherein the platinum metal rhodium or palladium, in particular Rhodium, is. 8. Process for hydroformylation of compounds that contain at least one ethylenically unsaturated double bond, by reaction with carbon monoxide and hydrogen in Presence of a hydroformylation catalyst, as in one of the Claims 1 to 7 defined. 9. The method according to claim 8, wherein one a) reacting the compound (s) containing at least one ethylenically unsaturated double bond in a reaction zone in the presence of carbon monoxide, hydrogen and the catalyst, b) withdrawing a discharge from the reaction zone and subjecting it to a separation into a product-enriched fraction and a catalyst system-enriched fraction, c) optionally subjecting the fraction enriched in catalyst system contained in step ii) to a workup and d) the fraction, optionally worked up, enriched in the catalyst system is at least partially returned to the reaction zone. 10. The method according to claim 9, in which a catalyst is used , which has at least one polymeric ligand Heterophosphacyclohexan structural element, and in which the Separation in step ii) and / or processing in step iii) includes ultrafiltration. 11. Process for the hydrocyanation of compounds that contain at least one ethylenically unsaturated double bond, by reaction with hydrogen cyanide in the presence of a Catalyst comprising at least one complex of nickel with at least one ligand as in one of claims 1 to 7 Are defined. 12. Use of a catalyst as in one of claims 1 defined to 7, for hydroformylation, hydroacylation, Hydroamidation, hydroesterification, aminolysis, alcoholysis, Hydrocarbonylation, hydroxycarbonylation, isomerization, Carbonylation or hydrogenation.