MXPA99006543A - Process for preparing aldehydes by hydroformylation - Google Patents

Abstract

The invention concerns a process for preparing aldehydes by reacting with hydrogen and carbon monoxide at a temperature of between 20 and 170°C and a pressure of between 1 and 300 bar an olefinically unsaturated C3-C5 compound in the presence of an aqueous phase containing rhodium and sulphonated triarylphosphines as catalyst and between 1 and 35 wt%of a compound of formula (1), R(OCH2CH2)nOR1, R standing for hydrogen, a straight-chain or branched C1-C4 alkyl group or a C1-C4 hydroxyalkyl group, R1 standing for hydrogen or a methyl group, and n standing for an integer from 3 to 50.

Description

PROCEDURE FOR THE PREPARATION OF ALDEHYDES THROUGH HYDROFORMILATION DESCRIPTIVE MEMORY The present invention relates to a process for the preparation of aldehydes by the reaction of olefinic compounds having from 3 to 5 carbon atoms with hydrogen and carbon monoxide at a superatmospheric pressure in the presence of an aqueous phase comprising rhodium and sulfonated triarylphosphines. as a catalyst It is known that aldehydes and alcohols can be prepared by the reaction of olefins with carbon monoxide and hydrogen. The reaction is catalyzed by the hybrid metal carbonyls, preferably those of the metals of group Vlll of the Periodic Table. In addition to cobalt, which is widely used industrially as a catalyst metal, rhodium has over time increased its importance. In contrast to cobalt, rhodium allows the reaction to be carried out at low pressure; in addition, the direct-chain n-aldehydes are preferentially formed and the iso-aldehydes are formed only to a subordinate degree. Finally, significantly less hydrogenation of the olefins to saturated hydrocarbons occurs when the rhodium catalysts are used than when the cobalt catalysts are used.

In the processes that have been introduced into the industry, the rhodium catalyst is used in the form of modified hydrido-rhodium carbonyls containing additional ligands which may, if appropriate, be used in excess. It has been found that tertiary phosphines or phosphites are particularly useful as ligands. Its use makes it possible to reduce the reaction pressure below 30 MPa. However, the separation of the reaction products and the recovery of the catalysts homogeneously dissolved in the reaction product create problems in this process. In general, the reaction product is distilled from the reaction mixture. However, in practice, due to the thermal sensitivity of the aldehydes and alcohols formed, this method can only be used in the hydroformylation of lower olefins, ie, olefins having up to about 5 carbon atoms in the molecule. The hydroformylation of long chain olefin or olefinic compounds containing functional groups forms products having a high boiling point and these can not be separated from the rhodium complex catalyst homogeneously dissolved by distillation. The thermal stressing of the material being distilled leads to considerable losses of desired products due to the formation of coarse oil and catalyst due to the decomposition of the rhodium complexes. The separation of the catalyst by the thermal means is avoided by the use of water soluble catalyst systems. Such catalysts are described, for example, in DE-C 26 27 354. The solubility of rhodium complexes is achieved herein by the use of sulfonated triarylphosphines as constituents of the complex. In this variant of the process, the catalyst is separated from the reaction product after the hydroformylation reaction is simply completed by the separation of the aqueous and organic phases, ie without distillation, and thus without the additional process steps. thermal. An additional feature of said process is that the n-aldehydes are formed with high selectivity from the terminal olefins and the iso-aldehydes are formed only to a very subordinate degree. In addition to the sulfonated triarylphosphines, the carboxylated triarylphosphines are also used as constituents of water-soluble rhodium complexes. It has been found that the use of water-soluble catalysts is useful in the hydroformylation of lower olefins, in particular propene and butene. However, if higher olefins such as pentene or hexene are used, the reaction rate is markedly reduced. An industrial-scale reaction is often no longer as economical as desired when olefins having four or more carbon atoms are used. In order to increase the conversion and / or the selectivity of the reaction to n-aldehydes in the hydroformylation of higher olefins by water-soluble catalysts, the addition of an amphiphilic reagent (DE 31 35 127 A1) or a solubilizer (DE 34 12 335 A1) has been recommended. According to both DE 31 35 127 A1 and DE 34 12 335, very high conversions are obtained using quaternary ammonium salts having a long-chain alkyl radical, while non-ionic substances based on polyethylene glycol lead to comparatively low conversions . As can be seen from Table 7 in DE 31 35 127, the hydroformylation of 1-dodecene by rhodium and monosulfonated triphenylphosphine (S-phbPCeHUSOaNa) without the addition of an amphiphilic reagent leads to a conversion of 56% ( Example 77), while the addition of Ci2H25 (OCH2CH2) 23? H (= "Brij 35") leads to a reduction in the conversion to 37% (Example 78). According to DE 34 12 335 (Table 4), the hydroformylation of hexene by trisodium and rhodium tri (m-sulfophenyl) phosphine without the addition of a solubilizer leads to a conversion of 36% (Example 10), whereas the addition of 2.5% triethylene glycol (Example 14) or 5% polyglycol 200 (Example 11) gives a conversion of 43.5% or 43% respectively. The addition of the solubilizer does not result in a significant increase in conversion, and increasing the amount of the solubilizer from 2.5% to 5% does not increase the conversion either. On the other hand, a very high conversion, for example from 86%, is achieved with a 2.5% addition of trimethylhexadecylammonium bromide. However, the use of the quaternary ammonium salts as an amphiphilic reagent or solubilizer is not without problem due to the poor biodegradability of these compounds. In this way, the presence of quaternary ammonium salts in wastewater leads to difficulties in the treatment of wastewater.

The amphiphilic and solubilizing reagents serve to assist in mass transfer between the individual phases and thus in the miscibility of the aqueous catalyst phase and the organic phase. An increase in the miscibility of the aqueous catalyst phase and the organic phase means an increased solubility of the organic phase in the aqueous phase and of the aqueous phase in the organic phase. In this way, increased amounts of amphiphilic reagent and solubilizer and also rhodium and water-soluble phosphine can be introduced into the organic phase and transported with the organic phase after phase separation. Furthermore, it is expected that with the increase in miscibility in the aqueous catalyst phase and the organic phase, the release required for the phase separation will no longer take place to a sufficient degree, if any, as a result of the formation of emulsions or solutions. A corresponding increase in miscibility is expected, particularly when the amount of amphiphilic reagents and aggregate solubilizers is increased. The increased discharge of rhodium, water-soluble phosphine and amphiphilic reagent or solubilizer by the organic phase is, as is the reduced phasemiscibility, undesirable, since rhodium, water-soluble phosphine and amphiphilic reagent or solubilizer must remaining in the aqueous catalyst phase and good demmisibility is an essential requirement for the separation of the organic and aqueous phases, which is necessary at the end of the hydroformylation.

In view of the above considerations, there is a need for a method that avoids the aforementioned drawbacks and, furthermore, that can be implemented industrially in a simple manner. This object is achieved by a process for preparing aldehydes. It consists of reacting an olefinically unsaturated compound having 3 carbon atoms with hydrogen and carbon monoxide at 20 to 170 ° C and from 1 to 300 bar in the presence of an aqueous phase consisting of rhodium and sulfonated triarylphosphines as catalyst and from 1 to 15% by weight of a compound of formula (1) R (OCH 2 CH 2) nOR 1, wherein the triarylphosphines they contain at least three radicals - (S? 3) M in which M are identical or different and M is H, an alkali metal ion, an ammonium ion, a quaternary ammonium ion, a 1/2 metal ion alkaline earth metal or 1 zinc ion, and wherein, in the formula (1) R is hydrogen, a straight or branched chain alkyl radical having from 1 to 4 carbon atoms, R 1 is hydrogen or a methyl radical, in particular hydrogen, and n is an integer from 3 to 50. Furthermore, the object is achieved by a similar procedure, but using an olefinically unsaturated compound having 4 carbon atoms and in the presence of 8 to 20% by weight of a compound of the formula (1). The object is also achieved by a similar procedure, but using an olefinically unsaturated compound having 5 carbon atoms and in the presence of 8 to 30% by weight of a compound of formula (1). In view of the aforementioned discoveries of DE 34 12 335 (table 4, examples 10, 14 and 11) and DE 31 35 127 (table 7, examples 77 and 78) for the hydroformylation of hexene and dodecene, the addition of the compounds of the formula (1) would not be expected. ) R (OCH2CH2) nOR1 in the amounts mentioned above in the reaction of olefinic compounds having only 3 to 5 carbon atoms would lead to a significant increase in the conversion and at the same time to a high selectivity with respect to the formation of n -aldehydes. If the propene is hydroformylated in the presence of an aqueous phase consisting of rhodium and trisulfonated triphenylphosphine, a very high reaction rate is obtained in the absence of an amphiphilic reagent or solubilizer. In view of this, it is surprising that a comparatively small addition of compounds of the formula (1) leads to a marked increase in the already very high propylene conversion rate. Furthermore, it was not expected that despite this increase in conversion the rate of formation of n-butanal to iso-butanal would be influenced only very slightly. The formation of n-butanal is reduced by only a very small amount compared to the process without the addition of the compounds of the formula (1). In view of the great influence that even a comparatively small addition of compounds of the formula (1) has on the conversion of propylene, it is also unexpected that the rhodium, the sulfonated triarylphosphine and the compound of the formula (1) remain virtually completely in the aqueous phase and do not get into the organic phase and do not get lost from the aqueous phase through the organic phase.

It is also generally surprising that in the hydroformylation of olefinic compounds having from 3 to 5 carbon atoms, even the addition of comparatively large amounts of compounds of the formula (1) R (OCH2CH2) nOR1 does not cause a significant increase in the amount of rhodium and sulfonated triarylphosphine in the organic phase and thus to increased catalyst discharge through the organic phase. Furthermore, it was not expected that, despite the comparatively large amounts of compounds of the formula (1) the organic phase demixibility and aqueous catalyst phase is sufficiently high to ensure the separation of organic phase and aqueous catalyst phase. Surprisingly, difficult-to-separate emulsions or homogeneous phases or solutions that can not be separated are not formed. The aqueous phase comprising the catalyst and the compound of formula (1) R (OCH2CH2) nOR1 can be prepared in a comparatively simple manner by dissolving a water-soluble rhodium salt, the sulfonated triarylphosphine and the compound of the formula (1) in Water. Suitable rhodium salts are, without making any claim to completion: rhodium sulfate (III), rhodium nitrate (III), rhodium carboxylates (III), such as rhodium acetate, rhodium propionate, rhodium butyrate and 2- Rhodium ethylhexanoate. The aqueous phase can be used directly in the hydroformylation or subjected in advance to a pre-formation of the catalyst under reaction conditions and subsequently used in a preformed form.

The olefinic compound used can be an aliphatic olefin or cycloaliphatic olefin having from 3 to 5 carbon atoms, in particular an aliphatic olefin having from 3 to 5 carbon atoms, preferably an aliphatic α-olefin having from 3 to 5 carbon atoms. of carbon. The olefinic compound may contain one or more carbon-carbon double bonds. The carbon-carbon double bond can be in a terminal or internal position. Preference is given to olefinic compounds having a terminal carbon-carbon double bond. Examples of α-olefin compounds (with a terminal carbon-carbon double bond) are alkenes, alkyl alkenoates, alkenyl alkanoates, alkenyl alkyl ethers and alkenols. Without mentioning all, the olefinic compounds that can be mentioned are propene, cyclopropene, butene, pentene, butadiene, pentadiene, cyclopentene, cyclopentadiene, allyl acetate, vinyl format, vinyl acetate, vinyl propionate, allil methyl ether, ethyl vinyl ether, and Ichiyl alcohol, in particular propene, 1-butene, mixtures available industrially containing essentially 1-butene and 2-butene, and 1-pentene. For the purposes of the present invention, the sulfonated triarylphosphines are phosphines containing one or two phosphorus atoms, which have three aryl radicals per phosphorus atom, wherein the aryl radicals are identical or different and each is a phenyl radical, naphthyl, biphenyl, phenylnaphthyl or binaphthyl, in particular a phenyl, biphenyl or binaphthyl radical, and the aryl radicals are connected to the phosphorus atom directly or by a group - (CH2) X-, where x is an integer from 1 to 4 , in particular from 1 to 2, preferably 1, and which contains at least three groups - (S? 3) M, where M are identical or different and each is H, an alkali metal ion, a of ammonium, a quaternary ammonium ion, Vz alkaline earth metal ion or zinc ion, in particular a metalalkaline ion, an ammonium ion or a quaternary ammonium ion, preferably a metalalkaline ion. The - (S? 3) M groups are usually located as substituents on the aryl radicals and give the triarylphosphines the required water solubility. As sulfonated triarylphosphines, preference is given to using the compounds of formula (2) wherein Ar1, Ar2 and Ar3 are identical or different and each is a phenyl or naphthyl radical, in particular a phenyl radical, and M are identical or different, in particular identical, and each is an alkali metal ion, a of ammonium, an ion of quaternary ammonium and 12 tons of alkaline earth metal or zinc oxide, in particular an alkali metal or ammonium ion, preferably an alkali metal ion, particularly preferably an alkali metal ion. On sodium. Trisodium tri (m-sulfophenyl) phosphine is particularly suitable as sulfonated triarylphosphine. Said trisodium tri (meta-sulfophenol) phosphine salt contains, due to its preparation by sulfonating triphenylphosphine, amounts of monosulfonated and disulfonated compounds.

Trisodium tri (m-sulfophenyl) phosphine corresponds to the following formula: Sulfonated triarylphosphines containing two phosphorus atoms can, for example, contain a radical - (CH2)? - Ar-Ar- (CH2)? -, where x is an integer from 1 to 4, in particular from 1 to 2 , preferably 1, Ar-Ar is biphenyl or binaphthyl, the group - (CH2) X- is, by a bond, in each case located in the ortho position when linking to the aryl-aryl of Ar-Ar connecting the two aryl radicals and is connected by another link to a phosphorus atom which in each case carries two identical or different aryl radicals, in addition, in particular phenyl radicals. Said triarylphosphines containing two phosphorus atoms have at least three -SO3M groups, in particular from 4 to 8 -SO3M groups, wherein M is as defined above. The -SO3M groups are usually located on the aryl radicals of the radical - (CH2) x-Ar-Ar- (CH2) x- and on the two other additional aryl radicals which are connected to the phosphorus.

Examples of said sulfonated triarylphosphines containing two phosphorus atoms are, without making any mention of completeness, represented by the following formulas (3) and (4): In (3), m-i and m2 are each, independently of one another, 0 or 1, with the compound of the formula (3) containing from 3 to 6 -SO3M groups.

In (4), m3, m4, m5 and m6 are each, independently of each other, 0 or 1, with the compound of formula (4) containing from four to eight, in particular from five to six, groups - SO3M.

Because the compounds (3) and (4) are prepared by sulfonating the corresponding phosphines of formulas (3a) and (4a) which do not contain -SO3M groups, (3a) (4a) they are usually obtained in the form of mixtures of compounds containing different numbers of -SO3M groups. Thus, a compound of formula (3) or (4) containing, for example, three -SO3M groups also contains compounds having only two -SO3M groups as well as compounds having four or five -SO3M groups. A compound of the formula (3) or (4) having, for example, five -SO3M groups usually also contains compounds having only three or four -SO3M groups, as well as compounds having six or seven -SO3M groups. The compounds of the formula (3) have a maximum of six -SO3M groups, while the compounds of the formula (4) have a maximum of eight -SO3M groups. For this reason, mixtures of the compounds of the formula (3) or (4) having a different number of -SO3M groups are generally used.

The sulfonated triarylphosphines described above have, due to their sulfonate radicals, a solubility in water which is sufficient to carry out the process. The aqueous phase comprising rhodium and the compounds of the formula (2) as the catalyst and the compound of the formula (1), is usually used in a corresponding amount of 2 x 10"6 to 5 x 10" 2 moles, in particular of 5 x 10"5 to 5 x 10" 2 moles, preferably 1 x 10"4 to 1 x 10" 3 moles, of rhodium per mole of olefinic compound. The amount of rhodium also depends on the type of olefinic compound to be hydroformylated. Although lower catalyst concentrations are possible, in some cases they can prove that they are not particularly suitable, because the reaction speed can be too slow and therefore not economical enough. The catalyst concentration can be up to 1x10"1 mole of rhodium per mole of olefinic compound, but comparatively high rhodium concentrations do not give particular advantages The aqueous phase comprising trisulfonated rhodium and triarylphosphines as catalyst and to the compound of the formula (1) ) R (OCH2CH2) nOH is usually used in a volume ratio of the olefinic compound from 10: 1 to 1:10, in particular from 5: 1 to 1: 5, preferably from 2: 1 to 1: 2. rhodium and the sulfonated triarylphosphines are used in a molar ratio of 1: 5 to 1: 2000. If a sulfonated triarylphosphine containing a phosphorus atom is used, for example a compound of the formula (2), the rhodium and the sulphonated triallylphosphine they are commonly used in a molar ratio of 1.10 to 1: 1000, in particular of 1:50 to 1: 200, preferably of 1:80 to 1; 120. If a sulfonated triarylphosphine containing two phosphorus atoms is used, (for example a compound of the formula (3) or (4)), the rhodium and the sulfonated triarylphosphine are usually used in a molar ratio of 1: 5 to 1: 100, in particular from 1: 5 to 1: 50, preferably from 1: 8 to 1: 15. The aqueous phase contains from 20 to 2000 ppm of rhodium. If a sulfonated triarylphosphine containing a phosphorus atom, for example a compound of the formula (2), is used, an aqueous phase containing from 100 to 1000 ppm, in particular from 200 to 500 ppm, is used in most cases. , preferably from 300 to 400 ppm of rhodium. If a sulfonated triarylphosphine containing two phosphorus atoms is used, for example compounds of the formula (3) and / or (4), in most cases an aqueous phase containing from 20 to 500 ppm is used, in particular from 30 to 150 ppm, preferably from 40 to 100 ppm of rhodium. The type of olefinic compound to be reacted can also influence to some extent the amount of the compound of the formula (1) R (OCH 2 CH 2) nOR 1 to be used. If the olefinic compound used is propene, it has frequently been found that it is appropriate to carry out the reaction in the presence of an aqueous phase containing from 1 to 15% by weight, in particular from 3 to 10% by weight, of the compound of the invention. Formula 1).

If the olefinic compound used is butene, it has frequently been discovered that it is suitable to carry out the reaction in the presence of an aqueous phase containing from 5 to 25% by weight, in particular from 8 to 20% by weight, of the compound of the invention. Formula 1 ). If the olefinic compound used is pentene, it has frequently been discovered that it is suitable to carry out the reaction in the presence of an aqueous phase containing from 5 to 35% by weight, in particular from 8 to 30% by weight, of the compound of the invention. Formula 1 ). At this point, it may be mentioned for the benefit of integrity that the compounds of the formula (1) R (OCH 2 CH 2) nOR 1, wherein R is hydrogen, a straight or branched chain alkyl radical having from 1 to 4 carbon atoms or a hydroxyalkyl radical having from 1 to 4 carbon atoms, in particular hydrogen, an alkyl radical having 1 to 2 carbon atoms or a hydroxyalkyl radical having from 1 to 3 carbon atoms, preferably hydrogen, methyl, hydroxymethyl or hydroxypropyl, and R1 is hydrogen or a methyl radical, in particular hydrogen, are substances that dissolve in water to a sufficient degree. Care should be taken at this point with the following compounds of the formula (1), in which R1 is hydrogen, and which are of particular interest. Without making any mention of completeness, the compounds of the formula R (OCH2CH2) nOH which may be mentioned are the polyethylene glycol of the formula H (OCH2CH2) nOH having an average molecular weight of about 200 (PEG 200), 400 (PEG 400 ), 600 (PEG 600) or 1000 (PEG) 1000), compounds of the formula CH 3 (OCH 2 CH 2) nOH having an average molecular weight of about 350 (M 350), 500 (M 500) or 750 (M 750), or compounds of the formula CH3CHOHCH2 (OCH2CH2) nOH having an average molecular weight of about 300 (300 PR), 450 (450 PR), 600 (600 PR) or 1000 (1000 PR), in particular polyethylene glycol having an average molecular weight of about 400 (PEG 400) and 600 (PEG 600), a compound of the formula CH 3 (OCH 2 CH 2) nOH having an average molecular weight of 500 (M 500) or a compound of the formula CH 3 CHOHCH 2 (OCH 2 CH 2) nOH having an average molecular weight of 450 (450 PR) and 600 (600 PR). For the purposes of the present invention, PEG 200 is a mixture of polyethylene glycols of the formula H (OCH 2 CH 2) nOH, wherein n is an integer from 3 to 6, PEG 400 is a mixture of polyethylene glycols of the formula H (OCH 2 CH 2) n OH , wherein n is an integer from 7 to 10, PEG 600 is a mixture of polyethylene glycols of the formula H (OCH 2 CH 2) nOH, wherein n is an integer from 11 to 16, and PEG 1000 is a mixture of polyethylene glycols of the formula H (OCH2CH2) nOH, where n is an integer from 15 to 30. In each case, an average molecular weight of approximately 200 (PEG 200), approximately 400 (PEG 400), approximately 600 (PEG 600) can be assigned to each mixture. or approximately 1000 (PEG 1000). For the purposes of the present invention, M 350 is a mixture of compounds of the formula CH 3 (OCH 2 CH 2) n OH, wherein n is an integer from 5 to 9, M 500 is a mixture of compounds of the formula CH 3 (OCH 2 CH 2) n OH , wherein n is an integer from 9 to 13, and M 750 is a mixture of compounds of the formula CH 3 (OCH 2 CH 2) n OH, wherein n is an integer from 12 to 20. Said mixtures can be assigned in each case a molecular weight corresponding average of approximately 350 (M 350), approximately 500 (M 500) or approximately 750 (M 750). For the purposes of the present invention, 300 PR is a mixture of compounds of the formula R (OCH 2 CH 2) nOH, wherein R is a β-hydroxypropyl radical CH 3 CHOHCH - and n is an integer from 6 to 9, 450 PR is a mixture of compounds of the formula R (OCH2CH2) nOH wherein R is a β-hydroxypropyl radical CH3CHOHCH2- and n is an integer from 8 to 14, 600 PR is a mixture of compounds of the formula R (OCH2CH2) nOH, wherein R is a ß-hydroxypropyl radical CH3CHOHCH2- and n is an integer from 12 to 20, and 1000 PR is a mixture of compounds of the formula R (OCH2CH2) nOH, wherein R is a β-hydroxypropyl radical CH3CHOHCH2- and n is an integer of 18 to 26. A corresponding average molecular weight of approximately 300 (300 PR) can be assigned to said mixtures in each case., approximately 450 (450 PR), approximately 600 (600 PR) or approximately 1000 (1000 PR). It has been found in several cases that it is useful to use a polyethylene glycol of the formula H (OCH2CH2) nOH, wherein n is an integer from 3 to 50, in particular from 4 to 30, preferably from 5 to 20, particularly preferably from 6 to 12, as the compound of the formula (1).

It has also been found that it is useful to use a compound (monoether) of the formula R (OCH2CH2) nOH, wherein R is a methyl radical or a β-hydroxypropyl radical and n is an integer from 3 to 50, in particular from 4 to 30, preferably from 5 to 20, as the composed of the formula (1). It is also possible to use any mixture of the compounds of the formula (1), called polyethylene glycols, polyethylene glycol ethers (monoethers) and polyethylene glycol diethers. The reaction is carried out in the presence of hydrogen and carbon monoxide. The molar ratio of hydrogen to carbon monoxide can be selected within broad limits and is usually from 1: 10 to 10: 1, in particular from 5: 1 to 1: 5, preferably from 2: 1 to 1: 2, particularly preferably from 1.2: 1 to 1: 1.2. The process is particularly simple if hydrogen and carbon monoxide are used in a molar ratio of 1: 1 or approximately 1: 1. In several cases, it is sufficient to carry out the reaction at a temperature of 50 to 150 ° C, in particular 100 to 140 ° C. In several cases, it has been found that it is useful to carry out the reaction at a pressure of 10 to 200 bar, in particular 20 to 150 bar, preferably 30 to 80 bar. During the reaction, the good mixing of the organic phase, the aqueous phase and the carbon monoxide / hydrogen must be ensured. The foregoing can be effected, for example, by continuous agitation and / or pumped circulation of the organic and aqueous phases. The organic phase usually comprises the olefinic compound, the aldehydes produced and also small amounts of the aqueous phase, while the aqueous phase usually comprises rhodium, sulfonated triarylphosphines, the compound of the formula (1), water and small amounts of the organic phase. . At this point, care must be taken again with the fact that the reaction conditions, in particular the concentration, pressure and temperature of the rhodium, also depend on the type of the olefinic compound to be hydroformylated. Comparatively reactive olefinic compounds require low rhodium concentrations, low pressures and low temperatures. In contrast, the reaction of relatively less reactive olefinic compounds requires higher rhodium concentrations, higher pressures and higher temperatures. The process can be carried out particularly successfully if an α-olefinic compound is used. However, other olefinic compounds containing internal carbon-carbon double bonds can also be reacted with good results. After the reaction is complete, the hydroformylation mixture is released from the carbon monoxide and hydrogen by depressurization and the reaction product, if suitable after cooling, is separated from the aqueous phase comprising the catalyst and the compound of the Formula (1) by phase separation. The aqueous phase comprising the catalyst and the compound of the formula (1) can be returned to the process of the invention, while the organic phase containing the reaction product is processed, for example by fractional distillation. The procedure can be carried out continuously or interrupted. The following examples illustrate the invention without restricting it.

EXPERIMENTAL PART 1.- Hydroformylation of 1-pentene.

EXAMPLE 1 a (experiment compared to examples 1b) to 1d) without addition of polyethylene glycol) I.- Preparation of the catalyst and preformation phase 60 mg (02.33 mmoles) of rhodium acetate (III) are dissolved in 39 ml of a 0.6 M tri (m-suIfophenyll) trisodium phosphine (Na-TPPTS) aqueous solution, corresponding to a molar ratio of rhodium to ligand of 1: 100, and 21 ml of degassed distilled water and introduced under a stream of nitrogen into a 200 ml steel autoclave. This catalyst solution is heated to 125 ° C under 25 bar of synthesis gas pressure (CO / H2 = 1/1) for 3 hours while stirring, with the solution becoming yellow.

II.- Hydroformylation. 26.3 ml (240 mmoles) of 1-pentene are added to the preformed catalyst solution from I at a reaction pressure of 30 bar and at 125 ° C through a 200 ml steel autoclave upstream using light pressure . The ratio of olefin to rhodium is 1039: 1. The hydroformylation reaction is started by igniting the magnetic stirrer. During a reaction time of 3 hours, the temperature is maintained at 125 ° C and the reaction pressure is kept constant within a pressure range of ± 2 bar by the manual addition of synthesis gas. After 3 hours have elapsed, the agitator and the heating are switched off, the autoclave is cooled to 40 to 50 ° C and the top product phase is separated from the catalyst phase in a separating funnel. The product phase and the catalyst phase are weighed. The composition of the product phase is determined by gas chromatography and 1 H-NMR spectroscopy, and the yield of hydroformylation products and the ratio of N-hexanal to iso-hexanal (2-methylpentanal) is determined from the composition. The rhodium content of the organic phase is, after digestion of the sample, determined by elemental analysis using atomic absorption spectrometry of graphite furnace. The yield of hydroformylation products is 49.4% and the n / iso ratio is 96: 4. The organic phase contains 0.05 ppm Rh. (Example 1a) in table 1).

EXAMPLE 1 b) I.- Preparation of the catalyst and preformation phase. 60 mg (0.233 mmoles) of rhodium acetate (III) are dissolved in 39 ml of a 0.6 M aqueous solution of tri (m-sulfophenyl) phosphine of trisodium (Na-TPPTS). 5 ml degassed polyethylene glycol 400 are added to this solution and the solution is formed at a total volume of 60 ml. This catalyst phase is introduced under a stream of nitrogen into a 200 ml steel autoclave and heated to 125 ° C under 25 bar synthesis gas pressure (CO / H2 = 1/1) for 3 hours while shake II.- Hydroformylation Using a method similar to example 1a) 30 ml (240 mmoles) of 1-hexane are added to the preformed I catalyst solution. The hydroformylation is carried out using a method similar to example 1a) at 125 ° C. C and 30 bar of synthesis gas. The product phase is analyzed using a method similar to example 1a). The yield of hydroformylation products is 70.1% and the n / iso ratio is 96: 4. (Example 1b) in table 1).

EXAMPLE 1c) The procedure of example 1b) is repeated, except that 7 ml of degassed polyethylene glycol 400 instead of 5 ml degassed polyethylene glycol 400 is now added to the catalyst phase and the total volume of the catalyst phase is formed up to 60 ml. The preforming and hydroformylation conditions are identical to Example 1 b). The hydroformylation product yield is 81.1% and the n / iso ratio is 96: 4. The organic phase contains 0.16 ppm Rh. (Example 1 c) in table 1).

EXAMPLE 1 d) The procedure of example 1b) is repeated, except that 10 ml of degassed polyethylene glycol 400 are added to the catalyst phase and the total volume of the catalyst phase is formed up to 60 ml. The preforming and hydroformylation conditions are identical to example 1 b), except that the duration of the hydroformylation reaction is 210 min (3.5 hours). The yield of the hydroformylation product is 88.0% and the n / iso ratio is 95: 5. The organic phase contains 0.08 ppm Rh. (Example 1d) in table 1).

EXAMPLE 1e) The procedure of example 1b) is repeated, except that 21 ml of degassed polyethylene glycol 400 are added to the catalyst phase. The hydroformylation preform conditions are identical to example 1 b). The hydroformylation product yield is 87.3% and the n / isso ratio is 91: 9. The organic phase contains 0.85 ppm Rh (Example 1e) in Table 1).

EXAMPLE 1f) Without addition of a compound of formula (1). The procedure of example 1a) is repeated, except that the reaction of the hydroformylation is carried out under a synthesis gas pressure of 50 bar. The yield of hydroformylation product is 74.8% and the n / isso ratio is 96: 4. The organic phase contains 0. 03 ppm Rh (Example 1f) in table 1).

EXAMPLE 1g) The procedure of Example 1f) is repeated, except that 5 ml of degassed polyethylene glycol 400 is added to the catalyst phase and the total volume of the catalyst phase is formed up to 60 ml. The preforming and hydroformylation conditions are identical to example 1f). The yield of hydroformylation product is 84.9% and the n / iso ratio is 95: 5. (Example 1g) in Table 1.

EXAMPLE 1h) (As example 1g) with a longer reaction time). The procedure of example 1g) is repeated, except that the hydroformylation reaction is carried out for 240 min (4 hours). The yield of hydroformylation product is 88.4% and the n / iso ratio is 96: 4. The organic phase contains 0.09 ppm Rh (Example 1 h) in Table 1).

EXAMPLE 1 i) The procedure of Example 1f) is repeated, except that 7 ml of degassed polyethylene glycol 400 is added to the catalyst phase and the total volume of the catalyst phase is formed up to 60 ml. The hydroformylation preform conditions are identical to example 1f). The yield of hydroformylation product is 84.8% and the n / iso ratio is 95: 5. (Example 1 ¡) in table 1).

EXAMPLE 1 i) The procedure of example 1f) is repeated, except that 10 ml of degassed polientylene glycol 400 are added to the catalyst phase and the total volume of the catalyst phase is formed up to 60 ml. The preforming and hydroformylation conditions are identical to example 1f). The yield of the hydroformylation product is 87.5% and the n / iso ratio is 94: 6. The organic phase contains 0.28 ppm Rh (Example 1j) in Table 1).

EXAMPLE 1k) (Use of a compound of formula CH3 (OCH2CH2) nOH). The procedure of example 1g) is repeated, except that, instead of 5 ml of polyethylene glycol 400, the same volume (5 ml) of a compound of formula CH3 (OCH2CH2) nOH, n = 5 to 9 (commercial product of Hoeschst , designation M 350) are added to the catalyst phase and the total volume of the catalyst phase is formed up to 60 ml. The preforming and hydroformylation conditions are identical to example 1g). The yield of hydroformylation product is 84.3% and the n / iso ratio is 95: 5. The organic phase contains 0. 07 ppm Rh (Example 1 k) in Table 1.

EXAMPLE 11) (Use of a compound of formula CH3CHOHCH2 (OCH2CH2) nOH (n = 8 to 14) The procedure of example 1g) is repeated, except that instead of 5 ml of polyethylene glycol 400 (PEG 400) the same volume (5 ml) of a compound of formula CH3CHOHCH2 (OCH2CH2) nOH, n = 8 a 14 (commercial product of Hoechst, designation 450PR) the catalyst phase is added and the total volume of the catalyst phase is formed up to 60 ml. The preforming and hydroformylation conditions are identical to example 1g). The hydroformylation product yield is 84.0% and the n / iso ratio is 95: 5. The organic phase contains 0. 09 ppm Rh (Example 11) in Table 1). Examples 1g), 1 k) and 11) show that the use of compounds other than formula (1) gives comparable results with respect to the yield of hydroformylation products, selectivity and rhodium content of the organic phase. Example 1 m) (use of a compound of formula H (OCH 2 CH 2) sOH (triethylene glycol)). The procedure of example 1g) is repeated, except that instead of 5 ml of polyethylene glycol 400 (PEG 400), the same volume of triethylene glycol is used and the total volume of the catalyst phase is formed up to 60 ml. The preforming and hydroformylation conditions are identical to example 1g). The yield of hydroformylation product is 79.8% and the n / iso ratio is 94: 6. The organic phase contains 0.06 ppm Rh (Example 1m) in Table 1). Example 1n) (use of a compound of formula CH3 (OCH2CH2) nOCH3 (n = 3 to 6). The procedure of example 1g) is repeated, except that instead of 5 ml of polyethylene glycol 400 (PEG 400), the same volume of a compound of formula CH3 (OCH2CH2) nOCH3 (n = 3 to 6), polyethylene glycol dimethyl ether) is used and the total volume of the catalyst phase is formed up to 60 ml. The preforming and hydroformylation conditions are identical to example 1g). The yield of hydroformylation product is 85.9% and the n / iso ratio is 95: 5 (Example 1 n) in Table 1) Experiments using compounds of formula (4) as triarylphosphine ligands containing two phosphorus atoms. Example 1) (example comparative to examples 1 p) and 1q) without addition of a compound of formula (1)).

I Preparation of the catalyst phase and pre-formation The catalyst phase is formed of 7.5 mg (0.028 mmol) of rhodium acetate (III), 1.8 ml of a solution of 2,2'-bis (diphenylphosphinomethyl) -1, 1 ' sulfonated sulfonate (Na-BINAS) of 0.162 molar corresponding to formula (4) and having a main number of sulfonate groups of 4 to 7, corresponding to a molar ratio of rhodium to ligand of 1: 10, and 58 ml of Distilled distilled water introduced under a stream of nitrogen into a 200 ml steel autoclave. This catalyst solution is heated to 125 ° C under 25 bar synthesis gas pressure (CO / H2 = 1/1) for 3 hours while stirring.

II Hydroformylation The hydroformylation reaction is carried out under a synthesis gas pressure of 50 bar and the formation and analysis of the organic phase is carried out using a method similar to experiment 1f). The yield of hydroformylation products is 76.1% and the n / iso ratio is 98: 2 (Example 1o) in Table 1).

EXAMPLE 1p) The procedure of example 1) is repeated, except that 5 ml of degassed polyethylene glycol 400 are added to the catalyst phase and the total volume of the catalyst phase is formed up to 60 ml. The yield of hydroformylation product is 76.1% and the n / iso ratio is 98: 2 (Example 1p) in table 1 ).

EXAMPLE 1q) The procedure of example 1) is repeated, except that 10 ml of a compound of formula CH3 (OCH2CH2) nOH, n = 9 to 13, (commercial product of Hoechst, designation M 500) are added to the catalyst phase and the total volume of the catalyst phase is formed up to 60 ml. The yield of hydroformylation product is 75.7% and the n / iso ratio is 98: 2 (Example 1q) in table 1 )- 2. Hydroformylation of 1-butene Example 2a) (experiment compared to examples 2b) to 2g) without addition of an additive of formula (1).

I Preparation of the catalyst phase and preformation 60 mg (0.233 mmol) of rhodium acetate (III) are dissolved in 39 ml of a 0.6 M solution of trisodium tri (m-sulfophenyl) phosphine (Na-TPPTS), corresponding at a molar ratio of rhodium to ligand of 1: 100, and 21 ml of degassed distilled water are introduced under a stream of nitrogen into a 200 ml steel autoclave. The catalyst solution prepared in this way is heated to 125 ° C under 25 bar synthesis gas pressure (CO / H2 = 1/1) for 3 hours while stirring, with the solution becoming yellow.

II Hydroformylation 12.46 g (224 mmoles) of liquid 1-butene are added to the preformed catalyst solution from I at a reaction pressure of 30 bar and at 125 ° C through a steel autoclave of 200 ml of stream upwards using light overpressure. (The precise amount is determined by weight difference). The olefin to rhodium ratio is 950: 1. The hydroformylation reaction is started by igniting the magnetic stirrer. During a reaction time the temperature is maintained at 125 ° C and the reaction pressure is kept constant within a pressure range of ± 2 bar by manual addition of synthesis gas. The reaction is stopped after 120 minutes because no more synthesis gas is absorbed. The agitator and the heater are turned off, the autoclave is cooled to 40 to 50 ° C and the upper product phase is separated from the catalyst phase in a separating funnel. The yield of hydroformylation products is determined by weight and chromatographic gas analysis of the organic phase; the ratio of n-pentanal to iso-pentanal (2-methylbutanal) is likewise determined by gas chromatography. In these series of examples, the duration of the hydroformylation reaction is a measure of the hydroformylation rate. In this example, it's 120 minutes. The performance of hydroformylation products is 88. 1% and the n / iso ratio is 96: 4. The organic phase contains 0.07 ppm Rh (Example 2a) in table 2).

EXAMPLE 2b) I Preparation of the catalyst phase and preformation 60 mg (0.233 mmol) of rhodium acetate (III) is dissolved in 39 ml of a 0.6 M aqueous solution of trisodium tri (m-sulfophenyl) phosphine (Na-TPPTS), 3 ml of degassed polyethylene glycol 400 are added to this solution and the solution is formed to a total volume of 60 ml. This catalyst phase is introduced under a nitrogen stream into a 200 ml steel autoclave and is pre-formed at 125 ° C under 25 bar synthesis gas pressure (CO / H2 = 1/1) for 3 hours while shake II Hydroformylation 15.56 g (277 mmoles) of 1-butene are added to the preformed catalyst solution of I corresponding to an olefin to rhodium ratio of 1186: 1. The hydroformylation is carried out using a method similar to that of Example 2a) at 125 ° C under 30 bar synthesis gas. No further decrease in pressure occurs after two hours. The hydroformylation product yield is 87.2% and the n / iso ratio is 96: 4. The organic phase contains 0.07 ppm Rh. Therefore, with the amount of 1-butene increased by 23.6%, 22% plus 1-butene is converted into hydroformylation products in the same reaction time without the n / iso selectivity being changed or the rhodium content of the organic phase rising. (Example 2b) in table 2).

EXAMPLE 2c) The catalyst phase is prepared and pre-formed using a method similar to example 2a), except that 6 ml of degassed water is replaced by 6 ml of degassed polyethylene glycol. After pre-forming, 13.34 g (238 mmoles) of 1-butene, corresponding to an olefin to rhodium ratio of 1017: 1, are added. The reaction is completed after only 90 minutes. The yield of hydroformylation product is 85.9% and the n / iso ratio is 96: 4. Therefore, taking into account the increased amount of 1-butene and the decreased reaction time compared to example 2a), 38% more than 1-butene are converted into hydroformylation products per unit of time as in example 2a) . (Example 2c) in table 1).

EXAMPLE 2D) The catalyst phase is prepared and pre-formed using a method similar to example 2a), except that 9 ml of degassed water is replaced by 9 ml of degassed polyethylene glycol. After pre-processing, 13.89 g (247 mmoles) of 1-butene are added, corresponding to an olefin to rhodium ratio of 1058: 1. The hydroformylation reaction is completed after only 60 minutes. The yield of the hydroformylation product is 89.3% and the n / iso ratio is 94: 6. Therefore, taking into account the increased amount of 1-butene and the decreased reaction time compared to example 2a), 2.2 times of 1-butene are converted into hydroformylation product per unit of time as in example 2a). The rhodium content of the organic phase is 0.2 ppm (Example 2d) in Table 2) EXAMPLE 2e) The catalyst phase is prepared and pre-formed using a method similar to example 2a), except that 12 ml of degassed water is replaced by 12 ml of degassed polyethylene glycol 400. After pre-forming, 13.57 g (242 mmoles) of 1-butene are added, corresponding to an olefin to rhodium ratio of 1034: 1. The hydroformylation reaction is complete after only 45 minutes. The yield of hydroformylation product is 88.3% and the n / iso ratio is 94: 6. Therefore, taking into account the increased amount of 1-butene and the reduced reaction time compared to example 2a), 2.9 times of 1-butene are converted into hydroformylation products per unit of time as in example 2a) .

(Example 2e) in table 2) EXAMPLE 2f) (Use of a compound of formula CHgíOchgCHg ^ OH, n = 9 to 13) The catalyst phase is prepared and pre-formed using a method similar to example 2d), except that, instead of 9 ml of polyethylene glycol 400 degassing, the same volume of a compound of formula CH3 (OCH2CH2) nOH, n = 9 to 13 (commercial product of Hoechst, designation M 500) are used. After pre-forming, 13.52 g (241 mmoles) of 1-butene are added, corresponding to an olefin to rhodium ratio of 1031: 1. The hydroformylation reaction is complete after 60 minutes. The hydroformylation product yield is 87.1% and the n / iso ratio is 95: 5.

Therefore, taking into account the decreased amount of 1-butene and the reduced reaction time compared to example 2a), 2.13 times of 1-butene are converted to hydroformylation products per unit of time as in example 2a). (Example 2f) in Table 2) EXAMPLE 2G) (Use of a compound of the formula CHgfOCHgCHgjn OCH3, n = 3 to 6) The catalyst phase is prepared and pre-formed using a method similar to example 2d), except that, instead of 9 ml of degassed polyethylene glycol 400, the same volume of a compound of formula CH 3 (OCH 2 CH 2) n OCH 3, n = 3 a 6 is used. After pre-forming, 12.41 g (221 mmoles) of 1-butene are added, corresponding to an olefin to rhodium ratio of 946: 1. The hydroformylation reaction is complete after 50 minutes. The yield of hydroformylation product is 85.9% and the n / iso ratio is 95: 5. Therefore, taking into account the reduced reaction time, 40.0% more than 1 -butene is converted into hydroformylation products per unit of time than in example 2a). (Example 2g) in table 2). 3. HYDROFORMILATION OF PROPENO 3-1. Description of the experimental apparatus The reaction apparatus used for the continuous hydroformylation of propene consists of a reactor (volume: 11), a high pressure separator connected downstream of the reactor and a phase separation vessel connected downstream of the high pressure separator . During hydroformylation, the reactor contains aqueous catalyst solution, unreacted propene, reaction products and synthesis gas. An agitator installed in the reactor ensures a good mix. Propene and water are measured inside a submerged tube that projects into the reactor. The addition of water serves to replace the quantities of water that are carried with the hydroformylation product and are removed from the aqueous catalyst solution. The reaction mixture is removed from the reactor through a submerged dip tube inside the reactor and fed to a high pressure separator. In the high pressure separator, the reaction mixture separates into gaseous and liquid constituents. The gaseous constituents contain essentially unreacted synthesis gas, small amounts of propene and the reaction products are discharged from the high pressure separator, and, after cooling, they are separated from the organic products in an additional, downstream separator. The unreacted synthesis gas released from the organic materials is, after recompression, returned to the reaction. The liquid constituents containing essentially the aqueous catalyst solution and the reaction mixture are taken from the high pressure separator and fed to the phase separation vessel connected downstream of the high pressure separator. In the phase separation vessel, the separation of the reaction product and the aqueous catalyst solution occurs. The reaction product forming the upper phase is separated and subsequently distilled. The lower phase comprising the aqueous catalyst solution is removed from the phase separation vessel and returned to the reactor by means of a pump. In this way, the aqueous catalyst solution is circulated. 3. 2 EXPERIMENTAL PROCEDURE EXAMPLE 3.2a) (Comparative experiment without addition of polyethylene glycol 400) The aqueous catalyst solution consists of 200 ppm of rhodium, tri (m-sulfophenyl) phosphine of trisodium (Na-TPPTS) and rhodium in a molar ratio of 100: 1.

It is prepared by dissolving the corresponding amount of rhodium acetate (III) in an aqueous Na-TPPTS solution and preforming the catalyst solution at 122 ° C under the conditions of hydroformylation in the presence of synthesis gas (CO / H2 = 1/1). The reactor (volume: 1 l) equipped with an agitator is filled with 65% catalyst solution (650 ml) in operational state. The total volume of the catalyst solution is 850 ml, that is, 200 ml of catalyst solution are present in the circulation system (high pressure separator, phase separation vessel and lines) connected downstream of the reactor 83.5 g / h of propene and 0.0955 standard cubic meters per hour of synthesis gas are continuously fed to the reactor. The pressure is 50 bar and the reaction temperature is 122 ° C. The contents of the reactor are mixed vigorously by means of the stirrer. The main residence time of the catalyst solution is 0.43 h-1. The separated catalyst solution in the phase separator vessel (1.5 l / h) is returned to the reactor. The conversion of propene is 90%. This corresponds to a productivity of 0.2 kg of crude hydroformylation product per I of catalyst solution and hour (0.2 kg (1 cat x h) .The ratio of n-butyraldehyde to 2-methylpropanal is 93: 7.

EXAMPLE 3.2.B) Hydroformylation of propene with addition of polyethylene glycol 400 The procedure of Comparative Example 3.2.a) is repeated, except that the aqueous catalyst solution contains 9.5% by weight of polyethylene glycol having an average molecular weight of 400 (PEG 400), the propene supplied is increased to 100 g / h and the Amount of synthesis gas is increased to 0.102 standard cubic meters per hour. The conversion of propene is now from 95% to 96%. This corresponds to a productivity of 0.25 kg of crude hydroformylation product per I of catalyst solution and hour (0.25 kg (cat. I x h)). The ratio of n-butyraldehyde to 2-methylpropanal is 91: 9.

TABLE 1 Hydroformylation of 1-pentene Constant conditions: T = 125 ° C, 240 mmol of olefin, total volume of catalyst phase = 60 ml. e% by weight of additive based on catalyst phase 8450 PR = CH3CHOHCH2 (OCH2CH2) n = 8 to 14 2 Ratio of n-hexanal to 2-methylpentanal (so-hexanal) 7 TEG = H (OCH2CH2) 3OH 3 Contents Rhodium of the organic phase 8 DMPEG = CH3 (OCH2CH2) nOCH3; n = 3 to 6 4 PEG = PEG 400 = H (OCH2CH2) nOH; n = 7 to 10 9 M 500 = CH 3 (OCH 2 CH 2) "OH; n = 9 to 13 TABLE 2: Hydroformylation of 1-butene Constant conditions: Pressure = 50 bar. T = 125 ° C, use of TPPTS as a ligand in a TPPTS: Rh ratio of 100: 1, total volume of catalyst phase = 60 ml. 1 or V, or by weight of additive based on the catalyst phase PEG = PEG 400 = H (OCH 2 CH 2) nOH; n = 7 to 10 Ratio of n-pentanal to 2-methylbutanal (iso-pentanal) 6 M 500 = CH 3 (OCH 2 CH 2) n OH; n = 9 to 13 3 Rhodium content of the organic phase 7 DMPEG = CH3 (OCH2OCH2) nOCH3; n = 3 to 6 Main reaction rate defined as mmoles of aldehyde formed per minute of reaction time

Claims (34)

NOVELTY OF THE INVENTION CLAIMS

1. - A process for preparing aldehydes, which comprises reacting an olefinically unsaturated compound having three carbon atoms with hydrogen and carbon monoxide at 20 to 170 ° C and 1 to 300 bar in the presence of an aqueous phase consisting of rhodium and sulfonated arylphosphines as a catalyst and from 1 to 15% by weight of a compound of formula (1) R (OCH2CH2) nOR1, wherein the triallylphosphines contain at least three radicals - (S? 3) M in which M are identical or different and M is H, an alkali metal ion, an ammonium ion, a quaternary ammonium ion, an alkaline earth metal ion medium or zinc ion medium, and wherein, in the formula (1), R is hydrogen, a straight or branched chain alkyl radical having 1 to 4 carbon atoms or a hydroxyalkyl radical having 1 to 4 carbon atoms, R 1 is hydrogen or a methyl radical and n is an integer e 3 a 50. 2.- A process for the preparation of aldehydes, which comprises reacting a co olefinically unsaturated compound having 4 carbon atoms with hydrogen and carbon monoxide at 20 to 170 ° C and 1 to 300 bar in the presence of an aqueous phase consisting of rhodium and triallylphosphine sulphonated as a catalyst and 8 to 20% by weight of a compound of formula (1) R (OCH

2 CH 2) nOR 1, wherein the triallylphosphines contain at least 3 radicals - (S 3) M in which M is identical or different and M is H, one metal alkaline, an ammonium ion, a quaternary ammonium ion, an alkaline earth metal medium or a zinc ion medium, and wherein, in the formula (1), R is hydrogen, a straight chain alkyl radical or branched that has 1 to 4 carbon atoms or a hydroxyalkyl radical having 1 to 4 carbon atoms, R 1 is hydrogen or a methyl radical and n is an integer from 3 to 50.

3. A process for the preparation of aldehydes, which comprises reacting a compound olefinically unsaturated that has 5 carbon atoms with hydrogen and carbon monoxide at 20 to 170 ° C and 1 to 300 bar in the presence of an aqueous phase consisting of rhodium and sulphonated triallylphosphines as catalyst and from 8 to 30% by weight of a compound of formula (1) R (OCH 2 CH 2) nOR 1, wherein the triallylphosphines contain at least 3 radicals - (S? 3) M in which M is identical or different and M is H, an alkali metal ion, an ammonium ion, a quaternary ammonium ion, an alkaline earth metal ion or zinc ion medium, and wherein, in formula (1), R is hydrogen, a straight or branched chain alkyl radical having 1 to 4 carbon atoms or a hydroxyalkyl radical having 1 to 4 carbon atoms, R 1 is hydrogen or a methyl radical and n is an integer from 3 to 50.

4. The process according to any of the preceding claims, further characterized in that the olefinically unsaturated compound used is an aliphatic olefin having from 3 to 5 carbon atoms.

5. The process according to one or more of the preceding claims, further characterized in that the olefinic compound used is an aliphatic alpha-olefin having 3 to 5 carbon atoms.

6. The process according to one or more of the preceding claims, further characterized in that the sulfonated triallylphosphines are compounds of formula (2) Ar1 S03M Ar2 SO3M wherein Ar1, Ar2 and Ar3 are identical or different and each is a phenyl or naphthyl radical and M is identical or different and is each an alkali metal, an ammonium ion, a quaternary ammonium ion or a half of alkaline earth metal or half zinc ion.

7. The process according to any of the preceding claims further characterized in that the sulfonated triarylphosphine used is a trisulfonated triphenylphosphine.

8. The process according to one or more of claims 1 to 6, further characterized in that the sulfonated triarylphosphine used is trisodium tri (m-sulfophenol) phosphine.

9. The method according to one or more of the preceding claims, further characterized in that the aqueous phase is used in an amount corresponding to 2 x 10"6 to 5 x 10" 2 mmole of rhodium per mole of olefinic compound.

10. The process according to one or more of the preceding claims, further characterized in that the rhodium and the sulfonated triarylphosphines of the formula (2) are used in a molar ratio of 1: 10 to 1: 1000.

11. The process according to one or more of the preceding claims, further characterized in that the rhodium and the sulfonated triarylphosphines of the formula (2) are used in a molar ratio of 1: 50 to 1: 200.

12. The process according to one or more of the preceding claims, further characterized in that the aqueous phase contains from 100 to 1000 ppm of rhodium when sulfonated triarylphosphines of the formula (2) are used.

13. The method as claimed in one or more of the preceding claims, further characterized in that the aqueous phase contains from 200 to 500 ppm of rhodium when sulfonated triarylphosphines of the formula (2) are used.

14. The process as claimed in one or more of the preceding claims, further characterized in that the aqueous phase contains. from 300 to 400 ppm of rhodium when sulfonated triarylphosphines of the formula (2) are used.

15. - The process as claimed in one or more of the preceding claims, further characterized in that the sulfonated triarylphosphines are compounds of formula (3) wherein irp and rti2 are, independently of one another, 0 or 1 and the compounds of formula (3) contain from 3 to 6 -SO3M groups, wherein M is as defined above.

16. The process as claimed in one or more of the preceding claims, further characterized in that the sulfonated triarylphosphines are compounds of formula (4) wherein m3, m4, m5 and m6 are, independently of one another, 0 or 1 and the compounds of formula (4) have from four to eight -SO3M groups, wherein M is as defined above.

17. The process as claimed in one or more of the preceding claims, further characterized in that the rhodium and the sulfonated triarylphosphines of the formula (3) or (4) are used in a molar ratio of 1: 5 to 1: 100 .

18. The process as claimed in one or more of the preceding claims, further characterized in that the rhodium and the sulfonated triarylphosphines of the formula (3) or (4) are used in a molar ratio of 1: 5 to 1: 50. .

19. The process according to one or more of the preceding claims further characterized in that the rhodium and the sulfonated triarylphosphines of formula (3) or (4) are used in a molar ratio of 1: 8 to 1: 15.

20. The process as claimed in one or more of the preceding claims, further characterized in that the aqueous phase contains from 20 to 500 ppm of rhodium when sulfonated triarylphosphines of the formula (3) or (4) are used.

21. The process as claimed in one or more of the preceding claims further characterized in that the aqueous phase contains from 30 to 150 ppm of rhodium when sulfonated triarylphosphines of formula (3) or (4) are used.

22. - The process as claimed in one or more of the preceding claims, further characterized in that the aqueous phase contains from 40 to 100 ppm of rhodium when sulfonated triarylphosphines of the formula (3) or (4) are used.

23. The process as claimed in one or more of the preceding claims, further characterized in that the propene as an olefinic compound is reacted in the presence of an aqueous phase containing from 3 to 10% by weight of the compound of formula (1).

24. The process as claimed in one or more of the preceding claims, further characterized in that the compound of formula (1) used is a polyethylene glycol of formula H (OCH2CH2) nOH, wherein n is an integer from 3 to 50.

25. The process as claimed in one or more of the preceding claims, further characterized in that the compound of formula (1) used is a polyethylene glycol of formula H (OCH2CH2) nOH wherein n is an integer from 4 to 30.

The process as claimed in one or more of the preceding claims, further characterized in that the compound of formula (1) used is a polyethylene glycol of formula H (OCH2CH2) nOH, wherein n is an integer from 6 to 12.

27 The process as claimed in one or more of the preceding claims, further characterized in that the compound of formula (1) used is a compound of formula R (OCH 2 CH 2) n OH wherein R is a methyl radical or β-hydroxypropyl radical and n is an integer from 3 to 50.

28.- The process as claimed in one or more of the preceding claims, further characterized in that the compound of formula (1) used is a compound of formula R (OCH2CH2) nOH, wherein R is a methyl radical or β-hydroxypropyl radical and n is an integer from 4 to 30.

29. The process as claimed in one or more of the preceding claims, further characterized in that the reaction is carried out at 50 to 150 °. C.

30. The process as claimed in one or more of the preceding claims, further characterized in that the reaction is carried out at 100 to 140 ° C.

31. The method as claimed in one or more of the preceding claims, further characterized in that the reaction is carried out at 20 to 150 bar.

32. The method as claimed in one or more of the preceding claims, further characterized in that the reaction is carried out at 30 to 80 bar.

33. The process as claimed in one or more of claims 1 to 32, further characterized in that the reaction is carried out at 100 to 140 ° C.

34. - The process as claimed in one or more of claims 1 to 33, further characterized in that the reaction is carried out at 20 to 150 bar. The method as claimed in one or more of claims 1 to 34, further characterized in that the reaction is carried out at from 30 to 80 bar.