MXPA99000287A

MXPA99000287A - Procedure for the preparation of aldehi

Info

Publication number: MXPA99000287A
Application number: MXPA/A/1999/000287A
Authority: MX
Inventors: Bahrmann Helmut
Original assignee: Celanese Gmbh
Priority date: 1997-12-22
Filing date: 1998-12-16
Publication date: 1999-09-01

Abstract

The present invention relates to a process for preparing aldehydes by hydroformylation of olefins or olefinically unsaturated compounds in the presence of at least one rhodium compound and a non-aqueous non-ionic liquid of the formula (Q +) to Aa-, wherein Q + is a quaternary ammonium cation and / or single charge phosphonium or the equivalent of a multiple charged ammonium and / or phosphonium cation and Aa- is a triarylphosphine sulfonata

Description

PROCEDURE FOR THE PREPARATION OF ALDEHYDES DESCRIPTIVE MEMORY The present invention relates to a process for the preparation of aldehydes by hydroformylation of olefins or olefinically unsaturated compounds in the presence of at least one rhodium compound and in the presence of a non-aqueous ionic ligand liquid of the formula (Q +) a? -a ~ • where Q + is a single-charged quaternary ammonium and / or phosphonium cation or the equivalent of a multiple-charged ammonium and / or phosphonium cation and Aa_ is a sulphonated triallylphosphine. As valuable intermediate compounds, the aldehydes have great economic importance. From these it is possible to prepare, for example, alcohols, carboxylic acids and amines which are used simultaneously as starting materials to produce important end products. It is known that aldehydes can be prepared by reacting olefins with carbon monoxide and hydrogen. The reaction is catalyzed with hydridometalic carbonyls, preferably those of the metals of group VIII of the Periodic Table of the Elements. Although cobalt was the first catalyst metal widely used in the industry, methods for preparing aldehydes using rhodium as the catalyst metal have now been established in the industry.

The preparation of aldehydes can be carried out in a single organic phase. The catalyst, for example rhodium / triphenylphosphine complex, is present here as a solution in the organic reaction mixture. In addition, the preparation of 5 aldehydes can also be carried out in the presence of an organic solvent; the solvents used are, for example, toluene, xylene or tetrahydrofuran. However, the separation of the reaction products and the recovery of the catalysts homogeneously dissolved in the reaction product present problems in this process. In general, the reaction product of the reaction mixture is distilled, but in practice, due to the thermal sensitivity of the aldehydes formed, this method can only be used in the hydroformylation of olefins , ie olefins having up to about carbon atoms in the molecule. In addition, the thermal stressing of the material being distilled can lead to considerable product losses as a result of the formation of byproducts and losses of products.

Catalyst as a result of the decomposition of the catalytically active complexes. These deficiencies can be avoided, if the hydroformylation reaction is carried out in a two-phase system. Such a procedure is described, for example, in DE-C 26 27 354. This process is distinguished by the presence of an organic phase comprising the starting olefins and the reaction product and an aqueous phase in which the catalyst is dissolved. The catalysts used are water-soluble rhodium complexes containing water-soluble phosphines as ligands. The phosphines include, in particular, triallylphosphines trialkylphosphines and arylated or alkylated diphosphines whose organic radicals are substituted by sulphonic acid groups or carboxyl groups. Its preparation is known, for example, from DE-C-26 27 354. The hydroformylation process carried out in a two-phase system in the presence of an aqueous phase containing catalyst is particularly useful in the hydroformylation of lower olefins, in particular ethylene and propylene. However, if higher olefins are used, such as hexene, octene or decene, the conversion is attenuated. The attenuation in the conversion is caused by the decrease in solubility of the higher olefins in the water, since it is assumed that the reaction between the reactants is carried out in the aqueous phase. The olefin conversion is significantly increased, if the phase transfer reagent (solubilizer) is added to the aqueous catalyst solution. In accordance with EP-B-0 562 451, the solubilizers which have been found to be useful are, in particular, cationic solubilizers of the formula [AN (R1R2R3)] + E ~, wherein A is a straight or branched chain alkyl radical, having from 6 to 25 atoms of carbon, R, R, R3 are identical or different and E ~ is an anion, in particular sulfate, tetrafluoroborate, acetate, methosulfate, benzenesulfonate, alkylbenzenesulfonate, toluenesulfonate, lactate or citrate. Carrying out the hydroformylation process in a two-phase system in the presence of an aqueous phase containing catalyst requires not only sufficient solubility of the olefin in the aqueous phase, but also sufficient stability of the olefin to be reacted towards Water. For this reason, water-sensitive olefins, such as acrylic esters or unsaturated acetals, can not be used in this process. To overcome this disadvantage, without yielding to the advantage of the two-phase hydroformylation process, the use of non-polar perfluorinated hydrocarbons has been proposed, e.g. perfluoromethylcyclohexane as the immiscible non-aqueous phase or the organic reaction product, for the catalytic hydroformylation of olefins. However, specific fluorinated ligands, such as tris- (1H, 1H, 2H-perfluorooctyl) phosphine, are necessary to dissolve the rhodium complexes in perfluorinated hydrocarbons (Science 1994, 266, 72). Another way of carrying out the catalytic reactions in a non-aqueous two-phase system is described in CHEMTECH, September 1995, pages 26 to 30. According to this, non-aqueous ionic liquids are liquid at room temperature, v. gr. a mixture of 1,3-dialkylimidazolium chloride and aluminum chloride, and / or ethylaluminum dichloride can be used as non-aqueous solvents in which the catalyst complex is present as a solution. In the prior art, the l-n-butyl-3-methylimidazolium cation is abbreviated as BMI +. An example of a reaction carried out satisfactorily in this manner is the dimerization of olefins in the presence of nickel complexes, e.g. the dimerization of propene to give isomeric hexanes or the dimerization of butene to give isooctenes. Its reaction product forms the upper phase while the nonaqueous ionic liquid containing catalyst forms the lower phase and can be separated by simple phase separation. The non-aqueous ionic liquid containing catalyst can be returned to the process. It is known from Am. Chem. Soc., Div. Pet. Chem (1992), 37, pages 780 to 785, that a non-aqueous ionic liquid which comprises l-butyl-3-methylimidazolium chloride and aluminum chloride can serve as a solvent in which, after the addition of ethylaluminum dichloride and NÍCI2 (PR3), wherein R is isopropyl, the dimerization of propene is carried out. The use of low melting phosphonium salts, e.g. Tetrabutylphosphonium bromide, as a solvent in hydroformylation reactions is described in Journal of Molecular Catalysts, 47 (1988), pages 99-116. According to this, the hydroformylation of olefins, e.g. 1-octene, using ruthenium-carbonyl complexes in the presence of ligands containing nitrogen or phosphorus, e.g. 2, 2'-bipyridyl-1,2-bis (diphenylphosphino) ethane, at temperatures of 120 to 180 ° C gives a mixture of n-nonanol and n-nonanal. In this process, n-nonanol is obtained in a proportion of up to 69% by weight, based on the mixture, so that the complicated distillation step is required to isolate the desired n-nonal. EP-A-0 776 880 explains the hydroformylation of olefins in the presence of quaternary ammonium salts and / or phosphonium as a solvent, preference being given to the use of the cation l-n-butyl-3-methylimidazolium BMT * as a cation. However, use was also made of quaternary diamine salts in which the cation has the formula R1R2N + = CR3-R5-R3C = N + R1R2, wherein R, R2, R3 are identical or different and each is hydrogen or a hydrocarbon radical having 1 to 12 carbon atoms and R is alkylene, e.g. methylene, ethylene or propylene, or phenylene. Suitable anions are, for example, hexafluorophosphate, hexafluoroantimonate, tetrachloroaluminate and tetrafluoroborate. These quaternary ammonium and / or phosphonium salts are liquid at less than 90 °, preferably at less than 85 ° C and particularly preferably at less than 50 ° C. The hydroformylation catalyst is present therein as a solution. The hydroformylation catalyst comprises cobalt, rhodium, iridium, ruthenium, palladium or platinum, as active metal, and a tertiary phosphine or tertiary sulfonated phosphine, a tertiary arsine, tertiary styrene or a phosphite, as a ligand. According to EP-A-0 776 880, the molar ratio of the ligand to the metal is 9.5 some examples of suitable compounds containing the active metals and from which the hydroformylation catalyst is formed under the reaction conditions are dicarbonyl ethyl acetate rhodium and rhodium-carbonyl Rhg (CO)] _ g. Particular preference is given to carrying out the hydroformylation reaction at 30 and up to 90 ° C. Angew. Chem. 1995, 107, No. 23/24, pages 2941 a 2943, also discloses the use of 1,3-dialkylimidazole salts that are liquid at room temperature as a catalyst-containing solvent which is immiscible with the organic reaction mixture to carry out hydroformylation reactions. Here, dicarbonylrodium acetylacetonate is added as a catalyst precursor to a solution of triphenylphosphine in BMI + hexafluorophosphate, and the molar ratio of phosphorus (III) to rhodium can vary from 3 to 10. The catalyst is preformed by the addition of synthesis gas containing hydrogen and carbon monoxide in a volume ratio of 1: 1. After the addition of 1-n-pentene, the reaction is carried out using synthesis gas of the same composition at a temperature of 80 ° C. In this case also, the organic product phase can be separated from the non-aqueous ionic liquid containing catalyst in a simple manner by decanting. All known methods for hydroformylation of olefins use a non-aqueous ionic liquid as a solvent for the catalytically active metal complexes. The use of non-aqueous ionic liquids as solvents introduces additional anions that do not serve as ligands, e.g. hexafluoroantimonate or hexafluorophosphate, in the hydroformylation process. In addition, the prior art known as Angew. Chem. 1995, 107, No. 23/25, pages 2941 to 2943, and EP-A-0 776 880 teaches about a molar ratio of phosphorus to rhodium from 3 to 10. No relationships are disclosed in the prior art higher molars of phosphorus to rhodium. A higher molar ratio of phosphorus to rhodium presumably results in precipitation or an increased loss of the phosphine ligand from the described non-aqueous ionic liquid. A disadvantage of the known processes is, apart from the loss of phosphine ligand, the loss of the catalytically active metal from the non-aqueous ionic liquid to the organic phase. According to the prior art, this disadvantage can be overcome by using charged ligand, e.g. monosulfonated or trisulfonated triphenylphosphine, instead of neutral ligands, e.g. triphenylphosphine, since it is expected that the charged ligands increase the solubility of the catalytically active metal compounds in the non-aqueous ionic liquid. Even if it is possible to reduce the loss of the catalytically active metals in this way by the use of charged ligands, the yields of aldehydes are reduced to only 16-33% (Angew, Chem, 1995, 107, No. 23/25). , pages 2941 to 2943, EP-A-0 776 880). It was therefore an object of the invention to develop a process using a non-aqueous ionic ligand and, after the addition of a catalytically active metal and / or its compound, gives the desired aldehydes simply and in high yields. The invention provides a process for preparing aldehydes by reacting monoolefins, unconjugated polyolefins, cycloolefins or derivatives of this class of compounds with carbon monoxide and hydrogen at temperatures of 20 to 150 ° C and pressures of 0.1 to 20 MPa in the presence of a liquid nonaqueous ionic ligand of the formula (Q +) to Aa ~ and at least one rhodium compound, wherein Q + is a single-charged quaternary ammonium and / or phosphonium cation or the equivalent of an ammonium and / or phosphonium cation of multiple charge and Aa_ is a triarylphosphine of the formula where Ar] _, Ar2 and Ar3 are identical or different aryl groups having from 6 to 14 carbon atoms, the substituents Y ^, Y2 and Y3 are straight or branched alkyl or alkoxy radicals, identical or different, having from 1 to 4 carbon atoms, chloro, bromo, hydroxyl, cyano, nitro or amino groups of the formula NR R, wherein the substituents R] _ and R2 are identical or different and are hydrogen, straight or branched chain alkyl groups , which have 1 to 4 carbon atoms, ml / m2 and m3 are identical or different and are whole numbers of 0 to 5, ri] _, ri2 and n are identical or different and are integers of 0 to 3, where at least one of the numbers n ^, 112 and n3 is equal to or greater than 1, is already nQ_ + n2 + n3, and amines and / or phosphines derived from Q + are present in an excess of up to 5 equivalents on the amounts stoichiometrically required for the formation of (Q +) to Aa ~ or alkali metal and / or alkaline earth metal salts of triarylphosphine Aa ~ are present in an excess of up to 5 equivalents over the amount stoichiometrically required for the formation from (Q +) to Aa ~. It has surprisingly been found that the nonaqueous liquids of ionic ligands of the invention are, after the addition of rhodium and / or its compounds, very useful as a catalyst system for the hydroformylation of olefins or olefinically unsaturated compounds. It has been found that the use of non-aqueous ionic ligands in hydroformylation processes allows the use of a high molar ratio of rhodium phosphorus up to 1000 to 1. A high excess of ligand, e.g. of triphenylphosphine sulfonated, has a stabilizing effect on the catalytically active metal complexes during the catalysis cycle.

In the following, "catalyst system" means the non-aqueous ionic ligand liquid together with the catalytically active rhodium compounds. Stabilized catalyst systems have a low rhodium loss rate and allow frequent recirculation of the used catalyst system to the hydroformylation process without decreasing the catalyst activity and the observed selectivity. Stabilized catalyst systems yield higher aldehyde yields and have longer lives of catalyst operation than unstabilized catalyst systems. When non-aqueous ionic liquids and non-aqueous ionic liquid liquids are used, the prolongation of the catalyst operating lives, as is known to be achievable by means of stabilized catalyst systems, is of particular importance, since the spent catalyst phase, after the discharge of the hydroformylation process, it represents a substantial salt load with which it has to be treated by expensive reprocessing and / or disposal. The depletion of the catalyst system is indicated by an attenuation of the catalyst activity and the selectivity at a level lower than that which is economically acceptable. The decreases in catalytic activity and selectivity are caused, for example, by the accumulation of catalytic degradation products. If two-phase processes are carried out on non-aqueous ionic liquids, the excessively rapid exhaustion of the catalyst system, which requires the subsequent discharge of the hydroformylation process, is therefore a particular disadvantage. The non-aqueous ionic ligand liquids of the invention make it possible to employ a molar ratio of phosphorus to rhodium up to 1000 to 1 which is known to increase the stability and therefore the life of the catalysts substituted with phosphine. It can be assumed that the catalytically active compounds are formed from rhodium, which is added either in the metal form or as usual rhodium, and from the non-aqueous ionic ligand liquid in the presence of carbon monoxide and hydrogen. The non-aqueous ligand fluid ionic and the catalytically active rhodium cond form the catalyst system. The use of non-aqueous ionic ligand liquids of the invention in the hydroformylation reactions makes it possible to dispense with the addition of additional anions which do not serve as ligands in such processes. The non-aqueous ionic ligand liquids of the invention may comprise amines and / or phosphines derived from Q + in an excess over the amount stoichiometrically required for the formation of (Q +) to Aa ~ or alkali metal or alkaline earth metal salts of triarylphosphine Aa ~ in an excess over the amount stoichiometrically required for the formation of (Q +) to Aa_. In general, the excess over the amount stoichiometrically required for the formation of (Q +) to Aa ~ is up to 5 equivalents of amines and / or phosphines derived from Q + or alkali metal or alkaline earth metal salts of triarylphosphine Aa ~; this excess is preferably 0 to 1 equivalent. The Q + cations which can be used to prepare the nonaqueous ionic ligand liquors of the invention are quaternary ammonium and / or phosphonium cations of the formula + NR1R2R3R4 or + PR1R2R3R4 or the formula R1R2N + = CR3R4 and R1R2P + = CR3R4, wherein R1 , R2, R3 and R4 are identical or different and each is hydrogen, with the exception of NH4 +, or a straight or branched chain hydrocarbon radical having from 1 to 20 carbon atoms, for example an alkyl, alkenyl, cycloalkyl radical , arylaryl, aryl or aralkyl. Other cations suitable for preparing the non-aqueous ionic ligand liquids of the invention are heterocyclic ammonium and / or phosphonium cations of the formulas which have 1, 2 or 3 nitrogen atoms and / or phosphorus in the ring. The heterocycles have from 4 to 10, preferably 5 or 6, ring atoms. R1 and R are as defined above. Other suitable Q + cations are the quaternary ammonium and phosphonium cations of the formulas R1R2 + N = CR3 -X-R3C = + NR1R2 R1R2 + P = CR3 -X-R3C = + PR1R2 wherein R1, R and R are identical or different and are as defined above and X is an alkylene or phenylene radical. R1, R2 and R3 are, for example, methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, tertiary butyl, amyl, methylene, ethylidene, phenyl or benzyl groups. X is 1, 2-phenylene, 1,3-phenylene, 1,4-phenylene or an alkylene radical, for example a methylene, ethylene, propylene or 1-4-phenylene radical. Other Q + cations which are suitable for preparing the nonaqueous ionic ligand cycles of the invention are the N-butylpyridinium, N-ethylpyridinium, ln-butyl-3-methylimidazolium, diethylpyrazole, l-ethyl-3-methylimidazolium, pyridinium, triethylphenylammonium cations. and tetrabutylphosphonium. Other Q + cations which are suitable for preparing non-aqueous ionic ligand liquids of the invention are the quaternary ammonium and / or phosphonium cations of the formulas.

R1R2R3N + 4? ). N + R4R5R6 (quaternary diamines) RlR2R3p +. x j. P + R R5R6 (quaternary diphosphines wherein R1, R, R3, R4, R5 and RS are identical or different and are hydrogen, branched or straight chain hydrocarbon radicals having from 1 to 20 carbon atoms, for example, alkyl, alkenyl, cycloalkyl, alkylaryl, aryl radicals or aralkyl and X is 1,2-phenylene, 1,3-phenylene, 1,4-phenylene or an alkylene radical (CHR 7) b, wherein R 7 is hydrogen or a hydrocarbon radical having from 1 to 5 carbon atoms , for example methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or t-butyl, and b is an integer from 1 to 8. Some examples of X are the methylene, ethylene, propylene, butylene and 1,4-phenylene. Reference is hereinafter made to the quaternary ammonium cations of the formula R R R N + (X) N + R R R, as quaternary diamines. Quaternary diamines which are suitable for preparing the non-aqueous ionic ligand liquids of the invention include those quaternary diamines of the formula R 1 R 2 R 3 N + (CHR 7) b N + R 4 R 5 R 6 in which R 1, R 2, R 3, R 4, R 5 and R are identical or different and each one is hydrogen, n-butyl, n-pentyl, n-hexyl, n-heptyl, i-heptyl, n-octyl, i-octyl, n-nonyl, i-nonyl, n-decyl, i-decyl , n-undecyl, i-undecyl, n-dodecyl or i-dodecyl, r is hydrogen, methyl or ethyl and b is 2, 3, 4, 5 or 6. Quaternary diamines are particularly suitable for preparing non-aqueous liquids of ionic ligand of the invention are those which are derived from l-amine-3-dialkylaminopropanes of the formula.

R1R2N-CH2-CH2-CH2-NH2 wherein R and R are straight or branched chain alkyl radicals, identical or different, having from 4 to 20 carbon atoms, for example n-pentyl, n-hexyl, n-heptyl, i-heptyl, n-octyl radicals , i-octyl, i-nonyl, n-nonyl, n-decyl, i-decyl, n-undecyl, i-undecyl, n-dodecyl or i-dodecyl. The non-aqueous ionic ligand liquids of the invention can be prepared particularly advantageously if l-amino-3- (di-n-heptyl) aminopropane, 1-amino-3- (di-i-heptyl) -aminopropane is used. , l-amino-3- (di-n-octyl) -aminopropane, l-amino-3- (di-i-octyl) aminopropane, l-amino-3- (di-n-nonyl) aminopropane, l-amino -3- (di-i-nonyl) -aminopropane, l-amino-3- (di-amino-3-di-n-undecyl) aminopropane, l-amino-3- (di-i-undecyl) aminopropane, l -amino-3 - (di-n-dodecyl) aminopropane or l-amino-3- (i-dodecyl) -aminopropane, to prepare the quaternary diamines. ^ L-amino-3-dialkylaminopropanes are prepared by reacting the N, N- (dialkyl) amine of the formula R 1 R 2 NH where R 1 and R 2 are straight or branched chain alkyl radicals, identical or different, from 4 to 20 carbon atoms. carbon, in particular n-butyl groups, n-pentyl, n-hexyl, n-heptyl, i-heptyl, n-octyl, i-octyl, i-nonyl, n-nonyl, n-decyl, i-decyl, n-undecyl, i-undecyl, n -dodecyl or i-dodecyl, with acrylonitrile according to known methods (see Ullmanns Encyclopedia of Industrial Chemistry Vol. A2, 1985). Additional diamines derived from Q +, it is possible to use tricyclodecanediamine and N, N-dimethyltriocyclode decanediamine. The triallylphosphines Aa ~ used to carry out the process of the invention obtainable from the alkali metal and / or alkali metal salts of the triarylphosphines of the formula where Ar ^, Ar2 and Ar3 are identical or different aryl groups having from 6 to 14 carbon atoms, the substituents Y] _,? 2 and? 3 are straight or branched alkyl or alkoxy radicals, identical or different, that have 1 to 4 atoms carbon, chloro, bromo, hydroxyl, cyano, nitro or amino groups of the formula NR R, wherein the substituents R ^ _ and R2 are identical or different and are hydrogen, straight-chain or branched alkyl groups, having 1 to 4 carbon atoms, M is lithium, sodium, potassium, calcium or barium, m ^, rri2 and I? I3 are identical or different and are integers from 0 to 5, flfc n] _, 112 and n3 are identical or different and are integers of 0 to 3, wherein at least one of the numbers n ^, n2 and 3 is equal to or greater than 1, which are known from DE-A-26 27 354. The preferred triarylphosphines are those in the which the groups Arx, Ar2, Ar3 are phenyls groups, each of Y] _, Y2 and Y3 is a methyl, ethyl, methoxy or ethoxy group and / or a chlorine atom, and the cationic radicals M are inorganic fc cations of sodium, potassium, calcium or barium. Particularly suitable triarylphosphines are those in the Where Ar ^, Ar2 and Ar3 are a phenyl group, m ^, m2, 1113 are 0, ri] _, n2 and n3 are 0 or 1 and the sum of n ^ + n2 + n3 is from 1 to 3 and in which sulfonated groups are in the meta position. Aqueous solutions of the sodium, potassium, calcium or barium (sulfophenyl) diphenylphosphine, di (sulfophenyl) -25-phenylphosphine or tri (sulfophenyl) -phosphine salts are particularly suitable. It is also possible to use mixtures of these aqueous solutions. However, it is advantageous to use a single aqueous solution of salt of one of the alkali metals and / or the above-mentioned alkali ferrous metals, in particular an aqueous solution of sodium or potassium salt; this solution may also contain a mixture of (sulfophenyl) -diphenylphosphine di (sulfophenyl) phenylphosphine and tri (sulfophenyl) phosphine. A suitable mixture is obtained to carry out the hydroformylation process of the invention, in the sulfonation of triphenylphosphine, as is known, by example, by DE-A 26 27 354. If tricyclodecanediamine or N, N'-dimethyltricyclo-decanediamine is used as the amine to prepare the non-aqueous ionic liquid, a mixture having a content as high as possible should be used. di (sulfophenyl) -phenylphosphine. The process for preparing the non-aqueous ionic ligand liquid is a subject subject to consideration of a patent application filed on the same day. The process of the invention can be used to react monoolefins, unconjugated polyolefins, cyclic olefins and derivatives of these unsaturated compounds. The olefins can be straight chain or branched and the double bonds can be terminal or internal. Some examples of olefins that can be used in some process are ethylene, propylene, 1-butene, 2-butene, 1-pentene, 2-methyl-1-butene, 1-hexene, 2-hexene, 1-heptene, 1-octene , 3-octene, 3-ethyl-1-hexene, 1-decene, 3-undecene, 4-4-dimethyl-l-nonene, dicyclopentadiene, vinylcyclohexene, cyclooctadiene and styrene. Some derivatives of the types of olefins mentioned that can be hydroformylated by the claimed method are, for example, alcohols, aldehydes, carboxylic acids, esters, nitriles and halogen compounds, allyl alcohol, acrolein, methacrolein, crotonaldehyde, methyl acrylate, crotonate of ethyl, diethyl fumarate and diethyl methalate and acrylonitrile. The process of the invention allows the hydroformylation, in particular, water sensitive, and olefin derivatives, e.g. vinyl acetate, vinyl propionate, vinyl butyrate, allyl acetate, allyl propionate, allyl butyrate, acrylates having from 4 to 20 carbon atoms, acroleindialkylacetals of alkyl groups containing from 1 to 17 carbon atoms and others from olefin olefin derivatives having a group sensitive to hydrolysis, v.gr. an ester or amide group, and the molecule, with good yields. The process is used particularly satisfactorily olefins and olefin derivatives having from 2 to 20 carbon atoms. The reaction mixture comprising the olefin used and the aldehyde formed can be used as an organic phase, with or without the addition of solvent. If a solvent is used, preference is given to the use of toluene, o-xylene, m-xylene, p-xylene, mesitylene, benzene, cyclohexane, tetrahydrofuran, n-hexane, n-heptane or n-octane.

Rhodium is used as a metal or as a compound. The metallic form is used 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 monocarboxylic and polycarboxylic acids, e.g. Rhodium 2-ethylhexanoate, rhodium acetate, rhodium oxalate, rhodium propionate or rhodium malonate. It is also possible to use rhodium hydrogen salts of inorganic oxo acids v. rhodium nitrate or rhodium sulfate, the various oxides of rhodium or otherwise rhodium-carbonyl compounds, such as Rh3 (CO) 12 ° Rn6 (c °) 16 ° rhodium complexes, e.g. rhodium cyclooctadienyl rhodioacetylacetonate compounds. Rhodium-halogen compounds are less suitable because of the corrosive behavior of the halide ions. Preference is given to rhodium oxide and, in particular, rhodium acetate and rhodium 2-ethylhexanoate. The catalyst system can be formed first in a preforming step and then added as a previously formed catalyst system to the reaction mixture. In this case, the desired amount of rhodium, preferably as a solution of rhodium 2-ethylhexanoate, is added to the non-aqueous ionic ligand liquid and the reaction mixture is treated at a temperature of 100 to 120 ° C with a synthesis gas at a pressure of 0.5 to 5 MPa for a time up to 5 hours. After the previous formation of the catalyst, the reaction of the olefins with hydrogen and carbon monoxide is carried out at temperatures of 20 to 150 ° C, preferably 80 to 140 ° C and in particular 100 to 125 ° C, and pressures from 0.1 to MPa, preferably from 1 to 12 MPa and in particular from 3 to 7 MPa. The preliminary formation step can also be carried out in the presence of a solvent, eg in the presence of toluene, o-xylene, m-xylene, p-xylene, cyclohexane or heptane. Preference is given to using toluene or cyclohexane as the solvent. The composition of the synthesis gas, ie the ratio of carbon monoxide to hydrogen, can be varied within wide limits. In general, synthesis gas is used in which the volume ratio of carbon monoxide to hydrogen is 1: 1 or differs only a little from this value. The catalyst system can be prepared in an equally satisfactory manner under the reaction conditions, ie in the presence of the olefin. In addition, the olefin and the aldehyde can serve as a solvent for the catalyst. If an additional solvent is used, preference is given to the use of toluene, o-xylene, m-xylene, p-xylene, cyclohexane, mesitylene or n-heptane, in particular toluene or cyclohexane. The rhodium concentration is from 2 to 1000 ppm by weight, preferably from 3 to 400 ppm by weight and particularly preferably from 5 to 100 ppm by weight, based on the amount of olefin used. The at least sulfonated triarylphosphines Aa, which is a constituent of the non-aqueous ionic ligand liquid of the invention, are present in an excess based on the amount of rhodium used. ^ The rhodium ratio of triarylphosphine Aa Sulfonata, also expressed as the ratio of rhodium to phosphorus (III), can be varied within wide limits; in general, 2 to 1000 moles of phosphorus (III) may be employed per mole of rhodium. Preference is given to a molar ratio of phosphorus (III) to rhodium from 3 to 300 and in particular from 20 to 100. 10 The reaction can be carried out or intermittent or J continuously. After the reaction is complete, an organic upper phase containing aldehyde is obtained, the catalyst system is present as the lower base; these two phases can be prepared one from the other by simple separation of 15 phases. After phase separation, the catalyst system can be returned by the hydroformylation process. The following examples illustrate the process of the invention but do not constitute a restriction.

EXAMPLE 1 Hydroformylation of n-hexene in the presence of l-amino-3- (di-i-nonyl) aminopropane / trisulfophenyl-phosphine It was made use of a non-aqueous liquid ionic ligand comprising l-amino-3- (di-i-nonyl) minopropanol tri (sulfophenyl) phosphine as described in the patent application filed on the same day, which is incorporated herein by reference. An excess of 0.45 equivalent of sodium salts of triarylphosphine is present in the non-aqueous liquid of the ionic ligand used. 420 g of ionic ligand non-aqueous liquid was placed in a 1 liter autoclave and mixed with a solution of rhodium 2-ethylhexanoate in 2-ethylhexanol in an amount corresponding to a molar ratio of phosphorus (III) to rhodium a 1. Subsequently, n-hexene in such amount in rhodium concentration, based on the amount of olefin used, was 400 ppm by weight. The reaction with synthesis gas was carried out at a temperature of 125 ° C under a pressure of 4 MPa for a time of 1.5 hours. The reaction was then stopped, the autoclave was removed and the organic phase (the reaction product) was extracted through a submerged tube and analyzed. The olefin conversion is 71%, the ratio of n-heptanal to 2-methylhexanal is 69:31. The catalyst system was recirculated twice without conversion and without deterioration of the selectivity.

EXAMPLE 2 Hydroformylation of n-hexene in the presence of l-amino-3- (di-n-octyl) aminopropane / trisulfophenyl-phosphine Use was made of a non-aqueous ionic ligand liquid comprising l-amino-3- (di-n-octyl) aminopropanol tri (sulfophenyl) phosphine as described in the patent application filed on the same day, which is incorporated in the present by reference. An excess of 1.1 equivalent to l-amino-3- (di-n-octyl) aminophosphine being present in the non-aqueous liquid of the ionic ligand used. 485 g of ionic ligand non-aqueous liquid was placed in an autoclave with 306 g of cyclohexane and mixed with a solution of rhodium 2-ethylhexanoate in 2-ethylhexanol in an amount corresponding to a molar ratio of phosphorus (III) to rhodium from 136 to 1. Subsequently, n-hexene was added in such amount in rhodium concentration, based on the amount of olefin used, was 400 ppm by weight. The reaction with synthesis gas was carried out at a temperature of 125 ° C under a pressure of 2.5 MPa for a time of 45 minutes. The reaction was then stopped, the autoclave was removed and the organic phase (the reaction product) was extracted through a submerged tube and analyzed. The olefin conversion is 97%, the ratio of n-heptanal to 2-methylhexanal is 66:34.

EXAMPLE 3 Hydroformylation of n-hexene in the presence of l-amino-3- (di-n-octyl) aminopropane / trisulfophenyl-phosphine; recirculation tests The catalyst system used in Example 2 was repeatedly used for the hydroformylation of n-hexene under the same hydroformylation conditions in Example 1. As can be seen in Table 1, a yield of the aldehydes is observed, even after the multiple recirculation of the catalyst system. It was surprisingly found that when nonaqueous ionic ligand liquids of the invention are used, the rhodium loss rates (amount of rhodium found in 1 kg of the organic reaction product) decrease steadily over the multiple recirculation.

TABLE 1 Recirculation test for the hydroformylation of n-hexene using the catalyst phase in Example 2

Claims

NOVELTY OF THE INVENTION CLAIMS

1. A process for preparing aldehydes reacts as olefins, unconjugated polyolefins, cycloolefins or derivatives of this class of compounds with carbon monoxide and hydrogen at temperatures of 20 to 150 ° C and pressures of 0.1 to 20 MPa in the presence of a non-liquid liquid. aqueous ionic ligand of the formula (Q +) to Aa ~ y Por 1 ° minus a ferrous compound, wherein Q + is a quaternary ammonium cation and / or phosphonium charge wavelet or equivalent of an amino and / or phosphonium cation of multiple charge and Aa ~ is a triarylphosphine of the formula where Ar ^, Ar2 and Ar3 are identical or different aryl groups having from 6 to 14 carbon atoms, the substituents Y] _, Y2 and Y3 are straight or branched alkyl or alkoxy radicals, identical or different, having from 1 to 4 carbon atoms, chloro, bromo, hydroxyl, cyano, nitro or amino groups of the formula NR- ^ R, wherein the substituents R ^ _ and R2 are identical or different and are hydrogen, alkyl groups of chain straight or branched, having 1 to 4 carbon atoms, m ^,? ri2 and rri3 are identical or different and are numbers 10 integers from 0 to 5, n ^, n2 and n3 are identical or different and are fl integers from 0 to 3, where at least one of the numbers n ^, n2 and n3 is equal to or greater than 1, and is n ^ + n2 + n3, and amines and / or phosphines derived from Q + are present in an excess of up to 5 equivalents over the amounts Stoichiometrically required for the formation of (Q +) to Aa or salts of alkali metals and / or alkaline earth metals of triarylphosphine Aa are present in an excess of up to 5 equivalents over the amount stoichiometrically required for the formation of (Q +) a Aa ~.

2. The process according to claim 1, characterized in that amines and / or phosphines derived from (Q +) are present up to 1 equivalent over the amount estequeometrically required for the formation of (Q +) to Aa ~ or salts of metals alkaline or metal Alkaline-earths of the triarylphosphine Aa ~ are present in an excess of up to 1 equivalent over the amount estequeometrically required for the formation of (Q +) to Aa ~.

3. The process according to claim 1 or 2, wherein Q + is a quaternary ammonium cation and / or phosphonium of the formula + NR1R2R3R4, + PR1R2R3R4, R1R2N + = CR3R4 or R1R2P + = CR3R4, OR wherein R, R2, R3 and R are identical or different and each is hydrogen, with the exception of H +, or a straight or branched chain hydrocarbon radical has from 1 to 20 carbon atoms and in which the heterocycles have 4 to 10 ring atoms.

4. The process according to claim 1 or 2, Q + is a quaternary ammonium cation and / or phosphonium of the formula R1R2 + N = CR3-X-R3C = + NR1R2 or R1R2 + P = CR3-X-R3C = + PR1R2, wherein R1, R2 and R3 are identical or different and each one is hydrogen or a straight or branched chain hydrocarbon radical having 1 to 20 carbon atoms and X is an alkylene or phenyl radical.

5. The process according to claim 1 or 2, further characterized in that Q + is a cation N-butylpiperidinium, N-ethylpyridinium, l-n-butyl-3-methylmidazolium, pyridinium, triethylphenylammonium or tetrabutylphosphonium.

6. The process according to claim 1 or 2, wherein Q + is the quaternary ammonium cation and / or phosphonium of the formula R1R2R3N + (X) N + R4R5R6 or R1R2R3P + (X) P + R4R5Rd, wherein R1, R 2, R 3, R 4, R 5 and R 6 are identical or different and each is hydrogen or a straight or branched chain hydrocarbon radical having from 1 to 20 carbon atoms and X is 1,2-phenylene, 1,3-phenylene , 1,4- phenylene or a radical alkylene radical (CHR 7) b, wherein R 7 is hydrogen or a hydrocarbon radical having 1 to 5 carbon atoms and b is an integer from 1 to 8.

7. The process according to any of claims 1, 1 and 6, wherein R, R, R, R, R and R are identical or different and are n-butyl hydrogen, n-pentyl, n-hexyl, n-heptyl, i-heptyl, n-octyl, i-octyl, n-nonyl, i-nonyl, n-decyl, i-decyl, n-undecyl, i-undecyl, n - dodecyl or i-dodecyl, R is a hydrogen, methyl or ethyl or is 2, 3, 4, 5, or 6.

8. The process according to any of claims 1, 2 and 7, wherein R1 and R2 are identical or different and are n-butyl, n-pentyl, n-hexyl, n-heptyl, i-heptyl, n-octyl, i-octyl, n-nonyl, i-nonyl, n-decyl, i-decyl , n-undecyl, i-undecyl, n-dodecyl or i-dodecyl, R, R, R5 and R ° are hydrogen, R is hydrogen and b is 3.

9. The process according to claim 1 or 2, in where Q + is a tricyclodecanediamine cation or the N, N'-dimethyl tricyclodecanediaminium cation.

10. The process according to one or more of claims 1 to 9, further characterized in that from 2 to 1000 moles, preferably from 3 to 300 moles, in particular from 20 to 100 moles, of phosphorus (III) are used per rhodium mol

11. The process according to one or more of claims 1 to 10, further characterized in that the rhodium concentration is from 2 to 1000 ppm by weight, preferably from 3 to 400 ppm by weight and in particular from 5 to 400 ppm. 100 ppm by weight, based on the amount of olefin used.

12. The process according to one or more of claims 1 to 11, further characterized in that the reaction is carried out at 20 to 150 ° C, preferably at 80 to 140 ° C and in particular at 100 to 125 ° C. .

13. The process according to one or more of claims 1 to 12, further characterized in that the reaction is carried out at pressures from 0.1 to 20 MPa, preferably from 1 to 12 MPa and in particular from 3 to 7 MPa.

14. The process according to one or more of claims 1 to 13, further characterized in that olefins or olefin derivatives having 2 to 7 carbon atoms are used.

15. The process according to one or more of claims 1 to 14, further characterized in that the organic phase containing aldehyde and the nonaqueous liquid of rhodium-containing ionic ligand are separated from each other by phase separation and the liquid nonaqueous ionic ligand containing rhodium that has been separated seventy or partially to the hydroformylation reactor.

16. A catalyst for the hydroformylation of monolefins, unconjugated polyolefins, cycloolefins or derivatives of this class of compounds comprising rhodium and the non-aqueous ionic liquid of the formula (Q +) to Aa ~, wherein Q + is a cation of quaternary ammonium and / or single-charge phosphonium equivalent of a multiple-charged ammonium and / or phosphonium cation Aa ~ is a triarylphosphine of the formula where Ar ^, Ar2 and r3 are identical or different aryl groups having from 6 to 14 carbon atoms, the substituents Y1, Y2 and Y3 are straight or branched alkyl or alkoxy radicals, identical or different, having 1 to 2 carbon atoms. to 4 carbon atoms, chloro, bromo, hydroxyl, cyano, nitro or amino groups of the formula NR -'- R2, wherein the substituents R] _ and R2 are identical or different and are hydrogen, straight-chain alkyl groups or branched, having 1 to 4 carbon atoms, m] _, 12 and 1113 are identical or different and are integers from 0 to 5, nx, n2 and n3 are identical or different and are integers from 0 to 3, wherein at least one of the numbers n ^, n2 and n3 is equal to or greater than 1, is already n] _ + n2 + n3, and amines and / or phosphines derived from Q + are present in an excess of up to 5 equivalents on the quantities stoichiometrically required for the formation of (Q +) to Aa_ or salts of alkali metals and / or alkaline earth metals of the t riarylphosphine Aa ~ are present in an excess of up to 5 equivalents over the amount stoichiometrically required for the formation of (Q +) to Aa ~.