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WO2003053572A1 - Procede d'hydroformylation en presence d'un ligand polymere avec des elements structuraux phosphacyclohexane - Google Patents

Procede d'hydroformylation en presence d'un ligand polymere avec des elements structuraux phosphacyclohexane Download PDF

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WO2003053572A1
WO2003053572A1 PCT/EP2002/014691 EP0214691W WO03053572A1 WO 2003053572 A1 WO2003053572 A1 WO 2003053572A1 EP 0214691 W EP0214691 W EP 0214691W WO 03053572 A1 WO03053572 A1 WO 03053572A1
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catalyst
hydrogen
alkyl
phosphacyclohexane
reaction
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PCT/EP2002/014691
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English (en)
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Thomas Mackewitz
Konrad Knoll
Hartwig Voss
Rainer Papp
Rocco Paciello
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Basf Aktiengesellschaft
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Priority to DE10296000T priority Critical patent/DE10296000D2/de
Priority to AU2002358788A priority patent/AU2002358788A1/en
Publication of WO2003053572A1 publication Critical patent/WO2003053572A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
    • 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
    • B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
    • B01J31/1658—Polymer immobilised coordination complexes, e.g. organometallic complexes immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/40—Introducing phosphorus atoms or phosphorus-containing groups
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/52—Isomerisation reactions
    • 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
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • 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
    • 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

  • the present invention relates to a process for the hydroformylation of compounds which contain at least one ethylenically unsaturated double bond by reaction with carbon monoxide and hydrogen in the presence of a catalyst system which comprises at least one metal from subgroup VIII of the periodic table and at least one polymeric ligand.
  • the invention further relates to new catalysts and their use.
  • 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, especially those with internal and internal branched double bonds, are hydroformylated only very slowly.
  • ligand can be lost in the working up of reaction mixtures of the hydroformylation of higher olefins by distillation, and this ligand must be constantly added.
  • 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.
  • Trialkylphosphanes such as tricyclohexylphosphine are also able to hydroformylate internal olefins at higher temperatures in the medium pressure range, but are only slightly suitable for the hydroformylation of internal branched olefins due to their low activity.
  • the advantages of trialkylphosphines as cocatalysts in hydroformylation essentially lie in their thermal stability.
  • the low activity of the resulting catalyst systems is disadvantageous, which can only be compensated inadequately by increasing the oxogas pressure and by increasing the temperature.
  • hydroformylation catalysts can be removed from the reaction mixture as simply as possible, and essentially completely and without addition, and can be reused after any workup.
  • the isolation of the catalyst from the reaction mixture frequently causes problems.
  • high temperatures are often required that the catalysts partially decompose as a result of the thermal load.
  • the unpublished international application PCT / EP01 / 07219 describes phosphacyclohexanes and their use as ligands in hydroformylation catalysts. Up to two phosphacyclohexane groups can be bound to one polymer residue.
  • the object of the present invention is to provide an improved hydroformylation process which enables the catalyst system used to be easily separated from starting and end products.
  • good separation of higher-boiling aldehydes and / or alcohols or of higher-boiling by-products of the hydroformylation reaction should also be possible.
  • This object is achieved by a process for the hydroformylation of compounds which contain at least one ethylenically unsaturated double bond by reaction with carbon monoxide and hydrogen in the presence of a catalyst system which comprises at least one metal from subgroup VIII of the periodic table and at least one polymeric ligand, where the ligand has a polymer backbone different from polyamines, to which at least three phosphacyclohexane structural elements are bound.
  • the hydroformylation is preferably carried out in a reaction zone in a homogeneous phase.
  • conversion in the “homogeneous” phase means that the catalyst system used is sufficiently homogeneously distributed (solubilized) in the reaction mixture in order to catalyze the hydroformylation reaction.
  • the catalyst system is either dissolved homogeneously or distributed colloidally.
  • a catalyst is preferably used in the process according to the invention in which the phosphacyclohexane structural elements bonded to the polymer structure are selected from groups of the general formula I.
  • R 1 to R 10 independently of one another for hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, WCOO-M +, WS0 3 -M + , WP0 3 2 -M + 2 , W (NElE 2 E 3 ) + X-, W0R 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, wherein
  • 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,
  • two of the geminal residues (R 1 , R 2 ), (R 3 , R 4 ), (R 5 , R 6 ), (R 7 , R 8 ) and / or (R 9 , R 10 ) also contain an oxo - Can form group or together with the carbon atom to which they are attached, can represent a 3- to 8-membered carbo- or heterocycle, which may optionally be mono-, di- or triple with cycloalkyl, heterocycloalkyl, aryl and / or Hetaryl is fused,
  • radicals R and R 1 to R 10 can have an additional, trivalent phosphorus or nitrogen group capable of coordination
  • two adjacent atoms of the phosphacyclohexane ring can also be part of a condensed ring system with 1, 2 or 3 further rings,
  • one of the radicals R or R 1 to R 10 stands for a bond to the polymer structure or a group which is bonded to the polymer structure.
  • the ligands used according to the invention preferably have 3 to 20, particularly preferably 4 to 12, phosphacyclohexane structural elements bonded to the polymer structure.
  • the ligands advantageously have a lower viscosity in solutions compared to linear divalent polymeric ligands of the same molecular weight.
  • 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 8 -alkyl and very particularly preferably C 1 -C 4 -alkyl groups.
  • 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
  • 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 from cycloalkyl, aryl, hetaryl, halogen, NE i -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 7 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 in the context 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 which may optionally be substituted, where in the case of substitution these heterocycloaliphatic groups 1, 2 or 3, preferably 1 or 2, particularly preferably 1 substituent selected from alkyl, aryl, COOR a , COO "M + and ⁇ E X ⁇ 2 , preferably alkyl.
  • heterocycloaliphatic groups examples include pyrrolidinyl, piperidinyl, 2,2 , 6, 6-tetramethyl-piperidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl, tetrahydrothiophenyl, tetrahydrofuranyl, tetrahydropyranyl, 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 ⁇ -E 2 , alkylene-NE 1 E 2 , nitro, cyano or halogen.
  • Hetaryl is preferably 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, cycloalkyl, aryl, alkoxy, carboxyl, carboxylate, -S0 3 H, sulfonate, NE i E 2 , alkylene-NEiE 2 , trifluoromethyl or halogen.
  • alkyl, cycloalkyl and aryl radicals apply correspondingly to alkoxy, cycloalkyloxy, heterocycloalkoxy, aryloxy and hetaryloxy radicals.
  • the residues NE 1 E 2 and NEE 5 are preferably N, N-dimethylamino, 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 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 + stands for an alkali metal cation, such as. B. Li + , Na + or K + or for an alkaline earth metal 5 tall 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 connection, a distinction is made in condensed ring systems between an ortho-
  • each ring has an edge or two atoms in common with each neighboring ring, and a 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 is preferably compounds with repeating units which are selected from -CH 2 0 -) -, -CH 2 CH 2 0 -) -, -CH 2 -CH (CH 3 ) 0 -) -, -CH 2 -CH ( C 2 H 5 ) 0 -) - and - (CH 2 ) 4 0 -) -.
  • the number of repetition units is preferably in a range from 1 to
  • 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 repeating units, the order is arbitrary, i. H. it can be statistically different
  • polyoxyalkylenes 35 split, alternating or block repetitions.
  • the statements made above for the polyoxyalkylenes apply analogously to polyalkyleneimines, the oxygen atom being replaced in each case by a group R 1 , in which R 1 is hydrogen or C 1 -C 4 -alkyl.
  • Suitable polyoxyalkylenes are derived, for. B. of formaldehyde
  • 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. from Aziri-
  • 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 radical R in the formula I is preferably selected from alkyl, cycloalkyl and aryl radicals.
  • Preferred alkyl radicals are C 1 -C 2 alkyl radicals, which are linear or branched alkyl radicals
  • the radical R 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 preferably also represents a Cs-Cs-cycloalkyl radical, in particular cyclohexyl.
  • the carbon atom bound to the phosphorus atom is preferably not sp 2 hybridized.
  • the radical R 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
  • R 5 and R 6 in formula I preferably represent a double bonded oxygen atom.
  • At least two or three or four of the radicals R 1 to R 10 are preferably different from hydrogen.
  • cyclic structures which can be aliphatic, aromatic or heterocyclic.
  • Compounds of the formula I have the cyclic structures, for example in positions 2, 4 and 6.
  • the radicals R 1 to R 10 are preferably hydrogen and radicals as defined for R, particularly preferably alkyl or aryl and in particular C 1 2 alkyl radicals, 3 C aralkyl radicals, 7 C 3 alkylene radicals and / or C. 6 _ ⁇ 2 aryl residues.
  • 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. For example, it can be phenyl radicals (R 1 to R10) or naphthyl radicals. If the aryl groups are substituted, they preferably have one, two or three alkyl substituents, which are in particular methyl or ethyl radicals.
  • R and / or one or more of the radicals R 1 to R 10 are alkyl and aryl radicals, these can be fluorinated or perfluorinated.
  • Preferred fluorinated radicals are trifluoromethyl and pentafluorophenyl.
  • At least one of the radicals R and R 1 to R 10 in the compounds of the general formula I represents a polar (hydrophilic) group, which generally results in water-soluble catalysts.
  • the polar groups are preferably selected from WC00 ⁇ M + , WS0 3 -M + ,
  • At least one of the substituents R and R 1 to R 10 can have an additional, trivalent phosphorus or nitrogen group capable of coordination, whereby a bidentate or multidentate ligand is formed.
  • Phosphane, phosphinite, phosphonite, phosphoramidite and phosphite groups and ⁇ 5 -phospholyl complexes or phosphabenzene groups are particularly preferred.
  • 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 ⁇ -C ⁇ len 0 -Alky-.
  • the compound of the formula I is preferably selected from compounds of the general formulas Ia to Ig
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 independently of one another for hydrogen, alkyl, alkoxy, carboxyl, carboxylate, trifluoromethyl, -S0 3 H, sulfonate , E ⁇ 2 or alkylene-NE i E 2 , where E 1 and E 2 are independently hydrogen, alkyl or cycloalkyl, and R 21 , R 22 , R 23 , R 24 , R 25 , R 26 and R 27 independently of one another represent alkyl or cycloalkyl,
  • R ' represents hydrogen or phenyl
  • Phosphacyclohexane to which it is bound represent a fused ring system
  • one of the radicals R, R 'or R 11 to R 27 stands for a bond to the polymer structure or a group which is bonded to the polymer structure.
  • the radical R particularly preferably represents a bond or group which is bonded to the polymer structure.
  • the polymeric ligands used according to the invention preferably have a number average molecular weight in the range from 500 to 120,000, particularly preferably 1000 to 100,000, in particular 2,000 to 80,000.
  • the polymer backbone is preferably a branched, star-shaped or dendritic polymer backbone.
  • the polymer backbone preferably has the phosphacyclohexane structural elements at the chain end.
  • the phosphacyclohexane groups can be attached to the polymer residue by reaction of suitable complementary functional groups, for example in an addition or condensation reaction.
  • “complementary functional groups” are understood to be 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 phosphacyclohexanes can have such functional groups in the form of suitably functionalized radicals R 1 to R 10 . It is preferably R 1 to R 10 , in which the functional group via one of the aforementioned bridging groups W, z. B. a -CC 4 alkylene group, is bound to the phosphacyclohexane ring.
  • the phosphacyclohexanes can also have suitable groups capable of binding to a correspondingly complementarily functionalized polymer in the form of the radical R on the ring phosphorus atom. Then the functional groups usually over 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.
  • Metal atom (preferably -Li, -Na) -Hai
  • the polymer backbone is derived from a polymer which can be obtained by free-radical polymerization and is suitable for free, ⁇ , ⁇ -ethylenically unsaturated monomers and which contains groups which are capable of reacting with corresponding complementary groups of the phosphacyclohexanes.
  • branched polymers by radical copolymerization it is possible, for example, to use monomers with three or more ethylenically unsaturated double bonds for the polymerization.
  • monomers with three or more ethylenically unsaturated double bonds include, for example, the esters of trihydric or polyhydric alcohols with ⁇ , ⁇ -ethylenically unsaturated mono- or dicarboxylic acids. Suitable trihydric or higher alcohols are described below. Suitable ⁇ , ⁇ -ethylenically unsaturated carboxylic acids are, for example, acrylic acid and methacrylic acid.
  • Suitable star polymers can be produced by radical polymerization of monomers with suitable polyfunctional initiators.
  • suitable ⁇ , ⁇ -ethylenically unsaturated monomers and the attachment of the phosphacyclohexane groups reference is made to the following statements on radical polymerization.
  • Suitable initiators are, for example, aromatic acylium ions of the formula:
  • polymers which contain at least one copolymerized copolymer which is selected from compounds which have at least one, ⁇ -ethylenically unsaturated double bond and at least one active hydrogen atom per molecule are suitable.
  • these include e.g. B. the esters ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids, such as acrylic acid, methacrylic acid, Fu aric acid, maleic acid, itaconic acid, crotonic acid etc. with Ci to C 2 o-alkanediols, such as. B.
  • 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 - to C 2 -amino alcohols which have a primary or secondary amino group.
  • aminoalkyl acrylates and aminoalkyl methacrylates and their N-monoalkyl derivatives which, for. B. wear an N-Ci to Cs-monoalkyl radical, such as aminomethyl acrylate, aminomethyl methacrylate, aminoethyl acrylate, N-methylaminomethyl acrylate, etc.
  • 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 free-radically polymerizable, ⁇ , ⁇ -ethylenically unsaturated monomer which is selected from vinylaromatics, such as styrene, ⁇ -methylstyrene, o-chlorostyrene or vinyltoluenes, esters ⁇ , ⁇ -ethylenically unsaturated C 3 - bis C 6 mono- and dicarboxylic acids with Ci- to C 2 o-alkanols, such as. B.
  • vinylaromatics such as styrene, ⁇ -methylstyrene, o-chlorostyrene or vinyltoluenes
  • esters ⁇ , ⁇ -ethylenically unsaturated C 3 - bis C 6 mono- and dicarboxylic acids with Ci- to C 2 o-alkanols such as.
  • 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 ⁇ -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 has no amine hydrogens.
  • TMEDA tetramethylethylenediamine
  • di- or polyfunctional initiators or functionalized initiators for anionic polymerization polymers are obtained which have 3 or more metal atoms at the chain ends.
  • Such 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.
  • functionalized and suitably derivatized alkyl lithium initiators star-shaped polymers are obtained.
  • Suitable protected functionalized initiators are, for example, 6-lithium hexylacetaldehyde acetal,
  • halogenated or halogenated alkylated phosphacyclohexanes can be used, for example, on the phosphorus atom.
  • the polymer radical is preferably also derived from the above-mentioned radicals of different star polymers or dendritic polymers.
  • 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 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.
  • phosphacyclohexane groups can then be bound by reaction with halogenated, preferably halogen-alkylated, phosphacyclohexanes.
  • the phosphacyclohexane groups can also be bound to the polymer residue by reacting a phosphabenzene with an anionic polymer which still has free metal residues and the reaction product obtained is then hydrogenated with hydrogen in the presence of a hydrogenation catalyst.
  • Another object of the invention is a process for the preparation of a polymeric ligand of the general formulas II.a or II.b.
  • R represents a polymer radical obtainable by anionic polymerization which contains at least two further phosphacyclohexane structural elements
  • R 1 , R 3 , R 5 , R 6 , R 7 , R 9 and R 10 have the meanings given above,
  • step B) the reaction product (s) obtained in step A) is hydrogenated with hydrogen in the presence of a hydrogenation catalyst.
  • dienes such as butadiene
  • anionic polymerization results in phosphacyclohexadienes which have a polyalkylene radical in the 1-position which still has unsaturated side chains (1,2-product) or double bonds in the main chain (1,4-product).
  • these are converted completely or almost completely into the corresponding alkyl radicals.
  • the reaction product obtained in step A) contains at least one phosphacyclohexadiene of the general formula IV. A or IV.b.
  • Suitable catalysts for the hydrogenation of the phosphacyclohexadienes to phosphacyclohexanes are generally homogeneous or heterogeneous catalysts, as are usually used in the hydrogenation of aromatics. These include, for example, catalysts based on noble metals such as Pt, Pd, Ru and Rh or transition metals such as Mo, W, Cr, Fe, Co and Ni, which can be used individually or as mixtures and / or which increase activity and / or stability can be applied to supports such as activated carbon, aluminum oxide, diatomaceous earth, etc. According to a first preferred embodiment, homogeneous catalysts based on ruthenium or rhodium are used.
  • heterogeneous catalysts preferably Pd / C, Ru / Al 2 0 3 , Pt / C or Raney nickel are used.
  • a preferred heterogeneous catalyst is Pd / C.
  • the heterogeneous catalysts can be separated off after the hydrogenation by customary processes, for example by filtration.
  • the temperature during the hydrogenation is preferably in a range from 20 to 250 ° C., particularly preferably 40 to 180 ° C. and in particular 50 to 160 ° C.
  • the hydrogenation is first carried out at a temperature in the range from about 50 to 120 ° C. until essentially no more cyclohexadienes are present in the reaction mixture, since these tend to aromatize. This results in hydrogenation products which contain predominantly or exclusively phosphacyclohexenes.
  • phosphacyclohexenes are suitable as ligands for transition metal catalysts for hydroformylation. If an essentially complete hydrogenation is desired, the temperature is subsequently increased to up to 250 ° C. in order to complete the hydrogenation.
  • the hydrogen partial pressure is preferably between ambient pressure and 600 bar, particularly preferably 5 to 100 bar and in particular 10 to 80 bar.
  • At least one olefin can be added for the hydrogenation in order to convert any unreacted phosphabenzene still present in the reaction mixture into catalytically active species.
  • Any unconverted phosphabenzene still present in the reaction mixture of the hydrogenation can, according to a further suitable embodiment, also be separated off by extraction. If cycloalkanes are used as solvents for the preparation of the polymer ligands used according to the invention, separation is generally possible by adding at least one alcohol, such as methanol, ethanol or isopropanol, two phases being formed, one of which is polymeric ligand and the other Phosphabenzene is enriched.
  • alcohol such as methanol, ethanol or isopropanol
  • residual amounts of phosphabenzene can also be separated off by membrane filtration with a suitable membrane, as described in detail below.
  • Membrane filtration can also be used to separate polymeric ligands with different levels of functionality. So it can be different in the manufacture of anionic star polymers to form polymer mixtures Number of side chains come. Such mixtures can also advantageously be separated by membrane filtration.
  • Another object of the invention is a catalyst comprising at least one complex of a metal of subgroup VIII with at least one polymeric ligand, as previously defined.
  • the metal of subgroup VIII is preferably selected from cobalt, ruthenium, iridium, rhodium, nickel or palladium.
  • the use of rhodium as the transition metal is particularly preferred.
  • 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, bidentate and multidentate phosphine, phosphinite, phosphonite, phosphoramidite and phosphite ligands.
  • halides amines, carboxylates, acetylacetonate, aryl or alkyl sulfonates, hydride, CO, olefins, dienes, cycloolefins, nitriles, N-containing heterocycles, aromatics and heteroaromatics, ethers,
  • 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 multidentate phosphacyclohexane ligand capable of complex formation and n and m are all Represent numbers between 1 and 3.
  • the transition metal complex may also contain further radicals such as hydrido, alkyl or acyl radicals as ligands.
  • 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 C0 / H 2 used in the hydroformylation process according to the invention can be varied within wide ranges.
  • synthesis gas with CO / H 2 molar ratios of from 5:95 to 90:10 have been used successfully, it is preferred synthesis gas with CO / H 2 ratios of 40:60 to 70:30, particularly preferably a CO / H 2 ratio of about 1: 1 is used.
  • 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 phosphacyclohexane structural units, 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.
  • olefins are mentioned by way of example: ethene, propene, 1-butene, 1-hexene, 1-octene, -C 5 -C 2 o-01efine, 2-butene, linear internal C 5 -C 2 o-olefins and isobutene.
  • Suitable branched, internal olefins are preferably C 4 -C 20 olefins, such as 2-methyl-2-butene, 2-methyl-2-pentene, 3-methyl-2-pentene, branched, internal heptene mixtures, branched , internal octene mixtures, branched, internal nonene mixtures, branched, internal decene mixtures, branched, internal undecene mixtures, branched, internal dodecene mixtures etc.
  • Suitable olefins to be hydroformylated are furthermore C 5 -Cg-cycloalkenes, such as cyclopentene, cyclohexene, cycloheptene, cyclooctene and their derivatives, such as, for. B. whose C ⁇ -C 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 4 -C 2 o-olefins, such as 2-butene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, 2-0ctene, 3-0ctene , 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 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 technical olefin mixtures which can be used in the hydroformylation process according to the invention are also 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 frequently 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.
  • the reaction discharge can in principle be worked up by known processes. A method is preferred in which
  • 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.
  • the advantages of the catalysts according to the invention are particularly evident when the separation in step ii) and / or the workup in step iii) comprises ultrafiltration.
  • the distillative processing of the reaction discharge 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 of 0.1 to 1000 mbar, 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, are preferred Apparatus is used which causes low investment costs and, especially for higher olefins, allows the lowest possible distillation temperature, such as thin-film evaporators, wiper blade evaporators or falling-film evaporators, since the higher the temperature, the aldehydes formed in the reaction can enter into subsequent reactions such as aldol condensations.
  • this distillation essentially serves to separate 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, so-called 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. In particular, high boilers still contained should be avoided.
  • 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 can be returned to further processing for the recovery of transition metal from subgroup VIII of the periodic table and, if desired, the ligand used.
  • an amount of this compound which corresponds to the amount of transition metal from transition group VIII of the Periodic Table and ligand which has been discharged should be supplemented by feeding these compounds into the hydroformylation reaction.
  • the ligands according to the invention advantageously 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 from this distillation can be recycled into the reaction together with fresh olefin.
  • Advantageous for 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 of the reaction mixture in a wide range, but in which the catalyst complex and the ligand are insoluble or almost insoluble, so that it is possible will, by choosing the type and amount of solvent to precipitate the catalyst complex and the ligand, which can be returned to the hydroformylation after separation by decantation or filtration.
  • a large number of polar solvents which have hydroxyl, carbonyl, carboxamide or ether groups, that is to say alcohols, ketones, amides or ethers and mixtures of these solvents or mixtures of these solvents with water, are suitable as solvents.
  • 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. be carried out so that the distillation bottoms or part of the distillation bottoms before it is returned to the hydroformylation fed to a steam distillation apparatus and completely or partially freed from high boilers. It is also possible to carry out the distillation of the hydroformylation effluent continuously in the presence of water vapor 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 bottoms containing high boilers and subsequently condensing the steam distillate.
  • the water vapor is advantageously passed through the distillation bottoms in such a way that it does not condense in the distillation bottoms. 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 process can be operated continuously or batchwise. Refinements of such methods are described in WO 99/36382, to which reference is made here.
  • 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 retentate stream which is depleted in high boilers (and, where appropriate, in starting materials and oxo products) and enriched in catalyst and ligands, 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, ie wetting, of 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 rate in the module is generally 1 to 10, preferably 1 to 4 m / s.
  • the separation limit of the membranes is about 300 to 100,000 daltons, especially 500 to 20,000 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 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 z. 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 take place continuously or 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.
  • Heterophosphacyclohexane ligands containing ionic or polar groups are preferably used in such a hydroformylation process, so that the catalyst is highly soluble in the polar phase and "leaching" of the catalyst into the organic phase is prevented or at least largely prevented.
  • Suitable substituents are, for example, W'C00-M + , W'S0 3 -M +, W'P0 3 "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 W '(CH 2 CH 2 NR') X R ', where X ⁇ , M +, R ', W' and x have the meanings mentioned above.
  • Phosphacyclohexanes 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 via ultrafiltration. To separate the catalyst and obtain a catalyst-free product or high-boiling stream, the synthesis discharge, as described above, is brought into contact with a membrane under pressure 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 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 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 cyano-
  • Suitable olefins for hydrocyanation are generally the olefins previously mentioned as starting materials for hydroformylation.
  • adiponitrile in the presence of at least one catalyst according to the invention.
  • a hydrocarbon mixture is preferably used which has a 1,3-butadiene content of at least
  • 1,3-butadiene-containing hydrocarbon mixtures are available on an industrial scale. So z. B. in the refurbishment
  • Pure 1,3-butadiene can e.g. B. be isolated by extractive distillation from commercially available hydrocarbon mixtures.
  • the catalysts of the invention can advantageously be used for the hydrocyanation of such olefin-containing, in particular 1,3-butadiene-containing, hydrocarbon mixtures, as a rule 45 even 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.
  • 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.
  • GPC Gel permeation chromatography
  • a GPC analysis (calibration with a PS calibration kit from Polymer Laboratories and conversion to polybutadiene with Mark-Houwink constants) gave a number-average molecular weight M n of approximately 48,000. Analysis of the solution gave a phosphorus content of 270 ppm ,
  • Example 4 150 g of the solution obtained in Example 2 were mixed with 305 g of isopropanol and mixed vigorously. After phase separation, the lower, orange-colored phase was separated off, taken up in 108 g of cyclohexane and mixed with 215 g of isopropanol. The mixture obtained was mixed vigorously. After phase separation, the lower, orange-colored phase was separated off and taken up in 110 g of cyclohexane. 31 P-NMR spectroscopy of the solution obtained showed an enrichment of isomeric 2,6-bis (2,4-dimethylphenyl) -4-phenylphosphacyclohexadienyl-functionalized star-shaped polybutadienes to 94%. Analysis of the solution showed a phosphorus content of 105 ppm.
  • Example 4 Example 4:
  • Example 3 138 g of the solution obtained in Example 3, together with 15 mg (0.06 mmol) of rhodium dicarbonylacetylacetonate and 17.0 g of 1-octene, were transferred to a 300 ml autoclave flushed with hydrogen. 20 bar of hydrogen were injected at room temperature. The reaction mixture was heated to 80 ° C. with vigorous stirring using a gassing stirrer. A reaction pressure of 80 bar was then set using hydrogen. During the reaction, the pressure in the autoclave was kept at the pressure level by repressing via a pressure regulator. After a reaction time of 36 h, the temperature was raised to 160 ° C. at constant pressure. After a further 50 h reaction time, the autoclave was cooled and let down.
  • the reaction discharge obtained was freed from low boilers in an oil pump vacuum at approx. 40 ° C. Analysis of the solution gave a rhodium content of 60 ppm and a phosphorus content of 130 ppm (P / Rh molar ratio 7).
  • Example 5 Preforming a solution of rhodium / 2,6-bis (2,4-dimethylphenyl) -4-phenylphosphacyclohexyl-functionalized star-shaped poly (ethene-co-butene)
  • Example 4 42.3 g of the solution obtained in Example 4 were mixed with 8.2 g of 9N oxo oil. The solution was then freed from low boilers in an oil pump vacuum at approx. 70 ° C. The residue obtained was diluted with 28.4 g of 9N® oxo oil (from BASF Aktiengesellschaft, high-boiling solvent from the hydroformylation of isomeric octenes) and 80 ml of cyclohexane and then transferred together with 8.9 mg of rhodium dicarbonylacetylacetonate to a 300 ml autoclave. 20 bar of CO / H 2 were injected at room temperature. The reaction mixture was heated to 140 ° C. with vigorous stirring.
  • 9N® oxo oil from BASF Aktiengesellschaft, high-boiling solvent from the hydroformylation of isomeric octenes
  • the rhodium / phosphacyclohexane catalyst solutions obtained by hydrogenation were, if appropriate after dilution with further oxo oil and optionally with the addition of further rhodium dicarbonyl acetylacetonate, transferred to a 100 ml autoclave flushed with synthesis gas.
  • 5 bar CO / H (1: 1) were pressed in cold at room temperature.
  • the reaction mixture was heated to the desired reaction temperature within 30 min with vigorous stirring using a gassing stirrer.
  • the olefin was then pressed in via a lock.
  • the desired reaction pressure was then immediately set using CO / H 2 .
  • the pressure in the reactor was kept at the pressure level by pressing through a pressure regulator. If necessary, samples were taken during the reaction.
  • the autoclave was cooled, decompressed and emptied. The samples were analyzed by GC using correction factors.
  • dimerbutene obtained by nickel-catalyzed dimerization of n-butenes; degree of branching 1.06; composition: 15% n-octenes, 68% methylheptenes) , 17% dimethylhexenes and trimethylpentenes
  • 12.5 g xylene obtained at 140 ° C. and 80 bar CO / H 2 according to the general experimental procedure, a conversion of dimerbutene of 63% after 1 h and 89% after 4 h.
  • the yield of nonanals was 54% after 1 h and 77% after 4 h.
  • the yield of nonanols was 1% after 1 h and 4% after 4 h.
  • the solution used was introduced under inert conditions into a stirred pressure membrane test cell with a capacity of approx. 30 ml, connected to a nitrogen supply, heated to the appropriate operating temperature, then brought to the appropriate operating pressure by supplying nitrogen and permeate on the low-pressure side of the membrane taken.
  • a membrane in disk form from Inocermic GmbH was used.
  • the separating layer made of Ti0 2 on a coarse-pored ceramic substructure has a pore size of 5 nm according to the manufacturer, which corresponds to a separating limit of approx. 10 kD measured with a solution made of polyethylene glycol.
  • the free membrane area was 3.8 cm 2 .
  • the cell was relaxed and the solution concentrate (retentate) was removed under inert conditions.
  • the retention of phosphorus and rhodium was calculated from the phosphorus and, if appropriate, rhodium content determination of the insert, the retentate and the permeate and the concentration factor MK (insert / retentate) and, if appropriate, after evaluating the 31 P-NMR spectrum.
  • the average permeate flow in kg / m2-h was calculated from the permeate weight, the test time and the membrane area.
  • Example 2 With the solution obtained in Example 2, the results listed in Table 1 were obtained in a membrane filtration at 40 ° C. and 10 bar according to the general experimental procedure.
  • Table 1 Results of the discontinuous membrane filtration tests with a solution of 2,6-bis (2,4-dimethylphenyl) -4-phenylphosphacyclohexadienyl-functionalized star-shaped polybutadiene and 2,6-bis (2,4-dimethylphenyl) -4 -phenylphosphabenzol

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Abstract

L'invention concerne un procédé d'hydroformylation de composés contenant au moins une liaison double insaturée éthyléniquement, par réaction avec du monoxyde de carbone et de l'hydrogène, en présence d'un système de catalyseur comprenant au moins un métal du VIIIème groupe secondaire de la classification périodique des éléments et au moins un ligand polymère. L'invention concerne en outre de nouveaux catalyseurs et leur utilisation.
PCT/EP2002/014691 2001-12-21 2002-12-20 Procede d'hydroformylation en presence d'un ligand polymere avec des elements structuraux phosphacyclohexane WO2003053572A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE10296000T DE10296000D2 (de) 2001-12-21 2002-12-20 Verfahren zur Hydroformylierung in Gegenwart eines polymeren Liganden mit Phosphacyclohexan-Strukturelementen
AU2002358788A AU2002358788A1 (en) 2001-12-21 2002-12-20 Method for hydroformylation in the presence of a polymeric ligand comprising phosphacyclohexane structural elements

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DE2001163347 DE10163347A1 (de) 2001-12-21 2001-12-21 Verfahren zur Hydroformylierung in Gegenwart eines polymeren Liganden mit Phosphacyclohexan-Strukturelementen
DE10163347.5 2001-12-21

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007085321A1 (fr) * 2006-01-26 2007-08-02 Evonik Oxeno Gmbh Procédé de séparation de catalyseurs renfermant un complexe métallique à partir de mélanges de télomérisation
WO2017150337A1 (fr) 2016-03-01 2017-09-08 株式会社クラレ Procédé de production de composé dialdéhyde

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102016204256A1 (de) * 2016-03-15 2017-09-21 Evonik Degussa Gmbh Prozessintensivierung des Hydroformylierungs-Verfahrens

Citations (4)

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Publication number Priority date Publication date Assignee Title
US3160593A (en) * 1960-01-29 1964-12-08 Shell Oil Co Mineral oil compositions
GB1109787A (en) * 1965-03-29 1968-04-18 Shell Int Research New phosphine derivatives and their use in the hydroformylation of olefinic compounds
US3496204A (en) * 1965-03-29 1970-02-17 Shell Oil Co Tertiary organophosphine-cobalt-carbonyl complexes
WO2002000669A2 (fr) * 2000-06-26 2002-01-03 Basf Aktiengesellschaft Phosphacyclohexanes et leur utilisation dans l'hydroformylation d'olefines

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
US3160593A (en) * 1960-01-29 1964-12-08 Shell Oil Co Mineral oil compositions
GB1109787A (en) * 1965-03-29 1968-04-18 Shell Int Research New phosphine derivatives and their use in the hydroformylation of olefinic compounds
US3496204A (en) * 1965-03-29 1970-02-17 Shell Oil Co Tertiary organophosphine-cobalt-carbonyl complexes
WO2002000669A2 (fr) * 2000-06-26 2002-01-03 Basf Aktiengesellschaft Phosphacyclohexanes et leur utilisation dans l'hydroformylation d'olefines

Non-Patent Citations (1)

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Title
BELLER M ET AL: "PROGRESS IN HYDROFORMYLATION AND CARBONYLATION", JOURNAL OF MOLECULAR CATALYSIS. A, CHEMICAL, ELSEVIER, AMSTERDAM, NL, vol. 104, no. 1, June 1995 (1995-06-01), pages 17 - 85, XP000937494, ISSN: 1381-1169 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007085321A1 (fr) * 2006-01-26 2007-08-02 Evonik Oxeno Gmbh Procédé de séparation de catalyseurs renfermant un complexe métallique à partir de mélanges de télomérisation
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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