MXPA95004637A - Procedure for the preparation of formilcarboxil acid esters - Google Patents

Abstract

A process for the preparation of di- and polyformylcarboxylic esters is described by hydroformylation of polyunsaturated fatty acid esters. The reaction is carried out in the presence of an aqueous solution containing, as a catalyst, complex radiocarbonyl / phosphine compounds and, additionally, a surfactant.

Description

PROCEDURE FOR THE PREPARATION OF FORMILCARBOXILIC ACID ESTERS DESCRIPTION OF THE INVENTION The invention relates to a process for the preparation of esters of di- and poly-yl-carboxylic acids, by the hydrolyzing of polyunsaturated fatty acid esters, &n the presence of an aqueous solution containing compounds rhodiumcarbonyl / phosphine complexes as a catalyst and, additionally, a surfactant. The hydrophobicity of the stools of unsaturated fatty acids is of increasing interest. This is mainly because natural raw materials or substances prepared from natural raw materials, which are available in large quantities, are often used as starting materials. The reaction products of hydroformylation, the mono- or polycarboxylic acid esters, which may even contain double reactive ligatures, are desired intermediates. They can be processed additionally to multipurpose products, such as polyamines, polyurethanes, alkyd resins, softeners and synthetic lubricants. The hydroflumeration of higher olefinically polyunsaturated compounds has already been investigated several times. In said reaction, it is problematic that the high molecular weight of the starting material and the reaction product makes purification and rec. Catalyst ion dissolved homogeneously in the reaction product, for example, by distillation. By using polyunsaturated compounds with isolated double bonds, but which are found between each other, the hyíroforroilßciún is achieved by avoiding the subsequent isomerization of the double ligature only with the help of complex catalyst systems of rhodiumcarbon and phosphine. tertiary A decisive problem for the profitability of the process is the loss-free separation of the homogeneously dissolved catalyst system, of the reaction product; as well as its recirculation in active form to the hydroformylation reactor. Until now, it has only been possible to separate the rhodium / phosphine catalyst from the reaction mixture containing the formyl fatty acid ester from the hydroformylation of the monounsaturated fatty acid ester. However, the procedure allows recovery of the quantities used, in which the catalyst remains inactive, and the phosphine portion of the catalyst system is completely lost (3. Amec Oil Chem. Soc., Volume 50, 4-55 (1973). )). The methyl esters of linoleic acid and linolenic acid can be hydroformylated in the presence of heterogeneized rhodiumcarbonyl / phosphine complex catalysts on a polysilope base (Chemikee-Zeitung, 115 (1991, pages 39 et seq.)). The process produces, by the addition of the methyl ester of linoleic acid, the ester of mono- and di-formyl stearic acid in yields up to 95%, based on the di-unsaturated ester used. Also the linoleic acid produces, by hydroformylation in the presence of said catalyst system, exclusively the diforyl compound; In contrast, in all cases, the threefold products are obtained in smaller quantities. The rhodium portion is in the middle approximately O.SY of the original noble metal used. No less important is that a portion of the catalyst metal is homogeneously dissolved in a weight equal to the fixed metal, so that the hydroformylation can not only take place in a solid bed of catalyst, but also in solution. Therefore, there was a need for a process that would allow the hydroformylation of acid esters in unsaturated cases, where the polyunsaturated fatty acid esters could be hydrolyzed not only partially, but in their entirety. Additionally, the loss of noble metal should be avoided. The need described above is solved by means of a process for the preparation of esters of fldi- and polyfor-ilcarboxylic acids. It is characterized by reacting the ester of polyunsaturated fatty acids and monoalcohols of low molecular weight, at temperatures of 100 up to 10 ° C and at pressures of 5 35 MPa, in the presence of an aqueous solution containing the complex rhodium phosphine compound as catalysts, and additionally a surfactant, with carbon and hydrogen core. The hydroformylation of olefins with more than 6 carbon atoms per molecule, in the presence of an aqueous solution, which contains complex rhodium compounds as catalyst and also, as a dissolving aid, a quaternary ammonium salt, is known from EP-B -157 316. An improvement to this process can be found in EP-B-163 231- *. According to the teachings of this patent document olefins of 6 to 20 carbon atoms are reacted with hydrogen and carbon monoxide, the presence of rhodium or a sulfonated arylphosphine, whose cation is a quaternary ammonium ion. Both procedures refer exclusively to the reaction of monounsaturated compounds which, additionally, do not contain any functional group. Surprisingly, according to the new procedure it is possible to hydrophorate at the same time the double bonds contained several times in the molecule of ester and also the double internal ligatures; so that, for example, diformyl products can be obtained from n-unsaturated compounds and t-formyl products from t-unsaturated compounds. The starting compounds for the process according to the invention are the esters, one component of which is a polyunsaturated fatty acid, especially di-unsaturated and tri-unsaturated, from & to 25 carbon atoms, preferably 10 to 20 carbon atoms per molecule, and whose other component is a saturated alcohol of 1 to 10 carbon atoms per molecule, preferably methanol. These steres are obtained from natural oils, which can eventually be refined and destined, by transesterification. Examples of natural oils that serve as a base for the acid components of the starting ester are: cottonseed oil, thistle oil, peanut oil, pumpkin seed oil, linseed oil, corn oil, soybean oil and sunflower oil. Co-catalysts are used in the process, which compounds rhodium compounds, which contain soluble complex-soluble phosphite, ie salts whose anion is a phosphine, which contain at least one sulfonated or carboxylated aromatic radical. The term "phosphine" further includes those trivalent phosphorus compounds, in which the phosphorus atom ingredient is a heterocyclic ring. The aromatic radical can be attached directly or through other groups, to the phosphine atom of the phosphine. Examples of the aromatic radicals are the phenyl and naphthyl radicals. They may be sulfonated or carbonized one or more times and, additionally, may be substituted with other groups of atoms or atoms, such as alkyl, hydroxyl, halide. The monophosphine anions preferably correspond to the general formula (I): / ftr1 / \ / Y -'- n / •• "• / X1BM / / p 12 \ \ \ Yian \" \ X3M \ / Ar3 \ Y: 3n 3 (1) In it, each of Ar: 1-, Ar12, Ar3 means a fepilo or naphthyl group; yield one of Y - »Y58, Y3 is an alkyl group of zadens. straight or branched, of the 4 carbon atoms, an alkoxy group, an halogen atom, the OH-, CN-, N02 or R ^ -R8-N groups, where R x and R12, in each case, represents a straight or branched chain alkyl group, ds 1 to 4 carbon atoms; each of X? -, Xra, X3 is a sulphonate radical IS03 ~ > and / or carboxylate (C00 ~); ni, n2 and n3 are the same or different, and are whole numbers from 0 to 5. M is an alkali metal ion, a chemical equivalent of an alkaline metal or zinc ion, an ammonium or quaternary ammonium ion of the general formula N (R Rl * R! 3R?) - wherein each of R3, Rl-, s, R * > represents a straight or branched chain alkyl group, of 1 to carbon atoms. Preferred are compounds of the above-described general formula, in which each of Ar1-, Ar58, Ar3 means a phenyl radical and cs.da. one of X1-, X22, X3 means a sulphonate radical located in the meta position with respect to phosphorus (tis (m-sulfonatofeni 1) phosphine, abbreviated TFPTS). Another monophosphine group suitable as a component of the catalyst is obtained by sulfoalkylation of dialkyl or diarylphosphines with 1,2-, 1,3- or 1,4-sultones: (CH2) n / '\ R-CH S02 \ / \ / 0 (wherein n = 0, 1 or 2 and R = H, alkyl); for example, which corresponds to: CH2 CH2 S02 A2P-Wa + i i > A2P (CH2), 4-S03Na CH2 O \ / CH2 wherein A represents the same or different alkyl or aryl radicals. The anion can also be obtained, in addition to monophosphines, also from polyphosphonates, especially diphosphines, which contain at least one sulfonated or carboxylated aromatic radical. Diphosphine anions are preferably obtained from diaryl compounds of the general formula (2) ( which are substituted with at least one sulphonate radical (S03 ~ 5 or carboxylate (C00 ~). In the general formula, the R? -representan ally or different alkyl, cycloalkyl, phenyl, tolyl or naphthyl radicals, the R12 are the same or different and meaning hydrogen, alkyl or alkoxy radicals of the 14-carbon atoms, in addition, cycloalkyl, aryl or aryloxy radicals of 6 to carbon atoms, or a ringed benzene ring, the m are the same or different and represent whole numbers of O to 5 and the n are possibly the same or different and represent integers from 0 to 4. Sulfonated compounds which are accessible by ordinary methods are preferred. Proven products of this class of compounds are those products which are obtained by sulfonation. , 2'-bisídi fen.i lfosf ino et il) -l, 1 '-bifepi lo or 2,2'-bis (diphenylphosphinoethyl) -1, 1'-biphenyl. As an example of the anions of a heterocyclic phosphorus compound, there can be mentioned 3,4-dimet i 1-2, 5,6-tris (p-sulfonatophenyl) -l 1 -fosfanorbornadiene.

Alkali salts or ammonium salts, especially the sodium salts, of the sulphonated or carboxylated phosphines are usually used as the catalyst ingredient. An essential condition of the new process is the addition of a surfactant (also referred to as a solution promoter, phase transfer agent, surfactant or amphiphilic reagent) to the aqueous catalyst solution. By the designation of surfactants it is meant materials or mixtures of materials that are treatable with both the aqueous phase (the catalyst) and also with the organic phase (the unsaturated fatty acid ester) and in both phases are soluble at least at elevated temperatures. The purpose of the surfactant is to improve the solubility of the fatty acid ester ep the catalyst solution. This is achieved when the portion of the surfactant is added to the micelles above the characteristic micelle-forming concentration of each surfactant (see Ullmanns Encyclopaedia der technischen Chemie, 4- edition, 19 & 2, volume 22). , pages 4-64-, 4-65). The ester molecules are found in the micelles and in that way are transported in the water-soluble catalyst phase, in which the reaction with the isnt is gas takes place. In correspondence with its structure, anionic surfactants, such as soaps, are differentiated. alkyl sulfates, alkylbenzene sulphonates and phosphates, cationic surfactants, the most important representatives of which are the salts of tetraalqui lamopio; amphoteric surfactants (amphotensidates 5 containing zwitterionic hydrophilic groups and represented by aminocarboxylic acids, betaine, sulfobetaine as well as amine oxide, and finally, nonionic surfactants, among others). which may be mentioned are the alkyl ethers and polyalkylene glycol alkyl phenol, the fatty acid alkylamine and the fatty acid ester, and the amphoteric surfactants are preferred for use in the process according to the invention. especially, the cationic surfactants, for example: tety'ahexy-lamonium bromide, tetradecylammonium bromide, N-dodecyl-1, N, N-tri and 1-amoxy bromide, N-tetradecylN bromide, NN- tri eti lamonium, N-hexadecyl-M, N, N-trimethylammonium bromide, N-octadecyl-N, N, N-tri and ylammonium bromide and amphoteric surfactants, such as: N, Nd imet i Idodeci laman ia ~ betaine; N-oxide or of N, N-dimethyloxylamine, N, N-dimethyldecylamine N-oxide, N, N-N-dimethydodocylamine N, N, -dimet and Itetradec-amine N-oxide. The surfactants can be used as individual substances or as mixtures. The concentration of the surfactant ep the aqueous catalyst solution is above the critical micelle forming concentration, which is given under the reaction conditions of the hydroformylation reaction. The reaction of the poly fatty acid ester instilled with hydrogen and carbon dioxide is carried out at temperatures of 100 to 100 ° C, especially 120 to 450 ° C and pressures of 5 to 35 MPa, preferably 15 to 50 ° C. 20 MPa. . The catalyst can be added preformed to the reaction system. With equally good results, the rhodium or rhodium compounds and the aqueous solution of the sulphonated or carboxylated phosphodies can also be added to the reaction mixture under the reaction conditions also in the presence of the fatty acid. In addition to the metal rhodium in finely divided form, rhodium salts soluble in water, such as rhodium chloride, rhodium sulfate, rhodium acetate; or co-compounds soluble in organic media, such as rhodium 2-e and hexanoate or co-insoluble compounds, such as rhodium oxide. The concentration of rhodium in the aqueous catalyst solution is between 100 and 600 ppm by weight, preferably between 300 and 400 ppm by weight, with respect to the solution. In order to effect the isomeization of the unsaturated fatty acid ester, the sulfonated or carbohydrated phosphine is added in an amount such that for each mole of rhodium there is at least 20 moles, preferably 4-0 to 60 moles of P (III).

The pH value of the aqueous catalyst solution should not be a value of less than 3. In general, a pH value of between 5 and 10, preferably between 6 and & . The composition of the synthesis gas, that is, the ratio of carbon monoxide to hydrogen, can vary within wide limits. In general, synthesis gas is used in which the volumetric ratio of carbon monoxide to hydrogen is 1: 1 or slightly less than that value. The reaction can be carried out intermittently or continuously. The process according to the invention will be illustrated by means of the following examples; however, it is not limited by the modalities indicated.

EXPERIMENT PROCEDURES It is used for the synthesis of the di- and triformyl derivatives of the methyl esters of fatty acid, by hydroformylation, ethyl esters of polyunsaturated fatty acid, as well as technical mixtures of methyl esters of lipo-fatty acid, which have a 55% "methyl ester of linolenic acid, 15% linoleic acid methyl ester and 2% oleic acid methyl ester; the remainder, methyl ester of saturated fatty acid or a mixture consisting of 90 μg of linolenic acid methyl ester and 10% of lipophilic acid methyl ester. The reaction is carried out in a V4A steel autoclave, 160 ml, with a pressure-resistant drip funnel, pressure gauge, burst-proof window and thermoelement. A propeller agitator, magnetically coupled, with gasification perforations, serves for the intensive mixing of the reaction ingredients. The preparation of the catalyst solution is carried out in a stirred tube, washed with argon, in which the corresponding amounts of rhodium compound (Rh4 (C0) .l2, HRh (CO) (NaT0PPTS) 3 or Rh2 < S04 > 3), the phosphine ligand, oxygen-free water, and the tepsicant agent. The pH value of the catalyst solution is controlled with NaHCO3 or with alkali metal hydroxide. In order to prepare the hydroformylation catalyst itself, the catalyst solution is pretreated in an autoclave gasified with argon and 1 avant with synthesis gas, under stirring and under the conditions of temperature and pressure of the hydroformation, for one hour, with the synthesis gas. Finally, the unsaturated ester is added dropwise. The pressure can be measured, during the reaction, with a manometer, equipped with a packed glass. After the reaction is completed, the autoclave is cooled, slowly loosens and the reaction mixture is poured into a separatory funnel. The aqueous and organic fasss are separated, the organic phase is collected in ether and washed twice with twice the amount of distilled water. By means of an assumed distribution of the rhodium in the organic phase, it is then washed further with a solution of NaTPPTS. The organic phase is dried over Na 2 SO 4, filtered, the ether is distilled off and the hydroformylation product is subjected to analysis. The hydration reaction product to the corresponding hydroxy and lithium compound is carried out with 10% by weight (with respect to the hydroforming product) of Raney nickel suspended in metapol, as a catalyst, at 100 ° C and at a pressure of 14-MPa. of H2. An equal volume amount of methanol is used as the solvent. The reaction product released by filtration of the catalyst and by distillation of the methanol is characterized by its fat chemical information data (iodine number, carbonyl number, hydroxy number).

EXAMPLE 1 g of a technical mixture of linoleic acid ester (mixture of esters corresponding to the catalyst phase) together with 20 czcz of an aqueous catalyst solution are placed in a 160 ml autoclave, stirred magnetically. The product contains O.O.sub.mole (200 ppm by weight) of Rh, 1.6 mmol of NaTPPTS (ratio P / Rh = 20), 3.2 mmol of tetradecyl bromide and the ion (concentration 7.5 times the technical value) and the pH value is regulated to ñ, with a2C03. At a reaction pressure of 20 MPa and at a temperature of J20 ° C, the two liquid phases and the gas phase are thoroughly mixed. After a reaction time of 2 hours, the autoclave is cooled, the reaction product is opened and treated as described above. The reaction was 100% effected. The reaction product had a composition of 26 weight percent of monoformic product, with respect to the ester mixture used, 30% by weight of diformyl product, with respect to the methyl ester portion of linoleic acid and of acid linolenic acid and 4-7 weight percent of trichydroformy products, with respect to only the methyl ester portion of linolenic acid, in the ester mixture. The result of the above calculation of the yield is also obtained by all other test methods with the technical mixture of the methyl ester of fatty linoleic acid.

EXAMPLES 2 TO 6 Hydropormi larop technical mixtures of li-noleico-fatty acid methyl ester, such as that described in example 1, but with variation of surfactants, in the presence of rhodiumcarbonyl / NaTPPTS catalyst systems, soluble in water. The results are summarized in table 1.

TABLE 1 pH of the% ep weight of the solution E i. Tertiary active agent. MF DF TF Reac 2 CC16H33N * ÍCH3) 33Br & 30 33? +2 4 3 CCldH37N - ': CH3) 33Br at 29 44- hO 100 4 CC12H25N "(CH3) 33Br &33 26 29 96 Cii + H29 (CHS) 2N - 0 5.6 32 Ll 36 99 6 CC12H2 (CH3) 2N * 3CH2C00- 5.6 39 17 5 76 Mr, DF, TF = mono-, di- and tri-formyl products. Reac = reaction.

EXAMPLE 7 A technical mixture of fatty linoleic acid ester, such as that described in Example 1, was hydrocoformilized, but by means of a triple concentration of rhodium (600 ppm rhodium) and twice the ratio of P / Rh (4). -0: 1). The reaction was quantitative. The mixture produced contained: 27% by weight of monoformi product 30% by weight of product diformi 52% by weight of triformi product » EXAMPLES ñ A 1Q The concentration of the surfactant had a decisive influence on the two-phase icerof hydroformylation, as indicated by the following examples & To 10. In order to be able to carry out a micellarm-supported hydroformylation, the critical concentration forming icela c.m.c. of surfactant. In the premicle scale (value 0.65 of the technician c.m.c '), despite the fact that hydroformylation is possible, as seen in example S, however, the reactivity becomes difficult as the concentration of surfactant increases. The results, especially of the tri-formulated products, increase and the reaction is quantitative. The performance of several tests with different concentrations of the cationic surfactant tetradscyltr ime ammonium bromide are summarized in table 2. The reaction conditions correspond to those of example 1; however, the Rh concentration in the aqueous phase was 275 ppm by weight. The volumetric ratio of catalyst phase to organic phase was 3: 1.

TABLE 2 Concentrac.ß.c., Respec- tion of apect to people ten- concentrasiaactiva, techni- c tion- Reaction HF DF TF Ei.Ko. ÍBül.1.1) ca [% oescí (? Sn peso i 6 0.016 0.65 55 32 19 11 9 0.053 2.50 95 29 24- 33 0.107 5. 0 100 27 33 52

Claims (1)

NOVELTY of the INVENTION CLAIMS 1. - Px'ocess to prepare esters of di- and polormomethylcarbonate acid, characterized in that a pol-unsaturated fatty acid ester and low molecular weight monoalcohols are reacted with carbon monoxide and hydrogen, at 100-160 ° C and a pressure of 5 to 35 MPa, in the presence of an aqueous solution containing as a catalyst rhodium-phosphine complex compounds and, additionally, a solution pro solution. 2. Method according to claim 1, further characterized in that the fatty acids are unsaturated or unsaturated d i and contain from 6 to 25 carbon atoms in the molecule. 3 - Px'ocediiento in accordance with claim 1 or 2, further characterized in that the unsaturated fatty acids contain 10 to 20 carbon atoms in the molecule. 4. Method according to any of claims 1 to 3, further characterized in that the low molecular weight mopaalcohales are saturated and contain from 1 to 10 carbon atoms in the molecule. 5. Process according to any of claims 1 to 4, further characterized in that the monoalcohol is methanol. 6. Method according to any of claims 1 to 5, further characterized in that the fasphine is an onophosphine of the general formula: • 5 X: LM Ar3- / \ / Y'Ln / X'-2M / / > Ar = 5 \ \ \ Y < 3n \ * \ X M \ / 0 t- \ Y: 3n (1) 5 wherein, each of Ar-'1-, Ar53, fu-3 means a phenyl or naphthyl group; each of Y1"Y'-2, Y3 is a straight or branched chain alkyl group, of the 4 carbon atoms, an alkoxy group, an halogen atom, the OH-, CN-, Q2 or R groups: LRía-N, where R? - and R12, in each case, represents an alkyl group of 0 straight or branched chain, of 1 to 4 carbon atoms, each of a-, Xa, Xa is a sulphonate radical ( S03 ~) and / or carboxylate (COO ™); ni, n3 and n3 are the same or different, and are whole numbers of a 5. H is an alkali metal ion, a chemical equivalent of an alkali metal ion- or 5 zinc, an ammonium or quaternary ammonium ion of the general formula N (R3R1 + RBRA) * wherein each of R3, R1-, R "3, R? represents a straight or branched chain alkyl group, from 1 to 4 carbon atoms. 7. Process according to any of claims 5, characterized in that the reaction products of dialkyl- or diarylphosphines with 1,2-, 1,3- or 1, '- + are used as monophosphines. -butansultonas. 6. Method according to any of claims 1 to 5, further characterized in that the diphosphines of the general formula are used as phosphine: (H2C) m (CH2) m (R2)? (R2) n (2) wherein the R1 represent the same or different alkyl, cycloalkyl, phenyl, tolyl or naphthyl radical; R12 are the same or different and denote hydrogen, alkyl or alkoxy radicals of 1 to 14 carbon atoms, cycloalkyl, aryl or aryl radicals of 6 to 14 carbon atoms, or a ringed benzene ring; the m are the same or different and represent integers from 0 to 5; and the n are eventually the same or different, and represent integers from 0 to 4. 9. Method of conformity with any of claims 1 to 6, further characterized in that a cationic surfactant or an amphoteric surfactant is used as the surfactant. 10. Process according to claim 9, which is further characterized in that the cationic surfactants are the tetraalkylammonium salts. 11. Method according to claim 9, further characterized in that the amphoteric surfactants are betaine or amine oxide. 12. Method according to any of claims 1 to 11, further characterized in that the concentration of the surfactant in the aqueous catalyst solution is above the critical concentration of micelle formation. 13. Method according to any of claims 1 to 12, characterized in that it performs the reaction at a temperature of 120 to 14-0 ° C and a pressure of 15 to 20 MPa. 14. Method according to any of claims 1 to 13, further characterized in that the concentration of rhodium in the aqueous solution catalyst is between 100 and 600 ppm by weight, preferably between 3O0 and 4-00 ppm by weight, with respect to the solution. 15. Method according to any of claims 1 to 1 * - +, further characterized because for each mole of rhodium there are at least 20 moles, preferably 4-0 to 60 moles of P (III) in the form of a phosphine. 16. - Method according to any of claims 1 to 15, further characterized in that the pH value of the aqueous catalyst solution is at least 3, preferably 5 to 10 and, especially, 6 to 10. PROCEDURE FOR THE PREPARATION OF FORMILCARBOXILIC ACID ESTERS SUMMARY OF DESCRIPTION < = A process for the preparation of esters of di- and polyflucarboxylic acid is described by hydroformylation of polyunsaturated fatty acid esters. The reaction is carried out in the presence of an aqueous solution which; 10 contains as complex catalyst complexes of rod iocarbonyl / phosphine and, additionally, an age-iodine > surfactant. t

1. 5 CR / mvs *