TW200417540A - Process for the hydroformylation of olefinically unsaturated compounds, in particular olefins, in the presence of cyclic carbonic esters - Google Patents

Abstract

The present invention relates to a process for preparing aldehydes by hydroformylation of olefinically unsaturated compounds catalyzed by metals of groups 8 to 10 of the Periodic Table of the Elements in the presence of cyclic carbonic esters and ligands which contain no sulfonic acid or sulfonate group.

Description

200417540 (1) 发明. Description of the invention [Technical field to which the invention belongs] The present invention relates to a method for preparing aldehydes by catalyzing aldehydes by catalyzing metals in Groups 8 to 10 of the periodic table in the presence of a cyclic carbonate. [Prior art] The process of olefin compounds, carbon monoxide and hydrogen reacting in the presence of a catalyst to form an aldehyde with one more carbon atom is called aldolization (oxidation method). The catalysts used in these reactions are often compounds of transition metals of groups 8 to 10 of the periodic table, especially compounds of rhodium and cobalt. Compared with catalysis by cobalt compounds, aldehydes using rhodium compounds usually have the advantages of high chemical selectivity and regioselectivity, so they are usually more economical. Rhodium-catalyzed aldehydes are usually carried out using a complex comprising rhodium and a preferred trivalent phosphorus compound as a ligand. For example, compounds derived from phosphines, phosphites and phosphonates are often used as ligands. For comments on aldolization of olefins, please refer to B. CORNILS, WA HERRMANN, " Applied Homogeneous Catalysis with O rga η ometa 11 ic Compounds ,,, V 〇]. 1 9 9 6 o Aldolization is often performed in the presence of a solvent, so that the catalyst can be easily recycled after separation of the reaction products. Many continuous annealing methods using rhodium catalysts use high-boiling mixtures of by-products formed during the aldehyde formation as solvents. This method is described, for example, in DE 2 062 7 03, DE 2 7 1 5 6 8 5, DE 2 8 02 922 or EP 01 7 1 83. In addition to high boiling compounds, inert organic liquids (DE 3 (2) (2) 200417540 1 2 6 2 6 5) and reaction products (aldehydes, alcohols), aliphatic and aromatic hydrocarbons, esters, Ethers and water (DE 4 4 1 9 8 9 8) were used as solvents. GB 1 1 97 902 uses saturated hydrocarbons, aromatics, alcohols and normal paraffins to achieve this purpose. The addition of one or more polar organic substances to the aldolization process is disclosed, for example, in WO 01/68248, WO 01/68249, WO 01/68252. In this case, the polar substance is a substance selected from the following types of compounds: nitriles, cyclic acetals, alcohols, pyrrolidines, lactones, formamidines, Asus, and water. The use of carbonates as polar additives in cobalt-catalyzed aldehyde reactions is also known (US 2 992 45 3). In this case, the carbonate is not used as a solvent, but as a promoter in the presence of an organic scale complex. The molar ratio of the carbonate to the cobalt compound is 1: 2. According to the required catalytic effect, the amount of olefin is more than 1000 times more than the catalytic metal and carbonate. The technical community also describes the simultaneous use of polar and non-polar solvents (99/38832, WO 01/68247, WO 01/68248, WO 01/68249, WO 0 1/68250, WO 01/6825], WO 01/68242). The following are mentioned as non-polar solvents: aliphatic, cycloaliphatic and aromatic hydrocarbons, ethers, amines, carboxylic acid esters, ketones, silanes, polysiloxanes and carbon dioxide. The reason for using polar or non-polar solvents in the quenching reaction is to increase the stability of the catalyst in the reaction, and it is easier to process the aldehyde product. When the catalyst is separated from the reaction product (for example, steamed), the catalyst is often found to be inactive. Therefore, there are many attempts to replace the steam-saturation processing with a more gentle method (such as extraction). Thus' for example US 6 187 962 and EP 09 992 691 describe a -6-(3) (3) 200417540 palladium-catalyzed aldehyde formation in the presence of W or polynitrile, which in turn separates the product phase and the catalyst-containing phase And make the latter recycle. In u S 5 6 4 8 5 5 4 using polar solvents (such as water, ketones, alcohols, nitriles, ammonium amines, glycols and carboxylic acids) for selective extraction of high boiling compounds and selection of catalyst complexes Sexual extraction. US 5 138 101 describes the use of an alcohol / water mixture to extract reaction products. In summary, it can be said that many polar and / or non-polar solvents have been used in the aldolization reaction. Those skilled in the art now know that most of the solvents described are not inert under the conditions of aldolization. For example, aldehydes can react with customary phosphite ligands. The addition of water and / or carboxylic acids can cause the hydrolytic decomposition of phosphites, phosphonates, and phosphite ligands. Amidoamine can displace the ligand from the metal center because of its complex nature. Alkadiene is known as a catalyst toxin (PWNMvan Leuven in P.W.N.M.van Leeuven, C.Cl aver, `` Rhodium Catalyzed Hydroformy] ati ο n M. K1 er Academic Publishers j Dordrecht 5 Boston, London, 2000). In addition, a part of the solvent may reduce the yield due to the reaction with the aldehyde. Thus, for example, alcohols and diols lead to the formation of acetals, and the addition of carboxylic acids catalyzes difficult-to-control aldol condensation reactions. In addition, it is known that the aldehyde formation method can improve the selectivity to linear aldehydes. Even if an additional solvent is used under ideal conditions, it should not only improve the processing, but also the selectivity. JP 1 0-2 2 6 6 6 2 describes an aldehyde formation method of an olefin compound, in which a rhodium catalyst is used together with a sodium salt of a sulfonated triphenylphosphine as a secondary catalyst, that is, (4) (4) 200417540 is used Improved catalyst. This reaction is performed in the presence of a polar solvent and a carboxylic acid. The polar solvent may be, for example, dimethylmethylene, cyclobutyl, N-methylpyrrolidone, N, N-dimethylformamide, acetonitrile, butanediol, polyalkylene glycol, or ethylene glycol carbonic acid. ester. The polar solvent can be recycled to the aldolization reaction with the acid and the catalyst. In this method, alkanediol carbonate is used as the first solvent. However, in addition to the alkanediol carbonate, a carboxylic acid is additionally used. Although this is recyclable, the presence of such additional compounds can contaminate the desired target product. First, the acid itself can cause contamination, or by-products due to acid catalysis (such as aldol condensation) can produce undesirable impurities. The use of the aforementioned method also limits the aldolization of terminal olefins, which are relatively reactive. If it is a less reactive olefin, that is, an internal olefin, especially an internally highly branched olefin, the catalyst activity is much lower than that required for industrial applications. [Summary of the Invention] The object of the present invention is to propose a composition of a solvent or a solvent mixture and a ligand for use in an aldolization reaction without the aforementioned disadvantages. It is now unexpectedly discovered that in a method using a conventional solvent, if the catalytic aldehyde is subjected to catalytic aldehydes in the presence of a cyclic carbonate as a solvent, the yield of olefins to be reformed to better terminal aldehydes can be increased, and the processing of the reaction mixture can become more It is simple and can increase the stability of the catalyst, and if a ligand containing no sulfonic acid or sulfonic acid group is used, a carboxylic acid may not be added. [Embodiment] The following staggered examples describe the method of the present invention, but the present invention is not limited to these. Those skilled in the art can infer other variations, which are also the subject of the present invention and whose scope is indicated by the scope of the description and patent application. The present invention therefore proposes a method for the aldolization of an ethylenically unsaturated compound (especially an olefin) having 3 to 24 carbon atoms in the presence of at least one Group 8 g metal of the Periodic Table of the Elements, wherein the aldolization 1 莫耳。 Based on at least 0.1 Mole. / 〇 at least one cyclic carbonate having the general formula I

R * (I) R2 0 where R1, R2, R3, R4 are the same or different, and each is H or a substituted or unsubstituted aliphatic, alicyclic ring with] to 27 carbon atoms Group, aromatic, aliphatic-alicyclic, aliphatic-aromatic or alicyclic-aromatic hydrocarbon group, Xin η is 0 to 5, X is divalent substituted with 1 to 27 carbon atoms Or it can be carried out without substitution of an aliphatic, cycloaliphatic, aromatic, aliphatic-alicyclic or aliphatic-aromatic hydrocarbon group, and at least one ligand having no sulfonic acid group or sulfonic acid group. The consequence of using ligands that do not contain sulfonate or sulfonate and (especially) non-sulfonated phosphine ' ' is that no carboxylic acid is required in the reaction mixture for the aldolization. The preferred coordination system contains nitrogen, phosphorus, arsenic or antimony as a donor atom, and -9- (6) (6) 200417540 is particularly preferred as a phosphorus-containing ligand. The ligand may be a single ligand or a multi-ligand. If it is a palmate ligand, a racemate or a mirror image isomer or a non-image isomer may be used. Particularly important examples of phosphorus ligands are phosphines, phosphine oxides, phosphites, phosphonates and phosphinates. When a residual acid is added to the method of the present invention, a carbonate as a solvent can be used in combination with a ligand (hydrolyzed in the presence of an acid, so that long-term stability in the presence of an acid is low). The substituents R1 to R4 and X may be the same or different, and are substituted with 0, N, NΗ, N-alkyl or N-dialkyl. In addition, these groups may have a functional group such as halogen (fluorine, chlorine, bromine, iodine), -0Η, -0R, -C (0) group, -C N or -C (0) 0 alkyl group. In addition, if these groups are at least three atoms away from the ester group, the C, C Η or C Η 2 group can be substituted by 0, N, NΗ, N-alkyl or N-dialkyl. Replacement. The alkyl group may still have i to 27 carbon atoms. In the method of the present invention, it is preferred to use ethylene glycol carbonate, propylene glycol carbonate, butanediol carbonate, or a mixture thereof, for example, a mixture of ethylene glycol carbonate and propylene glycol carbonate (volume ratio = 50: 50) as the Cyclic carbonated vinegar. · The cyclic carbonate should be used in an amount of at least 0.1 mole% based on the olefin used or the bright-bond unsaturated compound used, preferably in an amount within the range of 0.1 to 1.06 mole ° /. 0. 1-1 0 5 Mole% 0. 1-1 0 4 Mole% 0. 1-1 0 3 Mole% 0. 1-1 0 0 Mole% -10- (7) (7) 200417540 0. 1-10 mole% 0. 1-1 mole%. Other solvents may be used in addition to the cyclic carbonate. In particular, in the modified form, the aldehyde reaction of the present invention is therefore based on at least 0.1 moles based on olefins or ethylenically unsaturated compounds. /. It is carried out in the presence of at least one solvent immiscible with cyclic carbonic acid _I. The carbonate having the general formula I has a dielectric constant exceeding 30. The non-polar solvent which is immiscible with the cyclic carbonate I and is used in the method of the present invention has a dielectric constant lower than 20, preferably from 1.1 to 10, especially from 1.1 to 5. Possible non-polar solvents are substituted or unsubstituted hydrocarbons having 5 to 50 carbon atoms, such as high-boiling by-products of the aldolization reaction, Texanol or propylene or butene for tetramerization or polymerisation A mixture of isomers obtained by subsequent hydrogenation, namely tetrabutane, pentabutane, tetrapropane and / or pentapropane. It is also possible to use olefins or ethylenically unsaturated compounds with 3 to 24 carbon atoms, especially for aldehydes or olefinically unsaturated compounds as starting materials. To avoid by-products, non-polar solvents are used in the aldolization. The reaction conditions should be substantially inert. In the method of the present invention, the reaction mixture may be single-phase or two-phase in the overall conversion process in the aldehydeization reactor. However, during the reaction, the feed mixture may also be composed of two phases at a low conversion rate, and become a single phase at a high conversion rate. The single-phase feed mixture can become a biphasic product during the process of the invention -11-(8) (8) 200417540 mixture. The method of the present invention can be carried out using various catalytically active metals and, if necessary, various ligands. Possible catalytically active metals are metals from groups 8 to 10 of the periodic table, such as rhodium, cobalt, platinum or ruthenium. As mentioned previously, the method of the invention is performed in the presence of a ligand such as a phosphonate, phosphate, phosphine oxide, phosphine and / or phosphinate or phosphinine or phosphinane . The choice of ligands for metal addition in the method of the present invention is limited to the absence of sulfonate or sulfonate-containing ligands, and especially no sulfonated arylphosphine. The choice of ligands to be added depends, in particular, on the olefin or olefin mixture used or on the ethylenically unsaturated compound used and on the desired product. Preferred coordination systems are ligands containing nitrogen, phosphorus, arsenic or antimony donor atoms; phosphorus-containing ligands are particularly preferred. The ligand may be a single ligand or a multi-ligand, and if it is a palmate ligand, a racemate or a mirror image isomer or a non-image isomer may be used. Particularly important examples of phosphorus ligands are phosphines, phosphine oxides, phosphites, phosphonates and phosphonates. Examples of phosphines are triphenylphosphine, tris (p-tolyl) phosphine, tris (m-tolyl) phosphine, tris (o-tolyl) phosphine, tris (p-methoxyphenyl) phosphine, tris (p-fluorophenyl) Group) phosphine, tris (p-chlorophenyl) phosphine, tris (p-dimethylaminophenyl) phosphine, ethyldiphenylphosphine, propyldiphenylphosphine, third butyldiphenylphosphine, N-butyldiphenylphosphine, n-hexyldiphenylphosphine, c-hexyldiphenylphosphine, dicyclohexylphenylphosphine, tricyclohexylphosphine, tricyclopentylphosphine, triethylphosphine, tris (naphthyl) Phosphine, tri-2-furylphosphine, tribenzylphosphine, benzyldiphenylphosphine, tri-n-butyl-12- (9) (2004) 4040740-based phosphine, tri-isobutylphosphine, tri-third Butylphosphine, bis (2-methoxyphenyl) phenylphosphine, neocapryl diphenylphosphine, sulfonated triphenylphosphine (such as tris (m-sulfofluorenylphenyl) phosphine, (m-sulfofluorenylphenyl)) Alkali metals, alkaline earth metals, ammonium or other salts of diphenylphosphine; 1,2-bis (dicyclohexylphosphino) ethane, bis (dicyclohexylphosphino) methylamine, 1,2-bis ( Monoethylstilbene) ethene, 1,2-bis (2,5-diethylstilbene) ethane, 1,2 -Bis (2,5-diethylphosphoryl) benzene [Et-DUPHOS], 1,2-bis (2,5-diethylphosphoryl) ethane [£ ^ 3 卩 £], 152- Bis (dimethylphosphino) 'ethane, bis (dimethylphosphino) methane, 1,2-bis (2,5-dimethylphosphino) benzene [Me-DUPHOS], 1,2- Bis (2,5-dimethylphosphoryl) ethane [! ^ 卜 ΒΡΕ], 1,2-bis (diphenylphosphino) benzene, 2,3-bis (diphenylphosphino) bicyclo [2.2.1] Hept-5-ene [NORPHOS], 2, 2, bis (diphenylphosphino) -151, binaphthyl [BINNAP], 2,2, bis (diphenylphosphino)-] , 1, _bi, benzene [BISBI], 2; 3-bis (diphenylphosphino) butane, 1; 4-bis (diphenylphosphino) butane, 1,2-bis (diphenyl) Phosphino) ethane, bis (2-diphenylphosphinoethyl) phenylphosphine,] bis- (diphenylphosphino) ferrocene, bis (diphenylphosphino) methane, 1,2-bis (Diphenylphosphino) propane, 2; 2,2-bis (di-p-.tolylphosphine binaphthyl), 0-isopropylidene-253-dihydroxy_1,4-bis (diphenylphosphine) Group) butane [010?], 2- (diphenylphosphino) -2 '... methoxy _;!,], Binaphthyl, 1 2_diphenylphosphino-phenyl) isoquinoline , : | J,〗-tris (diphenylphosphino) ethane, and / or tris (hydroxyphenyl) phosphine. Examples of phosphine include 2,6-dimethyl-4-phenylphosphine, 2, 6-Bis (2,4-dimethylphenyl) -4-phenylphosphine and other ligands described in WO 00/55164. Examples of phosphanes include 2,6-bis (2,4-di (Methylphenyl) -Businyl-4-phenylphosphine, 1-octyl_2,4; 6-triphenylphosphine and others described in WO -13- (10) (10) 200417540 02 / 00669 ligand. Examples of phosphites are trimethyl phosphite, triethyl phosphite, tri-n-propyl phosphite, triisopropyl phosphite, tri-n-butyl phosphite, triisobutyl phosphite, and tri- Tertiary butyl ester, tris (2-ethylhexyl) phosphite, triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2-tert-butyl) phosphite Methyl-4-methoxyphenyl) ester, tris (2-tert-butyl-4-methylphenyl) phosphite, and tris (p-toluene) phosphite. Other examples are sterically hindered phosphite ligands, as described in (especially) EP 1 5 5 5 0 8, US 4 66 8 6 5 1, US 4 74 8 26 1, US 4 769 49 8, US 4 7 74 361, US 4 8 3 5 299, US 4 8 8 5 401, US 5 05 9 710, US 5 113 022, US 5 1 79 055, US 5 260 491, US 5 2 64 616, US 5 2 8 8 918, US 5 3 60 938, EP 472 071, EP 518 24 1 and WO 9 7/207 95. It is preferred to use triphenyl phosphite substituted with 1 or 2 isopropyl and / or third butyl substituents (preferably ortho to the phosphite group). Description of use in (Special) EP 1 09 9 6 7 7, EP 1 0 9 9 6 7 8, WO 02.00670, JP 10279587, EP 472017, WO 01/21627, WO 97/4 0 00 1, WO 9 7/40002 The bisphosphite ligands in US 4,769,498, EP 2 1 3 63 9 and EP 2 1 4622 are particularly good.

Examples of phosphonates are methyldiethoxyphosphine, phenyldimethoxyphosphine, phenyldiphenoxyphosphine, 6-phenoxy-6H-dibenzo [c, e] [], 2 ] Oxaphosphine (ph 〇sph 〇 ri η) and its derivatives (where all or part of the hydrogen atom is replaced by a syl or aryl or halogen atom) and WO 98/43 93 5, JP 09-2 6 8 1 5 2 and the ligands described in DE 198 10 794 and German patent applications DE 199 54 7 21 and DE 1 9 9 5 4 5 1 0. -14-(11) (11) 200417540 Conventional phosphinate coordination systems are described in, inter alia, US 5 7 1 0 344, WO 9 5 06627, US 5 360 938, JP 07082281. Examples are diphenyl (phenoxy) phosphine and its derivatives (where all or part of the hydrogen atoms are replaced by alkyl or aryl or halogen atoms), diphenyl (methoxy) phosphine, diphenyl ( Ethoxy) phosphine and the like. The active catalyst complex used in the aldolization reaction is formed from a metal salt or compound (catalyst precursor), a ligand, and a synthesis gas. This preferably occurs in situ during the aldehyde formation process. Conventional catalyst precursors are, for example, octanoate, nonanoate, and acetopyruvate. The molar ratio of the metal to the ligand is from 1/1 to 1/1 0 0, and preferably from 1/1 to 1/5 0. The concentration of the metal in the reaction mixture is preferably in the range of 1 ppm to 1 000 ppm, and more preferably in the range of 5 PPm to .3 00 ppm. The starting material used in the process of the present invention is a compound containing an ethylenic (ethylenic) unsaturated CC double bond, an olefin or a mixture of olefins, especially 3 to 24 (preferably 4 to 16) , Especially 4 to I 2) mono-olefins having carbon atoms and having a terminal or internal c double bond, such as dioxin or acetylene, 2-methyl-butene, 2-methyl-2 -butene, 3 -methyl-]-butane / 3, ... 2-or 3 -hexene, c 6 -olefin mixture (ene) obtained by dimerization of propylene, heptene, 2- or 3-methylhexene, Dimerization of octene, 2-methylheptene, methylheptene, 5-methyl-2-heptene, 6-methyl-2-heptene, 2-ethylhexene, ^ ene, butene Heterogeneous C 8 -olefin mixture prepared by (dibutene), C8-olefin mixture prepared by dimerization of isobutene, non-thin, 2 'or 3-methyloctene, trimerization of propylene C9-olefin mixture (S propylene), decene, 2-ethyl-1-octene, dodecene, -15-15 of (12) (12) 200417540 of tetramerization of butene Olefin mixture (tetrapropylene or tributene), tetradecene, hexadecene produced by trimerization C] 6-olefin mixture (tetrabutene) prepared by tetramerization of butene and olefin mixture prepared by copolymerization of olefins having different numbers of carbon atoms (preferably 2 to 4) , If appropriate, after distillation into fractions with the same or similar chain length. It is also possible to use olefins or olefin mixtures prepared by Fischer-Trohsch synthesis and olefins prepared by oligomerization of ethylene or olefins that can be prepared by displacement reactions. Preferred starting materials are C4-, C6-, C8-, C9-, C12- or C16-olefin mixtures. The volume ratio of carbon monoxide to hydrogen in the synthesis gas is usually from 2: 1 to 1: 2, especially 1: 1. The synthesis gas is preferably used in excess, for example up to three times the stoichiometric amount. The aldolization is usually carried out at a pressure of 1 to 350 bar, preferably a pressure of 5 to 270 bar. The pressure used depends on the structure of the feed olefin, the catalyst used and the desired effect. Thus, for example, alpha-olefins can be converted to the corresponding aldehydes in high space-time yields in the presence of rhodium catalysts at pressures below 64 bar. Conversely, for olefins having internal double bonds, especially branched olefins, higher pressures are preferred. The reaction temperature in the method of the present invention is preferably 20 to 250 ° C, preferably 60 to 180 ° C, and more preferably 90 to 15 ° C (TC is better. After aldehyde, it can be borrowed and reduced. Most of the synthesis gas is removed by pressure. After the aldolization reaction, it is better to separate the product and catalyst solution by phase separation. Contains any unreacted olefin or ethylenically unsaturated compounds, reaction • 16- (13) ( 13) 200417540 The reactor output of products, reaction by-products, at least one cyclic carbonate, possible non-polar solvents, catalysts and possible free ligands is introduced into a phase separation device, such as a retention vessel. (Settler) According to the present invention, a heat exchanger may be configured to cool the output of the reactor. According to the present invention, the phase separation is performed at a temperature of 0 ° C to 130 ° C. At 10 ° c to 60 ° t The phase separation is carried out at a pressure of 1 bar to 270 bar, but preferably at the same pressure as selected for the aldehyde formation step. Depending on the starting material used, the Separation produces, for example, essentially from unreacted olefins or ethylenically unsaturated compounds, catalyst complexes A relatively light phase composed of a substance, a selective free ligand and a non-polar solvent and returned to the reactor, and a heavy phase mainly containing at least one cyclic carbonate, a reaction product, and a reaction by-product, and further processed. According to the iodine atom, this is achieved by separation into aldehydes (alcohols), unreacted olefins or ethylenically unsaturated compounds, residual solvents and by-products, and can be performed by, for example, distillation. The separated solvents are recycled Back to the aldolization reactor. The composition of these phases is determined by the type of ligand used, the residual olefin or content, and the type and amount of the solvent used. Due to the fact, different phases can be easily found The method of the invention can be carried out in several variations.

Variation A In this variation of the method, the output from the aldehyde reaction is separated into ± the part containing the catalyst and the cyclic carbonate and the part mainly containing the aldehyde product. -17- (14) (14) 200417540 This method can be used when using polar catalysts and other non-polar solvents. The non-polar solvent can also be the same as the feed olefin or ethylenically unsaturated compound used, so that the aldolization reaction does not proceed to complete_specialization (for example, only 90%, preferably 80%) or can be Other ethylenically unsaturated compounds are added during and / or after the reaction. The variation A of the method is illustrated in Figure 1: the synthesis gas (1), the bright hydrocarbon or ethylenically unsaturated compound (2), and the catalyst solution (3) (preferably containing a cyclic carbonate) in the aldehyde reaction Reactor (4). The reactor output (5) can be used to remove excess synthesis gas (7) in the decompression vessel (6) as appropriate. The liquid stream (8) obtained in this way is separated into a heavy phase (10) in a settler (9), which contains the main part of a cyclic carbonate and a catalyst, and a light phase (1 1). Contains deactivated products, unreacted olefins or ethylenically unsaturated compounds and, if used, non-polar solvents. Depending on the catalyst system used, it may be better to remove the catalyst residues from subsequent processes through an appropriate separation stage (1 2). The liquid stream (1 1) or (1 3) is then sent to the separation stage (1 4). In this case, the reaction products (aldehyde and alcohol) (15) are separated and sent to a further processing or hydrogenation step. The fraction (] 6) also contains, for example, residual cyclic carbonate, high-boiling by-products, reaction products, and (if used) other non-polar solvents added. Part (16) can be recycled back to the aldehyde reforming reactor (4). The process of discarding unwanted by-products is preferably performed before recycling. The catalyst separation can be carried out in the form of extraction by feeding at least a part (16) directly into the liquid stream (8). The extraction can be a single-stage extraction or operated countercurrently, co-currently, or alternatingly in a multi-stage process. -18- (15) (15) 200417540

Variation B In this variation of the method, the reactor output from the aldehydeization reaction is separated into a portion mainly containing a catalyst and a non-polar solvent and a portion mainly containing an aldehydeization product and a cyclic carbonate. This method variation can be used when adding a non-polar solvent or solvent mixture that is immiscible with the cyclic carbonate. This variation is particularly useful when no other feed olefins or other ethylenically unsaturated compounds are added or when the aldolization reaction system proceeds to a high conversion rate or a complete conversion rate. The addition of a non-polar solvent makes Variation B particularly useful in the case of a non-polar catalyst system containing, for example, a phosphite ligand. Variation B of this method is described below with reference to FIG. 2: In the aldehydeization reactor (4), the synthesis gas (1.) and the olefin or ethylenically unsaturated compound (2) It is preferred that the reaction is performed in the presence of a cyclic carbonate (3). The output of the reactor (5) is to remove excess syngas (7) 'in the separator (6) as appropriate, and send it to the separator (9) in the form of a liquid stream (8). In this case, the light shell phase (1 0) containing the catalyst, unreacted olefin or unreacted ethylenically unsaturated compound, and a non-polar solvent is the heavy phase (1 1) containing the reaction product and cyclic carbonate. Separation. Part (10) is preferably recycled to the aldehydeization reactor. Part (1)) can be seen in Gu Yi: remove the catalyst residue in (1 2), and then send it to the steaming and retaining stage (14). In this case, the reaction product (15) and the cyclic carbonate (16) are separated from the latter, and then are transported to the | chemical reactor (4). The catalyst separation can also be performed in the form of extraction by introducing at least one fraction (16) into the liquid stream (8). The extraction can be performed in a single stage or in a multistage procedure under countercurrent, cocurrent or alternating current. -19- (16) (16) 200417540 Variation c In this aldolization reaction, it is separated into a part mainly containing a catalyst and an olefin or an ethylenically saturated compound, and a part mainly containing an aldehyde product and a cyclic carbonate. Serving. Various olefins or ethylenically unsaturated compounds, olefin mixtures or isomer mixtures can be added before and after the aldolization reaction. It is preferred to use the same olefin / olefin mixture or ethylenically unsaturated compound. This variant of the method is particularly useful when using non-polar catalysts and no other non-polar solvents. In method variation c, there may be other variations: other hydrocarbons or ethylenically unsaturated compounds are sent after the actual aldolization reaction, or the aldolization reaction proceeds only to a specific partial conversion rate (for example, 50 to 7) 0%). Figure 3 illustrates a variation of this method: in the aldehydeization reactor (4), the olefin or ethylenically unsaturated compound (1) and the synthesis gas (2) are reacted in the presence of a cyclic carbonate (3). The catalyst is preferably present in the hydrocarbon-burning phase. The output (5) of the aldehyde reforming reactor can remove excess synthesis gas (7) in a container (6) and perform phase separation in a suitable container. Prior to this, a new feed of dilute hydrocarbons (9) can be introduced via mixed fractions (8). Introduced;): When the hydrocarbon compound is used, the reactor output is usually cooled by a heat exchanger (not shown). This phase separation produces a light phase (1 1) containing an olefin or unreacted ethylenically unsaturated compound and a catalyst; this phase is recycled to the aldolization reactor (4). The heavy phase (10) contains a reaction product and a cyclic carbonate, and is vaporized (] 3) after selective removal of the catalyst 2). In this case, the reaction product (1 4) and the cyclic Carbonate (] 5) > 20 > (17) (17) 200417540 is separated and the latter is recycled to the aldehydeization reactor. The catalyst separation is also performed in single-stage extraction or in the form of multi-stage, countercurrent, cocurrent, or alternating current extraction. The aforementioned modified gas system of the method of the present invention includes separation of reactor output and selective aldehyde product; this can be performed by, for example, distillation. However, other separation methods can also be used, such as the extractions described in, inter alia, WO 01/68247, EP 0 922 691, WO 99/38832, US 5 648 554 and US 5 138 101, or described in (especially ) Penetration in DE 1953641, GB 1312076, NL 8 7 00 8 8 1, DE 3 8 42 8 19, WO 94 1 9 1 04, DE 1 9632 600 and EP 1 1 0 3 3 03. When the separation is performed industrially, various methods can be adopted. The separation is preferably performed by a falling film evaporator, a short-path evaporator or a thin film evaporator or a combination of these devices. The advantage of this combination can be, for example, that the synthesis gas and a portion of the product and the starting olefins that are still present in the mixture can be separated in the first step (eg in a falling film evaporator), and the catalyst can be used in Finally, it is separated in a second step (for example in a thin-film evaporator). This extraction and separation is preferably performed continuously. It can be designed as a single-stage method or operated countercurrently or alternatingly as a multi-stage method. The reaction product mixture from which the catalyst, excess synthesis gas and major solvents (cyclic carbonates) have been removed is then divided into aldehydes (alcohols), olefins or ethylenically unsaturated compounds, solvents and by-products. This can be achieved, for example, by distillation. The olefin or ethylenically unsaturated compound and / or solvent that has been separated from the reaction product mixture or the aldolization product may be recycled to the aldolization reaction. When the target product is not the aldehyde itself, but an alcohol derived from it, the reaction product mixture from which the synthesis gas and possible solvents have been removed can separate olefins 21-(18) (18) 200417540 (isolate ethylenically unsaturated compounds ) Before or after hydrogenation, after that, it is left to be processed by a steam bin to produce pure alcohol. In all method variations, the catalyst-containing fraction is preferably recycled to the aldolization reaction. This is of course not related to the composition of the part where the catalyst is dissolved. The method of the invention can be performed in single or multiple stages. In this case, the first aldehydeization reaction can be followed by the second aldehydeization stage, and the internal olefins that are difficult to be aldehydeized are converted to the desired aldehyde under the "more intense" operating conditions. However, it is better to separate the unreacted first The olefins and products and unreacted products are sent to the subsequent fermentation stage. In this case, partitions are generated again in different method variants; if after the reactor output is separated, various parts contain unreacted olefins, catalysts, and free ligands that may also be present, then A completely different catalyst system (different metals and / or different ligands) is used in the second aldolization stage. It is of course impossible if all parts do not contain unreacted soot, catalyst and possible free ligands. In this case, it is preferable to add a high-concentration catalyst or ligand system to the unreacted olefin to convert the olefin which is more difficult to be aldehyde-formed into the desired product. In all cases, it is necessary to add the aforementioned amount of cyclic carbonate in the subsequent aldehyde formation stage. Cyclic carbonates can also be used in other metal-catalyzed reactions. Applications include, for example, cyanation, hydrocyanation, isomers of olefins, hydration, Heck reactions, condensation reactions (such as aldol condensation or hydration), or esterification reactions. The following examples are only used to illustrate the present invention, but not to limit the scope of the present invention. The scope of the present invention is only defined by the scope of the description and patent application. -22-(19) (19) 200417540 Example 1 (Variation A) A 3 liter stirring autoclave was placed under nitrogen with 1.07 g of propylene glycol carbonate, 0.22 g of rhodium nonanoate, and 3.4 g of phosphorous acid. Tris (2,4-di-tert-butylphenyl) ester. The germanium concentration in the reaction mixture was 40 ppm 'and the molar ratio of phosphorus to rhodium was 10. After heating under a synthesis gas (molar ratio of hydrogen to carbon monoxide: 1: 1) to 100 t :, 280 g of 1-octene was introduced. The aldolization was carried out at a reaction pressure of 200 bar and a pressure of 100. (: Stirring at temperature. After a reaction time of 50 minutes, the conversion of 1-octene is 76%. The selectivity of n-nonanal is 65%. This corresponds to a yield of 49.4% of n-nonanal. Example 2 (Comparative Experiment of Example 1): Another experiment was performed in the same manner as in Example 1, except that tetrabutylene was used instead of propylene glycol carbonate as the solvent. After 50 minutes of aldolization, the conversion of bustene The rate is 92%. The selectivity of n-nonanal is 34%. This corresponds to a yield of 31.3%. Comparison of two experiments shows that the selectivity and yield of linear aldehydes can be obtained by using Zhou Bing Z _ carbonate increased. Example 3 (Variation B) 1070 g of propylene glycol carbonate, 0.26 g of rhodium nonanoate, 5.7 g of a phosphite ester ligand with a two-ligand general formula U and 2 73 g N-decane was placed in a 3 liter booster under nitrogen. This corresponds to a germanium concentration of 4 〇ρρηι, and the molar ratio of phosphorus to the surface is 20. At the pressure of the synthesis gas (the molar ratio of CO-H2 is- 23- (20) 200417540 1: 1) After heating to 10 crc, a mixture of 280 g of internal octene was introduced.

The aldolization is carried out at a temperature of 10 and a synthesis gas pressure of 20 bar. After the reaction was completed, the mixture was cooled to room temperature and phase separated. The hydrocarbon phase containing the active catalyst complex is held in the reactor. The propylene glycol carbonate phase containing most of the aldehyde was discharged from the reaction and processed in a thin film evaporator at 125t and 25 hPa to produce crude aldehyde. The obtained bottom product propylene glycol carbonate was used together with 140 g of an olefin mixture and a catalyst solution remaining in the reactor, and then used in another aldolization reaction using the aforementioned method. (A total of eight more uses, refer to Table 1, Experiments 3.1 to 3.8). Μ

ο

Me0 (li) Example 4 (Comparative Experiment of Example 3) Another series of experiments were performed using the method of Example 3, except that tetrabutyl alcohol was used instead of glycerol carbonate and n-decane as solvents ( This tetrabutane system is a mixture of c] 6 · methane formed by oligomerization, followed by hydrogenation of 1-butene). -24- (21) (21) 200417540 After the reaction is completed, the whole reaction mixture is distilled in a thin film evaporator at 125 ° C and 25 hPa. Overhead product crude aldehyde was produced. The bottom product is a hydrocarbon mixture mainly containing tetrabutane and catalyst. This solution was reused with another 140 grams of an olefin mixture using the method described above for another aldolization reaction. (A total of eight more uses, refer to Table 1, experiments 4.1 to 4.8). In the experimental series described in Examples 3 and 4, the conversion rate was measured by continuously measuring the amount of synthetic gas consumed. The time dependence of the conversion rate allows the calculation of the overall rate constant, which is a measure of catalyst activity. Various reaction systems can be compared with the first reaction experiment series by normalizing to the overall rate constant. Table 1 shows the normalized overall rate constants for multiple reuse cycles of the examples. After the comparison, it was shown that the catalyst activity of the examples of the present invention is easily maintained, but the catalyst activity of the conventional method used in the comparative example is greatly reduced. Therefore, using the method of the present invention can greatly increase catalyst stability. -25- (22) 200417540 Table 1-Comparative Example 3 of Examples 3 and 4 Relative overall rate constant [-] Example 4 Relative overall rate constant l ·] 3.0 1 4.0 1. .000 3. .1 1.110 4.1 0.855 3.2 1.035 4.2 0.909 3.3 0.982 4.3 0.726 3.4 0.990 4.4 0.834 3 .5 0.942 4.5 0.728 3.6 1.009 4.6-3 .7 0.805 4.7 0.592 3.8 1.000 4.8 0.3 13 Note: In the case of Example 4.6, the measurement is defective, so the number is not recorded. [Brief Description of the Drawings] Fig. 1 illustrates a variation A of the method of the present invention. Fig. 2 illustrates a variation B of the method of the present invention. Fig. 3 illustrates a variation C of the method of the present invention. Comparison of main components 1 Synthetic gas 2 Olefins or ethylenically unsaturated compounds 3 Catalyst solution 4 Aldehyde reactor 5 Reactor output

-26- (23) (23) 200417540 6 Decompression vessel 7 Excessive synthesis gas 8 Liquid stream 9 Settler 1 〇 Heavy phase 1 1 Light phase 1 2 Separation phase 13 Liquid phase M separation phase 1 5 Reaction product 1 6 Part

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Claims (1)

(1) 200417540 The scope of application for patents is one in the presence of at least one of Group 8 metal catalysts of the Periodic Table of the Elements. 1¾ • Alkylated unsaturated compounds with 3 to 24 carbon atoms The method wherein the aldolization is based on at least 0.1 mol% of an ethylenically unsaturated compound of at least one cyclic carbonate fluorene having the general formula I. (I) Where ^ 'R2' R3 and R4 are the same or different, and each is Η or substituted or unsubstituted aliphatic, cycloaliphatic, or square with 2/4 carbon atoms' aliphatic J purpose Cyclic, aliphatic_A α such as% cycloaliphatic-aromatic hydrocarbon group, η system is 0 to 5, Even π group I is a bivalent substituted or non-substituted divalent, aromatic, aliphatic, or aliphatic hydrocarbyl group with at least 27 carbon atoms per month. At least one type does not contain alcohol. In the presence of a ligand of hydrazone, sulfonate or sulfonate.-For example, the scope of patent application No. 1 R3, R4 and X is selected from ο, N, fluorine, chlorine, bromine, 5ft, -oh, 〇 alkyl The same or different substituents are taken. 3 · The method as described in the item of the scope of patent application, wherein R1, R2, NH, N-alkyl and N-dialkyl, CN, -C (O) alkyl or < (〇) 〇 Generation. The method of item, wherein the aldolization is carried out in the presence of a solvent of at least 0.1 mol% based on the ethylenically unsaturated compound at -28- (2) (2) 200417540, which is compared with the cyclic Carbonate I is relatively non-polar and immiscible with cyclic carbonate I. 4. The method according to item 3 of the patent application, wherein a substituted or unsubstituted hydrocarbon having 5 to 50 carbon atoms or an ethylenically unsaturated compound or olefin having 3 to 24 carbon atoms is used as a non- Polar solvents. 5. The method according to any one of claims 1 to 4, wherein the output from the fermentation reaction is separated into a part mainly containing a catalyst and the cyclic carbonate and a part mainly containing an aldehyde product. Serving. 6. The method according to any one of claims 1 to 4, wherein the output from the aldehyde reaction is separated into a part mainly containing a catalyst and a non-polar solvent and mainly containing an aldehyde product and the ring Carbonic acid vinegar, part. 7. The method according to any one of claims 1 to 4, wherein the output from the aldehyde reaction is separated into a part mainly containing a catalyst and an unreacted ethylenically unsaturated compound and mainly containing an aldehyde Product and part of the cyclic acid ester. 8. The method according to any one of claims 1 to 4, wherein the catalyst-containing portion is recycled to the aldolization reaction. 9. The method according to any one of claims 1 to 4, wherein the cyclic carbonate used is ethylene glycol carbonate, propylene glycol carbonate-butanediol carbonate, or a mixture thereof. 10. The method according to any one of claims 1 to 4, wherein the aldolization is based on a phosphonate, a phosphite, a phosphine oxide, a phosphine, a phosphonium phosphinate, a phosphinine, and / Or phosphorane (pIlOsphinane) in the presence of -29- (3) (3) 200417540 line. 1 1 · The method according to any one of claims 1 to 4, wherein the unreacted ethylenically unsaturated compounds (olefins) are separated from the reactor output or separated from the aldehyde product and are recycled to The aldolization reaction. 1 2. The method according to any one of claims 1 to 4, wherein the unreacted ethylenically unsaturated compound is separated from the reactor output or from the aldehyde product, and is used in the second reaction stage . -30-