TWI293950B - Process for preparing aldehydes by hydroformylation of olefinically unsaturated compounds, catalyzed by unmodified complexes of metals of groups 8 to 10 of the pte in the presence of cyclic carbonic esters - Google Patents

Abstract

Catalytic hydroformylation of 3-24 carbon (C) olefinically unsaturated compounds, using an unmodified catalyst containing group 8-10 metal(s), is carried out in the presence of not less than 1 wt.%, with respect to the reaction mixture, of a cyclic carbonate ester (I), comprising an optionally substituted (cyclo)alkylene or arylene carbonate. Catalytic hydroformylation of 3-24 carbon (C) olefinically unsaturated compounds, using an unmodified catalyst containing group 8-10 metal(s), is carried out in the presence of not less than 1 wt.%, with respect to the reaction mixture, of a cyclic carbonate ester of formula (I), comprising an optionally substituted (cyclo)alkylene or arylene carbonate. R1, R2, R3, R4 = H or optionally substituted 1-27 C aliphatic, alicyclic, aromatic, aliphatic-alicyclic, aliphatic-aromatic or alicyclic-aromatic hydrocarbyl; n = 0-5; X = divalent, optionally substituted 1-27 C aliphatic, alicyclic, aromatic, aliphatic-alicyclic or aliphatic-aromatic hydrocarbyl.

Description

1293950 (1) Field of the Invention The present invention relates to an unmodified metal which is derived from an ethylenically unsaturated compound (especially an olefin) derived from a metal of Groups 8 to 10 of the Periodic Table of the Elements. A process for the catalytic aldehyde formation of a aldehyde to prepare an aldehyde, which is carried out in the presence of a cyclic carbonate as a solvent. [Prior Art] An aldehyde process in which an olefin compound, carbon monoxide, and hydrogen are reacted in the presence of a catalyst to form one more carbon atom is called hydroformylation (oxidation method). The catalyst used in these reactions is often a compound of a transition metal of Groups 8 to 10 of the Periodic Table of the Elements, especially a compound of ruthenium and cobalt. The hydroformylation using a ruthenium compound generally has the advantage of being chemically selective and having a higher regioselectivity than the catalyzed catalysis of the compound, and is therefore generally economically attractive. The hydroformylation catalyzed by ruthenium is usually carried out using a compound comprising ruthenium and a compound of Group 15 of the elemental periodic table as a ligand (preferably a trivalent phosphorus compound). For example, a compound derived from a phosphine, a phosphite, and a phosphonate is often used as a ligand. For a review of the hydroformylation of olefins, see B. CORNILS, WA HERRMANN, "Applied Homogeneous Catalysis with Organometallic Compounds", Vo 1. 1 & 25 VCH, Weinheim, New York, 1 996 o terminal olefins can be modified by phosphine The quality of the catalyst is easily reacted in the presence of the catalyst. On the other hand, internal olefins, especially internal highly branched olefins, require -5-I293950 (2) strong active ligands, such as phosphite ligands. In addition, it has been found that "original" or unmodified ruthenium is suitable for olefins which are difficult to hydroformylate. These catalysts comprise one or more metal species which are under hydroformylation conditions and which are free of modified ligands I' formed from metal salts. For the purposes of this patent application, the modified coordination system is a compound containing one or more of the donor atoms of Group 15 of the Periodic Table of the Elements. However, the modified ligand does not include an alkoxy group, a carbonyl group, or a hydrogen group. Or an alkyl group, an aryl group, an allyl group, a decyl group or an olefin ligand, and does not include a counter ion for forming a metal salt of a catalyst, such as a halogen group such as fluorine, chlorine, bromine or iodine, an ethyl group. Pyruvate, carboxylate such as acetate, 2-ethylhexanoate, hexanoate, octanoate or citrate. The modified coordination system used in the present invention is a ligand containing a donor atom selected from Group 15 of the periodic table, such as nitrogen, phosphorus, arsenic or antimony, especially phosphorus. The ligand may be a mono- or poly-ligand, and if it is a palm ligand, a racemate or a mirror image or a non-image isomer may be used. Particularly important examples of phosphorus ligands are phosphine, phosphine (Phosphinine), phosphine (p h 〇 s p h i n a n e ), phosphine oxide, imidate, phosphonate and phosphinate. Examples of phosphines are triphenylphosphine, tris(p-tolyl)phosphine, tris(m-tolyl)phosphine tris(o-tolyl)phosphine, tris(p-methoxyphenyl)phosphine, tris(p-fluoro) Phenyl)phosphine, tris(p-chlorophenyl)phosphine, tris(p-dimethylaminophenyl)phosphine, ethyldiphenylphosphine, propyldiphenylphosphine, tert-butyldiphenylphosphine , n-butyldiphenylphosphine, n-hexyldiphenylphosphine, c-hexyldiphenylphosphine, dicyclohexylphenylphosphine, tricyclohexylphosphine, tricyclopentylphosphine, triethylphosphine, tris(1) -naphthyl)phosphine, tris-2-furylphosphine, tribenzylphosphine, -6-1293950 (3) benzyl diphenylphosphine, tri-n-butylphosphine, tri-isobutylphosphine, tri- Tributylphosphine, bis(2-methoxyphenyl)phenylphosphine, neocapped diphenylphosphine, sulfonated triphenylphosphine (such as tris(m-sulfonylphenyl)phosphine, (m-sulfophenyl) An alkali metal, alkaline earth metal, ammonium or other salt of diphenylphosphine; 1,2-bis(dicyclohexylphosphino)ethane, bis(dicyclohexylphosphino)methane, 1,2-double ( Diethylphosphino)ethane, 1,2,bis(2,5-diethylphosphonium), Y, 1,2-bis (2,5-di Benzophosphonyl) benzene [Et-DUPHOS], 1,2-bis(2,5-diethylphosphonium), et al. [Et-BPE], 1,2-bis(dimethylphosphino) Ethane, bis(dimethylphosphino)methane, 1,2-bis(2,5-dimethylphosphonium)benzene [Me-DUPHOS], 1,2-bis(2,5-dimethylphosphine) Mercapto) ethane [M e-ΒΡΕ], 1,2-bis(diphenylphosphino)benzene, 2,3-bis(diphenylphosphino)bicyclo[2.2.1]hept-5- Alkene [NORPHOS], 2, 2, bis(diphenylphosphino)-1,15-binaphthyl |> by human], 2,2' bis(diphenylphosphino)-1,1'- Biphenyl [BISBI], 2,3-bis(diphenylphosphino)butane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)ethane , bis(2-diphenylphosphinoethyl)phenylphosphine, 1, Ρ > bis-(diphenylphosphino)ferrocene, bis(diphenylphosphino)methane, 1,2-double ( Diphenylphosphino)propane, 2,2'-bis(di-p-tolylphosphino)-1,1'-binaphthyl, 0-isopropylidene-2,3-dihydroxy-154-double (diphenylphosphino)butane [1)1〇?], 2-(diphenylphosphino)-2'-methoxy-1,1'-binaphthyl, 1-(2-diphenylphosphine -1-naphthyl)iso D , 1,15 Bu 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 others described in WO 00/55164 Ligand. Examples of phosphines include 2,6-bis(2,4-dimethylphenyl)-1-octane 1293950 (4) phenyl-4-phenylphosphane, 1-octyl-2,4,6- Triphenylphosphane and other ligands described in WO 02/00669. Examples of phosphites include trimethyl phosphite, triethyl phosphite, tri-n-propyl phosphite, triisopropyl phosphite, tri-n-butyl phosphite, triisobutyl phosphite, and trisphosphite- Third butyl ester, tris(2-ethylhexyl) phosphite, triphenyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, tris(2-third butyl) Base 4-methoxyphenyl) ester, tris(2-tert-butyl-4-methylphenyl) phosphite, tris(p-toluene) phosphite. Other examples are sterically hindered phosphite ligands as described in (especially) EP 1 5 5 5 08, US 4 66 8 65 1 , US 4 74 8 26 1 , US 4 769 498, US 4 774 36 1 US 4 835 29 9, US 4 885 401, US 5 059 710, US 5 113022, US: 5 179055, US 5,262,891, US 5,264,616, US 5 2 8 8 918, US 5 360 938, EP 4 72 071, EP 5 1 8 24 1 and WO 97/20795. Among the sterically hindered phosphites, mention may be made of triphenyl phosphite, which may be substituted by one or two isopropyl and/or tert-butyl substituents, preferably in the ortho position relative to the phosphite group. . Other bisphosphite coordination systems are described in particular in EP 1 099 677, EP 1 099 67 8 , WO 02/00670, JP 1 0279 5 87, EP 4720 17 , WO 0 1/2 1 627, WO 97/4000 1 Mentioned in WO 97/40002, US 476949 8, EP 2 1 3 63 9 and EP 214622. Examples of phosphonates are methyldiethoxyphosphine, phenyldimethoxyphosphine, phenyldiphenoxyphosphine, 6-phenoxy-6H-dibenzo[c5e][l,2]oxy Phosphorin and its derivatives (all or part of which are replaced by 1293950 (5) alkyl or aryl or halogen atoms) and WO 9 8/43 9 3 5, JP 09-268152 and DE 198 The ligands described in German Patent Application No. DE 199 54 721 and DE 199 54 510. Conventional phosphonite coordination systems are described, among others, in US 5 710 344, WO 95 06627, US 5 3 60 93 8 , JP 07 0 8 22 8 1 . Examples are diphenyl(phenoxy)phosphine and derivatives thereof in which all or part of the hydrogen atoms are replaced by an alkyl or aryl or halogen atom, diphenyl(methoxy)phosphine, diphenyl ( Ethoxylated phosphines and the like.

In the industrial hydroformylation, the reaction product, the unreacted starting material and the catalyst are usually separated by distillation. This hydroformylation is therefore carried out in the presence of a high boiling solvent to produce a fraction containing a high boiling catalyst which can be recycled to the process by distillation. - In many continuous industrial hydroformylation processes using a ruthenium catalyst, the high-boiling mixture of by-products formed in the hydroformylation is used as a solvent, for example, as DE 2 062 703 'DE 2 7 15 685, DE 2 8 02 92 2 , EP 〇1 7 1 83. In addition to high boilers, inert organic liquids (DE 3 1 26 2 65 ) and reaction products (aldehydes, alcohols), aliphatic and aromatic hydrocarbons, esters, ethers and water can be used (DE 4 4 1 9 898 ) as a solvent. In GB 1 1 97 902, saturated hydrocarbons, aromatics, alcohols and normal paraffins are used for this purpose. The addition of one or more polar organic materials during the hydroformylation is disclosed, for example, in WO 01/68248, WO 01. /68249, WO 01/68252. In this case, the polar substance is selected from the group consisting of nitriles, cyclic acetals, alcohols, pyrrolidines, lactones, formamides, and subclasses -9 - 1293950 (6) And water. In the hydroformylation of relatively long-chain olefins (C-6), high temperature and low temperature are required to separate the catalyst from the reaction product and possibly unreacted starting materials by distillation. Sometimes the ruthenium-containing catalyst will decompose to a considerable extent during this distillation, regardless of whether or not an additional ligand is used. This situation makes the loss of catalyst in the process, which has a great negative impact on the economics of the program. It has been found that the unmodified product is particularly unstable. The most common claim by those skilled in the art is that the mononuclear complex HRh (CO) 3 (in the absence of a ligand for upgrading) is a species that is active in hydroformylation. The complex HRh(C 0)3 is stable only below 2 (TC temperature and high pressure (NS Imyanitov, Rhodium Express, (19.9), 10/11,3-64), and with dual core The species (self-inactive 'but as a container for the active catalyst) is balanced (EV Slivinskii, YA Rozovskii, GA Korneeva, VI Kurkin, Kinetics and Catalysis (1 998 ) .3 9 ( 6 ) , 764-774 ) (AR E Γ ma η 5 VI Kurkin, E. V· Slivinskii, SM Loktev. Neftekhimiya (1990), 3 0( 1 ), 46-5 2 ) ° Aldehyde-inert clusters with larger molecular weights from dinuclear hydrazine carbonyls Formation. Under the conditions of strong hydroformylation, the formation of low molecular weight clusters is reversible. It has been proved that the clusters of up to Rh4 (CO)! 2 can be regenerated. The stability of active species under hydroformylation conditions can also be proved (Yu. B. Kagan 5Y. A. Rrzovskii, EV Slivinskii, GA Korneeva, VI Kurkin, SM Loktev, Kinetilai Kataliz (1987), 28 (6), 1508-1511). Conversely, high molecular weight clusters cannot be converted back to acidification conditions. Active species (Yu. B. Kagan, EV Slivinskii, VI K Urkin, G. A. -10- 1293950 (7)

Korneeva, R. A. Aranovich, N. N. Rzhevskaya, S. M. Loktev, Neftekhimiya (1 9 8 5 ), 25 (6), 791-797). The formation of the Jun sheep collection is usually the cause of the formation of solid precipitates containing antimony and is the first step. This occurs during the distillation process, but sometimes also under the reaction conditions. The sediment containing cerium is deposited on the walls of the vessel and the wall of the vessel. This leads to a relatively uneconomical catalyst loss, which necessitates regular plant shutdowns and scrubbing in industrial applications. The ruthenium precipitate needs to be recovered by a complicated metallurgical route. On the one hand, because of the unattractive enthalpy as the attraction of the hydroformylation catalyst, and on the other hand, due to its instability, many cycles and/or recovery methods have been proposed. A series of methods for removing ruthenium from the reaction mixture are known to be carried out by solid adsorbents. Thus, for example, DE 1 9 54 3 1 5 proposes a weak to strong ion exchange resin based on polystyrene as an adsorbent. According to DE 2 0 4 5 4 1 6, the regeneration of the ion exchange resin which has been carried out is carried out by treating the mixture of a lower alcohol, an aliphatic amine and water in the presence of oxygen. The lanthanum contained in the lysate is converted to ruthenium chloride hydrate by evaporation and treatment with hydrochloric acid, which can again serve as a catalyst precursor. W 〇 02/204 5 1 and US 5 208 1 94 apply for a method of recovering ruthenium from an existing ion exchanger, which is calcined and from the ash obtained in the form of an oxide. In US 4 3 8 8 2 79, salts of metals of Groups 1 and 2 of the Periodic Table of the Elements, zeolite molecular sieves and ion exchange resins have been proposed as adsorbents. W Ο 0 1 /72 6 79 applies a method of adsorbing ruthenium on activated carbon, polydecanoic acid and alumina in the presence of hydrogen at a high temperature. Patent EP 0 3 5 5 8 3 7 describes a method of adsorbing ruthenium on a basic ion exchange resin which is ionically bonded to an organophosphorus -11-1293950 (8) monomer. Regeneration of the resin is carried out by dissolution of a solution containing an organophosphorus ligand. WO 97/03 93 8 applies a method of adsorbing active money substances and impurities onto an acidic ion exchange resin. The regeneration is carried out by dissolving the impurities in a neutral solvent in the first step and then dissolving the active hydrazine material using an acidic solvent. The catalyst recovered in this manner is suitably used in the hydroformylation after rehydrogenation. The disadvantage of all adsorption methods for recovering rhodium is that the problem of re-release of the active substance cannot be satisfactorily solved. It is apparent to those skilled in the art that the proposed solvent or solvent mixture for this project is not inert during hydroformylation and causes side reactions. For example, an acidic solvent induces a highly exothermic and uncontrolled aldol condensation of the aldehyde. The alcohol and amine undergo a condensation reaction with the aldehyde, thus reducing the product yield. Therefore, it is absolutely necessary to remove the aforementioned solvent or solvent mixture before the catalyst is recycled. This makes recycling complication extremely technically complex and expensive. Conversely, adsorption to ion exchangers, followed by ashing and metallurgical recovery, has reached some industrial importance. This method is a simple technique, but can of course be improved. • The use of an expensive basic ion exchanger as a consumable material, the metal oxide after ashing, and the metallurgical processing make the procedure steps more complicated. A series of processes are also known in which tethers are extracted from the reactor output by solution of each tether and recycled to the hydroformylation reactor after being re-released. Thus, hydrazine-catalyzed hydroformylation in the presence of a protonatable nitrogen-containing ligand, extraction of a ruthenium complex using an aqueous acid solution, deprotonation, and recycle of hydrazine to the program are known from DE 19603201. In DE 4230871, the aqueous solution is recycled directly to the reaction. In EP 0 5 3 8 73 2, -12-1293950 Ο) A method of extracting an output from a reactor using a phosphine aqueous solution under a synthetic gas pressure. WO 97/03 93 8 for the application of a water-soluble polymer, such as polyacrylic acid, maleic acid copolymer and phosphorous carboxymethylated polyvinylamine, polyethylenimine and polypropylene decylamine as a binder . EP 0 5 8 8 2 2 5 Application of pyridine, D-quine, 2,2,-bipyridine, 1,1 〇-phenanthroline, 2,2,-dipyridyl, 2,2',6',2 "-Tripyridine and porphyrin (which may be in sulfonated and/or carboxylated form) as a miscible agent. However, the complexing agents required for aqueous extraction are often expensive and difficult to obtain. In addition, these include two additional The step (extraction and catalyst release) requires an increase in engineering expenditure. Furthermore, a method is also known in which it is said that the addition of a ligand containing phosphorus (ΙΠ) prevents the formation of ruthenium precipitates when the reactor output is treated by distillation. (DE 3 3 3 8 3 4 0, US 4 5 4 0 0, 5 4 7 ). The regeneration or re-release of the acidified active hydrazine is carried out by oxidizing the phosphorus (III) ligand. The disadvantage is that the stabilizer is continuously consumed. The formed phosphorus (V) compound needs to be continuously taken out to prevent accumulation in the reactor system. Inevitably, some of the active forms are also discharged. This method can also be simultaneously applied to the technology. And improved by the combination. WO 82/03 8 5 6 applies for a distillation of the hydroformylation reactor output in the presence of oxygen In the presence of oxygen, a portion of the aldehyde formed in the hydroformylation process is oxidized to the corresponding carboxylic acid and reacted with the hydrazine species to form a soluble carboxylic acid hydrazine. The carboxylic acid can be recycled to the process. The disadvantage is that the yield of the desired product is reduced. The unpublished patent application DE 1 02 4 0 2 5 3 describes a modification of the phosphorus ligand by predominantly metals of Groups 8 to 10 of the Periodic Table of the Elements. Touch-13-1393950 (10) Hydroformylation in the presence of a medium using a cyclic carbonate as a solvent. The use of unmodified metal complexes of metals from Groups 8 to 10 of the Periodic Table is not described. 226662 describes a method for awakening a hydrocarbon compound in which a ruthenium catalyst is used together with a sodium salt of a sulfonated triphenylphosphine as a secondary catalyst, that is, a modified catalyst is used. The reaction is based on a polar component and a carboxy group. The polar component can be, for example, ethylene glycol carbonate. The polar component can be recycled to the hydroformylation reaction with the acid and the catalyst. However, the procedure can be used only for terminal olefins ( Relative activity). If it is internal olefin, special Internally highly branched olefins, the catalytic activity is much lower than that required for industrial use. It is known that the process of recycling or recovering hydrazine from the use of unmodified hydrazine as a hydroformylation catalyst can be improved from a technical and economic point of view. Therefore, the prior art does not include a method which is technically and economically satisfactory in that it is difficult to use an unmodified ruthenium as a catalyst for alkenylation of acetylation. Therefore, the object of the present invention is to propose a target for this level. There is a method of drastic improvement, in particular, a method of easily recovering a catalyst, which greatly reduces the deactivation of the catalyst, thereby preventing a large loss of the catalyst. [Summary of the Invention] It is now unexpectedly found in an ethylenically unsaturated compound. In the hydroformylation process, when the hydroformylation catalyzed by the unmodified ruthenium is carried out in the presence of a cyclic carbonate as a solvent, the selectivity and activity are increased, the processing of the reaction mixture becomes simple, and the catalyst stability is greatly improved. increase. The present invention therefore provides a catalytic aldehyde for an ethylenically unsaturated compound having from 3 to 24 carbon atoms using an unmodified catalyst comprising at least one metal of Groups 14-1423950 (11) 8 to 10 of the Periodic Table of the Elements. a method in which the hydroformylation is carried out in the presence of at least one cyclic carbonate having the formula I

Wherein R1, R2, R3, and R4 are the same or different, and each is a substituted or unsubstituted aliphatic, alicyclic, aromatic, aliphatic-alicyclic ring having from 1 to 27 carbon atoms. a family, an aliphatic-aromatic or alicyclic-aromatic hydrocarbon group, a η system of 〇 to 5, and a X-type divalent substituted or unsubstituted aliphatic or alicyclic group having 1 to 27 carbon atoms An aromatic, aliphatic-alicyclic or aliphatic-aromatic hydrocarbon group having a ratio of at least 1% by weight of the reaction mixture. The use of a carbonate as a solvent in the present invention allows it to be hydroformylated in the presence of an unmodified catalyst (especially a ruthenium catalyst), and the unmodified catalyst can be reused. The above-mentioned modified ligands which are generally used in the hydroformylation of rhodium catalysis have limited thermal stability, and the reaction temperature is usually limited to 120 to 13 ° C. In the reaction of a vinylidene-unsaturated compound which is difficult to hydroformylate (for example, an internal olefin, especially an internal highly branched olefin), the ligand-modified ruthenium catalyst is limited to the reaction temperature of the ligand thermal stability. And the industrially unsatisfactory activity is shown by the conventional reaction pressure of 1 to 270 bar -15-1293950 (12). On the contrary, the unmodified product has a much higher activity in the reaction of the ethylenically unsaturated compound which is difficult to hydroformylate. However, this low thermal stability is a disadvantage (N.S. Imyanitov, Rhodium Express, (1995), 10/11, 3-64). Examples of ethylenically unsaturated compounds which are difficult to hydroformylate are internal olefins, especially internal highly branched olefins, which are mixtures of isomers prepared by dimerization and oligomerization of propylene and n-butene. Forms such as tripropylene, tetrapropylene, dibutene, tributene, tetrabutene and pentabutene. The process of the present invention has, inter alia, the advantage that the long-term stability of the catalyst is longer than that of the catalyst used in conventional solvents. Further, the solvent used makes the separation of the catalyst and the reaction mixture simple because the catalyst is present in the phase in which the cyclic carbonate as a solvent is also present, regardless of the manner in which the processing is carried out (by distillation or via Phase separation). The mixture can be returned directly to the hydroformylation reactor as a catalyst solution. The separation of the reactor output into the product containing the product and the unreacted starting material by phase separation and the catalyst-containing fraction are much milder for the catalyst system than by the distillation process. Thermal stress is not generated on the catalyst under reduced pressure, so formation of inert metal catalyst materials and metal-containing precipitates are avoided. In the case of separation by steaming, it is also unexpectedly greatly avoided to be deactivated by the formation of inert metal catalyst materials and metal-containing precipitates. The process of the invention can be up to 220. The hydroformylation of internal highly branched olefins is carried out at a temperature of: a catalyst having a particularly high activity. The conversion and selectivity of the hydroformylation (especially those of internal highly branched olefins) can be increased accordingly. The method of the present invention is described, but the present invention is not limited to the specific embodiments of the present invention, such as the ones of the present invention, and other variations, which are also subject to the description and application of the present invention. Scope of the Patent Table 7f\° The present invention uses an unmodified catalyst comprising at least one metal of Groups 8 to 10 of the Periodic Table of the Elements to have an ethylenic unsaturation (2) having 3 to 24 carbon atoms (especially 7E fine smoke). In the catalytic | totalization process, the wake-up is carried out in the presence of at least one cyclic carbonate having the general formula I

Wherein R1, R2, R3, and R4 are the same or different, and each is H or a substituted or unsubstituted aliphatic, alicyclic, aromatic, aliphatic-lipid having 1 to 27 carbon atoms. a cyclo, aliphatic, aromatic or alicyclic aromatic hydrocarbon group,

η is 〇 to 5, X is a divalent substituted fluorene having 1 to 27 carbon atoms, unsubstituted aliphatic, alicyclic, aromatic, aliphatic-alicyclic or aliphatic-aromatic base , ^ The ratio of carbonate is at least 1 weight of the reaction mixture. . The substituents R to R and X may be the same or different and are substituted by hydrazine, hydrazine, hydrazine-alkyl or hydrazine-dialkyl. Furthermore, such groups may have a functional group such as halogen (fluoro, chloro, bromo, iodo), -〇H, -OR, _c -17-1293950 (14) )alkyl, -CN or -C ( Ο ) 0 alkyl. Further, if the groups are at least three atoms away from the ester group, the C, CH or CH2 group may be replaced by 0, 1^, 1^, 1^-alkyl or cardinyl dialkyl. . The alkyl group may still have from 1 to 27 carbon atoms. In the method of the present invention, ethylene glycol carbonate, propylene glycol carbonate, butanediol carbonate or a mixture thereof, for example, a mixture of ethylene glycol carbonate and propylene glycol carbonate (weight ratio = 50: 5 0) is preferably used. As a cyclic carbonate. In the process of the present invention, the proportion of the cyclic carbonate is from 1 to 98% by weight of the reaction mixture, preferably from 5 to 70% by weight, particularly preferably from 5 to 50% by weight. Other solvents may be additionally used in addition to the cyclic carbonate. In a special process variant, the hydroformylation reaction of the invention is therefore carried out in the presence of at least one non-polar solvent (immiscible with cyclic carbonate I). The carbonated vinegar having the general formula I has a dielectric constant of more than 30. The non-polar solvent which is immiscible with the cyclic carbonate I and which is used in the process of the invention has a dielectric constant of less than 20, preferably from 1.1 to 10, especially from 1.1 to 5. The use of additional (especially non-polar) solvents makes it possible, for example, to produce a reaction mixture in a single phase or in two phases, especially the output of the reactor. In this way, the processing used to process the reactor output can be simplified. The hydroformylation reaction product may be extracted using a non-polar solvent which is immiscible with the cyclic carbonate I, in which case the solvent may be present in the reaction mixture during the reaction or may be added only after completion of the reaction. Possible non-polar solvents are substituted or unsubstituted hydrocarbons having from 1 〇 to 50 carbon atoms, such as high boiling by-products of hydroformylation, -18-1293950 (15)

The mixture of isomers obtained by tetramerization or polymerization of Texanol or propylene or butene and subsequent hydrogenation, i.e., tetrabutane, pentabutane, tetrapropane and/or pentapropane. It is also possible to use olefins having 3 to 24 carbon atoms, especially olefins for hydroformylation, as non-polar solvents, by performing a hydroformylation reaction to incomplete conversion (for example, only to 95% conversion, to 9 Preferably, 0%, especially 80%) and/or additional olefinic sludge reaction mixture is added during and/or after the hydroformylation reaction. In the process of the invention, the proportion of the non-polar solvent is from 90% by weight of the reaction mixture, preferably from 5 to 50% by weight, especially from 5 to 30% by weight. To avoid by-products, the non-polar solvent is hydroformylated. It is generally inert under the conditions unless it is a vinyl-type unsaturated compound used. In the process of the present invention, the reaction mixture may be a single phase or a two phase in the overall conversion process in the hydroformylation reactor. However, the feed mixture may also be composed of two phases at a low conversion rate and a single phase at a high conversion rate during the reaction. The single phase feed mixture can be converted to a biphasic product mixture during the process of the invention. In addition, the phase properties are closely related to temperature. For example, a reaction mixture which is a single phase at the reaction temperature can be separated into two phases upon cooling. The reaction mixture which is two phases at the reaction temperature may also be a uniform sentence upon cooling. The process of the present invention can be carried out using various catalytically active metals of Groups 8 to 10 of the Periodic Table of the Elements, but it is preferred to use hydrazine. For the purposes of the present invention, an unmodified catalyst comprising a metal of Groups 8 to 10 of the Periodic Table of the Elements is a catalyst which does not comprise a modified ligand. For the purposes of this patent application, the modified ligand -19-1293950 (16) is a compound containing one or more host atoms of Groups 8 to 15 of the Periodic Table of the Elements. However, the modified ligand does not include a carbonyl group, a hydrogen group, an alkoxy group, an alkyl group, an aryl group, an allyl group, a fluorenyl group or an ene ligand, and does not include a counter ion for a metal salt formed by a catalyst. For example, a halogen group such as fluorine, chlorine, bromine or iodine, acetylpyruvate, a carboxylate such as acetate, 2-ethylhexanoate, hexanoate, octanoate or citrate. The best unmodified catalyst is HRh (CO) 3. The active catalyst complex used in the hydroformylation reaction is formed from a metal salt or a compound (catalyst precursor) and a synthesis gas. This preferably occurs in situ during the hydroformylation process. The conventional catalyst precursors are Rh (I), Rh (II) and Rh (III) salts, such as acetate, octoate, decanoate, ethyl phthalate, or halides, and ruthenium carbonyl. The concentration of the metal in the reaction mixture is preferably in the range of 1 p p m to 1 0 0 p p m , preferably in the range of 5 p p m to 3 0 0 ρ ρ ηι. The starting material for hydroformylation in the process of the invention is a compound containing ethylenically unsaturated CC double bonds, especially an olefin or a mixture of olefins, especially having from 3 to 24 (preferably from 4 to 16 in particular, especially 4) To 2) a monoolefin having a carbon atom and having a terminal or internal CC double bond, such as ^ or 2-pentane, 2-methyl-1-butan, 2-methyl-2-butane, 3-A a C 6 -olefin mixture (dipropylene), heptene, 2- or 3-methyl-1-hexene obtained by dimerization of ketone-1-butane, di, 2- or 3-hexene and propylene, Octene, 2-methylheptene, 3-methylheptene, 5-methyl-2-heptene, 6-methyl-2-heptene, ethyl-1-hexene, n-butene C i olefin mixture (diisobutylene) -20-1293950 (17), terpene, 2- or 3-methyl octene obtained by polymerization of an isomeric C8-olefin mixture obtained by polymerization and dimerization of isobutylene And tetramerization of C9-olefin mixture (tripropylene), terpene, 2-ethyl-1-octene, dodecene, propylene or trimerization of butene obtained by trimerization of propylene The prepared C] 2-olefin mixture (tetrapropylene or tributene), tetradecene, hexadecene An olefin mixture (tetrabutene) obtained by tetramerization of butene and an olefin mixture prepared by co-oligomerization of an olefin having a different number of carbon atoms (preferably 2 to 4), if appropriate, It is then divided into fractions having the same or similar chain length by distillation. It is also possible to use an olefin or olefin mixture obtained by Fischer-Trohsch synthesis and an olefin obtained by oligomerization of ethylene or an olefin which can be obtained by a displacement reaction. Preferred starting materials are C4-, C6-, Cs-, (:9-, C!2. or C16-olefin mixtures. Furthermore, the process of the invention allows for the hydroformylation of polymeric ethylenically unsaturated compounds, such as a polyisobutylene or a 1,3-butadiene copolymer or an isobutylene copolymer. The influence of the molecular weight of the polymerized olefin is extremely small, provided that the condensed hydrocarbon is sufficiently soluble in the awake medium. The molecular weight of the polymerized olefin is lower than 1 0 0 0 0 / mol is preferred, especially less than 5 000 g / mol. The volume ratio of carbon monoxide to hydrogen in the synthesis gas is usually from 2:1 to 1:2, especially 1. The synthesis The gas is preferably used in excess, for example up to three times the stoichiometric amount. The hydroformylation is usually carried out at a pressure of from 1 to 350 bar, preferably from 15 to 2 70 bar. Depending on the structure of the olefin, the catalyst used and the desired effect, for example, the α-olefin can be converted to a corresponding high-space-time yield in the presence of a rhodium catalyst at a pressure of less than 1 Torr. Aldehyde. Conversely, if it is an olefin having an internal double bond, especially a fraction of -21,939,950 (18) Branched olefins are preferred at higher pressures. The reaction temperature in the process of the invention is preferably from 20 to 22 Torr, more preferably from 100 ° C to 200 ° C, and from 150 ° C to 19 (TC is particularly preferred, especially 16). 〇 to i8 (TC. The reaction temperature above 150 °C is particularly improved. The ratio of the end to the internal double bond, because at high temperatures, more end double bonds become effective, and better ends, as a result of accelerated isomerism. The acidification of the location is increased. The process of the invention can be carried out batchwise or continuously. However, continuous operation is preferred. Suitable reactors include substantially all gas-liquid reactors known to those skilled in the art, such as spray agitation vessels or Bubble column or tubular reactor (with or without recirculation). A bubble column with a cascade and a tubular reactor equipped with a static mixing element. The reactor output obtained by the process of the invention contains possibly unreacted ethylene. Type unsaturated compound (olefin), reaction product, reaction by-product, at least one cyclic carbonate, possibly non-polar solvent and catalyst. The type and mass fraction of the olefin compound as the starting material, and any non-containing Depending on the type and mass fraction of the solvent and the type and mass fraction of the cyclic carbonate, the reactor output may be a single phase or a two phase. As described above, a cyclic carbonate may be appropriately added or Non-polar solvent to achieve or prevent phase separation The reactor output processing in the process of the invention can be carried out in two variations, depending on the phase nature of the reactor output. If it is a two-phase reactor output, It is preferred to carry out the processing via phase separation, which is referred to as variant A. If it is a single-phase reactor output, it is preferably processed by distillation, which is referred to as variant B. -22- 1293950 (19) Synthesis The gas is preferably removed by decompression to remove a major portion of the synthesis gas after the hydroformylation, prior to further processing of the reactor output according to variant A or B.

Variant A In this variant of the process, the output of the two-phase reactor from the hydroformylation reaction is separated by phase separation into fractions comprising mainly catalysts and cyclic carbonates and mainly comprising hydroformylation products and unreacted olefins or ethylene. The fraction of the unsaturated compound is preferred. This method variant can be used when using other non-polar solvents. The non-polar solvent may be the same as the starting olefin such that the hydroformylation reaction is not carried out to complete conversion (eg, only up to 95%, preferably 90%, particularly preferably 80%) and/or may be during the hydroformylation reaction and/or Additional olefins are then added to the reaction mixture. Variation A of the method of the present invention is illustrated by Figure 1, but the method is not limited to this embodiment: synthesis gas (1), olefin (2), and awake in a mixture of a cyclic carbonate or a plurality of cyclic carbonates. The catalyst (3) is reacted in the hydroformylation reactor (4). The reactor output (5) may optionally remove excess synthesis gas (7) in a reduced pressure vessel (6). The liquid stream (8) obtained in this manner is separated into a heavy phase (1 〇) in a separation device (9), which comprises a main portion of a cyclic carbonate and a catalyst, a high-boiling by-product, and a light phase. (1 1 ), which comprises a hydroformylation product, an unreacted olefin, and, if used, a non-polar solvent. The phase separation can be carried out at a temperature of from 0 ° C to 13 (at a temperature of TC of from 1 〇 ° C to 60 ° C. The phase separation can be carried out, for example, in a settling chamber -23-1293950 (20). The phase separation in the separation unit (9) is at a pressure of 1: for a pressure (preferably 15 to 270 bar), but is preferably the same pressure as used in the hydroformylation reactor (4). (9) The heat exchanger can be used to feed the liquid stream (5) (not shown in Figure 1). In the selective fraction, the catalyst residue can be taken out from the liquid stream (1 1 ). The liquid stream 1 3 ) then passes to the separation stage (1 4 ). In this case, the aldehyde (alcohol and alcohol) and the unreacted olefin (15) are fed to a further step. The olefins that have been separated from the liquid stream (15) can be sent back to the selective further reaction stage. Also separated fractions (for example, residual cyclic carbonates, reaction products, any non-polar solvents, and high-boiling by-products. Fractions (16) can be thrown back into the hydroformylation reactor (4). The by-product is carried out prior to recycling. The separation device (9) is subjected to extraction, and at least a portion of the fraction (16) and/or at least the hydrocarbon (2) is fed directly into the liquid stream (8). Preferably, the extraction is preferably a single-stage extraction or a countercurrent operation in a multi-stage process. The catalyst-containing discharge stream, for example from a liquid stream (separation stage (12), can be processed by known methods to Catalyst metal in the form of a catalyst.

Variant B In this method variant, the uniformization of the hydroformylation reaction is carried out by distillation into a product mainly comprising a hydroformylation product and possibly unreacted g 3 5 0 bar under pressure for the purpose of cooling, and cooling to the stage ( 1 2 (11) or (from the reaction product step processing or hydrogen with the reactor or 16) is added to other discarded or recycled processing preferred catalyst separation can be partially freshly burned continuously for downstream or alternating 10) or The relatively low-boiling fraction from the recovered re-energizer is an olefin or ethylene-24 1293950 (21) type unsaturated compound, and a high-boiling fraction mainly comprising a cyclic carbonate and a catalyst. Variation B of the process of the present invention is illustrated in Figure 2, which is not limited to this embodiment: synthesis gas (1), olefin (2), and a hydroformylation catalyst dissolved in a cyclic carbonate or a mixture of cyclic carbonates. (3) The reaction is carried out in a hydroformylation reactor (4). The reactor output can optionally remove excess synthesis gas (7) from the reduced pressure vessel (6). The liquid stream (8) obtained in this manner is separated in the separation device (9) to produce a partial boiling point phase (10) containing a main portion of a cyclic carbonate and a catalyst, and a waking product, an unreacted olefin, and (if used) Low boiling point phase of a non-polar solvent (1 1 ). The catalyst-containing fraction (10) is recycled to the hydroformylation reactor. This may optionally be handled by a processing step in which high boiling by-products and/or catalyst degradation products are removed (not shown in Figure 2). The fraction (1 1 ) may optionally be removed from the catalyst residue in the separation step (1 2 ). Stream 13 is then sent to the steaming stage (14). In this case, the hydroformylation product (aldehydes and alcohols) (16) is separated from the unreacted olefin (15) by distillation. The catalyst-containing discharge stream (e.g., liquid stream (1 〇) or from the separation stage (12)) can be obtained by methods known to those skilled in the art (e.g., from WO 02/2045 1 or US 5,20 8,194). Learn to process and recycle the catalyst metal in a reusable form. This hydroformylation product is further processed. The unreacted olefin (15) can be returned to the same hydroformylation reactor or fed to a selective second reaction stage. When the program is industrially carried out, the separation device can have a variety of different designs. The separation is preferably carried out by a falling film evaporation, a short path evaporator or a thin film evaporator or a combination of such devices. -25- 1293950 (22) The advantage of this combination is, for example, that the still-dissolved synthesis gas and the major portion of the product and the unreacted starting material can be self-catalyzed in the first step from the catalyst-containing alkanediol carbonate solution. Separation (e.g., falling film evaporator or flash evaporator), while removal of the residual alkanediol carbonate and separation of the product from the unreacted starting material can be carried out in a second step (e.g., combining two columns). In both variants A and B of the process of the invention, the reactor output from which the catalyst, excess synthesis gas and a major portion of the solvent (i.e., the cyclic carbonate or a mixture thereof) have been removed is preferably further separated into aldehydes. (Alcohols), olefins, solvents and by-products. As indicated above, this can be achieved, for example, by distillation. The olefin and/or solvent (alkane carbonate and/or non-polar solvent) which has been separated from the reaction output or from the hydroformylation product can be recycled to the hydroformylation reaction. The foregoing variations of the process of the invention include separating the reactor output and the selective hydroformylation product; this can be done, for example, by distillation. However, other separation methods can also be used, such as described in (especially) W Ο 0 1 / 6 8 2 4 7 , EP 0 9 22 6 9 1 , WO 99/3 8 8 3 2, US 5 64 8 5 54 And the extraction in US 5 1 38 ] 01, or as described in (especially) DE 1 9 5 3 64 1 , GB 1312076, NL 8 7 0 0 8 8 1 , DE 3842819, W Ο 9419104, DE 1 963 2600 and Penetration in EP 1 1 03 3 03. When the separation system is industrially carried out, various methods can be employed. The separation is preferably carried out by a drop film evaporator, a short path evaporator or a thin film evaporator or a combination of such devices. The extraction separation is preferably carried out continuously. It can be designed as a single-order method or in a multi-stage method in the form of countercurrent or alternating current. In all process variants, the catalyst-containing fraction is preferably recycled -26-1293950 (23) to the hydroformylation reaction. This is of course irrelevant to the composition of the fraction in which the catalyst is dissolved. When the target product is not the aldehyde itself but the alcohol derived therefrom, the reaction product mixture from which the synthesis gas and the catalyst have been removed and possibly the solvent may be hydrogenated before or after the olefin separation, and then processed by distillation to produce pure alcohol. . The method of the invention can be carried out in single or multiple orders. In this case, the first hydroformylation reaction may be followed by a second hydroformylation stage, and also under internal reaction conditions (such as high temperature and/or high pressure), which are difficult to hydroformylate internal olefins (especially internal highly branched olefins). Into the desired aldehyde. However, it is preferred to use unreacted hydrocarbons and hydroformylation products (aldehydes and alcohols) first, and the unreacted olefins are recycled to the same hydroformylation stage or to the second hydroformylation stage or even the later stage of the hydroformylation stage. In this case, the second hydroformylation stage can be carried out using completely different catalyst systems (i.e., different catalyst metals or ligand-modified catalyst metals). It is also possible (preferably) to add a higher concentration of catalyst to the unreacted olefin at this stage to effect olefin conversion which is relatively difficult to hydroformylate to the desired product. In all cases, it is necessary to add the aforementioned amount of cyclic carbonate to the further stage of the hydroformylation. In the process of the present invention, the ethylenically unsaturated compound to be used may also be a compound obtained in the form of an unreacted ethylenically unsaturated compound obtained from the reactor output of the first hydroformylation reaction. In this case, the entire reaction product mixture may be used or only a part thereof may be used, especially the portion containing most of the unreacted olefin compound from the first stage. Preferably, in the variant of the process, the first hydroformylation reaction is carried out in the presence of a ligand-modified catalyst. -27-1293950 (24) [Embodiment] The following examples are merely illustrative of the invention, and The scope defined by the description and the scope of the patent application is not limited. Example 1 (Variation A) 560 g of propylene glycol carbonate, 560 g of tri-n-butene and 0.08 8 g or 〇 02 25 g of ruthenium (II) ruthenate (corresponding to the mass of the reactor contents) Placed in a 2 liter agitated autoclave under a nitrogen atmosphere at a concentration of 5 ppm or 2 Torr. The autoclave is pressurized with the subsequent synthesis gas (CO/H2 1:1 mol) and heated to the desired reaction temperature. The reactor temperature was detected during heating. The reaction temperature was from 130 ° C to 18 (ΓC. The reaction pressure was 260 bar. During the reaction, other synthesis gas was introduced under pressure control. After 5 hours, the experiment was stopped and the reactor was cooled to ambient temperature. The reactor output is always composed of two phases and does not contain antimony precipitates. The composition of the lighter hydrocarbon phase separated in the phase separation vessel is detected by gas chromatography. The results of gas chromatography and reaction conditions (such as temperature and铑 Concentration) series are shown in Table 1. -28- 1293950 (25) Table 1: Three-n-butene was hydroformylated for 5 hours at 260 ° C and various temperatures. Recorded ratio (% by mass) and lighter Related to the hydrocarbon phase, the phase has removed any of the carboxylate and catalyst contained. In Experiment 6, the catalyst solution obtained by processing the reactor output of Experiment 5 was again used. No. T/°C c (Rh ) / C13-aldehyde C 1 3 -alcohol C 12- high boiler ppm /% /% HC/% /% 1 130 5 27 1 72 0 2 130 2 0 55 4 40 1 3 150 20 68 14 17 1 4 1 80 5 48 33 14 5 5 1 80 2 0 5 9 32 8 1 6 1 80 2 0 61 30 8 1

Example 2 (Variation B) Di-n-butene (5 60 g) was hydroformylated in the same manner as in Example 1. The reactor outputs of Runs 7 through 13 were always composed of a single phase and did not contain (铑) precipitates. In contrast to Example 1, the reactor output was analyzed by gas chromatography without treatment. The results of gas chromatography and reaction conditions (such as temperature, pressure and helium concentration) are summarized in Table 2. -29- 1293950 (26) Table 2: Hydroformylation of di-n-butene at various pressures, enthalpy concentrations and temperatures. The recorded ratio (in mass %) is the composition of the reactor output which has removed the carbonate and catalyst contained therein. No. T/°C p/bar c(Rh)/p pm C8- HC/% C9-aldehyde/% C9-alcohol/% 7 150 50 40 67.5 30.4 2.1 8 150 250 40 3.1 8 7.6 3.3 9 170 150 5 2 6.3 66.6 27.1 10 170 250 5 4.5 78.1 17.4 11 170 250 40 4.0 20.5 75.5 12 1 80 50 40 66.8 17.5 15.7 13 180 150 40 9.9 23.3 66.8 Example 3 (conventional method) Di-n-butene is carried out as in Example 2. Aldehydeation, using pentabutane in place of propylene glycol carbonate as a solvent. The reactor output of Experiment 1 4 showed a large amount of black (铑) precipitate. The aldehyde and unreacted olefin were then separated from the catalyst-containing solution in a thin film evaporator, and the catalyst solution was used in another hydroformylation (Experiment 15). The results of gas chromatography and the reaction conditions (such as temperature, pressure and helium concentration) are summarized in Table 2. -30- 1293950 (27) Table 3 · · Di-n-butene was hydroformylated in pentabutane at 15 Torr and 250 bar. The recorded ratio (in mass%) is the composition of the reactor output which has removed the pentabutane, by-products and catalyst contained therein. In Experiment 15, the obtained catalyst solution was again treated by distillation in Experiment 14. No. T/°C p/bar c(Rh)/p C8- C9-aldehyde C9-alcohol pm HC/% /% /% 14 1 50 250 4 0 75.4 23.4 1.2 15 150 250 Unknown 91.5 7.8 0.7 Experiment 1 to 1 The absence of an antimony precipitate in 3 indicates that the alkanediol carbonate as a solvent has a particularly stable effect on the antimony compound. In contrast, when an alkane was used as a solvent in a control experiment, a considerable amount of ruthenium precipitate was observed and when the catalyst was recycled, the activity was found to be greatly lowered (Experiments 14 and 15). In Experiment 16, the catalyst phase from Experiment 5 was used in the new hydroformylation. The olefin conversion rate remains constant over the range of experimental accuracy. Experiments have shown that the process of the present invention provides far greater chemical selectivity for the desired aldehydes and, in addition, allows the catalyst to be technically easily recycled without significant deactivation. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram showing a variation A of the method of the present invention, and Fig. 2 is a modification of the method B of the present invention. -31 - 1293950 (28) [Main component comparison table] 1 Synthetic gas 2 Olefin 3 Aldehyde catalyst dissolved in a mixture of cyclic carbonate or various cyclic carbonates 4 Aldehyde reactor 5 Reactor output 6 minus Pressure vessel 7 Excess synthesis gas 8 Liquid stream 9 Separation unit 10 Heavy phase 11 Light phase 12 Separation stage 13 Stream 14 Separation stage 1 5 Stream 16 Separation fraction

-32-

Claims (1)

Patent Application No. 1. A method for catalytically hydroformylating an ethylenically unsaturated compound having 3 to 24 carbon atoms using an unmodified catalyst comprising at least one metal of Groups 8 to 10 of the Periodic Table of the Elements, wherein The hydroformylation is carried out in the presence of a cyclic carbonate of the formula I Wherein R1, R, R and R4 are the same or different and each is H or a substituted or unsubstituted aliphatic, alicyclic, aromatic or aliphatic-fat having from 1 to 27 carbon atoms a cyclo, aliphatic-aromatic or alicyclic-aromatic hydrocarbon group, η is 〇 to 5, Χ is a divalent substituted or unsubstituted aliphatic or alicyclic group having 1 to 27 carbon atoms , aromatic, aliphatic-alicyclic or aliphatic-aromatic hydrocarbon group, = the ratio of the acid is at least 1% by weight of the reaction mixture. 2. The method of claim 1, wherein R1, R2, R3, r4 and X are selected from the group consisting of ruthenium, N, NH, N-alkyl and N-dialkyl, fluorine, chlorine, bromine, iodine Substituting the same or different substituents of -OH, -0R, _CN, <(〇)alkyl or _c(〇) 0 -alkyl. 3. The method of claim 1, wherein the hydroformylation is carried out in the presence of a solvent of from 5 to 50% by weight based on the reaction mixture of -33 to 1293950 (2), the solvent being compared to the ring The carbonate I is non-polar and is immiscible with the cyclic carbonate I. The method of any one of claims 1 to 3, wherein the reaction product derived from the hydroformylation is extracted using a non-polar solvent which is immiscible with the cyclic carbonate I. 5. The method of claim 3, wherein a substituted or unsubstituted hydrocarbon having from 丨 to 50 carbon atoms or an olefin having from 3 to 24 carbon atoms is used as the nonpolar solvent. The method of any one of claims 1 to 3, wherein the hydroformylation is carried out in the presence of HRh (CO) 3 as a catalyst. The method of any one of claims 1 to 3, wherein the reaction product mixture from the hydroformylation reaction is separated into a fraction mainly comprising a catalyst and the cyclic carbonate, and mainly comprising a hydroformylation product. Level. The method of any one of claims 1 to 3, wherein the catalyst-containing fraction is recycled to the hydroformylation reaction. The method of any one of claims 1 to 3, wherein the cyclic carbonate used is ethylene glycol carbonate, propylene glycol carbonate or butylene glycol carbonate or a mixture thereof. The method of any one of claims 1 to 3, wherein the unreacted ethylenically unsaturated compound is separated from the reactor output or from the hydroformylation product, and returned to the same hydroformylation reaction, or sent The second hydroformylation reaction 〇1 1 · The method of any one of claims 1 to 3, wherein the ethylenically unsaturated compound used in -34-1293950 (3) is derived from the first aldehyde The reactor output of the reaction is a compound in the form of an unreacted ethylenic compound. 12. The method of claim 2, wherein the ethylenically unsaturated compound used is a reactor output obtained from a first hydroformylation reaction in the presence of a catalyst modified by a ligand, and It is a compound in the form of an unreacted ethylenically unsaturated compound. -35- 1293950 柒(1) The representative figure specified in this case is: _j_图(二), the representative symbol of the representative figure in this case is a simple description: 1 Synthetic gas 2 Olefin 3 Dissolved in cyclic carbonate or various rings A mixture of carbonates, hydroformylation catalyst 4, hydroformylation reactor 5 reactor output 6 decompression vessel 7 excess synthesis gas 8 liquid stream 9 separation unit 10 heavy phase 11 light phase 12 separation stage 13 liquid stream 1 4 separation stage 15 Flow 16 Separation fraction 捌 If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: R4 4_