DE10108476A1 - Process for the preparation of aldehydes - Google Patents

Abstract

The invention relates to an improved method for hydro formylation of olefinically unsaturated compounds in the presence of a rhodium complex compound, which contains novel xanthene-skeleton based on diphosphines, and a rhodium-containing a catalyst for hydro formylation and one xanthene skeleton based diphosphine. The novel method is particularly suitable for hydro formylation of internal olefin to straight-chained aldehydes.

Description

The invention relates to an improved process for hydroformylation olefi niche unsaturated compounds in the presence of at least one rhodium connection, the new diphosphines based on the xanthene structure as a ligan that contains.

It is known that compounds which contain olefinic double bonds with carbon monoxide and hydrogen to form aldehydes (Oxosyn thesis). The process is not based on the use of olefinic hydrocarbons limited, but also extends to raw materials other than that Double bond still have functional groups, mainly those that remain unchanged under the reaction conditions.

Classic oxosynthesis works with cobalt as a catalyst. Its effect Samkeit is based on the formation of cobalt carbonyl compounds under the Exposure to hydrogen and carbon monoxide at pressures above 20 MPa and temperatures of about 120 ° C and more on metallic cobalt or cobalt compounds.

In the course of the further development of oxo synthesis, cobalt became increasingly replaced by rhodium as catalyst metal. Rhodium is used as a complex compound  used that, in addition to carbon monoxide, preferably phosphines Contains ligands. Rhodium as a metal allows it to close at low pressures work, moreover, higher yields are achieved and preferred formed more valuable unbranched products for further processing, if one assumes straight-chain terminal olefins.

Such a process is known from US-A-3,527,809 under the designation Never derdruck rhodium process known. An improvement on this process discloses US-A4,148,830. According to this procedure, the Kataly catalyst life and the yield of linear aldehydes are increased, if one before as a solvent for the catalyst and in excess Phosphine is the high-boiling condensation products of the structures ten aldehydes used. The removal of insoluble Rhodi avoid reconnections and the dissolved catalyst can be used in many Reuse catalytic cycles without a decrease in activity vity observed. The method known from US-A-4,148,830 is also known as "Hydroformylation process with liquid recycle" referred to.

Such a process variant is of particular importance in which the hydroformylation reaction is carried out under such conditions, in which internal olefins with high selectivity in the straight-chain Aldehydes are transferred, since the straight-chain aldehydes are often the ge Desired products are and as starting compounds for the Hydrofor Mylation mixtures of terminal and internal olefins who used the. Such a technically available olefin mixture is, for example referred to as raffinate-II butene-I / butene-II mixture. The transfer of internal olefins in the straight-chain aldehydes with high selectivity is known from EP-B1-0 213 639. Special ligands are used here Diphosphite used.

However, the widespread use of diphosphite ligands is reflected in their im Lower stability and higher compared to conventional phosphine ligands  Hydrolysis sensitivity to traces of water and acid turned on limits and that during the continuously operated hydroformyly Formation process phosphonous acids can be harmful to the Rhodium complex catalyst impact and thus to shorten the Lead catalyst life. You therefore have to get out of the pro be removed z. B. by treating the catalyst Solution with an alkaline ion exchanger before being returned to the Hydroformylation.

Another process for the hydroformylation of olefinic compounds with internal double bonds, which the straight-chain aldehydes with provides acceptable selectivities is known from DE-A1-198 38 742. In the however, diphosphine ligands disclosed in this document show only one relatively low solubility in organic solvents. For the however, technical implementation of hydroformylation reactions is one sufficient ligand solubility under reaction conditions absolutely necessary. One already observes in discontinuous processes with insufficient solubility deposits. Such deposits can in continuously operated processes in the reactor to blockages in Lead pipes and filters.

It was therefore the task to develop a process that it under economically acceptable conditions allowed, olefinically unsaturated ver bonds with high sales and high selectivity in the ge to transfer wheel-chain aldehydes, even when used as an insert substances for hydroformylation compounds with internal double bonds or mixtures of compounds with terminal and internal Double bonds can be used. Furthermore, it has to be provided Process an advantageously long catalyst life even over many Ka to show analysis cycles.  

The invention therefore consists in a process for the hydroformylation of olefinically unsaturated compounds with carbon monoxide and hydrogen at temperatures from 50 to 160 ° C. and pressures from 0.2 to 20.0 MPa in the presence of complex compounds containing rhodium and diphosphines, characterized in that that as diphosphines compounds of general formula I

in which R ¹ and R ^{2 are} each the same or different (C ₁ -C ₁₈ ) alkyl radicals, (C ₆ -C ₁₄ ) aryl radicals, (C ₇ -C ₂₄ ) aralkyl radicals or (C ₇ -C ₂₄ ) -alkylaryl radicals, R ^{3 represents} hydrogen or a radical -CHR ^a R ^b , in which R ^a and R ^{b are} each the same or different hydrogen, (C ₁ -C ₁₈ ) -alkyl-, (C ₁ -C ₈ ) alkoxy residues, unsubstituted or substituted with (C ₁ -C ₁₀ ) alkyl and / or (C ₁ -C ₁₀ ) alkoxy residues (C ₆ -C ₁₄ ) aryl residues or Are (C ₇ -C ₂₄ ) aralkyl residues, and R ^{4 are} (C ₁ -C ₁₀ ) alkyl residues, (C ₆ -C ₁₄ ) aryl residues, (C ₇ -C ₂₄ ) aralkyl residues Radicals or (C ₇ -C ₂₄ ) alkylaryl radicals can be used.

These diphosphines are derived from the xanthene structure as a base and attached oxaphosphine rings. The diphosphines of the general  Formula I and its manufacturing process is the subject of the same day Patent application filed to the hereby expressly referenced men will ("incorporated by reference").

Among the diphosphines of the general formula I, those diphosphines are particularly suitable in which R ¹ and R ^{2 are} each the same or different (C ₁ -C ₁₂ ) alkyl radicals, (C ₆ -C ₁₀ ) aryl radicals, (C Are ₇ -C ₁₀ ) aralkyl radicals or (C ₇ - C ₁₀ ) alkylaryl radicals,
R ^{3 represents} hydrogen or a radical -CHR ^a R ^b , in which R ^a and R ^{b are} each the same or different hydrogen, (C ₁ -C ₁₂ ) alkyl, (C ₁ -C ₄ ) alkoxy radicals, unsubstituted or with (C ₁ -C ₈ ) alkyl and / or (C ₁ -C ₄ ) alkoxy radicals substituted (C ₆ -C ₁₀ ) aryl radicals or (C ₇ -C ₁₀ ) aralkyl radicals Are residues, and R ^{4 is} (C ₁ -C ₈ ) alkyl residues, (C ₆ -C ₁₀ ) aryl residues, (C ₇ -C ₁₀ ) aralkyl residues or (C ₇ -C ₁₀ ) - Represent alkylaryl radicals.

The aryl radical is preferably in each case the phenyl or the naphthyl radical, the benzyl radical is preferably used as the aralkyl radical.

For example, R ¹ and R ^{2 are the} same or different and are methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, tertiary butyl, n-pentyl, i-pentyl, n-hexyl, i-hexyl, n -Heptyl, i-heptyl, n-octyl, i-octyl, n-nonyl, i-nonyl, n-decyl, i-decyl, phenyl, naphthyl, tolyl or benzyl.
R ³ stands for example for methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, n-pentyl, i-pentyl, 3,3-dimethylbutyl, n-hexyl, i-hexyl, n-heptyl, i -Heptyl, n-octyl, i-octyl, n-nonyl, i-nonyl, n-decyl, i-decyl, phenyl, naphthyl, tolyl or benzyl.
R ⁴ stands for example for methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, tertiary butyl, n-pentyl, i-pentyl, 3,3-dimethylbutyl, n-hexyl, i-hexyl, n- Heptyl, i-heptyl, n-octyl, i-octyl, n-nonyl, i-nonyl, n-decyl, i-decyl, phenyl, naphthyl, tolyl or benzyl.

The following diphosphines are particularly suitable: 2,7-bis (3,3-dimethylbu tyl) -9,9-dimethyl-4,5-bis (2,7-dimethyl-10-phenoxaphosphino) xanthene (II), 2,7,9-trimethyl-9-n-nonyl-4,5-bis (2,7-dimethyl-10-phenoxaphosphino) - xanthene (III), 2,7-di-n-decyl-9,9-dimethyl-4,5-bis (2,7-dimethyl-10-phenoxa phosphino) xanthene (IV), 2,7-di-n-hexyl-9,9-dimethyl-4,5-bis (2,7-dimethyl-10- phenoxaphosphino) xanthene (V), 2,7- (3,3-dimethylbutyl) -9,9-dimethyl-4,5- bis [2,7-di (3,3-dimethylbutyl) -10-phenoxaphosphino] xanthene (VI), 2,7- Dimethyl-9,9-dimethyl-4,5-bis [2,7-di (3,3-dimethylbutyl) -10-phenoxaphos phino] xanthene (VII).  

The sufficient solubility of the diphosphines is of particular importance the general formula I in the usual organic solvents, so What is high is that under process conditions it also spans many catalytic cycles there is no precipitation of the ligand.

The solubility of the individual ligands does not follow any easily understandable laws. Surprisingly, it was found that the radicals R ³ on the two aromatic carbon rings of the xanthene skeleton in the general formula I can have a particularly strong influence on the solubility, while the introduction of the substituents R ⁴ on the phenoxa phosphine radical alone takes only one has very little influence on solubility.

The increase in carbon atoms is not a criterion on which the soluble behavior can be read. Also solubility of the xanthene scaffold without phenoxaphosphine substituents not on that Solubility behavior of the ligand with phenoxaphosphine substituents conclude.

The solubility behavior of the diphosphines of the general formula I and the diphosphines which are particularly suitable for the process according to the invention (II) to (VII) will be filed in the same day as the patent application acts, to which express reference is hereby made ("incorporated by reference ").

The new process is carried out in a homogeneous reaction system. The term homogeneous reaction system essentially stands for one Solvent, catalyst, olefinically unsaturated compound and reacti onproduct composed homogeneous solution.  

The higher-boiling solvents have proven to be particularly effective Condensation compounds of the aldehydes to be produced, in particular the trimers of the aldehydes to be produced, proved to be by-products arise in the hydroformylation, as well as their mixture with the produc lend aldehydes, so that another solvent addition is not essential is required. In some cases, however, a solvent addition may occur prove appropriate. Organic compounds are used as solvents gene used in which starting material, reaction product and cataly sator system are soluble. Examples of such compounds are aromatic Hydrocarbons such as benzene and toluene or the isomeric xylenes or Mesitylene. Other common solvents are paraffin oil, cyclohexane, n-hexane, n-heptane or n-octane, ethers such as tetrahydrofuran, ketones or Texanol® from Eastman. The proportion of solvent in the reaction medium can be varied over a wide range and is normal usually between 20 and 90% by weight, preferably 50 to 80% by weight, based on the reaction mixture.

It has surprisingly been found that when using the be claimed diphosphines of the general formula I one for the continuous sufficient reaction concentration in the hydroformylation of diphosphine in the organic solution can be adjusted. in particular in particular, the diphosphines II, IV, V and VI have an excellent solubility in organic solvents.

Those obtained from rhodium and diphosphines of the general formula I. Complex compounds can be used as uniform complex compounds or can be used as a mixture of different complex compounds. The Rhodium concentration ranges from 1 to 1000 ppm by weight and is preferably 50 to 500 ppm by weight. In particular rhodium is used in concentrations of 100 to 300 ppm by weight, in each case based on the homogeneous reaction mixture. The phosphorus (III) con concentration in the form of the diphosphines can be up to due to their solubility  a value of 4 mol P (III) per kilogram of homogeneous reaction solution be put. The phosphorus (III) content usually moves in the Re action mixture between 10-400 mmol P (III), preferably between 10- 100 mmol P (III) and in particular 10-50 mmol P (III) per kilogram of reacti onsgemisch.

The stoichiometrically composed rhodium Find complex compound application. However, it has proven to be useful proved the hydroformylation in the presence of a catalyst system Rhodium-diphosphine complex compounds and free diphosphine, i.e. H. to carry out excess diphosphine, which with rhodium no com plex connection received more. The free diphosphine can be the same as in the rhodium complex compound, but it can also from this various diphosphines can be used as ligands. The free ligand can be a single compound or different from a mixture ner diphosphines exist. It is preferable to use 1 per mole of rhodium up to 20 mol phosphorus in the form of the diphosphines, however, the molar fraction of phosphorus may also be higher. Due to the good solubility of the inventor diphosphines used in accordance with the invention can also have a higher molar ver Set a ratio of up to 80 mol phosphorus per mol rhodium. Zweckmäßi however, one works in some cases with lower molar ratios of up to 20 mol Phosphorus per mole of rhodium.  

When using

the molar ratio of rhodium to phosphorus was 1:15 proven.

The reaction pressure is in the range of 0.2 to 20.0 MPa. Especially be It has proven useful to pressures between 1 to 12 MPa and in particular between between 1 and 5 MPa. Implementation of the olefinically unsaturated Compounds with hydrogen and carbon monoxide are made at temperatures from 50 to 160 ° C, preferably 60 to 150 ° C and in particular 75 to 140 ° C.

The composition of the synthesis gas can vary over a wide range ren. In general, the molar ratio between carbon monoxide and hydrogen between 1:10 and 10: 1. Mixtures containing carbon monoxide and hydrogen in a molar ratio of 1: 2 and 2: 1 are be particularly suitable. In particular, it has proven to be useful to syn use thesegas with a slight molar excess of hydrogen.

Rhodium is used either as a metal or as a compound. In metallic form, it is used either as finely divided particles or deposited in a thin layer on a support such as activated carbon, calcium carbonate, aluminum silicate, or alumina. Suitable rhodium compounds are salts of aliphatic mono- and polycarboxylic acids, such as rhodium 2-ethyl hexanoate, rhodium acetate, rhodium oxalate, rhodium propionate or rhodium ummalonate. Furthermore, rhodium salts of inorganic hydrogen and oxygen acids, such as rhodium nitrate or rhodium sulfate, the various rhodium oxides or rhodium carbonyl compounds such as Rh ₃ (CO) ₁₂ or Rh ₆ (CO) ₁₆ or complex compounds of rhodium, e.g. B. Cyclopentadienylrhodiumverbindungen or rhodium acetylacetonate, are used. Rhodium halogen compounds are less suitable because of their corrosive behavior of the halide ions.

Rhodium oxide and in particular rhodium acetate and Rho are preferred dium-2-ethylhexanoate.

The catalyst is usually formed from the components rhodium or rhodium compound, the diphosphine or the diphosphines of all base formula I and synthesis gas under the conditions of Hydrofor mylation reaction in the reaction mixture. But it is also possible to use the Ka to preform the Talysator and then the actual one Hydroformylation stage. The conditions of preforming generally correspond to the hydroformylation conditions.

The implementation can be carried out batchwise or continuously leads. The reaction product is distilled off from the catalyst and can then be further processed, e.g. B. distilled. According to Ab separation of the aldehyde remaining distillates containing the catalyst Onsrückstand is, if necessary, after adding fresh catalyst and Ent part of the aldehyde condensate formed in the course of the reaction tion products returned to the hydroformylation stage.

The reaction of the olefinically unsaturated compounds in the presence of the Rhodium-diphosphine complex compounds according to the invention can each  after use olefin mixture until almost complete conversion occurred will be. Often, however, one strives for a partial turnover, around the Selekti vity of straight-chain aldehydes. The partial turnover has been natural to move within an economically justifiable framework and lies in generally between 65 and 80%, based on the olefins used. The hydroformylation process according to the invention gives the desired ones linear aldehydes with excellent selectivity. Furthermore, it stands out Catalyst system used according to the invention by a high catalyst gate life out. Observe even after performing many cycles of catalysis you pay attention to excellent sales figures with excellent selectivities to the straight-chain aldehydes.

The method according to the invention is particularly advantageously suitable for Hydroformylation of olefinically unsaturated compounds with internal end double bonds, although also starting compounds with terminal Digen double bonds used by the inventive method can be. Straight-chain or branched olefinic ones can also be used unsaturated compounds are used. In addition, the olefi nisch unsaturated compound still contain functional groups, which are not changed in the course of the reaction.

Polyunsaturated olefinic compounds can also be used, such as. B. 1,3-butadiene or 1,3-pentadiene, which in addition to an internal double bond also contains a terminal double bond. Mixtures of olefinically unsaturated compounds with terminal and internal double bonds are also suitable. In particular, the mixture of butene-1 and butene-2 available in the art, also referred to as raffinate-II, a butene-1-depleted raffinate II, which is also referred to as raffinate III, or an octene-2 and / or octene -3-containing C ₈ olefin mixture can be used as the starting compound by the process according to the invention. The process according to the invention is particularly suitable for hydroforming olefinically unsaturated hydrocarbons having 4 to 12 carbon atoms. Suitable olefinically unsaturated compounds are, for example, butene-2, mixtures containing butene-2 and butene-1, octene-3, undecene-3, hexene-2, heptene-3, dimeric butenes, trimerpropylene, technically available olefin mixtures such as Dimersol® or Octol® ,

The crude aldehyde mixture obtained by the process according to the invention cal is separated from the catalyst by distillation, if appropriate cleaned and processed. Depending on the subsequent Pro it is also possible to directly, the crude aldehyde mixture. H. without too additional cleaning step to implement further.

Another embodiment of the present invention relates to a method for the production of carboxylic acids, alcohols or amines from olefinically un saturated compounds, the olefinically unsaturated compounds hydroformylated by the process according to the invention and thus obtained NEN aldehydes oxidized to carboxylic acids in a manner known per se, to Al alcohols are reduced or reductively aminated to amines.

The oxidation of the olefinically unsaturated compounds according to the invention aldehydes obtained can in a conventional manner, for example wise by the oxidation of the aldehydes with atmospheric oxygen or oxygen according to the procedures such. B. in Ullmann's Encyclopedia of Industrial Che mistry, 5th edition, Vol. A5, p. 239, VCH publishing company, Weinheim, 1986 are shown.

The catalytic hydrogenation of the process according to the invention Aldehydes obtained from olefinically unsaturated compounds to give alcohol len can be done in a manner known per se, for example according to the method von Ullmann's Encyclopedia of Industrial Chemistry, 5th ed., Vol. A1, p. 279, VCH publishing company, Weinheim, 1985 or G. H. Ludwig, hydrocarbon Processing, March 1993, p. 67.  

The reductive amination of the aldehydes obtained from olefinically unsaturated compounds by the process according to the invention can be carried out in a manner known per se, for example according to Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, vol. A2, p. 1, VCH Verlagsgesellschaft, Weinheim, 1985 to be carried out. Both ammonia, primary C ₁ -C ₂₀ amines or secondary C ₂ -C ₂₀ amines can be used as starting compounds for the production of amines.

The new process is particularly suitable for the hydroformylation of mixtures containing butene-1 and butene-2, which are necessarily obtained in considerable quantities as refinery by-products in the production of automotive fuels and in the production of ethylene by thermal cracking of higher hydrocarbons. They are obtained from the C ₄ crack cuts of the pyrolysis product by extracting the butadiene with a selective solvent and then separating off the isobutene, preferably by converting it to methyl tert-butyl ether. The pyrolysis product freed from butadiene is referred to as raffinate I. If isobutene is also removed, this is referred to as raffinate II. Instead of extracting the butadiene, it can also be partially hydrogenated to butenes in the C ₄ crack cut. After the isobutene has been separated off, a butene-1 / butene-2 mixture is obtained, which can be converted into n-valeraldehyde with high selectivity by the new process. Depending on the reaction conditions and the composition of the butene mixture, the olefin conversions are up to 80%, the resulting aldehyde mixture containing up to 95% by weight of n-valeraldehyde.

A further embodiment of the process according to the invention consists in the production of isomeric decane carboxylic acids and isomeric decyl alcohols from a mixture containing butene-1 and butene-2, which is converted to C ₅ -aldehydes by the process according to the invention.

The crude C ₅ -aldehyde mixture is first aldolized in a conventional manner in the presence of basic catalysts. Pretreatment of the aldehydes, e.g. B. a special cleaning is not required. Alkaline carbonates or alkali metal hydroxides, in particular compounds of sodium or potassium and amines, preferably tertiary amines, such as triethylamine, tri-n-propylamine, tri-n-butylamine, are used as catalysts. One works at temperatures from 60 to 160 ° C, in particular 80 to 130 ° C and at normal pressure or at up to about 1 MPa increased pressure. The reaction time is a few minutes to several hours and depends in particular on the type of catalyst and the reaction temperature. Due to its higher reaction rate, n-valeraldehyde primarily aldolises with itself or with isomeric valeraldehydes to decenals, but condensation of 2-methylbutanal or isoveraldehyde with one another completely disappears into the background.

Depending on the hydrogenation conditions chosen, the C ₁₀ aldol mixture obtained by condensation can either be partially reduced to the decanal in the presence of palladium-containing catalysts or completely to the decyl alcohol. The partial hydrogenation to the decanal and the subsequent oxidation with air or atmospheric oxygen to the decan carboxylic acid takes place in a known manner, for example analogously to the process for the production of 2-ethylhexanoic acid known from Ullmanns Encyklopadie der Technischen Chemie, 4th edition 1975, volume 9, p. 144 , The decan carboxylic acid obtained has a high content of 2-propylheptanoic acid.

For complete hydrogen deposition on the decenal to decyl alcohol ar is processed in a manner known per se with conventional hydrogenation catalyst ren, such as B. with catalysts based on nickel, chromium or copper. Ov Liche, the hydrogenation temperature is between 100 and 180 ° C and Pressure between 1 and 10 MPa. That after cleaning by distillation Decyl alcohol mixture is suitable due to its high content of 2-Pro pylheptanol excellent as an alcohol component in phthalic esters, which as  Find plasticizers. Plasticizer based on the after Draw obtained decyl alcohol mixture according to the method of the invention is characterized by excellent cold properties.

The preparation of the phthalic acid esters is, for example, from Ullmann, Ency Klopadie der Technischen Chemie, 1979, Vol. 18, page 536 ff. It is expedient to use phthalic anhydride with the decyl alcohol mixture in a molar ratio of 1: 2 in one step. The reaction speed can by catalysts and / or by increasing the reaction temperature be raised. To shift the balance towards ester formation push, it is necessary to remove the water formed from the reaction remove mix.

The invention is explained in more detail in the examples below, however not limited to the described embodiments.

example 1

Implementation of a butene-2 rich olefin mixture with a composition tion of 38 vol .-% butanes, 5.9 vol .-% 1-butene and 55.8 vol .-% cis and trans 2-butenes with 2,7-bis (3,3-dimetyl-butyl) -9,9-dimethyl-4,5-bis- (2,7-di methyl-10-phenoxa-phosphino) -xanthene (II) as a diphosphine ligand.

A 1 l stainless steel autoclave equipped with a stirrer was fed 80 g / h of the butene-2-rich olefin mixture and 60 Nl / h of the same volume of CO / H ₂ mixture so that 10 Nl / h of exhaust gas could be removed from the reactor [Nl / h means 1 liter of exhaust gas in the normal state (20 ° C and 1 at) per hour]. At the same time, 1000 g of the catalyst solution were circulated through the reactor per hour. The rhodium-2-ethylhexanoate and 2,7-bis (3,3-dimethyl-butyl) -9,9-dimethyl-4,5-bis- (2,7-dimethyl-10-phenoxa-phosphino) used -xanthene (II) were previously dissolved in 1000 g of Texanol® from Eastman and 500 g of valeraldehyde and placed in the reactor. The hydroformation was carried out continuously over 168 hours. The further reaction parameters as well as conversion and selectivities are shown in Table 1.

Table 1

Hydroformylation of a butene-2 rich olefin mixture in the presence of the diphosphine (II)

Example 2

Implementation of raffinate II with a composition of 10.5% by volume Butanes, 63.2 vol .-% 1-butene and 21.2 vol .-% cis and trans 2-butenes with 2,7-bis (3,3-dimetyl-butyl) -9,9-dimethyl-4,5-bis- (2,7-dimethyl-10-phenoxa phosphino) xanthene (II) as a diphosphine ligand.

A 1 l stainless steel autoclave equipped with a stirrer was fed 133 g / h of raffinate II and 190 Nl / h of the same volume of CO / H ₂ mixture in such a way that 10 Nl / h of exhaust gas could be removed from the reactor. At the same time, 1000 g of the catalyst solution were circulated through the reactor per hour. The rhodium 2-ethylhexanoate used and 2,7-bis (3,3-dimethylbutyl) -9.9-dimethyl-4,5-bis- (2,7-dimethyl-10-phenoxa-phosphino) - xanthene (II) were previously dissolved in 1000 g of Texanol® from Eastman and 500 g of valeraldehyde and placed in the reactor. The hydroformation was also carried out continuously over 168 hours. The further reaction parameters as well as conversion and selectivities are shown in Table 2.

Table 2

Hydroformylation of raffinate-II in the presence of diphosphine (II)

As Example 1 shows, even butene-2-rich mixtures can be used Sche, which is also known as raffinate III, even with high sales high selectivity in the straight-chain n-valeraldehyde.

Claims (21)

1. Process for the hydroformylation of olefinically unsaturated compounds with carbon monoxide and hydrogen at temperatures from 50 to 160 and pressures from 0.2 to 20 MPa in the presence of rhodium and diphosphine-containing complex compounds, characterized in that compounds of the general formula I are used as diphosphines
in which R ¹ and R ^{2 are} each the same or different (C ₁ -C ₁₈ ) alkyl radicals, (C ₆ -C ₁₄ ) aryl radicals, (C ₇ -C ₂₄ ) aralkyl radicals or (C ₇ -C ₂₄ ) alkylaryl radicals,
R ^{3 represents} hydrogen or a radical -CHR ^a R ^b , in which R ^a and R ^{b are} each identical or different hydrogen, (C ₁ -C ₁₈ ) -alkyl-, (C ₁ -C ₈ ) -alkoxy-Re, unsubstituted or substituted with (C ₁ -C ₁₀ ) alkyl and / or (C ₁ -C ₁₀ ) alkoxy radicals (C ₆ -C ₁₄ ) aryl radicals or (C ₇ -C ₂₄ ) aralkyl Are and R ^{4 is} (C ₁ -C ₁₀ ) alkyl, (C ₆ -C ₁₄ ) aryl, (C ₇ -C ₂₄ ) aralkyl or (C ₇ -C ₂₄ ) -Alkylaryl residues are used. 2. The method according to claim 1, characterized in that in the general formula IR ¹ and R ^{2 are} each the same or different (C ₁ -C ₁₂ ) alkyl radicals, (C ₆ -C ₁₀ ) aryl radicals, ( Are C ₇ -C ₁₀ aralkyl radicals or (C ₇ -C ₁₀ ) alkylaryl radicals,
R ^{3 represents} hydrogen or a radical -CHR ^a R ^b , in which R ^a and R ^{b are} each identical or different hydrogen, (C ₁ -C ₁₂ ) -alkyl-, (C ₁ -C ₄ ) -alkoxy-Re, unsubstituted or (C ₁ -C ₈ ) alkyl and / or (C ₁ -C ₄ ) alkoxy radicals substituted (C ₆ -C ₁₀ ) aryl radicals or (C ₇ -C ₁₀ ) aralkyl- Are residues, and R ^{4 is} (C ₁ -C ₈ ) alkyl residues, (C ₆ -C ₁₀ ) aryl residues, (C ₇ -C ₁₀ ) aralkyl residues or (C ₇ - C ₁₀ ) - Represent alkylaryl residues. 3. The method according to claim 1 or 2, characterized in that the Aryl radical is in each case the phenyl or naphthyl radical and the aralkyl Rest is the benzyl residue. 4. The method according to one or more of claims 1 to 3, characterized in that R ¹ and R ^{2 are the} same or different and methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, tertiary butyl, n Pentyl, i-pentyl, n-hexyl, i-hexyl, n-heptyl, i-heptyl, n-octyl, i-octyl, n-nonyl, i-nonyl, n-decyl, i-decyl, phenyl, Naphthyl, tolyl or benzyl mean that
R ³ for methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, n-pentyl, i-pentyl, 3,3-dimethylbutyl, n-hexyl, i-hexyl, n-heptyl, i-heptyl , n-octyl, i-octyl, n-nonyl, i-nonyl, n-decyl, i-decyl, phenyl, naphthyl, tolyl or benzyl and that
R ^{4 is} methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, tertiary butyl, n-pentyl, i-pentyl, 3,3-dimethylbutyl, n-hexyl, i-hexyl, n-heptyl, i-heptyl, n-octyl, i-octyl, n-nonyl, i-nonyl, n-decyl, i-decyl, phenyl, naphthyl, tolyl or benzyl. 5. The method according to any one of claims 1 or 2, characterized in that 2,7-bis (3,3-dimethylbutyl) -9,9-dimethyl-4,5- bis (2,7-dimethyl-10 -phenoxaphosphino) xanthene (II), 2,7,9-trimethyl-9-n-nonyl-4,5-bis (2,7-dimethyl-10-phenoxaphosphino) xanthene (III), 2,7-di-n - decyl-9,9-dimethyl-4,5-bis (2,7-dimethyl-10-phenoxaphosphino) xanthene (IV), 2,7-di-n-hexyl-9,9-dimethyl-4,5- bis (2,7-dimethyl-10-phenoxaphos phino) xanthene (V), 2,7- (3,3-dimethylbutyl) -9,9-dimethyl-4,5-bis [2,7-di (3, 3-dimethylbutyl) -10-phenoxaphosphino] xanthene (VI), 2,7-dimethyl-9,9-dimethyl-4,5-bis [2,7-di (3,3-dimethylbutyl) -10-phenoxaphosphino] xanthene (VII) used. 6. The method according to one or more of claims 1 to 5, characterized ge indicates that the hydroformylation at a rhodium concentration from 1 to 1000 ppm by weight, based on the homogeneous reaction gene mix, takes place and the molar ratio of rhodium to phosphorus in Reaction mixture is 1: 1 to 1:80. 7. The method according to one or more of claims 1 to 6, characterized ge indicates that the pressure is 1 to 12 MPa, preferably 1 to 5 MPa is. 8. The method according to one or more of claims 1 to 7, characterized ge indicates that the temperature 60 to 150 ° C and in particular 75 to Is 140 ° C. 9. The method according to one or more claims 1 to 8, characterized ge indicates that the concentration of rhodium in the homogeneous Reaction mixture 50 to 500 ppm by weight and in particular 100 to 300 ppm by weight is. 10. The method according to one or more of claims 1 to 9, characterized characterized in that the molar ratio of rhodium to phosphorus in Reaction mixture is 1: 1 to 1:20. 11. The method according to one or more of claims 1 to 10, characterized characterized that the hydroformylation in a solvent carries out, using as a solvent paraffin oil, aromatic kohlwas substances, ethers, aldehydes, ketones or higher boiling condensation use products of aldehydes, in particular trimers of aldehydes det.   12. The method according to one or more of claims 1 to 11, characterized characterized in that olefi as olefinically unsaturated compounds niche unsaturated compounds with internal double bonds or mixtures containing olefinically unsaturated compounds with in internal double bonds are used. 13. The method according to claim 12, characterized in that one olefi nically unsaturated compounds with 4 to 12 carbon atoms applies. 14. The method according to claim 13, characterized in that the olefinic unsaturated compound a mixture containing butene-1 and butene-2 is. 15. Process for the preparation of carboxylic acids from olefinically unsaturated Compounds, characterized in that the olefinically saturated compound according to one or more of claims 1 to 14 hydroformylated, the aldehyde mixture obtained from the hydroformyly separation stage and subsequently to Car in a manner known per se oxidized bonic acids. 16. Process for the preparation of alcohols from olefinically unsaturated Compounds, characterized in that the olefinically saturated compound according to one or more of claims 1 to 14 hydroformylated, the aldehyde mixture obtained from the hydroformyly separation stage and subsequently to Al in a manner known per se alcohol reduced or hydrogenated. 17. Process for the preparation of amines from olefinically unsaturated ver Bonds, characterized in that the olefinically unsaturated A compound according to one or more of claims 1 to 14 hydroformylated, the aldehyde mixture obtained from the hydroformylation stages  separated and subsequently in the presence of an amination catalyst and hydrogen with ammonia, a primary or se secondary amine aminated in a manner known per se. 18. Process for the preparation of mixtures of isomeric decyl alcohols Mixtures containing butene-1 and butene-2, characterized in that that the mixture containing butene-1 and butene-2 according to a or more of claims 1 to 11 hydroformylated, the Al obtained separates the dehyde mixture, the aldehyde mixture to form an aldol mixed condensed, the aldol mixture separated and to a Ge mixed isomeric decyl alcohols hydrogenated. 19. Process for the production of didecyl phthalate from butene-1 and butene-2 containing mixtures, characterized in that the butene Mixture containing 1 and butene-2 according to one or more of the Claims 1 to 11 hydroformylated, the aldehyde mixture obtained separates and condenses to form an aldol mixture, the aldol mix separated and hydrogenated to a mixture of isomeric decyl alcohols and the mixture of isomeric decyl alcohols with phthalic acid or phthal acid anhydride esterified. 20. Process for the preparation of mixtures of isomeric decan carboxylic acids from mixtures containing butene-1 and butene-2, characterized records that the mixture containing butene-1 and butene-2 ge hydroformylated according to one or more of claims 1 to 11, the Aldehyde mixture condensed to form an aldol mixture, the Al then separated to form a mixture of isomeric decanals hydrogenated and then to a mixture of isomeric decanoic acid ren oxidized.   21. Catalyst for hydroformylation of olefinically unsaturated compounds containing rhodium and a diphosphine of the general formula I, as in Claim 1 defined.