DE102005062029A1 - Preparing a composition of primary alcohol, useful as softeners for plastics, comprises dimerization of a monoolefin in presence of aluminum catalyst, hydroformylation of the dimer followed by catalytic hydrogenation of obtained aldehyde - Google Patents

Abstract

Preparation of a composition of 9-21C primary alcohol comprises: dimerization of 4-10C monoolefin containing internal and/or terminal double bonds in the presence of an aluminum catalyst (I); hydroformylation of the obtained olefin dimer composition by means of a carbon dioxide/hydrogen mixture in presence of a hydroformylation catalyst, which is homogeneously dissolved in a reaction medium; and catalytic hydrogenation of the obtained aldehyde composition to the corresponding alcohol. Preparation of a composition of 9-21C primary alcohol comprises: catalytic dimerization of 4-10C monoolefin containing internal and/or terminal double bonds; hydroformylation of the obtained olefin dimer composition by means of a carbon dioxide/hydrogen mixture in presence of hydroformylation catalyst, which is homogeneously dissolved in a reaction medium; and catalytic hydrogenation of the obtained aldehyde composition to the corresponding alcohol; where the dimerization is carried out at 160-260[deg]C in the presence of an aluminum catalyst (I) of formula AlRx(ORy)3x, and the hydroformylation is carried out in the presence of a rhodium complex dissolved in the reaction medium with a ligand containing phosphacyclohexane group, free ligand and optionally in the presence of a solvent at 50-250[deg]C and 10-100 bar. R, Ry : 1-10C alkyl; and x : 0-3.

Description

• a) katalytischen Dimerisierung interne und/oder endständige Doppelbindungen enthaltender Monoolefine mit 4 bis 10 Kohlenstoffatomen,
• b) die Hydroformylierung der erhaltenen Olefindimerzusammensetzung mittels eines CO/H₂-Gemisches in Gegenwart eines homogen im Reaktionsmedium gelösten Hydroformylierungskatalysators, und
• c) die katalytische Hydrierung der in Stufe b) erhaltenen Aldehydzusammensetzung zu den entsprechenden Alkoholen.

The present invention relates to a process for the preparation of compositions of primary, aliphatic alcohols having 9 to 21 carbon atoms comprising the steps of

• a) catalytic dimerization of internal and / or terminal double bonds containing monoolefins having 4 to 10 carbon atoms,
• b) the hydroformylation of the resulting Olefindimerzusammensetzung by means of a CO / H ₂ mixture in the presence of a homogeneously dissolved in the reaction medium hydroformylation catalyst, and
• c) the catalytic hydrogenation of the aldehyde composition obtained in stage b) to give the corresponding alcohols.

Higher alcohols with 9 to 21 carbon atoms find versatile use in the chemical industry. Thus, alcohols having 9 to 13 carbon atoms for example, after esterification with a dicarboxylic acid or a dicarboxylic acid anhydride, like phthalic anhydride, adipic acid, sebacic, azelaic acid or cyclohexanedicarboxylic acid as a plasticizer for Plastics, especially polyvinyl chloride used. Long-chain Alcohols having 11 to 15 carbon atoms are e.g. for the production of surfactants, whereas alcohols of even greater chain length, for example used for the production of lubricants.

A possibility for the preparation of such long-chain alcohols is the dimerization and / or oligomerization of steam crackers, FCC crackers, the Alfol process or the Fischer-Tropsch process in large quantities monoolefins available, the subsequent hydroformylation of the obtained dimers or oligomers and the subsequent one Hydrogenation of the relevant hydroformylation products.

The catalytic di- or oligomerization of monoolefins can be effected with different catalysts. Commonly used for the di- or oligomerization of monoolefins are, for example, acid catalysts, such as sulfuric acid, phosphoric acid, zeolitic or non-zeolitic molecular sieves (US Pat. No. 5,134,242) in the H.sup. ⁺ Form and other inorganic materials with acidic centers, for example layered silicates (review O'Connor et al., Catalysis Today 6, 329 (1990)). The acid-catalyzed di- or oligomerization of olefins usually gives highly branched di- or oligomers with a high proportion of internal double bonds.

A other economically relevant class of catalysts for di- or oligomerization of olefins are nickel-containing catalysts, both as homogeneous and as heterogeneous catalysts in industrial scale be applied.

DE-A 4,339,713, US-A 5,169,824 and DE-A-2 051 402 describe heterogeneous nickel-containing catalysts based on different support materials such as silica, alumina or aluminosilicates applied and optionally in addition may be doped with other metal atoms. In EP-A 202 670 is a nickel-containing supported catalyst used for oligomerization, in addition to an organoaluminum Impregnated compound has been. On zeolitic carriers Applied nickel catalysts are used, for example, in DE-A 2 347 235, EP-A 261 730 and EP-A 329 305 for the oligomerization of Used olefins.

method for the oligomerization of olefins by means of homogeneous nickel catalysts and the preparation of such catalysts are described in US-A 4,366,087 and US-A 4,398,049.

USA 2 695 327 relates to the dimerization of internal olefins by means of Aluminum-organic Links to mainly Vinylidene-containing dimers. Also, aluminum-organic compounds as a catalyst for the dimerization of α-olefins according to US-A 4 973,788, US-A 5,824,833 and US-A 5,695,100, wherein dimers be obtained with a high vinylidene group content. Internal olefins are not reacted under the reaction conditions used.

JP-A 45-17666 (1970) discloses the preparation of alcohol sulfates having surface active properties through the steps of dimerization of C ₄ to C ₁₀ α-olefins to C ₈ to C ₂₀ vinylidene olefins and their subsequent hydroformylation. Hydrogenation and sulfation. For hydroformylation, conventional cobalt and rhodium hydroformylation catalysts are used.

DE-A 19 912 418 describes a process for the preparation of surfactant alcohols and surfactant alcohol ethers. Starting from olefin mixtures with a defined minimum proportion of linear hexenes, Mixtures prepared with a predominant proportion of branched dodecenes, which are then derivatized to surfactant and then optionally alkoxylated. In the olefin mixture used, the sum of all the hexene isomers contained therein, ie the linear and branched hexene isomers, must be at least 60% by weight. Furthermore, the sum of the linear hexene isomers contained therein must be 30 to 80 wt .-%. For the dimerization, preference is given to using a heterogeneous catalyst which produces a dimer mixture which delivers less than 10% by weight of olefins with vinylidene groups.

DE-A 19 910 370 relates to a process for the preparation of surfactant alcohols and surfactant alcohol ethers by dimerization of olefin mixtures, Derivatization to primary Alcohols and optionally a subsequent alkoxylation. In this Procedures are used to dimerize olefin mixtures with at least 55 wt .-% hexene isomers, wherein the proportion of linear isomers less than 30% by weight, used.

DE-A 19859911 describes a process for the preparation of surfactant alcohols and surfactant alcohol ethers by metathesis of a C ₄ olefin mixture, separation of olefins having 5 to 8 carbon atoms, dimerization to olefin mixtures having 10 to 16 carbon atoms, derivatization to a surfactant alcohol and optionally a subsequent alkoxylation.

The long-chain olefins used in these processes have one relatively high degree of branching. Olefins with more than one branch per molecule However, they are usually relatively unreactive, so hydroformylation to work at high pressure and high temperature satisfactory sales and to achieve space-time yields. Such hydroformylation conditions do not interfere only the cost-effectiveness of the procedure, but also can to isomerization reactions and the formation of relatively highly branched Hydroformylierungsprodukte and subsequently highly branched alcohol mixtures to lead. However, many applications of these products are lower Degree of branching desired.

In Considering the dimerization of olefins using Brönsted-Acider or nickel-containing catalysts of relatively high proportion of multiply branched dimers and dimers with internal double bond was the present invention, the object of a method for producing of alcohols having 9 to 21 carbon atoms starting from internal and terminal ones Double bonds or only internal double bonds containing olefin compositions to find that makes it possible the alcohols over the stages of hydroformylation and hydrogenation at high conversions in obtained in good yield and with a low degree of branching.

• a) katalytischen Dimerisierung interne und/oder endständige Doppelbindungen enthaltender Monoolefine mit 4 bis 10 Kohlenstoffatomen,
• b) die Hydroformylierung der erhaltenen Olefindimerzusammensetzung mittels eines CO/H₂-Gemisches in Gegenwart eines homogen im Reaktionsmedium gelösten Hydroformylierungskatalysators, und
• c) die katalytische Hydrierung der in Stufe b) erhaltenen Aldehydzusammensetzung zu den entsprechenden Alkoholen, gefunden

das dadurch gekennzeichnet ist,
dass man in Stufe a) die Dimerisierung der Monoolefine mittels eine Katalysators aus einer oder mehreren Verbindungen der allgemeinen Formel I AlR_x(OR')_s-x in der R und R' gleich oder verschieden sind und für C₁- bis C₁₀-Alkylgruppen stehen und der Index x Null oder eine ganze Zahl von 1 bis 3 bedeutet, bei einer Temperatur von 160 bis 260°C vornimmt, und in der Stufe b) die Hydroformylierung in Gegenwart eines im Reaktionsmedium gelösten Komplexes von Rhodium mit einem eine Phosphacyclohexan-Gruppe enthaltenden Liganden, freiem Liganden und in An- oder Abwesenheit eines Lösungsmittels bei einer Temperatur von 50 bis 250°C und bei einem Druck von 10 bis 100 bar durchführt.Accordingly, a process for the preparation of compositions of primary aliphatic alcohols having 9 to 21 carbon atoms comprising the steps of

• a) catalytic dimerization of internal and / or terminal double bonds containing monoolefins having 4 to 10 carbon atoms,
• b) the hydroformylation of the resulting Olefindimerzusammensetzung by means of a CO / H ₂ mixture in the presence of a homogeneously dissolved in the reaction medium hydroformylation catalyst, and
• c) the catalytic hydrogenation of the aldehyde composition obtained in stage b) to give the corresponding alcohols

which is characterized
that in step a) the dimerization of the monoolefins by means of a catalyst of one or more compounds of general formula I AlR _x (OR ') _sx in which R and R 'are identical or different and are C ₁ - to C ₁₀ -alkyl groups and the index x is zero or an integer from 1 to 3, takes place at a temperature of 160 to 260 ° C, and in the Step b) the hydroformylation in the presence of a complex of rhodium dissolved in the reaction medium with a phosphacyclohexane group-containing ligand, free ligand and in the presence or absence of a solvent at a temperature of 50 to 250 ° C and at a pressure of 10 to 100 bar.

The according to the inventive method available Olefindimers generally have a very low degree of branching, expressed through the ISO index, of less than 1.0, preferably from 0.5 to 1.0 and in particular from 0.8 to 1.0. Even when used alone of internal olefins as a raw material, for example, 3-hexene, can still an ISO index of less than 1.05 can be achieved.

The ISO index is additive for the totality of those contained in the olefin composition Olefinkomponenten from the number of branches per molecule of the respective individual components times their percentage in the olefin composition. In order to determine the percentage of the individual olefin component in the olefin composition, its proportion in area percent from the gas chromatographic analysis of the olefin composition is generally used. The structural determination of the individual components, ie their number of branches per molecule, can be determined using commercially available or synthetically prepared reference substances and / or by GC-MS coupling and analysis of the mass spectrometric fragmentation pattern and / or by preparative gas chromatography (GC) in conjunction with ^FIG H and / or ¹³ C-NMR spectroscopic analysis of the sample obtained take place.

As catalysts for the dimerization of the C ₄ to C ₁₀ monoolefins, one or more of the organoaluminum compounds of the general formula I are used in the process according to the invention AlR _x (OR ') _sx used in which R and R 'are identical or different and are C _{1 to} C ₁₀ alkyl groups and the index x is zero or an integer from 1 to 3, preferably the number 3. Accordingly, it is preferable to use trialkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tributylaluminum, tripentylaluminum, trihexylaluminum, triheptylaluminum, trioctylaluminum, trinonylaluminum or tri-decylaluminum as catalysts. Particular preference is given to using triethylaluminum or the trialkylaluminum compound as the catalyst which carries, as alkyl group R, the alkyl group corresponding to the monoolefin to be dimerized, that is to say, for example, in the case of dimerization of hexene, the hexyl group.

The Trialkylaluminum compounds of general formula I are for Part for sale available or can e.g. by reacting alkali metal aluminum hydrides, such as lithium aluminum hydride, produced with the relevant monoolefin or monoolefin mixture become. The latter method can also be used for in situ generation the catalyst can be used in the reaction mixture.

to execution the dimerization will be the monoolefin and the catalyst serving aluminum-organic compound of the formula I or the in-situ generation the aluminum-organic compound used in the reaction mixture Alkali metal aluminum hydride in weight ratio of olefin / aluminum compound from 10/1 to 1000/1, preferably from 10/1 to 100/1, if desired in the presence of a solvent which is inert under the reaction conditions, preferably a saturated one Hydrocarbon, mixed and at elevated temperature and pressure implemented together. The implementation may be advantageous in one Temperature from 160 to 260 ° C, especially at 200 to 240 ° C carried out be set, wherein the pressure is preferably set so that the Reactants monoolefin and aluminum-organic compound homogeneous dissolved in the reaction mixture stay. The implementation dimerization with partial separation of olefin and catalyst but is also possible.

The Dimerization can be continuous, e.g. in tubular reactors or stirred tank cascades, or discontinuously, e.g. in stirred kettles. For workup, the reaction in the batch Operation after cooling and relaxation hydrolyzed and neutralized and the resulting Olefinimer and Olefinoligomere containing, organic phase of that formed in catalyst hydrolysis and neutralization Aluminum hydroxide and / or aluminum salts containing aqueous phase be separated by phase separation. From the organic phase can the Olefindimer and olefin oligomers isolated by distillation become. In the continuous operation of the dimerization process of the invention can be handled in an analogous manner, but it is advantageous also possible, the olefin dimer as well as olefin oligomers of the catalyst acting as Aluminum-organic compound I, preferably at reduced Pressure, distill off and the catalyst-containing bottoms again attributed to the dimerization reactor, wherein from time to time to avoid the accumulation of polymeric compounds and catalyst decomposition products diverted and disposed of a waste stream can be and the catalyst in the reactor by feeding fresh Catalyst supplemented can be.

mit der Bedeutung
R^α
Wasserstoff, C₁-C₁₀₀-Alkyl, Cycloalkyl, Heterocycloalkyl, C₇-C₂₀-Aralkyl, C₇-C₂₀-Alkaryl, C₆-C₁₂-Aryl, Hetaryl, W'COO^–M⁺, W'SO₃ ^–M⁺, W'PO₃ ^2–M⁺ ₂, W'NR^β ₃ ⁺X^–, W'OR^β, W'NR^β ₂, W'COOR^β, W'SR^β, W'(CHR^βCH₂O)_yR^β, W'(CH₂NR^β)_yR^β, W'(CH₂CH₂NR^β)_yR^β, W'((CH₂)₄O)_yR^β oder W'COR^β,
wobei in der Formel III die Reste R^α auch anstelle von oder zusätzlich zu der Gruppe W zusammen eine Brücke mit 1 bis 20 Kohlenstoffatomen bilden können, die Bestandteil einer cyclischen oder aromatischen Gruppe sein kann und durch Heteroatome unterbrochen sein kann,
wobei in der Formel III die Reste R^α auch anstelle von oder zusätzlich zu der Gruppe W zusammen für eine Polyoxyalkylen- oder Polyalkylenimin-Brücke mit mindestens 21 Kohlenstoffatomen stehen können,
R¹ bis R¹⁰
unabhängig voneinander Wasserstoff, C₁-C₂₀-Alkyl, C₇-C₂₀-Aralkyl, C₇-C₂₀-Alkaryl, C₆-C₁₂-Aryl, wobei eines oder mehrere Kohlenstoffatome durch Heteroatome ersetzt sein können, W'COO^–M⁺, W'SO₃ ^–M⁺, W'PO₃ ^2–M⁺ ₂, W'NR^β ₃ ⁺X^–, W'OR^β, W'NR^β ₂, W'COOR^β, W'SR^β, W'(CHR^βCH₂O)_yR^β, W'(CH₂NR^β)_yR^β, W'(CH₂CH₂NR^β)_yR^β, W'((CH₂)₄O)_yR^β, W'Halogen, W'NO₂, W'COR+ oder W'CN,
wobei in den Resten R^α und R¹ bis R¹⁰ ein oder mehrere Wasserstoffatome durch Fluor ersetzt sein können,
W und W' unabhängig voneinander Einfachbindungen oder Brücken mit 1 bis 20 Kohlenstoffatomen, die Bestandteil einer cyclischen oder aromatischen Gruppe sein können und durch Heteroatome unterbrochen sein können,
wobei W auch für eine Polyoxyalkylen- oder Polyalkylenimin-Brücke mit mindestens 21 Kohlenstoffatomen stehen kann,
R^β Wasserstoff, C1-20-Alkyl, Carbonylalkyl, Cycloalkyl oder Aryl,
M⁺ Kationäquivalent,
X^– Anionäquivalent,
y Zahl von 1 bis 240,
wobei zwei geminale Reste R¹ bis R¹⁰ eine Oxo-Gruppe bilden können und einer oder mehrere der Reste R^α und R¹ bis R¹⁰ eine zusätzliche, zur Koordination befähigte dreibindige Phosphor- oder Stickstoffgruppierung aufweisen können,
wobei jeweils zwei vicinale Reste zu anellierten aliphatischen oder aromatischen Ringen verbunden sein können,
wobei zwei vicinale Reste R¹ bis R¹⁰ auch für eine chemische Bindung stehen können,
wobei in den Verbindungen der allgemeinen Formel III auch zwei oder mehr Brücken W vorliegen können und wobei die nicht an die Brücke(n) W gebundenen Atome der Phosphacyclohexanringe auch wie für R¹ bis R¹⁰ definiert substituiert sein können,
wobei in den Verbindungen der Formel II auch einer der Reste R^α oder R¹ bis R¹⁰ und in den Verbindungen der Formel III auch einer der Reste R oder R¹ bis R⁸ oder die beiden Reste R^α gemeinsam oder eine Gruppe W auch für einen Polymerrest mit einem zahlenmittleren Molekulargewicht im Bereich von 500 bis 50000 stehen kann, aufgebaut aus Wiederholungseinheiten, die sich von Monomeren ableiten, die ausgewählt sind unter Mono- und Diolefinen, Vinylaromaten, Estern α,β-ethylenisch ungesättigter Mono- und Dicarbonsäuren mit C₁-C₃₀-Alkanolen, N-Vinylamiden, N-Vinyllactamen, unter Ringöffnung polymerisierbaren heterocyclischen Verbindungen und Mischungen davon.The resulting C ₈ to C ₂₀ olefin dimers may be added to the hydroformylation step to the corresponding C ₉ to C ₂₁ aldehydes. The hydroformylation is complexed in the presence of a CO / H ₂ mixture and with the aid of a homogeneously soluble in the reaction medium rhodium complex catalyst having a phosphacyclohexane ligand. Suitable phosphacyclohexane ligands and their preparation are described in WO 02/00669 and comprise ligands of the general formulas II and III

with the meaning
R ^α
Hydrogen, C ₁ -C ₁₀₀ -alkyl, cycloalkyl, heterocycloalkyl, C ₇ -C ₂₀ -aralkyl, C ₇ -C ₂₀ -alkaryl, C ₆ -C ₁₂ -aryl, hetaryl, W'COO ^- M ⁺ , W'SO ₃ ^- M ⁺ , W'PO ₃ ^2- M ⁺ ₂ , W'NR ^β ₃ ⁺ X ^- , W'OR ^β , W'NR ^β ₂ , W'COOR ^β , W'SR ^β , W '(CHR ^β CH ₂ O) _y R ^β , W '(CH ₂ NR ^β ) _y R ^β , W' (CH ₂ CH ₂ NR ^β ) _y R ^β , W '((CH ₂ ) ₄ O) _y R ^β or W' COR ^β ,
in the formula III, the radicals R ^{α may} also, instead of or in addition to the group W, together form a bridge having 1 to 20 carbon atoms, which may be part of a cyclic or aromatic group and may be interrupted by heteroatoms,
where, in the formula III, the radicals R ^{α may} also, instead of or in addition to the group W, together represent a polyoxyalkylene or polyalkyleneimine bridge having at least 21 carbon atoms,
R ¹ to R ¹⁰
independently of one another are hydrogen, C ₁ -C ₂₀ -alkyl, C ₇ -C ₂₀ -aralkyl, C ₇ -C ₂₀ -alkaryl, C ₆ -C ₁₂ -aryl, where one or more carbon atoms may be replaced by heteroatoms, W'COO ^- M ⁺ , W'SO ₃ ^- M ⁺ , W'PO ₃ ² -M ⁺ ₂ , W'NR ^β ₃ ⁺ X ^- , W'OR ^β , W'NR ^β ₂ , W'COOR ^β , W'SR ^β , W '(CHR ^β CH ₂ O) _y R ^β , W' (CH ₂ NR ^β ) _y R ^β , W '(CH ₂ CH ₂ NR ^β ) _y R ^β , W' ((CH ₂ ) ₄ O ) _y R ^β , W'halogen, W'NO ₂ , W'COR + or W'CN,
where in the radicals R ^α and R ¹ to R ¹⁰ one or more hydrogen atoms may be replaced by fluorine,
W and W 'are independently single bonds or bridges of 1 to 20 carbon atoms, which may be part of a cyclic or aromatic group and may be interrupted by heteroatoms,
where W can also be a polyoxyalkylene or polyalkyleneimine bridge having at least 21 carbon atoms,
R ^{β is} hydrogen, C 1-20 -alkyl, carbonylalkyl, cycloalkyl or aryl,
M ⁺ cation equivalent,
X ^- anion equivalent,
y number from 1 to 240,
where two geminal radicals R ¹ to R ¹⁰ can form an oxo group and one or more of the radicals R ^α and R ¹ to R ^{10 can have} an additional trivalent phosphorus or nitrogen grouping capable of coordination,
in each case two vicinal radicals can be connected to fused aliphatic or aromatic rings,
where two vicinal radicals R ¹ to R ^{10 can} also be a chemical bond,
wherein two or more bridges W can also be present in the compounds of general formula III and in which the atoms of the phosphacyclohexane rings not bonded to the bridge (s) W can also be substituted as defined for R ¹ to R ¹⁰ ,
wherein in the compounds of the formula II also one of the radicals R ^α or R ¹ to R ¹⁰ and in the compounds of the formula III also one of the radicals R or R ¹ to R ⁸ or the two radicals R ^α together or a group W also for a polymer radical having a number average molecular weight in the range of 500 to 50,000, composed of repeating units derived from monomers selected from mono- and diolefins, vinylaromatics, esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C ₁ C ₃₀ alkanols, N-vinylamides, N-vinyl lactams, ring-opening polymerizable heterocyclic compounds and mixtures thereof.

mit der Bedeutung:
R¹¹ bis R¹⁹
unabhängig voneinander Wasserstoff, C₁-C₂₀-Alkyl, C₇-C₂₀-Aralkyl, C₇-C₂₀-Alkaryl, C₆-C₁₂-Aryl, wobei eines oder mehrere Kohlenstoffatome durch Heteroatome ersetzt sein können, W'COO^–M⁺, W'SO₃ ^–M⁺, W'PO₃ ^2–M⁺ ₂, W'NR^β ₃ ⁺X^–, W'OR^β, W'NR^β ₂, W'COOR^β, W'SR_β, W'(CHR^βCH₂O)_yR^β, W'(CH₂NR^β)_yR^β, W'(CH₂CH₂NR^β)_yR^β,
wobei jeweils zwei vicinale Reste R¹¹ bis R¹⁵ und/oder R¹⁷ und R¹⁸ und/oder R¹⁶ und R¹⁷ und/oder R¹⁶ und R¹⁹ und/oder R¹⁸ und R¹⁹ zu Ringen verbunden sein können,
W' Einfachbindung oder Brücke mit 1 bis 20 Kohlenstoffatomen, die Bestandteil einer cyclischen oder aromatischen Gruppe sein kann,
R^β Wasserstoff oder C₁-C₆-Alkyl,
M⁺ Kation,
X^– Anion,
y Zahl von 1 bis 240,
wobei einer oder mehrere der Reste R¹¹ bis R¹⁹ eine zusätzliche, zur Koordination befähigte dreibindige Phosphor- oder Stickstoffgruppierung aufweisen können,
wobei R¹⁸ auch -W'-CR²⁰=CR²¹R²², wobei R²⁰, R²¹, R²² wie vorstehend für R¹¹ bis R¹⁹ definiert sind, bedeuten kann.Preferably, ligands of the general formula II are used, which are selected from the group of ligands of the general formula IV

with the meaning:
R ¹¹ to R ¹⁹
independently of one another are hydrogen, C ₁ -C ₂₀ -alkyl, C ₇ -C ₂₀ -aralkyl, C ₇ -C ₂₀ -alkaryl, C ₆ -C ₁₂ -aryl, where one or more carbon atoms may be replaced by heteroatoms, W'COO ^- M ⁺ , W'SO ₃ ^- M ⁺ , W'PO ₃ ² -M ⁺ ₂ , W'NR ^β ₃ ⁺ X ^- , W'OR ^β , W'NR ^β ₂ , W'COOR ^β , W'SR _β , W '(CHR ^β CH ₂ O) _y R ^β , W' (CH ₂ NR ^β ) _y R ^β , W '(CH ₂ CH ₂ NR ^β ) _y R ^β ,
wherein in each case two vicinal radicals R ¹¹ to R ¹⁵ and / or R ¹⁷ and R ¹⁸ and / or R ¹⁶ and R ¹⁷ and / or R ¹⁶ and R ¹⁹ and / or R ¹⁸ and R ^{19 may} be connected to rings,
W 'is single bond or bridge of 1 to 20 carbon atoms which may be part of a cyclic or aromatic group,
R ^{β is} hydrogen or C ₁ -C ₆ -alkyl,
M ⁺ cation,
X ^- anion,
y number from 1 to 240,
wherein one or more of R ¹¹ to R ^{19 may have} an additional trivalent phosphorus or nitrogen grouping capable of coordination,
wherein R ^{18 may} also be -W'-CR ²⁰ = CR ²¹ R ²² , wherein R ²⁰ , R ²¹ , R ^{22 are} as defined above for R ¹¹ to R ¹⁹ .

bevorzugt im erfindungsgemäßen Verfahren in der Hydroformylierungsstufe b) verwendet, in der die Gruppen Ar für gleiche oder verschiedene, vorzugsweise unsubstituierte oder C₁- bis C₄-Mono-Alkyl-substituierte Phenylgruppen und Alk für C₁- bis C₂₀-, vorzugsweise C₄- bis C₁₀-Alkylgruppen stehen, beispielsweise die Liganden der Formeln VI und VII

Of the ligands of the general formula IV in turn ligands of the type of the general formula V

preferably used in the process according to the invention in the hydroformylation stage b), in which the groups Ar are identical or different, preferably unsubstituted or C ₁ - to C ₄ -mono-alkyl-substituted phenyl groups and Alk is C ₁ - to C ₂₀ -, preferably C ₄ - to C ₁₀ -alkyl groups, for example the ligands of the formulas VI and VII

The mentioned ligands can be synthesized according to the methods given in WO 02/00699, to the full extent here Reference is made. For example, the phosphacyclohexane ligands of the formulas VI and VII by the addition of octene-1 to the phosphorus atom the corresponding aryl group-bearing phosphabenzene compounds in the presence of hydrogen and at elevated pressure.

The above-mentioned phosphacyclohexane compounds form, with rhodium compounds in the presence of CO / H ₂ mixtures, hydroformylation-active rhodium-carbonyl complexes of the formula RhL _o (CO) _p , where L is the respective phosphacyclohexane ligand and the indices o and p are whole Numbers from 1 to 3 are available. In the reaction medium of the hydroformylation under hydroformylation conditions, groups other than ligands, as a result of the mechanism of the hydroformylation reaction, can also be part of the hydroformylation-active rhodium complex, such as hydrido, alkyl and acyl groups.

Of the active carbonyl complex is usually made in situ from a rhodium salt or a rhodium complex compound, the ligand, hydrogen and Carbon monoxide formed; but he can also be made separately and be used.

Become the complex catalysts generated in situ, it is particularly preferred Precursor complexes such as rhodium acetylacetonate, rhodium (2-ethylhexanoate) or rhodium acetate in the presence of the corresponding phosphacyclohexane ligands one. Alternatively you can the Precursorkomplexe also in the presence of suitable Phosphacyclohexanvorstufen be used under the reaction conditions, the actual cocatalyst is formed.

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

The Hydroformylation takes place in known manner at temperatures from 50 to 250 ° C, preferably at temperatures of 80 to 150 ° C and pressures of 10 to 100 bar, preferably from 10 to 40 bar. Performing the reaction at higher temperatures and higher To press than the one indicated above is possible.

The Hydroformylation usually occurs in the presence of a 1- to 1000 times the molar excess, preferably a 2 to 100-fold excess of the ligand, based on the amount of transition metal used.

The reaction can be carried out in the presence of a solvent. Suitable examples are those which are selected from the group of ethers, supercritical CO ₂ , fluorocarbons or alkylaromatics, such as toluene and xylene. The solvent may also be a polar solvent. Suitable examples are those which are selected from the group of alcohols, dimethylacetamide, dimethylformamide or N-methylpyrrolidone. It is likewise possible to carry out the reaction in the presence of a high-boiling condensation product, for example of an oligomeric aldehyde, in particular in counter an oligomer of the aldehyde to be produced, which also acts as a solvent here. It is also possible to carry out the reaction in a two-phase mixture.

There the invention used Catalysts except their hydroformylation activity often too a certain activity in the hydrogenation of aldehydes, in addition to the aldehydes can also the alcohols corresponding to the aldehydes are formed as valuable products.

Of the Discharge of the hydroformylation stage is before its distillative Work-up relaxed. This is unreacted synthesis gas released, which can be attributed to the hydroformylation. The same applies to the unreacted to the gas phase during relaxation Olefin, which, optionally after distillative separation therein contained inert hydrocarbons, also in the hydroformylation to be led back can. The distillation of the relaxed hydroformylation output is generally pressed from 0.1 to 1000 mbar absolute, preferably from 1 to 500 mbar and especially preferably carried out from 10 to 400 mbar.

The Temperature and pressure set in the distillation have to, are dependent on the nature of the hydroformylation product and the distillation apparatus used. For the inventive method can In general, any distillation apparatus can be used. However, preference is given to using apparatuses which have low investment costs cause and one as possible allow low distillation temperature, such as thin film evaporator, wiper blade evaporator or falling-film evaporator, because with higher temperature, the formed Aldehydes in the reaction discharge Subsequent reactions such as aldol condensations can enter. Since this distillation essentially the separation of the hydroformylation aldehyde and alcohol and optionally still existing low boilers, such as unreacted olefin and inert, of high-boiling condensation products the aldehydes, so-called high boilers, and the catalyst and excess ligand serves, it may be appropriate the separated hydroformylation products and optionally olefins and Inert, another distillative purification based on conventional Manner performed can be subjected to. Thus, in particular, an accumulation still contained high boilers are avoided.

• a) der Destillationssumpf, der den Katalysator und überschüssigen Ligand enthält, insgesamt zurückgeführt werden, oder
• b) der Katalysator und überschüssiger Ligand mit einem Lösungsmittel, in dem der Katalysator und der überschüssige Ligand unlöslich oder nahezu unlöslich sind, ausgefällt und nur das Fällungsprodukt zurückgeführt werden, oder
• c) die im Destillationssumpf enthaltenen Hochsieder mittels Wasserdampfdestillation vom Katalysator und überschüssigem Liganden abgetrennt werden und nur der nach der Wasserdampfdestillation erhaltene Katalysator und überschüssige Liganden enthaltene Destillationssumpf in die Hydroformylierungsreaktion zurückgeführt werden, oder
• d) der Katalysator und überschüssiger Ligand durch Ultrafiltration des Destillationssumpfs gewonnen und das Retentat zurückgeführt werden, oder
• e) der Katalysator und überschüssiger Ligand durch Extraktion des Destillationssumpfs gewonnen werden, wobei z.B. zur Vermeidung einer Anreicherung von Hochsiedern im Kreislauf eine Kombination wenigstens zweier der Methoden a) bis e) möglich ist.

An advantage of the process according to the invention is the possibility of recycling the complex catalyst and the excess ligand from the distillation residue of the reaction mixture. It can either

• a) the total distillation bottoms containing the catalyst and excess ligand are recycled, or
• b) the catalyst and excess ligand are precipitated with a solvent in which the catalyst and excess ligand are insoluble or nearly insoluble, and only the precipitate is recycled, or
• c) the high boilers contained in the distillation bottoms are separated off from the catalyst and excess ligand by means of steam distillation and only the distillation bottoms contained after the steam distillation and excess ligands are returned to the hydroformylation reaction, or
• d) the catalyst and excess ligand are recovered by ultrafiltration of the distillation bottoms and the retentate is recycled, or
• e) the catalyst and excess ligand are obtained by extraction of the distillation bottoms, wherein for example a combination of at least two of the methods a) to e) is possible in order to avoid accumulation of high boilers in the circulation.

alternative may be to avoid accumulation of high boilers in the reaction mixture the hydroformylation also part of the distillation bottoms be removed from time to time and the other Work-up for recovery of rhodium and if desired fed to the ligand used become. In such an approach should be one of the discharged Amount of rhodium and ligand or a suitable ligand precursor, which under the reaction conditions of the hydroformylation the the actual ligand forms, corresponding amount of these compounds by feeding these compounds into the hydroformylation reaction added become.

Method a)

Preference is given to those phosphacyclohexane ligands which have such a high boiling point that in the distillation of the reaction output, 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 of this distillation can be recycled together with fresh olefin in the reaction.

This Process leads surprisingly to excellent results in the hydroformylation with distillative Work-up of the reaction output, since the ligands to be used very good stabilizers for are the thermolabile catalyst and even a high thermal stability exhibit. Losses of the ligand and the transition metal component of the Catalyst can be largely avoided, even if a very inexpensive distillation with a low number of theoretical plates, e.g. thin film evaporator or falling film evaporator is used.

There in this variant of the process all high-boiling by-products get back into the reaction, enters a certain leveling up the high boiler and it may be necessary continuously or to make a discharge of high boilers in batches. This can e.g. by doing so, as described in more detail below Variants b) or c) at least temporarily a separation of the catalyst complex and the excess ligand from the distillation bottoms makes and containing the predominantly high boilers Remove the rest.

Method b)

Advantageous for this Method of precipitation the catalyst complex and the excess ligand is a solvent, that with the organic constituents of the distillation bottoms of the Reaction discharge is miscible in a wide range, but in which the catalyst complex and the ligand are insoluble or nearly insoluble, so that it is possible is, by selecting the type and amount of the solvent, the catalyst complex and to precipitate the ligand, after separation by decantation or filtration in the hydroformylation to be led back can.

When solvent comes a big one Number of polar solvents, especially hydroxy, carbonyl, carboxamide or ether groups have, ie alcohols, ketones, amides or ethers and mixtures this solvent or mixtures of these solvents with water into consideration.

The The type and amount of the solvent to be used can be determined by the person skilled in the art determine in detail by a few hand tests. In general is the amount of solvent preferably kept low so that the recovery effort as possible is low. Accordingly, in the rule, based on the volume of the distillation bottoms, the 1 to 50 times, preferably 3 to 15 times the amount needed.

Method c)

A Another method for discharging high-boiling condensation products the aldehydes consists of these from the bottom of the distillation Separate by steam distillation. The steam distillation of the distillation bottoms may be discontinuous, ie batchwise, or continuously, the steam distillation in the distillation apparatus itself or a separate device for steam distillation can be made. For example can in the discontinuous embodiment of the method of Distillation sump before its return in the hydroformylation by passing water vapor all or partially freed from high-boiling condensation products, or the distillation bottoms may be of time depending on the high boiler at present in a separate apparatus of a steam distillation be subjected.

The continuous embodiment of the method can e.g. done so that the distillation bottoms or a part of the distillation bottoms before his return in the hydroformylation continuously a steam distillation apparatus supplied and in it is wholly or partly freed from high-boilers. As well Is it possible, the distillative workup of the hydroformylation discharge of to operate continuously in the presence of steam at the outset, at the same time as the aldehyde and the alcohol and the high boilers from the catalyst and the excess ligand separate. It goes without saying that in such a Procedure in a subsequent fractionation and distillation apparatus the value product of high boilers and possibly divorced from water Need to become.

The steam distillation is generally carried out in a conventional manner by introducing steam into the high boiler-containing distillation bottoms and subsequent condensation of the steam distillate. Advantageously, the steam is passed through the distillation bottoms so that it does not condense in the distillation bottoms. This can be effected by selecting the pressure and / or temperature conditions under which the steam distillation is carried out. It can be both reduced pressure be used or when using superheated steam and elevated pressure. In general, the 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. In this case, the water vapor with respect to the high-boiling condensation products of 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 completion of the steam distillation of the so completely or partially freed of high boilers catalyst and excess ligand containing distillation bottoms can be recycled to the hydroformylation.

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

Method d)

As a result the difference in the molecular weights of the catalyst complexes and excess ligands on the one hand and the high boilers remaining in the distillation bottoms on the other hand, it is also possible Catalyst complexes and ligands by ultrafiltration of the high boilers separate. This amounts to the average molecular weight of the ligand is preferably more than 500 Dalton, more preferably more than 1000 daltons.

The Method can be operated continuously or discontinuously. Embodiments of such methods are described in WO 99/36382, which is referred to here.

To a suitable continuous mode of operation are the educts reacted in the presence of the catalyst and ligand in a reactor. The reactor discharge is in a distillation apparatus in a Distillate stream containing the oxo products and in a residue separated. The catalyst-containing residue becomes continuous fed to a membrane filtration. This is the residue, high boilers (or a mixture of high boilers, educts and oxo products), Contains catalyst and ligands, worked up. The high boilers (and optionally educts and oxo products) permeate through the membrane. The high boiler (and possibly on educts and oxo products) depleted and on catalyst and Ligand-enriched retentate is added to the hydroformylation recycled.

To a suitable discontinuous mode of operation are the educts reacted in the presence of the catalyst and ligand in a reactor. At the end of the reaction, the reactor discharge is in a distillation apparatus in a distillate stream containing the oxo products, and in a residue stream separated. This catalyst-containing residue from the distillation is worked up in a membrane filtration. The high boiler (and optionally on starting materials and oxo products) depleted and Catalyst and ligand enriched distillation residue will be at the end of ultrafiltration in the reactor for the next batch the hydroformylation recycled.

The Ultrafiltration can be one-stage or multi-stage (preferably two-stage) operate. In each stage, the feed solution is added e.g. by means of a pressure pump brought to filtration pressure; the overflow, d. H. Wetting, the Membrane can then be returned by recycling a Part of the retentate be ensured in a second pump. To a significant top layer structure of the catalyst the membrane surface to avoid (concentration polarization), which leads to a decrease lead the permeate flow may be between membrane and the catalyst-containing solution is preferably maintained a relative speed in the range of 0.1 to 10 m / s. Further suitable measures To avoid a topcoat construction, e.g. mechanical movement the membrane or the use of agitators between the membranes. In the multi-stage variant of the permeate stream of a stage of fed downstream stage and the retentate this downstream Stage of the previous stage forwarded. Through this workup The permeate is a better retention reach the catalyst and the ligand.

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

The optimum transmembrane pressures between 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, between 0.5 to 100 bar, preferably 10 to 60 bar and at a temperature up to 200 ° C. Higher transmembrane pressures and higher temperatures lead to higher permeate fluxes. The overflow velocity in the module is usually 1 to 10, preferably 1 to 4 m / s. The catalyst concentration in the feed solution to the membrane is preferably 5 to 2000 ppm.

For the ultrafiltration, all membranes are suitable which are stable in the reaction system. The separation limit of the membranes is about 200 to 20,000 daltons, especially 500 to 5000 daltons. The separation layers can be made 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 usually applied to a single or multilayer porous substructure of the same or even several different materials as the separating layer. Examples are:

The Membranes can in flat, tube, multi-channel element, capillary or winding geometry be used for the corresponding pressure housing, the separation between retentate (catalyst-containing) and the Permeate (catalyst-free filtrate) are available.

• UF: Ultrafiltration;
• NF: Nanofiltration

The following tables list examples of such membranes.

• UF: ultrafiltration;
• NF: nanofiltration

Method e)

When Another variant may also be initially a distillative separation of the aldehydes / alcohols are carried out whereupon the catalyst-containing bottoms with a polar extractant such as. Water is treated. The catalyst enters the polar phase over, while High boilers remain in the organic phase. Preferably According to this variant, catalysts with water-soluble (hydrophilic) ligands or with ligands which can be converted into a water-soluble form, used. The catalyst can be recovered by reextraction or directly as such. Alternatively, you can the catalyst is extracted by a nonpolar solvent, whereupon the high boilers are separated.

As an alternative to a distillative work-up process, the work-up of the reaction effluent can also be carried out by extraction. Depending on the nature of the catalyst used, a polar or non-polar solvent which is substantially immiscible with the reaction effluent or with at least one of the solvents optionally present in the reaction effluent is added to the reaction effluent. If desired, a two-phase mixture of at least one polar and at least one nonpolar solvent may also be added to the reaction effluent for extraction. In the case of a two-phase reaction, the addition of a further solvent can be dispensed with as a rule. After phase separation in a suitable apparatus, a phase containing the hydroformylation products and higher boiling condensation products and a phase containing the catalyst are obtained. Particularly suitable polar phases are water and ionic liquids, ie salts which have a low melting point. In such a hydroformylation process, preference is given to using phosphacyclohexane ligands containing ionic or polar groups, so that a high solubility of the catalyst in the polar phase results and a leaching of the catalyst into the organic phase is prevented or at least substantially prevented. Examples of suitable substituents are W'COO ^- M ⁺ , W'SO ₃ ^- M ⁺ , W'PO ₃ ^2- M ²⁺ , W'NR ^β ₃ ⁺ X ^- , W'OR ^β , WNR ^β ₂ , W'COOR ^{β, β} W'SR, W '(CHR ^β CH ₂ O) _y R ^β, W' (CH ₂ NR ^β) _y R ^β and W '(CH ₂ CH ₂ NR ^β) _y R ^β, where X ^-, M ⁺ , R ^β , W 'and y have the meanings given above.

phosphacyclohexanes with non-polar residues can also with a nonpolar solvent be removed by phase separation. Particularly suitable are phosphacyclohexanes with lipophilic residues. In this way you can do a "leaching" of the catalyst at least prevent as far as possible.

In a preferred embodiment The workup of the reaction mixture can also directly over a Ultrafiltration done. In this case, the separation of the catalyst and recovering a catalyst-free product or high boiler stream the synthesis effluent, as described above, under pressure with a Membrane brought into contact and permeate (filtrate) on the back the membrane deducted at a lower pressure than on the feed side. You get a catalyst concentrate (retentate) and a virtually catalyst-free Permeate.

If the synthesis effluent directly to the membrane process with the synthesis pressure supplied The transmembrane pressure can be increased by increasing the permeate pressure be set.

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

The hydroformylation of the C ₈ to C ₂₀ olefin dimers prepared by the process according to the invention is carried out significantly faster by means of the phosphacyclohexane ligand-modified rhodium hydroformylation catalysts to be used than to olefin dimers of the same carbon number prepared by conventional Brönsted acid or nickel-containing dimerization catalysts were.

This results in several advantages:
Compared to previous methods, a smaller reaction space in the hydroformylation step is sufficient for the same amount of product due to the higher space-time yield, resulting in lower investment costs. Moreover, due to the higher olefin reactivity, shorter residence times can be set, resulting in a reduction in high boiler formation.

The hydrogenation of the C ₉ to C ₂₁ aldehyde / alcohol mixtures obtained in accordance with the invention to give the corresponding alcohols can be carried out in a manner conventional per se with hydrogenation catalysts of the prior art. In general, there is no limitation on the applicability of the prior art hydrogenation catalysts in the process of the present invention. Preferably, the hydrie tion in the present process in the liquid phase in the presence of a heterogeneous hydrogenation catalyst and gaseous hydrogen carried out.

suitable Hydrogenation catalysts are generally transition metals, e.g. Cr, Mo, W, Fe, Rh, Co, Ni, Pd, Pt, Ru, etc. or mixtures thereof to increase the activity and stability on carriers, such as. Activated carbon, alumina, diatomaceous earth, etc. are applied can. To increase the catalytic activity can Fe, Co and preferably Ni, also in the form of the Raney catalysts or be used as a metal sponge with a very large surface. Prefers is for the preparation in the process according to the invention a Co / Mo catalyst used. The hydrogenation of the aldehydes takes place dependent on from the activity the catalyst preferably at elevated temperatures and elevated pressure. Preferably, the hydrogenation temperature is about 80 to 250 ° C, preferably the pressure is about 50 to 350 bar.

The Hydrogenation can be carried out by the sump or trickle method, the Hydrogen gas in cocurrent or countercurrent through you reaction mixture guided can be. Can be advantageous for example, the hydrogenation process according to DE-A 1 941 633, DE-A 2 040 501 and EP-A 319 208 are used.

Out the reaction mixture obtained after the hydrogenation can according to usual, the cleaning process known to those skilled in the art, in particular by fractionated Distillation, the inventively prepared Alcohols are recovered pure.

The The following examples are given by way of example of the invention and have no limiting character with respect to Scope of application of the method according to the invention.

Examples:

General Experiment description for implementation the dimerization experiments A pressure-resistant reactor with effective emotion was purged with nitrogen and with catalyst and solvent filled. Thereafter, either a liquid Olefin or olefin mixture added or a gaseous olefin or Pressed olefin mixture. It was pressed on a bar pressure nitrogen and subsequently the reaction contents brought to reaction temperature. After expiration the reaction time was turned off the heater and the reactor at Reaching relaxed from room temperature. The reaction was under protective gas transferred to another vessel and controlled there at 10 to 15 ° C with 10% hydrochloric acid hydrolyzed. After phase separation, the organic phase was gas chromatographed analyzed and the dimer fraction by fractional distillation purely won.

Example 1: Dimerization of raffinate II

93.9 g raffinate (25.8% 1-butene, 50.2% 2-butene, 2.3% isobutene, 21.7 % Butanes) were mixed with 1.0 g of lithium aluminum hydride in 14 ml of heptane implemented. After 15 hours at 250 ° C, the reaction was terminated: conversion Butenes 68%; relationship Dimer / trimer = 4.7; Proportion of 2-ethyl-1-hexene 72%; Share twice or higher branched Dimers 2.1%; ISO index 0.94.

Example 2: Dimerization of raffinate II

1550 Raffinate II (25.8% 1-butene, 50.2% 2-butene, 2.3% isobutene, 21.7 % Butanes) were reacted with 50.0 g of triethylaluminum in 450 ml of heptane. After 22 h at 200 ° C the reaction was terminated: butene turnover 48%; Ratio dimer / trimer = 9.4; Proportion of 2-ethyl-1-hexene 72%; Proportion twice or more branched Dimers 2.5%; ISO index 0.96.

In Table 1 below shows the isomer distributions the dimerization of raffinate II to octene by the methods of US-A 4398049 - dimerization by means of a homogeneous nickel catalyst, DE-A 4339713 - dimerization by means of a heterogeneous nickel catalyst and the dimerization according to the invention compared with aluminum-organic catalysts.

Table 1: Isomer distribution

The Compounds of the table can be seen that the inventive method slightly hydroformylatable olefin dimers having a high content of terminal double bonds and a small proportion of poorly hydroformylatable dimethylhexenes supplies. The olefin dimers produced by the process according to the invention thus differ significantly in their isomer distribution of available by means of nickel catalysis Olefin dimers.

Example 3: Dimerization from 3-witches

100.2 g of 3-hexene was added with 3.0 g of triethylaluminum in 10 ml of heptane Reaction brought. After 22 h at 220 ° C, the reaction was terminated: Conversion 3-hexene 44%; relationship Dimer / trimer = 5.8; Proportion of 2-butyl-1-octene 69%; ISO index 1.03.

General experimental description to carry out hydroformylation experiments

Catalyst and solvent were mixed under nitrogen in a Schlenk tube. The resulting solution was transferred to a 70 ml or 100 ml autoclave purged with CO / H ₂ (1: 1). At room temperature, 5 bar of CO / H ₂ (1: 1) were pressed on. With vigorous stirring with a gassing stirrer, the reaction mixture was heated to the desired temperature over a period of 30 minutes. The olefin used was then pressed through a lock into the autoclave with CO / H ₂ overpressure. Then the desired reaction pressure was set immediately by means of CO / H ₂ (1: 1). During the reaction, the pressure in the reactor was maintained at the set pressure level by repressurizing CO / H ₂ via a pressure regulator. After completion of the reaction, the autoclave was cooled, depressurized and discharged. Analysis of the reaction mixture was performed by GC using correction factors.

Example 4: Low pressure hydroformylation of reactive isooctene

According to WO 02/00669, a catalyst solution starting from 0.90 g of rhodium dicarbonyl acetylacetonate, 10 g of 2,6-bis (2,4-dimethylphenyl) -4-phenylphosphabenzol and 120 ml of 1-octene in 50 ml of toluene at 160 ° C, 80 bar H ₂ and 3 d reaction time produced. The resulting solution was evaporated in an oil pump vacuum to dryness and the residue was taken up in 70 ml of toluene.

0.76 g of this catalyst solution was then evaporated to dryness in an oil pump vacuum. Starting from the remaining catalyst residue, 21.1 g (188 mmol) of reactive isooctene from Example 1 and 22.6 g of Texanol ^{® were} obtained at 110 ° C and 20 bar CO / H ₂ according to the general experiment, the results listed in Table 2.

Example 5: Medium pressure hydroformylation of reactive isooctene

According to WO 02/00669, a catalyst solution starting from 0.88 g of rhodium dicarbonyl acetylacetonate, 13 g of 2,6-bis (2,4-dimethylphenyl) -4-phenylphosphabenzol and 120 ml of 1-octene in 50 ml of xylene at 160 ° C, 80 bar H ₂ and 3 d reaction time produced. 0.94 g of the resulting catalyst solution was then evaporated to dryness in an oil pump vacuum. Starting from the remaining catalyst residue, 1.8 mg of rhodium dicarbonyl acetylacetonate, 24.5 g (218 mmol) of reactive isooctene from Example 2 and 24.6 g of Texanol ^{® were} obtained at 110 ° C and 80 bar CO / H ₂ according to the general experiment in Table 2 led results.

Example 6: Low pressure hydroformylation of reactive isooctene

According to WO 02/00669, a catalyst solution starting from 0.88 g of rhodium dicarbonyl acetylacetonate, 13 g of 2,6-bis (2,4-dimethylphenyl) -4-phenylphosphabenzol and 120 ml of 1-octene in 50 ml of xylene at 160 ° C, 80 bar H ₂ and 3 d reaction time produced. 0.94 g of the resulting catalyst solution was then evaporated to dryness in an oil pump vacuum. Starting from the remaining catalyst residue, 1.9 mg of rhodium dicarbonyl acetylacetonate, 24.7 g (220 mmol) of reactive isooctene from Example 2 and 24.6 g of Texanol ^® was obtained at 140 ° C and 20 bar CO / H ₂ according to the general experiment results listed in Table 2.

Example 7: Low pressure hydroformylation of reactive isooctene

According to WO 02/00669, a catalyst solution starting from 0.90 g of rhodium dicarbonyl acetylacetonate, 10 g of 2,6-bis (2,4-dimethylphenyl) -4-phenylphosphabenzol and 120 ml of 1-octene in 50 ml of xylene at 160 ° C, 80 bar H ₂ and 3 d reaction time produced. The resulting solution was evaporated in an oil pump vacuum to dryness and the residue was taken up in 70 ml of toluene. 0.33 g of this cata- gate solution were then evaporated in an oil pump vacuum to dryness. Starting from the remaining catalyst residue, 4.6 mg of rhodium dicarbonyl acetylacetonate, 24.1 g (215 mmol) reactive isooctene from Example 1 and 24.7 g of Texanol ^® was obtained at 140 ° C and 80 bar CO / H ₂ according to the general experimental procedure the results listed in Table 2.

Comparative Example 1 Low pressure hydroformylation of reactive isooctene

Starting from 7.5 mg (0.029 mmol) of rhodium dicarbonyl acetylacetonate, 0.167 g (0.59 mmol) Tricylohexylphosphan, 24.9 g (222 mmol) reactive isooctene from Example 2 and 24.8 g of Texanol ^® was obtained at 140 ° C and 20 bar CO / H ₂ according to the general experiment, the results listed in Table 3.

Comparative Example 2: Low pressure hydroformylation of isooctene

According to WO 02/00669, a catalyst solution starting from 0.88 g of rhodium dicarbonyl acetylacetonate, 13 g of 2,6-bis (2,4-dimethylphenyl) -4-phenylphosphabenzol and 120 ml of 1-octene in 50 ml of xylene at 160 ° C, 80 bar H ₂ and 3 d reaction time produced. 0.88 g of the resulting catalyst solution was then evaporated to dryness in an oil pump vacuum. Starting from the remaining catalyst residue, 1.3 mg of rhodium dicarbonyl acetylacetonate, 21.5 g (192 mmol) of iso-octene (obtained by nickel-catalyzed dimerization of n-butenes, iso-index of 1.06) and 23.2 g of Texanol ^® was obtained at 110 ° C and 20 bar CO / H ₂ according to the general experiment, the results listed in Table 3.

Comparative Example 3 Medium pressure hydroformylation of isooctene

According to WO 02/00669, a catalyst solution starting from 0.88 g of rhodium dicarbonyl acetylacetonate, 13 g of 2,6-bis (2,4-dimethylphenyl) -4-phenylphosphabenzol and 120 ml of 1-octene in 50 ml of xylene at 160 ° C, 80 bar H ₂ and 3 d reaction time produced. 0.94 g of the resulting catalyst solution was then evaporated to dryness in an oil pump vacuum. Starting from the remaining catalyst residue, 1.8 mg of rhodium dicarbonyl acetylacetonate, 24.8 g (221 mmol) of iso-octene (obtained by nickel-catalyzed dimerization of n-butenes, iso-index of 1.06) and 24.8 g of Texanol ^® was obtained at 110 ° C and 80 bar CO / H ₂ according to the general experiment, the results listed in Table 3.

Comparative Example 4 Medium pressure hydroformylation of isooctene

According to WO 02/00669, a catalyst solution starting from 0.88 g of rhodium dicarbonyl acetylacetonate, 13 g of 2,6-bis (2,4-dimethylphenyl) -4-phenylphosphabenzol and 120 ml of 1-octene in 50 ml of xylene at 160 ° C, 80 bar H ₂ and 3 h reaction zone Herge provides. 0.89 g of the catalyst solution obtained were then evaporated to dryness in an oil pump vacuum. Starting from the remaining catalyst residue, 1.7 mg of rhodium dicarbonyl acetylacetonate, 24.7 g (220 mmol) of iso-octene (obtained by nickel-catalyzed dimerization of n-butenes, iso-index of 1.06) and 24.7 g of Texanol ^® was obtained at 140 ° C and 20 bar CO / H ₂ according to the general experiment, the results listed in Table 3.

Comparative Example 5: Medium pressure hydroformylation of isooctene

According to WO 02/00669, a catalyst solution starting from 0.15 g of rhodium dicarbonyl acetylacetonate, 1.5 g of 2,6-bis (2,4-dimethylphenyl) -4-phenylphosphabenzol and 10 ml of 1-octene in 10 ml of toluene at 160 ° C. , 60 bar H ₂ and 5 d reaction time. 0.54 g of the resulting catalyst solution was then evaporated to dryness in an oil pump vacuum. Starting from the remaining catalyst residue, 4.3 mg of rhodium dicarbonyl acetylacetonate, 24.8 g (221 mmol) of iso-octene (obtained by nickel-catalyzed dimerization of n-butenes, iso-index of 1.06) and 25.0 g of Texanol ^® was obtained at 140 ° C and 80 bar CO / H ₂ according to the general experiment, the results listed in Table 3.

Claims (4)

Process for the preparation of compositions of primary, aliphatic alcohols with 9 to 21 Carbon atoms comprising the steps of a) catalytic dimerization internal and / or terminal double bonds containing monoolefins having 4 to 10 carbon atoms, b) the hydroformylation of the obtained Olefindimerzusammensetzung by means of a CO / H ₂ mixture in the presence of a homogeneously dissolved in the reaction medium hydroformylation catalyst, and c) the catalytic hydrogenation of the aldehyde composition obtained in stage b) to the corresponding alcohols, characterized in that in step a) the dimerization of the monoolefins by means of a catalyst of one or more compounds of general formula I AlR _x (OR ') _3-x I in which R and R 'are identical or different and are C ₁ - to C ₁₀ -alkyl groups and the index x is zero or an integer from 1 to 3, takes place at a temperature of 160 to 260 ° C, and in the Step b) the hydroformylation in the presence of a complex of rhodium dissolved in the reaction medium with a phosphacyclohexane group-containing ligand, free ligand and in the presence or absence of a solvent at a temperature of 50 to 250 ° C and at a pressure of 10 to 100 bar. Method according to claim 1, characterized in that that is dimerized a mixture of 1- and 2-olefins. Process according to claims 1 and 2, characterized that the olefin dimer has an ISO index of 0.8 to 1.0. Process according to Claim 1, characterized in that a catalyst of the general formula I AlR _x (OR ') _3-x I is used, in which the index x is the number 3, and R is an ethyl group or an alkyl group, with a number of carbon atoms which corresponds to the number of carbon atoms of the olefin to be dimerized.