TW200418785A - 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

The present invention relates to a process for preparing aldehydes by hydroformylation catalyzed by metals of groups 8 to 10 of the Periodic Table of the Elements in the presence of cyclic carbonic esters.

Description

200418785 ⑴ 发明, Description of the invention [Technical field to which the invention belongs] The present invention relates to a method for subjecting an ethylenically unsaturated compound (especially a hydrocarbon) to an unmodified metal derived from a group 8 to 10 metal of the periodic table. A method of catalyzing aldehydes to produce aldehydes, which is carried out in the presence of a cyclic carbonate as a solvent. [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 the catalysis of cobalt compounds, the aldehydes using rhodium compounds usually have the advantages of chemical selectivity and high regioselectivity, so they are usually economically attractive. Rhodium-catalyzed aldehydes are usually carried out using a complex containing rhodium and a compound of Group 15 of the Periodic Table of the Elements (preferably a trivalent phosphorus compound). For example, compounds derived from phosphines, phosphites and phosphonates are often used as ligands. For comments on aldolization of olefins, see B. CORNILS, WA HERRMANN, "Applied Homogeneous Catalysis with Organ ometallic Compounds,", V 〇1.1. &Amp; 2 5 VCH, Weinheim, New York, 1996 Phosphine-modified rhodium catalysts react easily in the presence of internal olefins, especially internally highly branched olefins, which require -5- (2) (2) 200418785 strong active ligands, such as phosphite ligands In addition, "raw" or unmodified rhodium has been found to be extremely suitable for olefins that are difficult to formaldehyde. These catalysts contain one or more metal species which are formed from metal salts under aldehyde formation conditions in the absence of modified ligands. For the purposes of this patent application, a modified coordination system is a compound containing one or more donor atoms of group 15 of the periodic table. However, modified ligands do not include alkoxy, carbonyl, hydrogen, alkyl, aryl, allyl, fluorenyl, or alkenyl ligands, nor do they include counterions for forming metal salts of catalysts. For example, a halo group such as fluorine, chlorine, bromine or iodine, acetopyruvate, a carboxylate such as acetate, 2-ethylhexanoate, hexanoate, caprylate or nonanoate. The modified coordination system used in the present invention is a ligand containing a donor atom selected from Group 15 of the Periodic Table of the Elements, such as nitrogen, phosphorus, arsenic or antimony, especially phosphorus. 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 phosphine, phosphinine, phosphinane, phosphine oxide, phosphite, phosphonate and phosphonate. Examples of phosphines are triphenylphosphine, tris (p-tolyl) phosphine, tris (m-tolyl) phosphine, bis (o-tolyl) phosphine, tris (p-methoxyphenyl) phosphine, $ (p-- Fluorophenyl) phosphine, tris (p-chlorophenyl) phosphine, tris (p-dimethylformyl) phosphine, ethyldiphenylphosphine, propyldiphenylphosphine, third butyldiphenylphosphine , N-butyldiphenylphosphine, n-hexyldiphenylphosphine, hexyldibenzylphosphine, dicyclohexylphenylphosphine, tricyclohexylphosphine, tricyclopentylphosphine, trisylphosphine, tris (naphthyl) phosphine , Tris-2-furylphosphine, tribenzylphosphine, -6-(3) (3) 200418785 benzyldiphenylphosphine, tri-n-butylphosphine, tri-isobutylphosphine, tri-tertiary-butyl Phosphine, bis (2-methoxyphenyl) phenylphosphine, neocapryldiphenylphosphine, sulfonated triphenylphosphine (such as tris (m-sulfofluorenylphenyl) phosphine, Alkali, alkaline earth metal, ammonium or other salts of phenylphosphine; 1,2-bis (dicyclohexylphosphino) ethane, bis (dicyclohexylphosphino) methane, 1,2-bis (diethyl) Phosphinyl) ethane, 1,2-bis (2,5-diethylphosphoranyl) ethane, 1,2-bis (2,5- Ethylphosphino) benzene [Et-DUPHOS], 1,2-bis (2,5-diethylphosphoniumdongyl) ethane [Et-BPE], 1,2-bis (dimethylphosphino) ) Ethane, bis (dimethylphosphino) methane, 1,2-bis (2,5-dimethylphospho I] east) benzene [Me-DUPHOS], 1,2-bis (2,5 -bis Methylphosphoranyl) ethane [M e-BPE], 1,2-bis (diphenylphosphino) benzene, 2,3-bis (diphenylphosphino) bicyclo [2.2.1] heptane- 5-ene [NORPHOS], 2,2, -bis (diphenylphosphino) -1,1, binaphthyl [31 > ^?], 2,2'-bis (diphenylphosphino) -1, 1'-biphenyl [BISBI], 2; 3-bis (diphenylphosphino) butane, 1,4-bis (diphenylphosphino) butane, 1,2-bis (diphenylphosphine) ) Ethane, bis (2-diphenylphosphinoethyl) phenylphosphine,] bis- (diphenylphosphino) ferrocene, bis (diphenylphosphino) methane, 1,2-bis (di Phenylphosphino) propane, 2,2'-bis (di-p-tolylphosphino) -1,1'-binaphthalene, 0-isopropylidene-2,3-dihydroxy-154-bis ( Diphenylphosphino) butane [010?], 2- (diphenylphosphino) -2'-methoxydiazepam, 1- (2-monobenzyl-1-calyl) iso-diquinone Lynn, 1515 Phosphino) ethane and / or tris (hydroxyphenyl) phosphine. Examples of phosphine include 2,6-dimethyl-4-phenylphosphine, 2,6-bis (2,4-dimethylbenzene ) -4-phenylphosphine and other ligands described in WO 00/5 5 1 64. Examples of phosphanes include 2,6-bis (2,4-dimethylphenyl) -1-octane -7- (4) (4) 200418785 yl-4-phenylphosphine, buxyl-2,4,6-triphenylphosphine and other ligands described in WO 02/00669. Examples of phosphites are trimethyl phosphite, triethyl phosphite, tri-n-propyl phosphite, triisopropyl phosphite, tri-n-butyl phosphite, triisobutyl phosphite, and tri- Tert-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 4 668 65 1, US 4 748 26 1, US 4 7 69 49 8, US 4 774 3 6 1.US 4 8 3 5 299, US 4 885401, US 5 059710, US 5 113 022, US 5 179055, US 5 260 491, US 5 264 616, US 5 2 8 8 9 1 8, US 5 3 6 0 93 8, EP 4 72 07 1, EP 5 1 8 24 1 and WO 97/2 07 9 5. Among the sterically hindered phosphites, mention may be made of triphenyl phosphite, which may be substituted with one or two isopropyl and / or third butyl substituents, preferably in an ortho position relative to the phosphite group . Other bisphosphite coordination systems are particularly EP 1 099 6 7 7, EP 1 09 9 6 7 8, WO 02/00670, JP 1 02 795 8 7, EP 4 72 0 1 7, WO 0 1/2 1 62 7, WO 97/4 000 1, WO 97/40002, US 47 6949 8, EP 2 1 3 6 3 9 and EP 2 1 4 622. Examples of phosphonates are methyldiethoxyphosphine, phenyldimethoxyphosphine, phenyldiphenoxyphosphine, 6-phenoxy-6H-dibenzo [c, e] [l, 2 ] Oxaphosphine (ph 〇sph 〇 ri η) and its derivatives (where all or part of the hydrogen atom is replaced by -8- (5) (5) 200418785 alkyl or aryl or halogen atom) and wo 9 8 / 43 9 3 5, JP 09-268152 and DE 198 10 794 and the ligands described in German patent applications DE 199 54 721 and DE 199 54 510. Conventional phosphinate coordination systems are described, inter alia, in US 5 7 1 0 344, WO 95 06627, US 5 3 60 93 8, JP 0 7 0 8 22 8 1 Moderate examples include diphenyl (phenoxy Group) 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, etc.

In industrial aldolization, reaction products, unreacted starting materials and catalysts are usually separated by distillation. The aldolization is therefore carried out in the presence of a high boiling point solvent to produce a fraction containing a high boiling point catalyst by distillation processing, which can be recycled to the process. In many continuous industrial aldolization processes using rhodium catalysts, high-boiling mixtures of by-products formed during the aldolization are used as solvents, such as, for example, DE 2 062 703, DE 2 715 685, DE 2 8 02 922, EP 〇 1 7 1 8 3 as described. In addition to high boiling compounds, inert organic liquids (DE 3] 26 2 6 5) and reaction products (aldehydes, alcohols), aliphatic and aromatic hydrocarbons, esters, ethers and water (DE 4 4 1 9 8 9 8) as a solvent. In GB 1 1 9 7 9 02, saturated hydrocarbons, aromatics, alcohols and normal paraffins are used to achieve this goal. The addition of one or more polar organic substances during the aldolization process is disclosed in, for example, 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-9- (6) (6 ) 200418785 class and water. In the aldolization of relatively long-chain dilute smoke (C g 6), high and low temperatures are required to separate the catalyst from the reaction products and possibly unreacted starting materials by vaporization. Sometimes rhodium-containing catalysts decompose to a considerable extent during this distillation, 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 process. The unmodified rhodium catalyst has been found to be particularly unstable. The most common claim made by those skilled in the art is that the mononuclear complex HRh (CO) 3 (in the absence of a modifying ligand) is an active species in the aldolization. The complex HRh (CO) 3 remains stable only at temperatures below 20 ° C and high pressure (NS Imyanitov, Rhodium Express, (1 995)? 10/11, 3-64), and is compatible with the dual-core species (itself Inactive, but as a container for active catalysts) keeps balance (EV Slivinskii, YA Rozovskii, GA Korneeva, VI Kurkin, Kinetics and Catalysis (1998) 539 (6), 764-774) (A ♦ R · E Γ ma η V. I. Kurkin, E. V. S 1 ivinskii 5 S. M. Loktev, Ne; ftekhimiya (1990), 30 (1), 46-52). Larger molecular weight aldehyde-formed inert clusters are formed from dinuclear rhodium carbonyl complexes. The formation of low-molecular-weight clusters is reversible under the conditions of a strong aldehyde reaction. Clusters up to Rh4 (CO)] 2 have been proven to be renewable. Stabilization of active species under aldehyde conditions can also be demonstrated (Yu · B. Kagan, YA Rrzovskii, EV Slivinskii, GA Korneeva. VI Kurkin, SM Loktev, Kinetilai Kataliz (1987), 28 (6), 1508-1511) . In contrast, high molecular weight clusters cannot be converted back to active species under aldehyde conditions (醛 υ. B. Kagan, E. V. Slivinskii, V. I. Kurkin, G. A. (7) (7) 200418785

Korneeva, R. A. Aranovich, N. N. Rzhevskaya, S. M. Loktev, Neftekhimiya (1985), 25 (6) 5 79 1 -797). The formation of the cluster is usually the cause of the formation of a rhodium-containing solid precipitate and is its first step. It occurs during distillation, but sometimes also under reaction conditions. The rhodium-containing precipitate is deposited on the container wall and the tube wall. This results in a relatively uneconomical loss of catalyst, making it necessary to periodically shut down and clean the plant during industrial applications. Rhodium deposits need to be recovered by complex metallurgical routes. On the one hand, because of the attractiveness of unmodified rhodium as an aldehyde catalyst, on the other hand, because of its instability, many recycling and / or recovery methods have been proposed. A series of methods are known for removing rhodium species from a reaction mixture by means of a solid adsorbent. Therefore, for example, DE 1 9 54 '31 5 proposes a weak to strong basic ion exchange resin mainly composed of polystyrene as an adsorbent. According to DE 20 4 5 4] 6, regeneration of a loaded ion exchange resin is carried out by treating a mixture of a lower alcohol, an aliphatic amine and water in the presence of oxygen. The rhodium contained in the eluate is converted into rhodium chloride hydrate by evaporation and treatment with hydrochloric acid, which can be used as a catalyst precursor again. WO 02/2045 1 and US 5 208 1 94 apply & a method for recovering rhodium from an already-loaded ion exchanger, which is calcined and rhodium in the form of a single oxide from the ash obtained. In US 4 388 279, salts of metals of groups 1 and 2 of the periodic table, zeolite molecular sieves, and ion exchange resins are proposed as adsorbents. WO 0 1/72 679 applies a method for adsorbing rhodium on activated carbon, polysilicic acid, and alumina in the presence of hydrogen at high temperature. The patent E P 0 3 5 5 8 3 7 describes a method for adsorbing rhodium on a basic ion exchange resin (which is ionic-bonded with an organic phosphorus compound -11-(8) (8) 200418785 modification). Regeneration of the resin is carried out by dissolution of a solution containing an organophosphorus ligand. W 0 9 7/0 3 9 3 8 applied for a method for adsorbing active rhodium material and impurities on acidic ion exchange resin. Regeneration is performed by dissolving impurities with a neutral solvent in the first step and then dissolving active rhodium species with an acidic solvent. The catalyst recovered in this way is suitably used in the aldolization after rehydrogenation. The disadvantages of all adsorption methods for the recovery of rhodium are the inability to satisfactorily solve the problem of re-release of active substances. Those skilled in the art will understand that the proposed solvent or solvent mixture for this project is not inert when it is aldolized, resulting in side reactions. For example, an acidic solvent induces a highly exothermic and difficult to control aldol condensation of the aldehyde. Alcohols and amines undergo condensation reactions with aldehydes, thereby reducing product yield. Therefore, it is absolutely necessary to remove the aforementioned solvent or solvent mixture before the catalyst is recycled. This makes the recycling concept technically very complicated and expensive. Conversely, adsorption on ion exchangers, followed by ashing and metal recovery of rhodium, has reached some industrial importance. This method is a simple technique, but of course it can be improved: the use of expensive alkaline ion exchangers as consumable materials, and the metallurgical processing of metal oxides after ashing make the program steps more complicated. A series of methods are also known in which rhodium is extracted from the reactor output by a solution of each complexing agent and recycled to the aldolization reactor after being released again. Therefore, rhodium-catalyzed aldehyde-formation in the presence of protonatable nitrogen-containing ligands, extraction of rhodium complexes with aqueous acid solutions, deprotonation and recycling of rhodium to this procedure are known from DE 196 03 201. In DE 4 230 871, the aqueous solution is directly recycled to the reaction. In EP 0 5 3 8 7 32, Shen (9) (9) 200418785 requested a method for extracting the output produced from the reactor using an aqueous phosphine solution under a synthetic pressure. W 0 9 7/0 3 9 3 8Apply a water-soluble polymer, such as polyacrylic acid, maleic acid copolymer and phosphorous carboxymethylated polyvinylamine, polyethylenimine and polyacrylamide , As a blending agent. EP 0 5 8 8 2 2 5 applies pyridine, [] quinoline, 2,2'-bipyridine, 1,10-phenanthroline, 2 5 2, · bi-D quinoline, 2,2 5,6 ' 5 2 "-bipyridine and pioline (which can be sulfonated and / or carboxylated) 'are used as complexing agents. However, complexing agents required for aqueous extraction are often expensive and difficult to obtain. In addition, these include two An additional step (extraction and catalyst release) requires increased engineering expenditure. In addition, a method is also known in which the addition of a ligand containing phosphorus (III) is said to prevent the production of rhodium when the reactor output is treated by distillation Shen Yuan (DE 3 3 3 8 3 4 0, US 4,4 00,547). The regeneration or re-release of the aldehyde-formed active rhodium material is carried out by oxidizing the phosphorus (III) ligand. The disadvantage is the continuous consumption of stabilizers. The formed phosphorus (V) compounds need to be continuously taken out to prevent accumulation in the reactor system. Some active forms of germanium are inevitably also discharged. This method can also be used in both technology and An improvement has been achieved in the whole process. WO 82/03 8 5 6 An application for distilling the output of an aldolization reactor in the presence of oxygen In the presence of oxygen, a part of the aldehyde formed in the aldehyde formation method is oxidized to the corresponding carboxylic acid, and reacts with the rhodium substance to form a soluble rhodium carboxylic acid. The carboxylic acid can be recycled to the process. The disadvantage is that the yield of the desired product is reduced. 尙 Unpublished patent application DE 1 0 2 4 0 2 5 3 describes a phosphorus-based ligand based on metals from groups 8 to 10 of the periodic table. Touch of Modification-13- (10) (10) 200418785 Aldehyde in the presence of a medium using a cyclic carbonate as a solvent. The unmodified metal complexes of Group 8 to 10 of the periodic table are not described. JP 1 0-226 662 describes a method for the aldehyde formation of olefin compounds, in which a rhodium catalyst is used with a sodium salt of a sulfonated triphenylphosphine as a secondary catalyst, that is, a modified catalyst is used. The reaction It is performed in the presence of a polar component and a carboxylic acid. The polar component may be, for example, ethylene glycol carbonate. The polar component may be recycled to the aldolization reaction together with the acid and the catalyst. However, the procedure may be For aldolization of terminal olefins (relatively active) only. For internal olefins 'Especially for highly internally branched olefins, the catalytic activity is much lower than that required for industrial use. Currently known methods for recycling or recovering rhodium from the process of using unmodified rhodium as the aldehyde catalyst can be both technical and economical. Therefore, the prior art does not include a method that is technically and economically satisfactory for the olefination of olefins that are difficult to use without modification of rhodium as a catalyst for the aldehydes. Therefore, the object of the present invention is to propose a method There are significant improvements to this level, especially methods that allow easy catalyst recovery, which greatly reduces catalyst inactivation and therefore prevents significant loss of catalyst. [Summary of the Invention] It is now unexpectedly discovered that during the aldehyde formation of ethylenically unsaturated compounds, selectivity and activity increase when the aldehyde catalyzed by unmodified rhodium is performed in the presence of a cyclic carbonate as a solvent The processing of the reaction mixture becomes simple, and the stability of the catalyst is greatly increased. The present invention therefore proposes an ethylenically unsaturated compound having 3 to 24 carbon atoms using an unmodified catalyst containing at least one metal of Group -14- (11) (11) 200418785 Group 8 to 10 of the Periodic Table of the Elements. Method for performing catalytic aldolization, wherein the aldolization is performed in the presence of at least one cyclic carbonate having the general formula I

Where R1, R2, R3, R4 are the same or different, and each is fluorene or a substituted or unsubstituted aliphatic, cycloaliphatic, aromatic, aliphatic-aliphatic having 1 to 27 carbon atoms Cyclic, aliphatic 'aromatic or cycloaliphatic-aromatic hydrocarbon group, η is 0 to 5, X is divalent substituted or unsubstituted aliphatic or alicyclic having 1 to 27 carbon atoms , Aromatic, aliphatic-alicyclic or aliphatic-aromatic hydrocarbon groups, the proportion of the carbonate is at least 1% by weight of the reaction mixture. φ The application of the present invention using carbonate as a solvent allows it to be aldehyde-formed in the presence of an unmodified catalyst (especially a rhodium catalyst), and the unmodified catalyst can be used again. The aforementioned modified ligands, which are generally used in germanation-catalyzed aldehydes, have limited thermal stability and usually limit the reaction temperature to 120 to 130 ° C. The reaction of the ligand-modified rhodium catalyst in the reaction of ethylene-type unsaturated compounds that are difficult to form (such as internal olefins, especially internally highly branched olefins) is limited by the reaction temperature of the ligand. And from 1 to 2 7 0 bar-15- (12) (12) 200418785 customary reaction pressure shows industrially unsatisfactory activity. In contrast, unmodified rhodium has a much higher activity in the reaction of an ethylenically unsaturated compound which is difficult to be reformed. However, this low-heat stability is a disadvantage (N.S. Imya nitov, Rhodium Express, (1995), 10/11, 3 -64). Examples of ethylene-type unsaturated compounds that are difficult to form are internal olefins, especially internally highly branched olefins, which are isomer mixtures prepared by dimerizing and oligomerizing propylene and n-butene. Forms such as tripropylene, tetrapropylene, dibutene, tributene, tetrabutene and pentabutene. The method of the invention has the advantage that the long-term stability of the catalyst is longer than that of the catalyst used in conventional solvents. In addition, the solvent used simplifies the separation of the catalyst from the reaction mixture, because the catalyst exists in the phase that also contains cyclic carbonate vinegar as a solvent, regardless of the method of processing (by distillation or via Phase separation). This mixture can be returned directly to the aldehydeization reactor in the form of a catalyst solution. The separation of the reactor output by a phase separation into a fraction containing the product and unreacted starting materials and a fraction containing the catalyst is much milder for the catalyst system than by distillation. No thermal stress is generated on the catalyst under reduced pressure, so the formation of inert metal catalyst substances and metal-containing precipitates is avoided. In the case of separation by distillation, the deactivation due to the formation of inert metal catalysts and metal-containing precipitates is also unexpectedly and greatly avoided. The method of the present invention can use a catalyst with particularly high activity to perform the internalization of highly branched olefins at a temperature of up to 220 ° C. The conversion and selectivity of this awakening (especially those with highly internally branched olefins) can therefore be enhanced. Hereinafter, the method of the present invention is described by examples, but the present invention is not limited to the specific embodiments such as -16- (13) 200418785. Those skilled in the art can deducate 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. 0 The present invention uses unmodified materials containing at least one Group 8 to 10 metal of the periodic table. In a method for catalytically deactivating an ethylenically unsaturated compound having 3 to 24 carbon atoms (especially; 1¾ smoke), the deactivation is performed in the presence of at least one cyclic carbonate having the general formula I

Where R R R R are the same or different, and each is Η or a substituted or unsubstituted aliphatic, cycloaliphatic, aromatic having 1 to 27 carbon atoms

Family, aliphatic, cyclic 'aliphatic marriage or alicyclic aromatic hydrocarbon group, η system is 0 to 5, X system is 1 to 2 7 substituted aliphatic, alicyclic, aromatic, radical, Bivalent substituted or non-aliphatic carbon atoms or 'alicyclic or aliphatic-aromatic hydrocarbons. The proportion of the carbonate is # 1, ^, and at least 1 weight of the reaction mixture. R4 and χ π, 1 are the same or different, and are functional groups such as halogen (fluorine, chlorine, odor, etc.) substituted by ο, ΝΝ, Ν- group or N, dialkyl. In addition, these groups It may have iodine), -OH, -OR, -c (0-17- (14) (14) 200418785) alkyl'-CN or -C (0) oalkyl. In addition, if these groups are at least three 0 atoms far from the ester group, the C, CH or CH2 group therein may be replaced by 0, N, NH, N-alkyl or N-dialkyl. The alkyl group may still have 1 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, such as a mixture of ethylene glycol carbonate and propylene glycol carbonate (weight ratio = 50: 50) As a cyclic carbonate. In the method of the present invention, the proportion of the cyclic carbonate is 1 to 98% by weight of the reaction mixture, preferably 5 to 70% by weight, and particularly preferably 5 to 50% by weight. Other solvents may be used in addition to the cyclic carbonate. In a special variant of the method, the aldolization reaction of the present invention is therefore carried out in the presence of at least one non-polar solvent (immiscible with cyclic carbonate I). Carbonates having the general formula Γ have 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 1.1 to 10, especially 1.1 to 5. The use of additional (especially non-polar) solvents makes it possible, for example, to produce a single-phase or two-phase reaction mixture, especially the output of a reactor. In this way, the processing used to process the reactor output can be simplified. The reaction product of the aldolization can be extracted with a non-polar solvent that is immiscible with the cyclic carbonate I. In this 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 10 to 50 carbon atoms, such as high boiling point by-products of the aldolization reaction, -18- (15) (15) 200418785

A mixture of isomers obtained by the tetramerization or hyperpolymerization of Texanol or propylene or butene and subsequent hydrogenation, namely tetrabutane, pentabutane, tetrapropane and / or pentapropane. It is also possible to use olefins having 3 to 24 carbon atoms, especially olefins used for silylation, as a non-polar solvent, by performing an aldolization reaction to incomplete conversion (for example, to only 95% conversion, 90% Preferably, especially 80%) and / or other olefins are added to the reaction mixture during and / or after the aldehyde reaction. In the method of the present invention, the proportion of the non-polar solvent is 0 to 90% by weight of the reaction mixture, preferably 5 to 50% by weight, especially 5 to 30% by weight. To avoid by-products, non-polar solvents need to be substantially inert under the conditions of the aldehyde reaction, unless they are ethylenically unsaturated compounds. In the method of the present invention, the reaction mixture may be a single amidine 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 two-phase product mixture during the process of the invention. In addition, the properties of this phase are closely related to temperature. For example, a reaction mixture that is a single phase at the reaction temperature can separate into two phases when cooled. A two-phase reaction mixture at the reaction temperature may also become homogeneous when cooled. The method of the present invention can be carried out using various catalytically active metals of groups 8 to 10 of the periodic table, but it is preferably carried out using money. For the purposes of the present invention, the group 8 to 10 of the Periodic Table of the Elements is included. The modified stomach catalyst is a catalyst that does not contain a modified ligand. For the purposes of this patent application, 'modified ligands -19- (16) (16) 200418785 are compounds containing one or more group 8 to 15 donor atoms of the periodic table. However, modified ligands do not include carbonyl, hydrogen, alkoxy, alkyl, aryl, allyl, fluorenyl, or alkenyl ligands, nor do they include counterions of metal salts for catalyst formation For example, halo groups such as fluorine, chlorine, bromine or iodine, acetamylpyruvate, carboxylates such as acetate, 2-ethylhexanoate, hexanoate, caprylate, or nonanoate. The best modified catalyst is HRh (CO) 3. The active catalyst complex used in the aldolization reaction is formed from a metal salt or compound (catalyst precursor) and a synthesis gas. This preferably occurs in situ during the aldehyde formation process. Conventional catalyst precursors are Rh (I), Rh (II), and Rh (III) salts, such as acetate, caprylate, nonanoate, acetamylpyruvate, or halide, and germanium carbonyl. The concentration of the metal in the reaction mixture is preferably in the range of 1 ρ Π1 to 100 p P ni, and more preferably in the range of 5 p P m to 300 p p m. The starting material used in the process of the present invention is a compound containing an ethylenically unsaturated C-C double bond, especially an olefin or an olefin mixture, especially having 3 to 24 (4 to 16 is preferred, especially Is 4 to 12) monoolefins having carbon atoms and having terminal or internal C-C double bonds, such as ^ or 2-pentene, 2-methyl-butene, 2-methyl-2-butene,% C6-olefin mixture (dipropylene) obtained by dimerization of methyl-p-butene, bu, 2- or 3-hexene, and propylene, heptene, 2- or 3-methyl-buxene, octane Ene, methylheptan, 3-methylheptane, 5-methyl-2-heptan, 6-methyl-2-heptane, 2-ethyl-1-hexene, n-butane Heterogeneous C8-olefin mixture prepared by polymerization, c8-carbon-burned hydrocarbon mixture (diisobutane) prepared by polymerization of one of isobutene -20-(17) (17) 200418785, nonene, 2 -Or C9-olefin mixture (tripropylene) produced by trimerization of 3-methyloctene, propylene, decene, 2-ethyl-buxene, dodecene, propylene .C] 2-olefin mixture (tetrapropene or tributene), fourteen carbons produced by trimerization of butene CI6-olefin mixture (tetrabutene) prepared by the tetramerization of olefin, hexadecene and butene, and oligomerization by olefins having different numbers of carbon atoms (preferably 2 to 4) The olefin mixture prepared, if appropriate, is separated by distillation into crane parts having the same or similar chain length. It is also possible to use olefins or mixtures of olefins obtained by Fischer-Trohsch synthesis and olefins obtained by oligomerization of ethylene or olefins which can be obtained by displacement reactions. Preferred starting materials are c4-, C6-, C8-, C9-, C! 2-, or C16-olefin mixtures. In addition, the method of the present invention can be used for the awakening of polymerized ethylenically unsaturated compounds, such as polyisobutylene or a 1,3-butadiene copolymer or an isobutylene copolymer. The effect of the molecular weight of the polymerized olefin is extremely small, a prerequisite of which is that the hydrocarbon burning is sufficiently soluble in the quenching medium. The molecular weight of the polymerized olefin is preferably less than 1,000 g / mole, especially less than 5,000 g / mole. The volume ratio of carbon monoxide to hydrogen in a 1%: 30% 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 fermentation is usually carried out at a pressure of 315 to 350 bar, preferably at a pressure of 15 to 270 bar. The pressure used depends on the structure of the feed olefin, the catalyst used and the desired effect. Thus, for example, α-olefins can be converted to the corresponding awake at a pressure of less than 100 bar in the presence of a rhodium catalyst at a high space-time yield. On the contrary, if it is an olefin having an internal double bond, especially a branched olefin of -21-(18) (18) 200418785, a higher pressure is preferred. The reaction temperature in the method of the present invention is preferably from 20 to 220 ° C, more preferably from 100 ° C to 200 ° C, particularly preferably from 150 ° C to 190 ° C, especially from 160 to 1 8 0 ° C. A reaction temperature above 150 ° C can improve the ratio of the terminal to internal double bonds in particular, because at high temperatures, as a result of accelerated isomerization, more terminal double bonds become effective, and the awakening of the preferred terminal positions increases. . The process according to the invention can be carried out batchwise or continuously. However, continuous operation is preferred. Suitable reactors include virtually all gas-liquid reactors known to those skilled in the art, such as jet agitation vessels or bubble column or tubular reactors (with or without recirculation). A stepped bubble column and a tubular reactor equipped with static mixing elements. The reactor output obtained by the method of the present invention includes a possibly unreacted ethylenically unsaturated compound (olefin), a reaction product, a reaction by-product, at least one cyclic carbonate, a possibly non-polar solvent, and a catalyst. Depending on the type and mass fraction of the olefin compound as the starting material, the type and mass fraction of any non-polar solvents contained, and the type and mass fraction of the cyclic carbonate, the reactor output can be a single phase or Biphasic. As described above, phase separation can be achieved or prevented by appropriately adding a cyclic carbonate or a non-polar solvent. The processing of the reactor output in the method of the present invention can be performed in two variants, depending on the phase properties of the reactor output. If it is a two-phase reactor output, it is better to process it through phase separation. This is called Variation A. If it is a single-phase reactor output, it is better to process it by distillation. This is called change. Form B. -22- (19) (19) 200418785 Synthetic gas is better after the aldolization ', before the reactor output is further processed and processed according to variation A or B, the main fraction of synthetic gas is removed by decompression.

Variation A In this variation of the method, the output of the two-phase reactor from the aldehydeization reaction is separated by phase separation into a fraction mainly containing catalysts and cyclic carbonates and mainly containing aldehydeization products and unreacted olefins or ethylene Fractions of type unsaturated compounds are preferred. This method variation can be used when using alternative non-polar solvents. The non-polar solvent may be the same as the starting olefin, so that the aldolization reaction does not proceed to complete conversion (for example, only up to 95%, preferably .90%, especially 80%) and / or may be used during the aldolization reaction and / Or add other olefins to the reaction mixture afterwards. Variation A of the method of the present invention is illustrated in FIG. 1, but the method is not limited to this embodiment: the synthesis gas (1), the olefin (2), and the aldolization dissolved in a cyclic carbonate or a mixture of a plurality of cyclic carbonates The catalyst (3) reacts in the aldehydeization reactor (4). The reactor output (5) may be optionally removed in a decompression vessel (6) from the excess synthesis gas (7). The liquid stream (8) obtained in this way is used for separation in the separation device (9) to produce a heavy phase (1 0), which contains the main part of the cyclic carbonate and catalyst, and high-boiling by-products, and the light phase. (11), which comprises an aldehyde product, unreacted hydrocarbons and (if used) a non-polar solvent. The phase separation can be performed at a temperature of 0 t to 130 ° C ', preferably 10 ° C to 60 ° C. Phase separation can be performed, for example, in a settling volume -23- (20) (20) 200418785. The phase separation in the separation device (9) is preferably performed under a synthesis gas at a pressure of 1 to 350 bar (preferably 15 to 270 bar), but is the same as that used in the aldehydeization reactor (4). It is particularly good to perform under pressure. The separation device (9) may optionally be performed by a heat exchanger to cool the production liquid stream (5) (not shown in Fig. 1). In the selective separation stage (: 2), the catalyst residue can be taken out from the liquid stream (1 1). The liquid flow (! 丨) or (1 3) then leads to the separation stage (1 4). In this case, the reaction products (acid and alcohol) and unreacted olefin (15) are separated and sent to a further processing or hydrogenation step. The olefins that have been separated from the liquid stream (15) can be returned to the same reactor or sent to a selective further reaction stage. Fraction 6), which is also separated, contains, for example, residual cyclic carbonates, reaction products, any other non-polar solvents added, and boiling point by-products. The fraction (1 6) can be discarded or recycled back to the aldehydeization reactor (4). The process of discarding unwanted by-products is preferably performed before recycling. The catalyst separation in the separation device (9) can be performed at least partially (1 6) and / or at least partially fresh; (: Greek smoke (2) is directly fed into the liquid stream (8). The extraction is preferably performed continuously and may be a single-stage extraction or operated countercurrently, co-currently, or alternatingly in a multi-stage process. The discharge stream containing the catalyst is, for example, from the liquid stream (10) or from the separation stage (1 2), can be processed by known methods to recover the catalyst metal in a reusable form. Variation B In this variation of the method, the uniform reactor output of the aldolization reaction is separated by distillation to include mainly aldolization. Relatively low-boiling fractions of products and possibly unreacted olefins or ethylene-24- (21) (21) 200418785 unsaturated compounds, and high-boiling fractions mainly containing cyclic carbonates and catalysts. Variations of the method of the invention The B series is illustrated in FIG. 2, and the method is not limited to this embodiment: the synthesis gas (1), the olefin (2), and the aldehyde catalyst (3) dissolved in a cyclic carbonate or a mixture of various cyclic carbonates are based on The reaction is carried out in an aldolization reactor (4). The output of the device can be used to remove excess synthesis gas (7) in the decompression vessel (6). The liquid stream (8) obtained in this way can be separated in the separation device (9) to produce a cyclic carbonate containing the main part and the catalyst High-boiling phase (1 0), and low-boiling phase (n) containing the aldehyde product, unreacted olefins and (if used) non-polar solvent. The catalyst-containing fraction (1 0) is recycled to the aldehyde This reactor may be processed by processing steps, where high-boiling by-products and / or catalyst degradation products are removed (not shown in Figure 2). The fraction (1 1) may be used in the separation step (1 2), as appropriate. Removal of catalyst residues. The liquid stream 1 3 is then sent to the vapor phase (1 4). In this case, the aldehydes (aldehydes and alcohols) (1 6) are distilled from unreacted olefins (1 5 ) Separation. The discharge stream containing the catalyst (such as the liquid stream (] 〇) or from the separation stage (12)) can be obtained by methods known to those skilled in the art (such as from W 0 0 2/2 0 4 5 1 Or US 5,208; 19 4)) processing to recover the catalyst metal in reusable form. The unreacted olefin (1 5) can be sent back to the same aldolization reactor or into a selective second reaction stage. When the process is carried out industrially, the separation device can have various designs. The separation is based on It is better to perform by falling film evaporation, short-path evaporator or thin film evaporator or a combination of these devices. -25- (22) (22) 200418785 The advantage of this combination is, for example, the synthetic gas that is still dissolved And the main part of the product and unreacted starting materials can be separated from the catalyst-containing alkanediol carbonate solution in the first step (such as a falling film evaporator or a flash evaporator) and the residual alkanediol carbonate is removed. Separation of the product from the unreacted starting material can be performed in the second step (for example, combining two columns). In the two variants A and B of the method of the present invention, the reactor output from which the catalyst, excess synthesis gas, and major solvents (ie, cyclic carbonate or a mixture of multiple thereof) have been removed is preferably further separated into aldehydes ( Alcohols), olefins, solvents and by-products. As indicated earlier, this can be achieved by, for example, distillation. The olefins and / or solvents (alkanediol carbonates and / or non-polar solvents) that have been separated from the reaction output or from the aldolization product can be recycled to the aldolization reaction. The aforementioned variation of the method of the present invention includes separating the reactor output and the selective aldehyde product; this can be performed, for example, by distillation. However, other separation methods can also be used, such as the extractions described in, inter alia, WO 0 1/6 824 7, EP 0 922 691, WO 99/38832, US 5 64 8 5 5 4 and US 5 138 101, Or described in (especially) DE 1 9 5 3 64 1, GB] 3] 2076, NL 870088 1, DE 3842819, WO 9419 1 04, DE 1 9 6 3 2 6 0 0 and EP 1 1 0 3 3 0 3 infiltration. 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 extraction and separation are preferably performed continuously. It can be designed as a single-stage method or operated countercurrently or alternatingly in a multi-stage method. In all method variations, the catalyst-containing fraction is preferably recycled -26- (23) 200418785 to the aldolization reaction. This is of course related to the dissolution of the catalyst. When the target product is not the aldehyde itself, but the reaction from which the synthesis gas and catalyst are removed and possibly the solvent is removed, the hydrogenation is performed before or after the olefin separation, and then the pure alcohol is distilled off. The method of the invention can be performed in single or multiple stages. This reaction can be followed by a second aldolization stage, which also converts internally highly branched alkenes, which are difficult to be aldolized, to the desired aldehyde at relatively high temperatures (e.g., high temperature and / or high pressure). However, the unreacted olefins and the aldolization products (aldehydes and alcohols) are first recycled to the same aldolization stage or sent to the second aldolization stage. In this case, the second aldehyde formation stage can be performed by the catalyst system (that is, different catalyst metals or modified by ligands. It is also possible (preferably) to add higher reactive olefins at this stage to make it relatively difficult In all cases where the aldehyde is converted to the desired product, the aforementioned amount of cyclic carbonate must be added. In the method of the present invention, the ethylenic unsaturation used is obtained from the reactor output of the first aldehyde reaction. The compound is in the form of an unsaturated compound. In this case, the product mixture or only a part thereof may be used, especially a part containing a one-stage unreacted olefin compound. This method is preferred in that the first aldolization reaction is based on a ligand When the composition of the modified touch fraction is free of raw alcohol, the product mixture can be distilled and processed under production conditions. The first aldehyde reaction conditions (such as hydrocarbons (especially, preferably, unreacted olefins or even later) Use a completely different catalyst metal) Concentration catalyst for unolefin conversion. The aldehyde compounds added to more sections can also include unreacted ethylene type. The overall reaction is mostly from the first variation -27- (24) (24) 200418785 in the presence of a medium-to-medium medium [Embodiment] The following examples are only used to illustrate the present invention, and not to limit the scope defined by the description & patent scope. Example 1 ( Variation A) 560 g of propylene glycol carbonate, 5 60 g of tri-n-butene and 0.0888 g or 0.0225 g of rhodium (II) nonanoate (corresponding to 5 ppm or 20 ppm based on the mass of the reactor contents) Concentration) placed in a 2 liter agitated autoclave under a nitrogen atmosphere. The autoclave was then pressurized with a synthetic gas (CO / H2 1: 1 mol) and heated to the desired reaction temperature. The reaction was detected during heating Temperature of the reactor. The reaction temperature is 1 3 (TC to 180. The reaction pressure is 2 600 bar. During the reaction, other synthesis gases are introduced under pressure control. After 5 hours, the experiment is stopped and the reactor is cooled down. To ambient temperature. The output of the reactor is always composed of two phases and does not contain rhodium precipitates. The composition of the lighter hydrocarbon phase separated in the phase separation vessel is obtained by gas chromatography U, ―-chromatographic Z results and reactions Conditions (such as temperature and money concentration) are shown in Table 1. -28- (25) 200418785 Table 1: Tri-n-butene is aldehydeized for 5 hours at 260 bar and various temperatures. The recorded proportions (in% by mass) are related to the lighter hydrocarbon phase which has removed any carboxylic acid esters contained And catalyst. In Experiment 6, the catalyst solution obtained by processing the reactor output of Experiment 5 was used again. Number T / ° C c (Rh) / C13-aldehyde C 1 3 -alcohol C 12- high boiling Ppm /% /% HC / ° / 〇 /% 1 13 0 5 2 7 1 72 0 2 130 20 5 5 4 40 1 3 1 50 20 68 14 17 1 4 180 5 48 33 14 5 5 1 80 2 0 59 3 2 8 1 6 1 8 0 20 61 30 8 1

Example 2 (Variation B) Di-n-butyrate '(560 g) was aldehydeized in the same manner as in Example 1. The reactor output of experiments 7 to 13 always consisted of a single phase and did not contain (money) precipitates. In contrast to Example 1, the reactor output was analyzed by gas chromatography without treatment. The results of gas chromatography and the reaction conditions (such as temperature, pressure, and germanium concentration) are shown in Table 2. -29- (26) 200418785 Table 2: Awake of di-n-butene under various pressures, germanium concentrations and temperatures. The recorded proportion (in mass ° /.) Is the output of the reactor $, the group $, and the carbonate and catalyst contained in the stomach _ output have been removed. T / ° C p / bar c (Rh) / p C8- C9-aldehyde C9-alcohol pm HC /% /% /% 7 150 50 40 67.5 30.4 2.1 8 150 250 40 3.1 87.6 3.3 9 170 150 5 26.3 66.6 27.1 10 1 70 250 5 4.5 78.1 17.4 11 1 70 250 40 4.0 20.5 75.5 12 180 50 40 66.8 17.5 15.7 13 180 1 50 40 9.9 2 3.3 66.8

Example 3 (conventional method) Di-n-butene was aldehydeized as in Example 2, except that pentabutane was used as a solvent instead of propylene glycol carbonate. The reactor output of Experiment 14 showed a large amount of black (rhodium) 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 chemical process (Experiment 15). The results of gas chromatography and the reaction conditions (such as temperature, pressure, and rhodium concentration) are shown in Table 2. -30- (27) 200418785 Table 3: Di-n-butene is aldehydeized in pentabutane at 150 ° C and 250 bar. The recorded ratio (in mass%) is the composition of the reactor output, which has been removed from pentabutane, by-products and catalysts. In Experiment 15 the catalyst solution obtained by distillation in Experiment 14 was used again. T / ° C p / bar c (Rh) / p C8- C9-aldehyde C9-alcohol pm H C /% /% /% 14 1 50 250 40 75.4 23.4 1.2 15 150 250 Unknown 9 1.5 7.8 0.7

The absence of germanium precipitation at all in Experiments 1 to 13 indicates that the alkanediol carbonate as a solvent has a special stabilization effect on the rhodium compound. In contrast, when alkane was used as a solvent in the control experiments, a considerable amount of germanium precipitated, and when the catalyst was recycled, it was found that the activity was greatly reduced (Experiments 14 and 15). In Experiment 16 the catalyst phase from Experiment 5 was used in the new aldehyde formation. Within the range of experimental accuracy, the olefin conversion rate remains fixed. Experiments have proved that the method of the present invention provides far higher chemical selectivity for the desired aldehydes. In addition, the catalyst can be technically easily recycled without significant deactivation. [Brief Description of the Drawings] Fig. 1 illustrates a variation a of the method of the present invention, and Fig. 2 illustrates a variation B of the method of the present invention. -31-(28) 200418785 [Comparison of main components] 1 Synthetic gas 2 Olefins 3 Aldehyde catalyst dissolved in cyclic carbonate or a mixture of cyclic carbonates 4 Aldehyde reactor 5 Reactor output 6 Subtract Pressure vessel 7 Excess synthesis gas f 8 Liquid stream 9 Separation device 1 0 Heavy phase 11 Light phase 1 2 Separation stage 13 Liquid stream 14 Separation stage 15 Liquid stream 16 Separated fractions

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Claims (1)

(1) 200418785 Scope of patent application 1. A method for catalytically aldehyde-modifying a compound having 3 to 24 carbon atoms using an unmodified catalyst containing at least one element of the Periodic Table, wherein the chemical compound I Group 8 to 10 gold ethylene type unsaturated system in the presence of cyclic carbonate Where 'R1, R2, R3, R4 are the same or different, and each is a substituted or unsubstituted aliphatic, aliphatic-alicyclic, aliphatic_aromatic or aliphatic of 27 carbon atoms. The cyclic-aromatic η system is 0 to 5, and the χ system is two having 1 to 27 carbon atoms. The aliphatic, cycloaliphatic, aromatic, aliphatic-alicyclic writing group is rt. The ratio is from 2 to 2. of the reaction mixture. The method according to item 1 of the scope of the patent application, wherein R4 and X are selected from 0, N, NH, N_ group and N_ chlorine, bromine, iodine, -OH,- 〇R, _CN, _c (〇) alk0-alkyl are substituted with the same or different substituents. ^ · The method according to the item in the scope of patent application, wherein is Η or has 1, 1, or 2 ring, aromatic hydrocarbon group, valence substituted or non-g aliphatic-aromatic hydrocarbon is less than 1% by weight. R], R2, R3, dialkyl, fluorine, radical, or -C (0) The aldolization is based on the -33- (2) (2) 200418785 reaction mixture in the presence of 5 to 50% by weight of solvent The solvent is non-polar compared to the cyclic carbonate I and is immiscible with the cyclic carbonate I. 4. The method according to any one of claims 1 to 3, wherein the reaction product from the aldolization is extracted with a non-polar solvent that is immiscible with the cyclic carbonate I. 5. The method according to item 3 of the patent application, wherein a substituted or unsubstituted hydrocarbon having 1 to 50 carbon atoms or an olefin having 3 to 24 carbon atoms is used as the non-polar solvent. 6. The method according to any one of claims 1 to 3, wherein the aldolization is performed in the presence of HRh (CO) 3 as a catalyst. 7 _ The method according to any one of claims 1 to 3, wherein the reaction product mixture from the aldehyde reaction is separated into a fraction mainly containing the catalyst and the cyclic carbonate and a fraction mainly containing the aldehyde product Fractions. 8. The method according to any one of claims 1 to 3, wherein the catalyst-containing fraction is recycled to the aldolization reaction. 9. The method according to any one of claims 1 to 3, wherein the cyclic carbonate used is ethylene glycol carbonate, propylene glycol carbonate or butanediol carbonate or a mixture thereof. 10 · The method according to any one of claims 1 to 3, wherein the unreacted ethylenically unsaturated compound is separated from the reactor output or separated from the acidified product, and sent back to the same aldehydeization reaction, or sent To the second aldehyde reaction 011. As in the method of any one of claims 1 to 3, the ethylenically unsaturated compound used in -34-(3) 200418785 is obtained from the first aldehyde The reactor output of the chemical reaction is a compound in the form of an unreacted ethylenic compound. 12. The method according to item 11 of the scope of patent application, wherein the ethylenically unsaturated compound used is a reactor output obtained from a first aldehyde reaction carried out in the presence of a ligand-modified catalyst And is a compound in the form of an unreacted ethylenically unsaturated compound. -35-