EP2043994A1 - Verfahren zur herstellung von alpha-hydroxycarbonsäuren - Google Patents

Verfahren zur herstellung von alpha-hydroxycarbonsäuren

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Publication number
EP2043994A1
EP2043994A1 EP07729501A EP07729501A EP2043994A1 EP 2043994 A1 EP2043994 A1 EP 2043994A1 EP 07729501 A EP07729501 A EP 07729501A EP 07729501 A EP07729501 A EP 07729501A EP 2043994 A1 EP2043994 A1 EP 2043994A1
Authority
EP
European Patent Office
Prior art keywords
alpha
alcohol
pressure
ammonia
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07729501A
Other languages
German (de)
English (en)
French (fr)
Inventor
Jochen Ackermann
Alexander May
Udo Gropp
Hermann Siegert
Bernd Vogel
Sönke BRÖCKER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Roehm GmbH
Original Assignee
Evonik Roehm GmbH
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Filing date
Publication date
Application filed by Evonik Roehm GmbH filed Critical Evonik Roehm GmbH
Publication of EP2043994A1 publication Critical patent/EP2043994A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/18—Preparation of carboxylic acid esters by conversion of a group containing nitrogen into an ester group
    • C07C67/20—Preparation of carboxylic acid esters by conversion of a group containing nitrogen into an ester group from amides or lactams
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/675—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids of saturated hydroxy-carboxylic acids

Definitions

  • the present invention relates to processes for the production of alpha-hydroxycarboxylic acid esters on an industrial scale.
  • the invention relates to a continuous process for the preparation of alpha-hydroxycarboxylic acid esters according to the preamble of claim 1.
  • alkyl (meth) acrylates Alpha-hydroxycarboxylic acid esters are valuable intermediates in the large-scale synthesis of acrylic acid esters and methacrylic acid esters, hereinafter referred to as alkyl (meth) acrylates.
  • alkyl (meth) acrylates find their main application in the preparation of polymers and copolymers with other polymerizable compounds.
  • methacrylic acid esters such as, for example, methyl methacrylate
  • HIBSM 2-hydroxyisobutyrate
  • a generic method is known from EP 0 945 423. "Disclosed herein is a process for producing alpha-hydroxycarboxylic acid esters, which comprises the steps of reacting an alpha-hydroxycarboxylic acid amide and an alcohol in the presence of a catalyst in a liquid phase while maintaining the ammonia concentration in the reaction solution at 0, 1 wt .-% or less holds that emerging ammonia is removed as gas in a gas phase. To remove the ammonia from the reaction solution as a gas in the gas phase, it is distilled off from the reaction solution. For this purpose, the reaction solution is heated to boiling and / or a strip gas, ie an inert gas, is bubbled through the reaction solution.
  • a strip gas ie an inert gas
  • the present invention relates to continuous processes for the preparation of alpha-hydroxycarboxylic acid esters in which alpha-hydroxycarboxamide is reacted with an alcohol in the presence of a catalyst to give a product mixture comprising alpha-hydroxycarboxylic acid esters, ammonia, unreacted alpha-hydroxycarboxamide and alcohol and catalyst; the process being characterized in that a ') starting material streams comprising, as starting materials, an alpha-hydroxycarboxylic acid amide, an alcohol and a catalyst are fed into a pressure reactor; b ') the educt streams in the pressure reactor at a pressure in the range of greater than 1 bar to 100 bar with each other; c ') discharging the product mixture resulting from step b') comprising alpha-hydroxycarboxylic acid ester, unreacted alpha-hydroxycarboxylic acid amide, ammonia, alcohol and catalyst from the pressure reactor; and d ') depletes the product mixture of alcohol and ammonia, wherein ammonia is
  • the ammonia resulting from the reaction according to the invention can be separated off relatively easily from alcohol, for example methanol, which is used for the alcoholysis or methanolysis of the alpha-hydroxycarboxamide. This is possible, although alcohol or methanol and ammonia are very difficult to separate in dissolved form under normal conditions.
  • alcohol for example methanol, which is used for the alcoholysis or methanolysis of the alpha-hydroxycarboxamide.
  • ammonia already accumulates in a very pure form and can thus be reused in various processes without further purification step.
  • the alcohol also accumulates in such a way that it is present in process-suitable quality and can be recycled, for example, into a production process.
  • the process of the invention avoids the use of aids for the separation of the ammonia, above all the use of inert gases as a stripping agent for the ammonia becomes unnecessary. Accordingly, in the process according to the invention, no larger amount of additional inert gas flow, which in turn would have to be separated from the ammonia, is produced.
  • the process of the present invention also has an extremely low tendency to form by-products.
  • the method according to the invention can be carried out inexpensively, in particular with low energy consumption.
  • the catalysts used for the alcoholysis of the alpha-hydroxycarboxamide can be used over a long period of time, without the selectivity or the activity decreases. In this respect, the catalysts have a long service life.
  • alpha-hydroxycarboxylic acid esters are prepared by the reaction between the reactants alpha-hydroxycarboxamide and alcohol in the presence of a catalyst.
  • the alpha-hydroxycarboxylic acid amides useful in the reaction of the invention usually include all those Carboxylic acid amides which have at least one hydroxyl group in the alpha position to the carboxylic acid amide group.
  • Carboxylic acid amides are well known in the art. Commonly included herein are compounds having groups of the formula - CONR'R "-, wherein R 'and R" independently represent hydrogen or a 1-30 carbon group comprising in particular 1-20, preferably 1-10 and especially 1-5 carbon atoms ,
  • the carboxylic acid amide may comprise 1, 2, 3, 4 or more groups of the formula - CONR'R "- These include, in particular, compounds of the formula R (-CONR'R"' n , in which the radical R has 1-30 carbon atoms Group which comprises in particular 1- 20, preferably 1-10, in particular 1-5 and particularly preferably 2-3 carbon atoms, R 'and R "has the abovementioned meaning and n is an integer in the range of 1-10, preferably 1-4 and more preferably 1 or 2 represents.
  • the term "1 to 30 carbon atoms” denotes residues of organic compounds having 1 to 30 carbon atoms.
  • aromatic and heteroaromatic groups it also includes aliphatic and heteroaliphatic groups, such as, for example, alkyl, cycloalkyl, alkoxy, cycloalkoxy, cycloalkylthio and alkenyl groups.
  • the groups mentioned can be branched or unbranched.
  • aromatic groups are radicals of mononuclear or polynuclear aromatic compounds having preferably 6 to 20, in particular 6 to 12, carbon atoms.
  • Heteroaromatic groups denote aryl radicals in which at least one CH group has been replaced by N and / or at least two adjacent CH groups have been replaced by S, NH or O.
  • Preferred aromatic or heteroaromatic groups according to the invention are derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane, diphenyldimethylmethane, bisphenone, diphenylsulfone, thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole, isoxazole, pyrazole, 1,3,4-oxadiazole , 2,5-Diphenyl-l, 3,4-oxadiazole, 1,3,4-thiadiazole, 1,3,4-triazole, 2,5-diphenyl-l, 3,4-triazole, l, 2.5 -Triphenyl-l, 3,4-triazole,
  • Preferred alkyl groups include methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl, tert-butyl, pentyl, 2-methylbutyl, 1,1 -Dimethylpropyl, hexyl, heptyl, octyl, 1,1,3,3-tetramethylbutyl, nonyl, 1-decyl, 2-decyl, undecyl, dodecyl, pentadecyl and the eicosyl group.
  • Preferred cycloalkyl groups include the cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups, optionally substituted with branched or unbranched alkyl groups.
  • Preferred alkenyl groups include the vinyl, allyl, 2-methyl-2-propylene, 2-butenyl, 2-pentenyl, 2-decenyl and 2-eicosenyl groups.
  • Preferred heteroaliphatic groups include the aforementioned preferred alkyl and cycloalkyl groups in which at least one carbon moiety is replaced by O, S or a group NR 8 or NR 8 R 9 , and R 8 and R 9 are independently one to six carbon atoms having alkyl, a 1 to 6 carbon atoms having alkoxy or an aryl group.
  • the carboxylic acid amides have branched or unbranched alkyl or alkoxy groups having 1 to 20 carbon atoms, preferably 1 to 12, suitably 1 to 6, in particular 1 to 4 carbon atoms and cycloalkyl or cycloalkyloxy groups having 3 to 20 carbon atoms, preferably 5 to 6 carbon atoms.
  • the radical R may have substituents.
  • substituents are i.a. Halogens, in particular fluorine, chlorine, bromine, and alkoxy or hydroxy radicals.
  • alpha-hydroxycarboxamides can be used in the process of the invention singly or as a mixture of two or three or more different alpha-hydroxycarboxamides.
  • Particularly preferred alpha-hydroxycarboxylic acid amides include alpha-hydroxyisobutyric acid amide and / or alpha-hydroxyisopropionic acid amide.
  • alpha-hydroxycarboxamides which are obtainable by cyanohydrin synthesis from ketones or aldehydes and hydrogen cyanide.
  • the carbonyl compound for example a ketone, in particular acetone, or an aldehyde, for example acetaldehyde, propanal, butanal, with hydrocyanic acid to give the respective cyanohydrin implemented. It is particularly preferred to react acetone and / or acetaldehyde in a typical manner using a small amount of alkali or an amine as the catalyst.
  • the cyanohydrin thus obtained is reacted with water to the alpha-hydroxycarboxylic acid amide.
  • This reaction is typically carried out in the presence of a catalyst.
  • a catalyst particularly suitable for this purpose are manganese oxide catalysts, as described, for example, in EP-A-0945429, EP-A-0561614 and EP-A-0545697.
  • the manganese oxide can be used in the form of manganese dioxide, which by treatment of manganese sulfate with potassium permanganate under acidic conditions (see Biochem.J., 50 p 43 (1951) and J.Chem.Soc, 1953, p 2189, 1953 ) or by electrolytic oxidation of manganese sulfate in aqueous solution.
  • the catalyst is often used in the form of powder or granules with a suitable grain size.
  • the catalyst can be applied to a support.
  • so-called slurry reactors or fixed-bed reactors can also be used here, which can also be operated as a trickle bed and are described inter alia in EP-A-956 898.
  • the hydrolysis reaction can be catalyzed by enzymes. Suitable enzymes include nitrile hydratases. This reaction is exemplary in "Screening, Characterization and Application of Cyanide-resistant Nitrile Hydratases" Eng. Life. Be. 2004, 4, no. 6 described.
  • the hydrolysis reaction can be catalyzed by acids, especially sulfuric acid. This is stated inter alia in JP Hei 4-193845.
  • Alcohols which can be used successfully in the process of the invention include all alcohols known to the person skilled in the art as well as precursor compounds of alcohols which under the stated conditions of pressure and temperature are capable of reacting with the alpha-hydroxycarboxamides in the sense of alcoholysis.
  • the reaction of the ⁇ -hydroxycarboxamide by alcoholysis with an alcohol preferably 1-10 carbon atoms, particularly preferably 1 to 5 Carbon atoms.
  • Preferred alcohols include methanol, ethanol, propanol, butanol, especially n-butanol and 2-methyl-1-propanol, pentanol, hexanol, heptanol, 2-ethylhexanol, octanol, nonanol and decanol.
  • Methanol and / or ethanol is particularly preferred as the alcohol, with methanol being particularly useful.
  • the use of precursors of an alcohol is possible in principle.
  • alkyl formates can be used.
  • methyl formate or a mixture of methanol and carbon monoxide are suitable.
  • the reaction between alpha-hydroxycarboxamide and alcohol is carried out in the context of the invention in a pressure reactor.
  • This is basically a reaction space to understand, which allows to maintain an overpressure during the implementation.
  • Overpressure in this context means a pressure greater than atmospheric pressure, i. in particular greater than 1 bar.
  • the pressure can be in a range from greater than 1 bar to less than or equal to 100 bar. It follows from the above that the pressure during the reaction / alcoholysis of the alpha-hydroxycarboxamide according to the invention as well as during the removal / removal of the ammonia from the product mixture is greater than atmospheric pressure or greater than 1 bar. In particular, this means that the ammonia formed during the reaction is distilled off from the mixture under a pressure of greater than 1 bar, wherein the use of auxiliaries such as strip gas for distillative removal of the ammonia is completely dispensed with.
  • the product mixture is depleted not only in ammonia but also in unreacted alcohol.
  • a product mixture results, inter alia, with the components, which are in principle very difficult to separate from one another, ammonia and methanol.
  • the said two components are removed directly as a mixture of substances from the product mixture.
  • the two substances are then an after-connected separation operation, for example, subjected to a rectification.
  • reaction step and the removal of the ammonia / alcohol from the product mixture are spatially separated from each other and carried out in different aggregates.
  • this includes continuous processes for the preparation of alpha-hydroxycarboxylic acid esters in which alpha-hydroxycarboxamide is reacted with an alcohol in the presence of a catalyst to give a product mixture comprising the alpha-hydroxycarboxylic acid esters, ammonia, unreacted alpha-hydroxycarboxamide and alcohol and Catalyst comprises; the process being characterized in that a ') starting material streams comprising, as starting materials, an alpha-hydroxycarboxylic acid amide, an alcohol and a catalyst are fed into a pressure reactor; b ') the educt streams in the pressure reactor at a pressure in the range of greater than 1 bar to 100 bar with each other; c ') discharging the product mixture resulting from step b') comprising alpha-hydroxycarboxylic acid ester, unreacted alpha-hydroxycarboxylic acid amide and catalyst from the pressure reactor; and d ') the product mixture depleted of alcohol and ammonia, wherein ammonia is
  • Product mixture comprising alpha-hydroxycarboxylic acid ester, unreacted alpha-hydroxycarboxamide and catalyst discharged from the column.
  • reaction of the educts and separation of ammonia / alcohol take place in two different spatially separated aggregates.
  • reactor / reaction space and separation unit for the separation of ammonia / alcohol from the product mixture are separated from each other.
  • the quality features mentioned can be further improved by repeating the reaction in the pressure reactor once or several times with the product mixture depleted in ammonia and alcohol in the bottom of the separation column (pressure distillation column), the reaction step being shifted to a plurality of pressure reactors connected in series are.
  • a process variant is particularly preferred which is characterized in that e ') the product mixture discharged in step d 2) is compressed to a pressure in the range from 5 to 70 bar; f) the thus compressed according to step e ') compressed mixture for reaction in another pressure reactor and react again; and g ') repeats steps b'2), c' l), d'l) and d'2) according to the aforementioned list.
  • n can be a positive integer greater than zero.
  • n is in the range of 2 to 10.
  • An expedient method modification provides that the above-mentioned and defined steps e ') to g') are repeated several times.
  • Very specific process variants comprise carrying out the reaction and depletion four times using four series-connected pressure reactors to give a product mixture which has been depleted in ammonia and alcohol four times. Accordingly, this process variant is characterized in that steps e ') to g') are repeated at least twice so that the reaction is carried out in total in at least four pressure reactors connected in series.
  • the pressure distillation column generally and preferably at a temperature in the range of about 50 0 C to about 160 0 C.
  • the exact temperature is typically set by the boiling system as a function of the prevailing pressure conditions.
  • the temperature in the reactor is preferably in the range of about 120 0 C - 240 0 C. It is particularly useful to lower the temperature from reactor to reactor, for example in steps in the range of 3 - 15 ° C, preferably 4 - 10 0th C and especially useful in 5 ° C increments. As a result, the selectivity of the reaction is positively influenced.
  • Another measure to increase the selectivity may also be to reduce the reactor volume from reactor to reactor. With decreasing reactor volume with increasing conversion one likewise obtains an improved selectivity.
  • the distance of the removal point to the bottom (column bottom) of the column is used for orientation as a relative location.
  • Particularly expedient in the context of the invention is that the expanded product mixture according to step c 'l) after each re-conversion in a pressure reactor closer to the bottom of the distillation column is fed, based on the feed point of the feed of the previous step c' l) ,
  • ammonia released in the alcoholysis in the process of the invention can easily be recycled to an overall process for the preparation of alkyl (meth) acrylates.
  • ammonia can be converted to hydrocyanic acid with methanol. This is set forth, for example, in EP-A-0941984.
  • the hydrocyanic acid can be obtained from ammonia and methane according to the BMA or Andrussow process, these processes being described in Ullmann's Encyclopedia of Industrial Chemistry 5th Edition on CD-ROM, keyword "Inorganic Cyano Compounds.”
  • the ammonia in an ammoxidation process such as the large-scale synthesis of acrylonitrile from ammonia, oxygen and propene are attributed to the acrylonitrile synthesis is under the keyword Sohio Process in Indutrial Organic Chemistry by K. Weisermehl and H.-J. Arpe on page 307 ff. Described.
  • the reaction temperature can also vary over a wide range, with the rate of reaction generally increasing with increasing temperature.
  • the upper temperature limit generally results from the boiling point of the alcohol used.
  • the reaction temperature is in the range of 40-300 0 C, more preferably 120-240 0 C.
  • any multi-stage pressure-resistant distillation column can be used, which preferably has two or more separation stages.
  • the number of separation stages in the present invention refers to the number of plates in a tray column or the number of theoretical plates in the case of a packed column or a packed column.
  • Examples of a multistage distillation column with trays include those such as bubble trays, sieve trays, tunnel trays, valve trays, slotted trays, sieve slotted trays, sieve trays, nozzle trays, centrifugal trays, for a multistage distillation column with packing such as Raschig rings, Lessing rings, Pall Rings, Berl saddles, Intalox saddles and for a multistage distillation column with packings such as Mellapak (Sulzer), Rombopak (Kühni), Montz-Pak (Montz) and catalyst bag packs, for example Kata-Pak.
  • packing such as Raschig rings, Lessing rings, Pall Rings, Berl saddles, Intalox saddles
  • packings such as Mellapak (Sulzer), Rombopak (Kühni), Montz-Pak (Montz) and catalyst bag packs, for example Kata-Pak.
  • a distillation column having combinations of regions of soils, regions of packing or regions of packing may also be used.
  • the ammonia-depleted product mixture has inter alia the desired alpha-hydroxycarboxylic acid ester.
  • For further isolation and purification of the ester can be in an appropriate process modification to the Remove ammonia-depleted product mixture through the bottom of the distillation column and feed to another second distillation column, where distilled off to obtain a depleted in both ammonia and alcohol mixture, the alcohol through the top of the column and preferably recirculated to a reactor.
  • a method is preferred in which the ammonia and alcohol depleted mixture is discharged through the bottom of the further distillation column and still another distillation column feeds, in which distilled off the alpha-hydroxycarboxylic acid over the top and the resulting mixture of ammonia, alcohol and alpha-hydroxycarboxylic ester depleted mixture, optionally after further purification steps, recycled to the reactor.
  • the alpha-hydroxycarboxylic acid ester product obtained from the top of the column is of high purity and can, for example, be supplied in an extremely advantageous manner to further reaction steps for obtaining alkyl (meth) acrylates.
  • the distillation apparatus preferably has at least one region, called a reactor, in which at least one catalyst is provided.
  • This reactor may, as described, preferably be within the distillation column.
  • the reaction according to the invention takes place in the presence of a catalyst.
  • the reaction can be accelerated, for example, by basic catalysts. These include homogeneous catalysts as well as heterogeneous catalysts.
  • water-resistant lanthanoid compounds as catalysts.
  • the use of this type of homogeneous catalysts in a process of the invention is novel and leads to surprisingly advantageous results.
  • the term "water resistant” means that the catalyst retains its catalytic ability in the presence of water, Accordingly, the reaction of the present invention can be carried out in the presence of up to 2% by weight of water without significantly affecting the catalytic ability of the catalyst.
  • the term "essential" means that the reaction rate and / or the selectivity decreases by at most 50%, based on the reaction without the presence of water.
  • Lanthanoid compounds denote compounds of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Td, Dy, Ho, Er, Tm, Yb, and / or Lu.
  • a lanthanoid compound is used which comprises lanthanum.
  • the lanthanide compound has a solubility in water of at least 1 g / l, preferably at least 10 g / l at 25 ° C.
  • Preferred lanthanoid compounds are salts which are preferably present in the oxidation state 3.
  • Particularly preferred water-resistant lanthanoid compounds are La (NCb) 3 and / or LaCl 3 . These compounds can be added as salts of the reaction mixture or formed in situ.
  • the reaction it may be advantageous if at most 10 wt .-%, preferably at most 5 wt .-% and particularly preferably at most 1 wt .-% of the alcohol in the reaction phase are removed from the reaction system via the gas phase.
  • the reaction can be carried out particularly inexpensively.
  • a particular process variant involves using as catalyst a soluble metal complex containing titanium and / or tin and the alpha-hydroxycarboxylic acid amide.
  • the catalyst used is a metal trifluoromethanesulfonate.
  • the metal is selected from the group consisting of the elements in the groups 1, 2, 3, 4, 11, 12, 13 and 14 of the Periodic Table.
  • preference is given to using those metal trifluoromethanesulfonates in which the metal corresponds to one or more lanthanides.
  • processes using heterogeneous catalysts may also be appropriate.
  • the successfully applicable heterogeneous catalysts include, inter alia, magnesium oxide, calcium oxide and basic ion exchangers and the like.
  • the catalyst is an insoluble metal oxide which comprises at least one selected from among Sb, Sc, V, La, Ce, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Tc, Re, Fe, Co, Ni, Cu, Al, Si, Sn, Pb and Bi.
  • the catalyst used is an insoluble metal selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Fe, Co, Ni, Cu, Ga, In, Bi and Te.
  • the alcoholysis preferably methanolysis
  • the alcoholysis can take place in the combination of a pressure rectification column and a plurality of pressure reactors shown in FIG.
  • the Hydroxyisocarbonklareamid for example, Hydroxyisobutyramid
  • methanol via line (2)
  • methanol / catalyst mixture via line (3)
  • RI first pressure reactor
  • a reaction mixture of the hydroxyisocarboxylic acid ester and ammonia, unreacted hydroxyisocaboxylic acid amide and methanol, catalyst and traces of a by-product are formed in the reactor (RI).
  • This mixture is released after leaving the reactor (RI) to a lower pressure stage and passed via line (5) in a pressure column (KI).
  • the column is preferably equipped with packings. There, the ammonia is separated from the reaction mixture with a portion of the methanol and recovered at the top as a distillate. The higher boiling components, the hydroxyisocarboxylic acid ester, the by-product and the unreacted hydroxyisobutyramide are withdrawn from the column with the remaining methanol, compressed to reactor pressure and fed to the second pressure reactor (R-2).
  • the reaction is preferably carried out in 4 pressure reactors connected in series (RI to R-4).
  • the product mixture leaving the column (KI) via the bottoms consists of the hydroxyisocarboxylic acid ester, traces of a by-product and the hydroxyisobutyramide. It is passed through line (9) into the still (K-2). There, the hydroxyisocarboxylic ester precipitates as distillate and is withdrawn via line (10).
  • the Hydroxyisocarbonklareamid / catalyst mixture leaves the column (K-2) via the bottom and is partially passed via the lines (12) and (4) back into the first pressure reactor (RI).
  • a partial flow (11) is fed to a thin-film evaporator (DI). This allows the discharge of a mixture of amide, the high-boiling by-product and the catalyst via line (13).
  • Example 1
  • Table 1 shows further examples, which were carried out in the specified experimental apparatus at a molar Eduktange of MeOH: HIBA of 14: 1, but different reaction temperatures and residence times.
  • Table 1 makes it clear that the selectivity to HIBSM ( ⁇ -hydroxyisobutyric acid methyl ester) not only from the ammonia concentration in Reaction mixture in the reactor, but also on the reaction parameters residence time and temperature and thus depends on an exact reaction regime.
  • HIBSM ⁇ -hydroxyisobutyric acid methyl ester
  • a methanol / catalyst mixture with a catalyst fraction of 1.0% by weight and alpha-hydroxyisobutyramide in a molar ratio of 7: 1 were continuously metered in over an experimental period of 48 h.
  • the reaction to HIBSM and ammonia was carried out at a pressure of 75 bar and a reaction temperature of 220 0 C with a residence time of 5 min.
  • the reaction was carried out using La (NCb) 3 as a catalyst.
  • the resulting product mixture was analyzed by gas chromatography.
  • the molar selectivity to alpha-hydroxyisobutyrate based on alpha-hydroxyisobutyramide was 99%, resulting in an ammonia concentration in the product mixture of 0.63 wt .-%.

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  • Chemical & Material Sciences (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP07729501A 2006-07-21 2007-05-25 Verfahren zur herstellung von alpha-hydroxycarbonsäuren Withdrawn EP2043994A1 (de)

Applications Claiming Priority (2)

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DE102006034273A DE102006034273A1 (de) 2006-07-21 2006-07-21 Verfahren zur Herstellung von Alpha-Hydroxycarbonsäuren
PCT/EP2007/055072 WO2008009503A1 (de) 2006-07-21 2007-05-25 Verfahren zur herstellung von alpha-hydroxycarbonsäuren

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DE (1) DE102006034273A1 (es)
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WO2023169810A1 (de) 2022-03-11 2023-09-14 Röhm Gmbh Verfahren zur herstellung von alpha-hydroxyisobuttersäuremethylester und dessen anwendung in der elektronik-industrie

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CA2658590A1 (en) 2008-01-24
RU2009105822A (ru) 2010-08-27
DE102006034273A1 (de) 2008-01-24
MX2009000597A (es) 2009-06-02
CN101489973A (zh) 2009-07-22
KR20090039730A (ko) 2009-04-22
US20090209781A1 (en) 2009-08-20
JP2009544640A (ja) 2009-12-17
WO2008009503A1 (de) 2008-01-24
TW200829548A (en) 2008-07-16

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