WO2003053571A2 - Catalyseur comprenant un complexe de metal du viiieme groupe secondaire a base d'un ligand heterophosphacyclohexane - Google Patents

Catalyseur comprenant un complexe de metal du viiieme groupe secondaire a base d'un ligand heterophosphacyclohexane Download PDF

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WO2003053571A2
WO2003053571A2 PCT/EP2002/014690 EP0214690W WO03053571A2 WO 2003053571 A2 WO2003053571 A2 WO 2003053571A2 EP 0214690 W EP0214690 W EP 0214690W WO 03053571 A2 WO03053571 A2 WO 03053571A2
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alkyl
catalyst
cycloalkyl
hydrogen
aryl
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WO2003053571A3 (fr
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Thomas Mackewitz
Rocco Paciello
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Basf Aktiengesellschaft
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Publication of WO2003053571A3 publication Critical patent/WO2003053571A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6596—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having atoms other than oxygen, sulfur, selenium, tellurium, nitrogen or phosphorus as ring hetero atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2419—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member
    • B01J31/2438—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member and further hetero atoms as ring members, excluding the positions adjacent to P
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
    • B01J31/2461—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring
    • B01J31/2466—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring comprising aliphatic or saturated rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
    • B01J31/2461—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring
    • B01J31/2471—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring with more than one complexing phosphine-P atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
    • B01J31/2461—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring
    • B01J31/248—Bridged ring systems, e.g. 9-phosphabicyclononane
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
    • C07F9/6584—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having one phosphorus atom as ring hetero atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper

Definitions

  • Catalyst comprising a complex of a metal of subgroup VIII.
  • the present invention relates to a catalyst which comprises at least one complex of a platinum metal of subgroup VIII with at least one heterophosphacyclohexane ligand, a process for hydroformylation in the presence of such a catalyst and the use thereof.
  • Hydroformylation or oxo synthesis is an important large-scale process and is used to produce aldehydes from olefins, carbon monoxide and hydrogen. These aldehydes can optionally be hydrogenated in the same operation with hydrogen to the corresponding oxo alcohols.
  • the reaction itself is highly exothermic and generally takes place under elevated pressure and at elevated temperatures in the presence of catalysts.
  • Cobalt catalysts were initially used for industrial processes.
  • rhodium catalysts have also become established in technology. Such systems generally show higher selectivities than systems containing cobalt.
  • phosphorus-containing ligands are generally used. These also make it possible to carry out the reaction with sufficient activity even at lower synthesis gas pressures.
  • triphenylphosphine and other triarylphosphines as cocatalysts has proven particularly useful for the hydroformylation of lower ⁇ -olefins.
  • a disadvantage of these cocatalysts is that higher olefins, in particular those with internal and internal branched double bonds, are hydroforitized only very slowly.
  • ligand which must be constantly added, can also be lost in the working up of reaction mixtures of the hydroformylation of higher olefins by distillation.
  • triarylphosphines can be degraded in the presence of rhodium and olefins, which leads to deactivation of the catalyst.
  • Monodentate, sterically hindered monophosphites have proven themselves experimentally for these olefins.
  • phosphites generally have the disadvantage of sensitivity to hydrolysis and the tendency towards degradation reactions (in particular at higher temperatures), which hinders their technical use.
  • No. 3,420,898 describes a one-stage hydroformylation process for the production of primary alcohols using a cobalt catalyst based on a monophosphabicycloalkane as ligand.
  • DE-PS 17 68 441 describes a process for the preparation of aldehydes and alcohols by oxo synthesis in the presence of a cobalt hydroformylation catalyst based on a 1,4-oxaphosphacyclohexane as ligand.
  • DE-OS 19 00 706 has a comparable disclosure content.
  • DE-OS 22 42 646 describes a process for the preparation of aldehydes and / or alcohols in the presence of a catalyst system composed of cobalt and a tri-substituted tertiary phosphine, in which the phosphorus atom is bound to at least one alkoxymethyl group.
  • a catalyst system composed of cobalt and a tri-substituted tertiary phosphine, in which the phosphorus atom is bound to at least one alkoxymethyl group.
  • This can be, for example, 1-isopropyl-1-phospha-3-oxacyclohexane.
  • the object of the present invention is to provide new catalyst systems for the hydroformylation of unsaturated compounds which are notable for high stability and higher activity compared to previously known systems.
  • the selectivity for the hydrogenation product should be as low as possible.
  • the present invention therefore relates to a catalyst comprising at least one complex of a platinum metal of VIII.
  • Ring systems in which two non-adjacent ring atoms of the heterophosphacyclohexane ring are part of a further common ring are not counted among the “unbridged” structural elements in the sense of this invention.
  • a catalyst based on a ligand which is selected from heterophosphacyclohexanes of the general formula I is preferred
  • a 1 , A 2 and A 3 independently of one another represent 0, S, S0 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 for hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, alkoxy, cycloalkoxy, heterocycloalkoxy, aryloxy or
  • R 1 for hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, WC00-M + , WS0 3 "M + , WP0 3 2 ⁇ M + 2 , W (NE 1 E 2 E 3 ) + X ⁇ , WOR f , W EiE 2 , WC00R f , W (S0 3 ) R f , WP0 3 RfR9, WSR f , W-polyoxyalkylene, W-polyalkyleneimine or WC0R f ,
  • R 2 to R 5 independently of one another for hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, WC00-M +, WS0 3 -M + , WP0 3 2 -M + 2 , W (NE 1 EE 3 ) + X-, W0R f , WE ⁇ 2 , WC00R f , W (S0 3 ) R f ,
  • W represents a single bond or a divalent bridging group with 1 to 20 bridge atoms
  • R f , R9, E 1 , E 2 and E 3 independently of one another represent hydrogen, alkyl, carbonylalkyl, cycloalkyl or aryl,
  • X- represents an anion equivalent
  • At least one of the radicals R 2 to R 5 is different from hydrogen, where in each case two of the geminal residues (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 represent a 3- to 8-membered carbo- or heterocycle, which is optionally additionally fused once, twice or three times with cycloalkyl, heterocycloalkyl, aryl and / or hetaryl,
  • radicals R 1 to R 5 and R a to R e can have an additional trivalent phosphorus or nitrogen group capable of coordination
  • heterophosphacyclohexane ring can also be part of a non-aromatic condensed ring system with 1, 2 or 3 further rings,
  • 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 the same or different heterophosphacyclohexane structural elements are covalently linked to one another,
  • alkyl encompasses straight-chain and branched alkyl groups. These are preferably straight-chain or branched C 1 -C 2 -alkyl, preferably C 1 -C 2 -alkyl and particularly preferably C 1 -C 6 -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, l-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, 1-propylbutyl, octyl, nonyl, decyl, dodecyl.
  • alkyl also includes substituted alkyl groups.
  • Substituted alkyl radicals preferably have 1, 2, 3, 4 or 5, in particular 1, 2 or 3, substituents, preferably selected and ter cycloalkyl, aryl, hetaryl, halogen, NE X E 2 , (NE 1 E 2 E 3 ) + , carboxyl, carboxylate, -S0 3 H and sulfonate.
  • cycloalkyl includes unsubstituted and substituted cycloalkyl groups.
  • the cycloalkyl group is preferably a C 5 -C cycloalkyl group, such as cyclopentyl, cyclohexyl or cycloheptyl.
  • cycloalkyl group preferably has 1, 2, 3, 4 or 5, in particular 1, 2 or 3, substituents, preferably selected from alkyl, alkoxy or halogen.
  • 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, C00R a , C00-M + and NE i E 2 , preferred Alkyl, can wear.
  • heterocycloaliphatic groups examples include pyrrolidinyl, piperidinyl, 2,2,6,6-tetramethyl-piperidinyl, imidazolidinyl, prazolidinyl, oxazolidinyl, morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl, tetrahydrothl-pyrethanyl, tetra-hydanyl Called dioxanyl.
  • Aryl is preferably phenyl, tolyl, xylyl, mesityl, naphthyl, anthracenyl, phenanthrenyl, naphthacenyl and in particular 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, -S0 3 H, sulfonate, NE 1 E 2 , alkylene-NE 1 ⁇ 2 , nitro, cyano or halogen.
  • Hetaryl is preferably prrolyl, 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, -S0 3 H, sulfonate, NE ⁇ -E 2 , alkylene-NE ⁇ -E 2 , trifluoromethyl or halogen.
  • alkyl, cycloalkyl and aryl radicals apply correspondingly to alkoxy, cycloalkyloxy, heterocycloalkoxy, aryloxy and hetaryloxy radicals.
  • the radicals NE 1 E 2 and NE 4 E 5 preferably represent N, N-dimethylaamino, N, N-diethylamino, N, N-dipropylamino, N, N-diisopropylamino, N, N-di-n-butylamino, N, N-di-tert-butylamino, N, N-dicyclohexylamino or N, N-diphenylamino.
  • Halogen represents fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.
  • Carboxylate and sulfonate in the context of this invention 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 -CC 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 + stands for 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- is preferably a carbonate, carboxylate or halide, particularly preferably Cl- and Br_ .
  • Condensed ring systems can be fused aromatic, hydroaromatic and cyclic compounds. Condensed ring systems consist of two, three or more than three rings. Depending on the type of linkage, a distinction is made in condensed ring systems between ortho-annulation, ie each ring has an edge or two atoms in common with each neighboring ring, and peri-annulation, in which one carbon atom belongs to more than two rings. Preferred among the condensed ring systems are ortho-condensed ring systems.
  • Polyoxyalkylene preferably stands for compounds with repeating units which are selected from -CH0 -) -, -CH 2 CH0 -) -, -CH ⁇ CHfCH ⁇ O -) -, -CH 2 -CH (C 2 H 5 ) 0 ⁇ - and • (CH) 4 0- r .
  • the number of repeat units is preferably in a range from 1 to 5 1000, preferably 1 to 240, in particular 2 to 100.
  • Low molecular weight polyoxyalkylenes have, for example, 1 to 20, such as, for example, B. 2 to 10 repetition units. In polyoxyalkylenes which have two or three different repeating units, the order is ' d ⁇ h " .
  • Suitable alkylene oxides are, for example, ethylene oxide, 1,2-propylene oxide, epichlorohydrin, 1,2- and 2,3-butyne
  • Suitable polyalkyleneimines are derived, for example, from aziridines (alkyleneimines) of the formula
  • R is hydrogen or alkyl.
  • the number average molecular weight of higher molecular weight polyoxyalkylene or polyalkylene imine residues is preferably in a range from about 400 to 50,000, particularly preferably 800 to 20,000, especially 1,000 to 10,000.
  • the heterophosphacyclohexanes used in the catalysts according to the invention have up to three additional heteroatoms or groups containing heteroatoms in the 6-ring.
  • the 6-ring In the 2- and 6-position (in the neighboring 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 S0 2 group in the 1,4-position.
  • 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 are in the 3 to 5 position to the phosphorus atom, a group of the formula -0-Si (R b R c ) -0-, wherein 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 0 and NR a , where R a preferably represents alkyl or cycloalkyl.
  • R a preferably represents a C 1 -C 8 -alkyl radical, in particular methyl, propyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl or octyl.
  • R a preferably furthermore represents a Cs-Cs-cycloalkyl radical, in particular cyclohexyl.
  • a 1 is particularly preferably 0 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 ⁇ -C ⁇ o-alkyl and
  • R d and R e are preferably both hydrogen.
  • a 1 and A 3 are particularly preferably selected from 0 and NR a and A 2 represents a group CR d R e , where R, R d and R e have the meanings given above.
  • a 1 and A 3 are then preferably both groups NR a , both radicals R a being C 1 -C 1 -alkyl, in particular propyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl or Stand octyl.
  • the radical R 1 is preferably selected from alkyl, cycloalkyl and aryl radicals.
  • the R 1 radical is preferably a C 2 -C 4 -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 Cs-Cg-cycloalkyl radical, in particular cyclohexyl.
  • 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.
  • Ligands of the formula are preferred
  • R 1 has the meanings given above.
  • heterophosphacyclohexanes of the formula I at least one of the radicals R 2 to R 5 is different from hydrogen.
  • 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 2 alkyl radicals, C 7 -C 3 aralkyl radicals, C 7 -C 3 alkaryl radicals and / or Cg-C ⁇ 2 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
  • the aryl groups can be phenyl, tolyl, xylyl or naphthyl radicals.
  • 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.
  • 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 + , WS0 3 -M + , WP0 3 2 " M + 2 , W (NE 1 E 2 E 3 ) + X ⁇ , WOR f , WNE ⁇ -E 2 , WCOOR f , W (S0 3 ) R f , WP0 3 R f R9, WSR f , W-polyoxyalkylene, W-polyalkyleneimine, W-halogen, WN0 2 , WCOR f or WCN, where W, M +, X ", E 1 , E 2 , E 3 , R f and R9 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 ⁇ 5 -phospholyl complexes or phosphabenzene groups are particularly preferred.
  • radicals R 2 to R 5 are preferably hydrocarbon radicals which have no further heteroatoms.
  • the bridges W are single bonds or bridges with 1 to 6 carbon atoms, which can be part of a cyclic or aromatic group. These can be single bonds as well as lower alkylene groups, e.g. C ⁇ -C ⁇ o-alkylene.
  • the heterophosphacyclohexanes used according to the invention have at least one divalent bridging group Y which covalently connects two identical or different ligands of the formula I.
  • the divalent bridging group Y preferably represents a C 1 -C 2 -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 heteraryl groups each have one, two or three substituents which are selected from alkyl, cyclo
  • Y preferably represents a C 1 -C 2 -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 0, S, NR ⁇ or SiR ß R ⁇ , where the radicals R ⁇ , R ⁇ and R ⁇ independently of one another represent hydrogen, alkyl, cycloalkyl, aryl or hetaryl.
  • the bridging groups Y are then preferably Ci-Cio-, particularly preferably
  • the bridging groups Y are preferably furthermore 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, S0 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,
  • 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,
  • Z represents a C 2 -C 3 alkylene bridge which is interrupted by 0, S or NR 25 or SiR 25 R 26 ,
  • B 1 and B 2 independently of one another represent 0, 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,
  • 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 - to 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, S0 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
  • R 17 , R 18 , R 19 and R 20 have the meaning given above and R 27 and R 28 independently of one another are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • group of the formula II.7 preferably represents a triptycendiyl group of the formula
  • 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 furthermore preferably represents a higher molecular weight polyoxyalkylene or polyalkyleneimine bridge with at least 21 carbon atoms.
  • 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 and especially 1,000 to 10,000. It is particularly preferred to use polyethylene oxides, copolymers of ethyl lenoxide and 1,2-propylene oxide, in which the alkylene oxides can be incorporated in any order, alternately or in the form of blocks, and polyethyleneimines.
  • 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 different from 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 which are selected from mono- and diolefins, vinyl aromatics, esters ⁇ , ⁇ -ethylenically unsaturated mono- and diearbonic acids with C 1 -C 30 -alkanols, N-vinyl amides, N- Vinyl lactams, ring-opening 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 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 ⁇ , ß-ethylenically unsaturated mono- and dicarboxylic acids are preferably selected from the esters of acrylic acid, methyl ⁇ thacryl Textre, maleic acid, Fu arklare, itaconic acid and crotonic acid.
  • the esters with C 1 -C 2 -alkanols are preferred. These include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, tert.
  • Vinyl aromatics suitable as monomers are, for example, styrene, ⁇ -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 the ring opening polymerization are, for example, cyclic ethers such as ethylene oxide and propylene oxide, cyclic amines, cyclic sulfides (ethylene sulfide, thietanes), lactones and lactams.
  • ⁇ -Caprolactone and ⁇ -Caprolactam are preferred.
  • the aforementioned monomers can be used individually, in the form of mixtures from the respective monomer class and generally as mixtures.
  • the polymers suitable as radicals are prepared by customary polymerization processes known to those skilled in the art. Depending on the monomers to be polymerized, this includes free-radical, cationic and anionic polymerization, including cationic and anionic ring-opening polymerization.
  • acceptor-activated ethylenically unsaturated compounds and ethene are preferably used as monomers.
  • 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 (poly lyalkene residue).
  • 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, can essentially only contain 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 of conjugated dienes during the polymerization are known to the person skilled in the art. This includes, for example, the addition of donor solvents, for example ethers, such as THF, or amines in anionic polymerization.
  • Polyolefins with repeating units of 1,2-addition products of conjugated dienes have pendant ethylenically unsaturated ones
  • 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, the ethylenically unsaturated side chains are generally at least partially converted into alcohol groups, ie ligands with polar side chains result. If in the compounds of the formula I one of the radicals R 1 to R 5 , R a to R e or a group Y is a polyolefin radical, it is preferably a polyethylene or polybutadiene radical.
  • the bridged heterophosphacyclohexanes used according to the invention preferably have 1, 2 or 3 bridging groups Y.
  • Bridged heterophosphacyclohexanes which have a bridging group Y are preferred.
  • the group Y is preferably bonded to the phosphorus atom or the carbon atom of the heterophosphacyclohexane ring adjacent to the phosphorus atom.
  • Bridged ligands are preferably selected from compounds of the general formula 1.1
  • a 1 , A 2 , A 3 , R 2 , R 3 and Y have the meanings given above
  • Another special embodiment are catalysts based on at least one heterophosphacyclohexane ligand which has a bridging group Y which stands for a polymer radical to which at least three heterophosphacyclohexane structural elements are bonded.
  • heterophosphacyclohexane structural elements are preferably bonded to the polymer radical Y.
  • heterophosphacyclohexane groups can be attached to the polymer residue by reaction of suitable complementary functional groups, for example in an addition or condensation reaction.
  • suitable complementary functional groups for example in an addition or condensation reaction.
  • the connection can continue to be made via complementary groups capable of electrostatic interaction.
  • “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 suitably functionalized radicals R 2 to R 5 or R a to R e . These are preferably radicals R 2 to R 5 in which the functional group has one of the bridging groups W mentioned above, eg. B. a -CC 4 alkylene group, is bound to the phosphacyclohexane ring.
  • 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.
  • the functional groups are usually a bridging group W, z. B. a -CC 4 alkylene group, bound to the phosphorus atom.
  • Preferred complementary functional groups are selected from the complementary functional groups in the overview below.
  • Metal atom (preferably -Li,
  • R alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl
  • the polymer radical is derived from a polymer obtainable by free-radical polymerization of suitable ⁇ , ⁇ -ethylenically unsaturated monomers which contains groups capable of reacting with corresponding complementary groups of the heterophosphacyclohexanes.
  • polymers are suitable which contain in copolymerized form at least one monomer which is selected from compounds gene, which have at least one, ß-ethylenically unsaturated double bond and at least one active hydrogen atom per molecule. These include e.g. B.
  • esters ß-ethylenically unsaturated mono- and dicarboxylic acids, such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid etc. with C ⁇ ⁇ to C 2 o-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.
  • esters of the aforementioned acids with triplets and polyols such as As glycerol, erythritol, pentaerythritol, sorbitol etc.
  • esters and amides of the aforementioned acids with C 2 -C 2 -amino alcohols which have a primary or secondary amino group. These include aminoalkyl acrylates and aminoalkyl methacrylates and their N-monoalkyl derivatives, which, for. B. wear an N-C ⁇ to Cs monoalkyl radical, such as aminomethyl acrylate, aminomethyl methacrylate, aminoethyl acrylate, N-methylaminomethylacrylate, etc.
  • vinyl aromatics which have at least one hydroxyl group, such as. 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 free-radically polymerizable, ⁇ , ⁇ -ethylenically unsaturated monomer which is selected from vinylaromatics, such as styrene, ⁇ -methylstyrene, o-chlorostyrene or vinyltoluenes, esters ⁇ , ⁇ -ethylenically unsaturated C 3 - To Cg mono- and dicarboxylic acids with Ci- to C 2 o-alkanols, such as. B.
  • 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.
  • the polymer residue is derived from a polymer obtainable by anionic polymerization of suitable monomers.
  • 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 ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with C 3 O -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 ⁇ -caprolactone and lactams, such as ⁇ -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 have 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.
  • TEDA tetramethylethylenediamine
  • polymers are obtained which have 3 or more metal atoms at the chain ends.
  • initiators are described by HL Hsieh and RP Quirk (loc. Cit.), Pp. 110-114 and the literature cited therein, to which full reference is made here.
  • star-shaped polymers eg polyisoprene
  • Suitable protected functionalized initiators are, for example, 6-lithium hexylacetaldehyde acetal, 4-bis (tri ethylsilyl) aminophenyllithium, 6- (tert-butyldimethylsiloxy) hexyllithium and 3- (tert-butyldimethylsiloxy) propyllithium.
  • halogenated or halogenated alkylated heterophosphacyclohexanes can be used, for example, on the phosphorus atom.
  • the polymer residue is preferably also derived from star polymers or dendritic polymers different from the abovementioned residues.
  • Star-shaped polymers are understood to mean those in which 3 or more unbranched chains start from a center.
  • Dendritic polymers are understood to mean those which have branched side chains.
  • the preparation of suitable star polymers is described by H.L. Hsieh and R.P. Quirk (loc. Cit.), Pp. 333-368 and the literature cited therein, to which reference is made here.
  • Suitable star polymers can be produced by radical polymerization of monomers with suitable polyfunctional initiators.
  • suitable, ß-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:
  • Suitable star polymers can also be produced by polyaddition of epoxides to trihydric and higher alcohols.
  • Suitable triols are, for example, glycerol or trimethylolpropane.
  • Suitable higher alcohols are, for example, erythritol, pentaerythritol and sorbitol.
  • Star polymers of this type generally have hydroxyl groups as end groups.
  • heterophosphacyclohexane groups can then be bound by reaction with halogenated, preferably haloalkylated, heterophosphacyclohexanes.
  • Heterophosphacyclohexanes which are selected from compounds of the general formulas Ia to Im are particularly preferably used as ligands (Ia) (Ib) (ic)
  • a 1 , A 1 ', A 2 , A 3 and A 3 ' independently of one another represent 0 or NR a , where R a represents hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
  • Rl and Rl 'independently of one another for C ⁇ -C 2 o-alkyl, Cs-Cs-cycloalkyl, Cg-C ⁇ 2- aryl, W-polyoxyalkylene, W-polyakyleneimine or a polymer residue with a number average molecular weight in the range of 500 to 50,000, which is composed of ethylene and / or butadiene, where W is a single bond or C ⁇ -C 4 alkylene,
  • R 6 , R 7 , R 8 , R 9 , R 10 , R ü , R 6 ', R 7 ', R 8 ', R 9 ', R 10 'and R 11 ' independently of one another for hydrogen, alkyl, alkoxy, Carboxyl, carboxylate, trifluoromethyl, -S0 3 H, sulfonate, NEE 2 or alkylene-NEiE 2 , where El 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 ⁇ -C ⁇ o-alkyl, Cs-Cs-cycloalkyl or phenyl.
  • radicals A 1 , A 1 ', A 2 , A 3 and A 3 ' are preferably independently of one another 0 or NR a , where R a is hydrogen or C oder- C ⁇ o-alkyl, preferably methyl, ethyl, isopropyl, tert-butyl and octyl.
  • the radicals R i and in the compound Ik are preferably C ⁇ -C ⁇ o-alkyl, preferably methyl, ethyl, isopropyl, tert-butyl, octyl and Dodecyl, as well as Cs-Cg-cycloalkyl, especially cyclohexyl.
  • the radicals R 6 , R 7 , R 8 , R 9 , R 10 and R u are preferably, independently of one another, hydrogen, C ⁇ -C 4 -alkyl, preferably methyl, Ethyl, isopropyl, tert-butyl, and C ⁇ -C 4 alkoxy, preferably methoxy.
  • heterophosphacyclohexanes are examples of preferred compounds:
  • DE-OS 19 00 706 describes a process for the preparation of 1,4-oxaphosphacyclohexanes from divinyl ether and hydrogen phosphide or a monosubstituted phosphane.
  • No. 3,005,020 describes a process for the synthesis of 1,3-dioxa-5-phosphacyclohexanes from bis (1-hydroxyalkyl) phosphanes and an aldehyde. 5
  • 0 SU 652 184 describes the synthesis of 1,3-dioxa-2-sila-5-phosphorinanes.
  • reaction step i) reacting the P-H-functional heterophosphacyclohexane with at least one ethylenically unsaturated compound, reaction step i)
  • a first embodiment of the process for the preparation of heterophosphacyclohexanes substituted in the 1-position comprises the reaction according to one of the three following reaction variants:
  • reaction step i) all compounds which contain one or more ethylenically unsaturated double bonds are suitable for the reaction in reaction step i).
  • olefins such as ⁇ -olefins, internal straight-chain and internal branched olefins, functionalized olefins, oligomeric and polymeric compounds which have at least one ethylenically unsaturated double bond, etc.
  • reaction step i) can take place in the presence of a solvent.
  • aromatics such as benzene, toluene and xylenes, cycloalkanes, such as cyclohexane, aliphatic hydrocarbons, etc.
  • the reaction takes place in the olefin used for the reaction as a solvent, this generally in a large molar excess over the heterophosphacyclohexane is used.
  • reaction step i) takes place in the presence of at least one radical generator.
  • Suitable free-radical formers are the customary polymerization initiators known to those skilled in the art, as are used for free-radical polymerization.
  • organic peroxides e.g. B. peresters 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
  • 4,4 'azobis (4-cyanovaleric acid) include e.g. B. the Vazo® brands from Du Pont, such as Vazo 52, 67 and 88, the number denoting the temperature at which the initiator has a half-life of 10 hours. Azo initiators are preferably used.
  • the radical generator is preferably used in an amount of 0.001 to 10% by weight, particularly preferably 0.01 to 5% by weight, based on the total amount of the ethylenically unsaturated compounds.
  • reaction temperature is preferably 20 to 200 ° C., particularly preferably 50 to 150 ° C.
  • the specialist chooses the suitable reaction temperature based on the decomposition falling temperature, ie the corresponding half-life of the initiator at this temperature.
  • step i) is carried out in the presence of at least one acid or at least one 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 e.g. Acetic acid.
  • Suitable bases are alkali metal bases, such as sodium hydroxide solution, potassium hydroxide solution, sodium carbonate, 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, and also ammonia and amines.
  • a ines such as trimethylamine, triethylamine, triisopropylamine, etc. are preferably used. Rhodium compounds and complexes are preferred. The latter generally advantageously enable the ligands according to the invention and those used according to the invention and the hydroformylation catalysts based on them to be prepared in situ.
  • reaction step i) takes place at a temperature in a range of approximately
  • a second embodiment of the process according to the invention for the preparation of heterophosphacyclohexanes substituted in the 1-position comprises reacting the PH-functional heterophosphacyclohexanes with at least one compound of the formula R! - ⁇ i or ⁇ i-YX 2 , where ⁇ i and X 2 are displaceable for a nucleophile Group (leaving group) and R 1 and Y have the meanings given above.
  • the nucleophilically displaceable groups (leaving groups) ⁇ i and X 2 of the compounds of the formulas R ⁇ —X 1 or X x -YX 2 are the usual leaving groups known to the person skilled in the art from nucleophilic substitution.
  • the groups R i and Y can generally have all of the meanings mentioned above.
  • This variant of the process 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 ⁇ i -YX 2 results in dinuclear, each in the 1-position bridged heterophosphacyclohexanes, bridges with any number of carbon atoms being accessible.
  • this process also enables the production of dinuclear compounds with bridges with odd-numbered bridge atoms.
  • the PH-functional heterophosphacyclohexanes are reacted with at least one compound R i - ⁇ l or ⁇ ! -YX 2 first metalated on the phosphorus atom.
  • Metallization means the formal exchange of the hydrogen atom for a metal atom.
  • Suitable reagents for the metalation are generally very strong bases, for example alkali metal and alkaline earth metal hydrides as well as Li, Mg, Al, Sn and Zn organic compounds.
  • Organolithium compounds are preferred. These include, for example, n-butyl lithium, sec-butyllithium, tert. -Butyllithium, Phenyllithium etc.
  • Suitable reagents for the metalation are further 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 , phospholes, phosphabenzenes and monodentate and bidentate phosphine , Phosphinite, phosphonite, phosphoramidite and phosphite ligands.
  • the group of platinum metals includes ruthenium, rhodium, palladium, osmium, iridium and platinum.
  • the catalysts according to the invention preferably comprise at least one complex of rhodium or palladium, in particular of rhodium.
  • the catalysts active in the hydroformylation are generally transition metal complexes of the general formula ML n (C0) 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 represent integers between 1 and 3.
  • the transition metal complex may 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 generally formed in situ from a transition metal salt, preferably a rhodium salt, or a transition metal complex compound, preferably a rhodium complex compound, the ligand, hydrogen and carbon monoxide; but it can also be manufactured and used separately.
  • complex catalysts are generated in situ, it is particularly preferred to use precursor complexes such as rhodium dicarbonyl acetylacetonate, rhodium (2-ethylhexanoate) or rhodium acetate in the presence of the corresponding phosphacyclohexane ligands.
  • precursor complexes such as rhodium dicarbonyl acetylacetonate, rhodium (2-ethylhexanoate) or rhodium acetate in the presence of the corresponding phosphacyclohexane ligands.
  • composition of the synthesis gas CO / H 2 used in the hydroformylation process according to the invention can be varied within wide limits.
  • synthesis gas with CO / H 2 molar ratios from 5:95 to 90:10 can be used successfully, synthesis gas with CO / H 2 ratios from 40:60 to 70:30 is preferred, and CO / H 2 - is particularly preferred. Ratio of about 1: 1 applied.
  • the hydroformylation takes place in a manner known per se at 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 optimum temperature and pressure are essentially dependent on the olefin used.
  • ⁇ -olefins are particularly preferably hydroformylated at temperatures from 80 to 120 ° C. and pressures from 10 to 40 bar.
  • 1-Alkenes are preferably hydroformylated at temperatures from 80 to 120 ° C.
  • the pressure is preferably in a range from 10 to 40 bar.
  • Olefins with a vinylidene double bond are preferably hydroformylated at 100 to 150 ° C.
  • the pressure is preferably 10 to 40 bar. Carrying out the reaction at temperatures and pressures higher than those specified above is not excluded.
  • internal and internal olefins branched on the double bond are particularly preferably hydroformylated at temperatures from 120 to 180 ° C. and pressures from 40 to 100 bar.
  • the hydroformylation is generally carried out in the presence of a 1- to 1000-fold molar excess, preferably a 2- to 100-fold excess of the ligand, based on the amount of transition metal used.
  • 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 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, ⁇ -C 5 _ 2 o-01efine, 2-butene, linear internal C 5 _ 20 -olefins and isobutene.
  • Suitable branched internal olefins are preferably C 4 _ 2 o-olefins such as 2-methyl-butene-2, 2-methyl-2-pentene, 3-methyl-2-pentene, branched, internal heptene mixtures, branched , internal octene mixtures, branched, internal none mixtures, branched, internal decene mixtures, branched, internal undecene mixtures, branched, internal dodecene mixtures, etc.
  • C 4 _ 2 o-olefins such as 2-methyl-butene-2, 2-methyl-2-pentene, 3-methyl-2-pentene, branched, internal heptene mixtures, branched , internal octene mixtures, branched, internal none mixtures, branched, internal decene mixtures, branched, internal undecene mixtures, branched, internal dodecene mixtures, etc.
  • Suitable olefins to be hydroformylated are furthermore C 5 _s-cycloalkenes, such as cyclopentene, cyclohexene, cycloheptene, cyclooctene and their derivatives, such as, for. B. whose C ⁇ _ 2 o-alkyl derivatives with 1 to 5 alkyl substituents.
  • Suitable olefins to be hydroformylated are also vinyl aromatics, such as styrene, ⁇ -methylstyrene, 4-isobutylstyrene etc.
  • Suitable olefins to be hydroformylated are furthermore ethylenically unsaturated polypropene and polyisobutene.
  • olefins are mentioned by way of example: 3-pentenenitrile, 4-pentenenitrile, 3-pentenoate, 4-pentenoate, (meth) acrylic ester, vinyl glycol diacetate, 2,5-dihydrofuran and butenediol diacetate.
  • Suitable substrates are di- and polyenes with isolated or conjugated double bonds.
  • the following olefins are mentioned by way of example: 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 2 O-olefins, such as 2-butene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, 2-octene, 3-octene, 4-octene etc. and mixtures thereof.
  • 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.
  • thermal cracking steam cracking
  • catalytic dehydration and - chemical dehydration by chlorination and dehydrochlorination.
  • Thermal cracking leads predominantly to ⁇ -olefins, while the other variants result in olefin mixtures which generally also have relatively large proportions of olefins with an internal double bond.
  • Suitable olefin mixtures are furthermore the 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 (ethanolysis).
  • Suitable industrial olefin mixtures which can be used in the hydroformylation process according to the invention are furthermore selected from dibutenes, tributenes, tetrabutenes, dipropenes, tripropenes, tetrapropenes, mixtures of butene isomers, in particular raffinate II, dihexenes, dimers and oligomers from the Dimersol® process from IFP, Octolprocess® of Hüls, polygas process etc.
  • 1-Butene-containing hydrocarbon mixtures such as raffinate II are also preferred.
  • 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. Suitable are, for example, those which are selected from the group of ethers, supercritical CO 2 , fluorocarbons or alkylaromatics, such as toluene and xylene.
  • the solvent can also be a polar solvent.
  • those which are selected from the group of alcohols, dimethylacetamide, dimethylformamide or N-methylpyrrolidone are suitable.
  • the catalysts used according to the invention often have a certain activity in the hydrogenation of aldehydes in addition to their hydroformylation activity, the alcohols corresponding to the aldehydes can also be formed as valuable products in addition to the aldehydes.
  • reaction discharge can in principle be worked up by known processes.
  • a method is preferred in which
  • a catalyst is used for the hydroformylation which comprises at least one polymeric ligand with a heterophosphacyclohexane structural element and in which the separation in step ii) and / or the workup in step iii) comprises ultrafiltration.
  • the distillative workup of the reaction product is first described below.
  • the discharge from the hydroformylation stage is generally relaxed before it is worked up by distillation. This releases unreacted synthesis gas, which can be recycled in the hydroformylation.
  • the distillation of the relaxed hydroformylation output is generally carried out at pressures from 0.1 to 1000 mbar absolute, preferably at 1 to 500 mbar and particularly preferably from 10 to 400 mbar.
  • the temperature and pressure which have to be set in the distillation depend on the type of hydroformylation product and the distillation apparatus used. Any distillation apparatus can generally be used for the process according to the invention. However, apparatuses are preferably used which cause low investment costs and, particularly for higher olefins, allow the lowest possible distillation temperature, such as thin-film evaporators, wiper blade evaporators or falling-film evaporators, since the aldehydes formed in the reaction discharge can undergo subsequent reactions such as aldol condensations at a higher temperature.
  • this distillation essentially serves to separate off the hydroformylation products aldehyde and alcohol and any low boilers still present, such as unreacted olefin and inerts, from high-boiling condensation products of the aldehydes, known as high boilers, and the catalyst and excess ligand, it may be expedient to use the separate hydroformylation products and optionally olefins and inerts, a further distillative purification, which can be carried out in a conventional manner. This is particularly intended to avoid the build-up of high boilers still present.
  • 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
  • distillation bottoms which contain the catalyst and excess ligand, are returned in total, or
  • part of the distillation bottoms can also be removed from the process from time to time and returned to further processing for the recovery of the transition metal of subgroup VIII of the periodic table and, if desired, the ligand used.
  • Subgroup of the periodic system and ligand corresponding amount of this compound are supplemented by supplying these compounds in the hydroformylation reaction.
  • Preferred ligands according to the invention are those which have such a high boiling point that, when the reaction product is distilled, the entire ligand-transition metal complex and all or at least most of the ligand not required for complex formation remain in the bottom of the distillation and the bottom is off this distillation can be returned to the reaction together with fresh olefin.
  • An advantage of this method of precipitating the catalyst complex and the excess ligand is a solvent which is miscible with the organic constituents of the distillation bottoms from the reaction effluent, but in which the catalyst complex and the ligand are insoluble or almost insoluble, so that it becomes possible, by choosing the type and amount of solvent, to precipitate the catalyst complex and the ligands, which can be returned to the hydroformylation after separation by decantation or filtration.
  • a large number of polar solvents which primarily have hydroxyl, carbonyl, carboxamide or ether groups, ie alcohols, ketones, amides or ethers, come as solvents as well as mixtures of these solvents or mixtures of these solvents with water.
  • the person skilled in the art can determine the type and amount of the solvent to be used in a few manual tests.
  • the amount of solvent is kept as low as possible so that the recovery effort is as low as possible. Accordingly, generally 1 to 50 times, preferably 3 to 15 times, the amount required, based on the volume of the distillation bottoms.
  • Another method for discharging high-boiling condensation products of the aldehydes is to separate them from the bottom of the distillation by means of steam distillation.
  • the steam distillation of the distillation bottoms can be carried out batchwise, or batchwise, or continuously, the steam distillation being able to be carried out in the distillation apparatus itself or in a separate device for steam distillation.
  • the distillation bottoms can be completely or partially freed from high-boiling condensation products by passing steam through them before being returned to the hydroformylation, or the distillation bottoms can be subjected to steam distillation from time to time in a separate apparatus, depending on the amount of high boilers.
  • the continuous design of the method can e.g. B. done so that the distillation bottoms or part of the distillation bottoms continuously fed to a steam distillation apparatus before being returned to the hydroformylation and completely or partially freed of high boilers therein. It is also possible to carry out the distillative workup of the hydroformylation effluent continuously in the presence of steam, in order to separate the high boilers from the catalyst and the excess ligand at the same time as the aldehyde and the alcohol. It goes without saying that with such a procedure, the valuable products of high boilers and possibly of water must be separated in a subsequent fractionation and distillation device.
  • Steam distillation is generally carried out in a conventional manner by introducing steam into the distillation sump containing high boilers and subsequently condensing the steam distillate.
  • the water vapor is thus advantageous passed through the distillation sump so that it does not condense in the distillation sump. This can be achieved by choosing the pressure and / or temperature conditions under which the steam distillation is carried out. Reduced pressure can be used, or increased pressure when using superheated steam.
  • steam distillation is carried out at a temperature of 80 to 200 ° C. and at a pressure of 1 mbar to 10 bar, preferably from 5 mbar to 5 bar.
  • the water vapor with respect to the high-boiling condensation products of the aldehydes (high boilers) contained in the bottom is generally passed through the distillation bottoms in a weight ratio of water vapor: high boilers of 10: 1 to 1:10. After the steam distillation has ended, the catalyst which has been freed from high boilers in whole or in part and distillation bottoms containing excess ligand can be returned to the hydroformylation.
  • the average molecular weight of the ligand is preferably more than 500 daltons, particularly preferably more than 1000 daltons.
  • the starting materials are reacted in the presence of the catalyst and ligand in a reactor.
  • the reactor discharge is separated in a distillation apparatus into a distillate stream containing the oxo products and into a residue.
  • the catalyst-containing residue is continuously fed to a membrane filtration.
  • the residue which contains high boilers (or a mixture of high boilers, starting materials and oxo products), catalyst and ligands, is worked up.
  • the high boilers (and possibly educts and oxo products) permeate through the membrane.
  • the depleted in high boilers (and possibly educts and oxo products) and in ca Talent and ligand-enriched retentate stream is returned to the hydroformylation.
  • the starting materials are reacted in the presence of the catalyst and ligand in a reactor.
  • the reactor discharge is separated in a distillation apparatus into a distillate stream which contains the oxo products and into a residue stream.
  • This catalyst-containing residue from the distillation is worked up in a membrane filtration.
  • the distillation residue depleted in high boilers (and optionally in starting materials and oxo products) and enriched in catalyst and ligands is returned to the reactor for the next batch of hydroformylation at the end of ultrafiltration.
  • the ultrafiltration can be operated in one or more stages (preferably two stages).
  • the feed solution is e.g. B. brought to filtration pressure by means of a pressure pump; the overflow, d. H. Wetting, the membrane can then be ensured by recycling part of the retentate stream in a second pump.
  • a relative speed in the range of 0.1 to 10 m / s is preferably maintained between the membrane and the catalyst-containing solution.
  • Other suitable measures for avoiding a top layer structure are e.g. B. mechanical movement of the membrane or the use of agitators between the membranes.
  • the permeate stream is fed to a stage of the downstream stage and the retentate stream of this downstream stage is fed to the previous stage. By working up the permeate, better retention of the catalyst and the ligand can be achieved.
  • the different stages can be equipped with the same or with different membranes.
  • the optimal transmembrane pressures between the retentate and permeate are essentially dependent on the diameter of the membrane pores and the mechanical stability of the membrane at the operating temperature and, depending on the type of membrane, are between 0.5 to 100 bar, preferably 10 to 60 bar and at a temperature of up to 200 ° C. Higher transmembrane pressures and higher temperatures lead to higher permeate flows.
  • the overflow speed 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.
  • the separating layers are generally applied to a single- or multi-layer porous substructure made of the same or several different materials as the separating layer. Examples are:
  • the membranes can be used in flat, tube, multichannel element, capillary or winding geometry, for which the corresponding pressure housing is available, which allows a separation between retentate (containing catalyst) and permeate (catalyst-free filtrate).
  • a distillative separation of the aldehydes / alcohols can also be carried out first, whereupon the catalyst-containing bottoms with a polar extractant such as. B. water is treated.
  • the catalyst passes into the polar phase, while high boilers remain in the organic phase.
  • catalysts with water-soluble (hydrophilic) ligands or with ligands which can be converted into a water-soluble form are preferably used.
  • the catalyst can be recovered by a re-extraction or directly recycled as such.
  • the catalyst can be extracted with a non-polar solvent, after which the high boilers are separated off.
  • the reaction discharge can also be worked up by extraction.
  • 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.
  • 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.
  • the addition of a further solvent can generally be dispensed with.
  • the extraction can be continuous or done discontinuously. A suitable continuous extraction is countercurrent extraction.
  • a phase 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.
  • 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, WC00-M +, W'S0 3 -M + , W'P0 3 2 -M 2+ , W'NR ' 3 + X-, W'OR', WNR ' 2 , W'COOR', W 'SR', W '(CHR'CH 2 0) x R', W '(CH 2 NR') X R 'and
  • Heterophosphacyclohexanes with non-polar residues can also be removed with a non-polar solvent by phase separation. Heterophosphacyclohexanes with lipophilic residues are particularly suitable. In this way, a "leaching" of the catalyst can be prevented at least as far as possible.
  • the reaction mixture can also be worked up directly by means of ultrafiltration.
  • the synthesis discharge as described above, is brought into contact with a membrane under pressure and permeate (filtrate) is drawn off on the back of the membrane at a lower pressure than on the feed side.
  • permeate filament
  • a catalyst concentrate retentate
  • a practically catalyst-free permeate are obtained.
  • the transmembrane pressure can be adjusted by increasing the permeate pressure.
  • the essentially catalyst-free permeate obtained can be further separated into products and high boilers by customary processes known to those skilled in the art, such as distillation or crystallization.
  • the hydroformylation process used according to the invention can have higher isoaldehyde contents in the aldehyde than in a corresponding rhodium / triphenylphosphine-catalyzed hydroformylation process. mixed. This is advantageous for certain applications, e.g. B. for the production of neopentyl glycol.
  • the catalysts used according to the invention show a high selectivity for aldehydes and alcohols in the hydroformylation. Paraffin formation by hydrogenation of educt alkenes is significantly lower compared to a rhodium / triphenylphosphine-catalyzed hydroformylation process.
  • the catalyst can also be used in other suitable reactions.
  • suitable reactions examples are hydroacylation, hydrocyanation, hydroamidation, hydroesterification, aminolysis, alcoholysis, hydrocarbonylation, hydroxycarbonylation, carbonylation, isomerization or transfer hydrogenation.
  • hydrocyanation catalysts comprise complexes of nickel.
  • the metal is zero-valued in the metal complex according to the invention.
  • the metal complexes can be prepared as previously described for use as hydroformylation catalysts. The same applies to the in situ production of the hydrocyanation catalysts according to the invention.
  • a suitable nickel complex for the preparation of a hydrocyanation catalyst 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 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.
  • 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% on 1,3-butadiene and the rest on monoolefins and polyunsaturated hydrocarbons and alkanes eliminated. 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. be isolated by extractive distillation from commercially available hydrocarbon mixtures.
  • the catalysts according to the invention can advantageously be used for the hydrocyanation of such olefin-containing, in particular 1,3-butadiene-containing, hydrocarbon mixtures, as a rule also without prior purification of the hydrocarbon mixture by distillation.
  • the effectiveness of the catalysts impairing olefins, such as. B. alkynes or cumulenes can optionally be removed from the hydrocarbon mixture by selective hydrogenation before the hydrocyanation. Suitable processes for selective hydrogenation are known to the person skilled in the art.
  • the hydrocyanation according to the invention can be carried out continuously, semi-continuously or batchwise.
  • Suitable reactors for the continuous reaction are known to the person skilled in the art and are described, for. B. in Ullmann's Encyclopedia of Industrial Chemistry, Volume 1, 3rd edition, 1951, p. 743 ff.
  • a stirred tank cascade or a tubular reactor is preferably used for the continuous variant of the process according to the invention.
  • Suitable, optionally pressure-resistant reactors for the semi-continuous or batchwise execution are known to the person skilled in the art and are described, for. B. in Ullmann's Encyclopedia of Industrial Chemistry, Volume 1, 3rd Edition, 1951, pp 769 ff.
  • an autoclave is used for the method according to the invention, which can, if desired, be provided with a stirring device and an inner lining.
  • the hydrocyanation catalysts according to the invention can be separated from the discharge of the hydrocyanation reaction by customary processes known to the person skilled in the art and can generally be used again for the hydrocyanation.
  • the catalyst precursor, heterophosphacyclohexane ligand and solvent were mixed under nitrogen inert gas in a Schlenk tube.
  • the solution obtained was transferred to a 70 ml or 100 ml autoclave flushed with CO / H (1: 1).
  • 2-5 bar C0 / H 2 (1: 1) were injected.
  • the reaction mixture was heated to the desired temperature within 30 min.
  • 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).
  • the pressure in the reactor was kept at the pressure level by injecting synthesis gas through a pressure regulator.
  • the autoclave was cooled, decompressed and emptied. Analysis of the reaction mixture was performed by gas chromatography (GC) using correction factors.
  • GC gas chromatography

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Abstract

L'invention concerne un catalyseur comprenant au moins un complexe de métal platine du VIIIème groupe secondaire avec au moins un ligand hétérophosphacyclohexane, ainsi qu'un procédé d'hydroformylation en présence d'un catalyseur de ce type, de même que son utilisation.
PCT/EP2002/014690 2001-12-21 2002-12-20 Catalyseur comprenant un complexe de metal du viiieme groupe secondaire a base d'un ligand heterophosphacyclohexane WO2003053571A2 (fr)

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DE2001163400 DE10163400A1 (de) 2001-12-21 2001-12-21 Katalysator umfassend einen Komplex eines Metalls der VIII. Nebengruppe auf Basis eines Heterophosphacyclohexanliganden

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017150337A1 (fr) 2016-03-01 2017-09-08 株式会社クラレ Procédé de production de composé dialdéhyde

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