WO2003022793A1 - Verfahren zur herstellung von (meth)acrylsaeureestern - Google Patents
Verfahren zur herstellung von (meth)acrylsaeureestern Download PDFInfo
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- WO2003022793A1 WO2003022793A1 PCT/EP2002/009814 EP0209814W WO03022793A1 WO 2003022793 A1 WO2003022793 A1 WO 2003022793A1 EP 0209814 W EP0209814 W EP 0209814W WO 03022793 A1 WO03022793 A1 WO 03022793A1
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- acrylic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- the present invention relates to a process for the preparation of (meth) acrylic acid esters by reacting alcohols with a largely anhydrous crude (meth) acrylic acid in the presence of at least one strongly acidic catalyst and an inhibitor or inhibitor mixture in a homogeneous, liquid phase, in which despite the use of Crude (meth) acrylic acid high purity (meth) acrylic acid esters can be obtained in high yield.
- Crude (meth) acrylic acid is understood here to mean the (meth) acrylic acid-containing mixture which occurs after the absorption of the reaction gases of propane / propene / acrolein or isobutane / isobutene / methacrolein oxidation in an absorption medium and subsequent separation of the absorption medium or that is obtained by fractional condensation of the reaction gases.
- the obtained (meth) acrylate to be even with the use of crude (meth) acrylic acid in high purity and substantially free of ethers, saturated esters, such as acetates and propionates, aldehyde and other carbonyl-containing, as well as high-boiling Mauko 'mponenten obtained.
- the polymers or copolymers prepared on the basis of (meth) acrylic esters are generally of great economic importance in the form of polymer dispersions, for example as adhesives, paints or textile, leather and paper auxiliaries.
- the polymer dispersions should be largely free of volatile impurities, such as lower aldehydes, especially C 3 -C 4 -aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde, acrolein, methacrolein and isobutyraldehyde, or furfural , Benzaldehyde and other carbonyl-containing secondary components, such as acetone, as well as acetic acid, propionic acid, protoanemonine (5-methylene-2 (5H) -furanone), and ether of the alcohol used, acetic acid, propionic acid, maleic acid ester and Michael Additive products from the alcohol used and the (meth) acrylic acid
- volatile impurities such as lower
- Pure or pre-cleaned (meth) acrylic acid is generally understood to mean (meth) acrylic acid, the purity of which is ind. 99.5 wt .-% and is essentially free of aldehydic, other carbonyl-containing and high-boiling components.
- This (meth) acrylic acid is generally purified by multi-stage crystallization or, if appropriate, by chemical treatment with an aldehyde scavenger and distillation.
- This process requires at least a pre-cleaned acrylic acid, since otherwise volatile acetic and propionic acid esters are leveled by reflux in the column attached to the reactor.
- US Pat. No. 5,187,309 proposes an esterification process which starts with aqueous acrylic acid (30-50% water). The esterification takes place at 50-110 ° C. in the presence of an acid as a catalyst and the esterification mixture is fed to a distillation unit together with the aqueous acrylic acid. Acrylic acid is obtained as the bottom product, water, alkanol and acrylic ester are condensed at the top of the column and then worked up further. The acrylic acid is returned directly to the esterification or a partial stream is purified by distillation beforehand (separation of high boilers and polymer). The mixture containing ester is mixed with water washed free of alkanol and then the target ester isolated by distillation.
- the disadvantage of the process is that there are high losses of valuable product (approx. 5.9% with respect to ester production, see Example 1, Table 1, Stream F9), and large amounts of residues are obtained (approx. 4.5% with respect to. Target ester, Stream F4) and a high energy requirement is necessary because large amounts of water (esterification water and water of aqueous acrylic acid; approx. 3 mol / mol ester) must be evaporated.
- the acrylic acid losses in the wash water are also high (approx. 1% with regard to esters, Stream F7).
- No. 3,875,212 proposes the use of an organic solvent with a boiling point of 100-160 ° C. in the esterification in order to remove the water of esterification from the reaction mixture as an azeotrope.
- the process consists in that the acrylic acid is esterified with the alkanol in the presence of sulfuric acid and the solvent, and the water of esterification is continuously separated off by distillation as an azeotrope with the acrylic ester and the solvent.
- the reactor discharge breaks down into an aqueous phase and an organic phase which is subjected to steam distillation in order to recover the acrylic ester and the solvent and to separate them from the polymer and high boilers.
- the aqueous phase which contains the unreacted acrylic acid, sulfuric acid and polymer, is filtered for the purpose of separating the polymer and fed back to the reactor.
- US 4,280,010 describes a process for the preparation of ether-free lower acrylic acid esters, in which the esterification at 80-130 ° C., in the presence of 0.1-3% sulfuric acid or 1-8% sulfonic acid and in the case of an acrylic acid: alkanol Ratio of 1: 1 - 2 is carried out.
- a reaction temperature of 85-110 ° C is preferably suggested, since at higher temperatures the formation of ether and the tendency to polymerize take over (column 2, lines 53-57).
- the target ester, the esterification water and the alkanol are discharged in gaseous form and condensed.
- the condensate divides into two phases, the water phase is separated and the organic phase ⁇ partly worked up by distillation and partly used as reflux. First, the alkanol separated as an azeotrope with the target ester and returned to the reactor and then the target ester isolated from the bottom product.
- a disadvantage of this process is that pure acrylic acid has to be used and that large amounts of residues are obtained (3-7%, with respect to the target ester).
- No. 4,076,950 describes a process for the preparation of acrylic acid esters by acid-catalyzed esterification of acrylic acid with alkanols and separation of a crude ester distillate, which consists of target ester, esterification water and excess alkanol, in which essentially anhydrous ("substantial anhydrous") ester is fed to the reactor is used to obtain a raw ester distillate free of acrylic acid and to maintain the composition of the ester / alkanol and ester / water azeotropes.
- the crude ester distillate must then also be subjected to a fine neutralization (“polish neutralization”), in which the otherwise usual phase separation problems and the problems associated therewith only arise to a small extent in the distillative workup.
- the crude ester distillate is washed with water during the condensation, after the phase separation the organic ester phase is washed again with water and then dewatered by distillation.
- the process requires the use of already purified ester to maintain the azeotropes in the reactor and requires two washes and several distillation stages and is therefore uneconomical. Furthermore, it does not allow the use of raw acrylic acid.
- US 4,464,229 proposes to carry out the esterification of acrylic acid with a molar deficit of alkanol (1: 0.5-1).
- the process consists in separating the acrylic esters, water and alkanol from the esterification mixture, consisting of acrylic acid, acrylic ester, water and alkanol, in a distillation column, using water-free and alkanol-free acrylic esters as the reflux (bottom of the low boiler removal).
- the return flow rate is adjusted so that a certain water content is reached in the distillate. In the case of methyl acrylate, this should be 3 - 8%. However, this means that 116 - 477 kg of methyl acrylate pre-purified by distillation are required as reflux per 100 kg of methyl acrylate formed.
- the organic phase of the distillate is fed to a low boiler distillation, if appropriate after carrying out an extraction (see column 4, line 21).
- the sump consisting mainly of acrylic acid, is at least 200 up to 600% of the amount of freshly added (meth) acrylic acid and is returned to the esterification reactor, preferably after separation of high-boiling by-products and polymer by distillation.
- the condensate from the low boiler distillation breaks down into a water phase, which is discharged, and an organic phase, which is completely recycled as reflux.
- the bottom of the low-boiling column is partly used as reflux in the first distillation column (see above) and the rest is worked up to acrylic ester in a further distillation step. Incurred water phases can be worked up in an alcohol recovery process, which is not explained in detail.
- the process is complex, it requires pure (meth) acrylic acid as the starting product and large (meth) acrylic acid amounts and large amounts of ester which have been pre-purified by distillation are circulated as refluxes.
- the object was achieved by a process for the preparation of (meth) acrylic acid esters by reacting (meth) acrylic acid with an alcohol in the presence of at least one acid catalyst and at least one polymerization inhibitor in a reaction zone b), consisting of at least one reactor bl) with at least , least one connected distillation unit b2), whereby one
- the distillate of the distillation unit b2) is treated with a washing liquid (washing step c)),
- the method according to the invention fulfills the task and consists in the fact that:
- a raw (meth) acrylic acid can be used as the starting material.
- esterification is carried out at a temperature at which the Michael adducts are partially split back.
- the target ester contained in the low boiler fraction of the low boiler separation e) can be recovered in a further distillation step (low boiler reprocessing f) as the bottom product f2) and partially introduced into the low boiler removal e) and partially applied as reflux to the reactor column b2).
- the process according to the invention can be used both for the production of methacrylic acid and of acrylic acid esters, preferably for the production of acrylic acid esters and is described below by way of example for acrylic acid esters.
- the crude (meth) acrylic acid is prepared in a manner known per se, as a rule by heterogeneously catalyzed gas phase partial oxidation of at least one C 3 or C 4 precursor of (meth) acrylic acid, such as, for example, propane, propene, acrolein or Isobutane, isobutene or methacrolein, with molecular oxygen at elevated temperature.
- C 3 or C 4 precursor of (meth) acrylic acid such as, for example, propane, propene, acrolein or Isobutane, isobutene or methacrolein
- the starting gas is generally diluted with gases which are inert under the chosen reaction conditions, such as nitrogen (N 2 ), C0 2 , saturated Ci-C ß hydrocarbons and / or water vapor, and in a mixture in the preparation of (meth) acrylic acid with molecular oxygen (0 2 ) or an oxygen-containing gas at elevated temperatures (usually 200 to 450 ° C) and optionally increased pressure, passed over solid, transition-metallic mixed oxide catalysts containing e.g. Mo and V or Mo, W, Bi and Fe and oxidatively in ( Meth) acrylic acid converted.
- gases which are inert under the chosen reaction conditions, such as nitrogen (N 2 ), C0 2 , saturated Ci-C ß hydrocarbons and / or water vapor, and in a mixture in the preparation of (meth) acrylic acid with molecular oxygen (0 2 ) or an oxygen-containing gas at elevated temperatures (usually 200 to 450 ° C) and optionally increased pressure, passed over solid, transition-metallic mixed oxide catalysts containing e.g
- reaction zone can be carried out in several stages or in one stage, each with 1, 2 or more reaction zones and / or catalyst beds, which can have a composition and / or reactivity which can vary from reaction zone to reaction zone.
- Exemplary processes are, for example, in DE-A 19 62 431, DE-A 29 43 707, DE-C 12 05 502, EP-A 257 565, EP-A 253 409, DE-A 22 51 364, EP-A 117 146 , GB-B 1 450 986 and EP-A 293 224.
- methacrolein can also be obtained through aldol condensation.
- propionaldehyde and formaldehyde are obtained and then, for example, converted into methacrylic acid as described above.
- the acrylic gas-containing product gas mixture used according to the invention is preferably obtained from the partial oxidation of propane, propene and / or acrolein.
- the resulting hot reaction gas mixture contains not only the (condensable) acrylic acid and condensable secondary components, e.g. Acetic acid, propionic acid, acetone, acrolein, allyl acrylate, the above-mentioned lower aldehydes and water, a high proportion of non-condensable components such as carbon oxides, nitrogen or oxygen.
- condensable acrylic acid and condensable secondary components e.g. Acetic acid, propionic acid, acetone, acrolein, allyl acrylate, the above-mentioned lower aldehydes and water, a high proportion of non-condensable components such as carbon oxides, nitrogen or oxygen.
- DE-OS 43 08 087 recommends the use of a high-boiling mixture of 0.1 to 25% by weight ortho-dimethyl phthalate based on a mixture consisting of 70 to 100% for the separation of acrylic acid from reaction gases of catalytic oxidation by countercurrent absorption 75% by weight diphenyl ether and 25 to 30% by weight diphenyl.
- the crude acrylic acid is then obtained by separation from the absorbent by distillation.
- the absorbed acrylic acid can be subjected to a desorption or stripping process after absorption or before distillation in order to reduce the content of aldehyde or other carbonyl-containing secondary components.
- the crude acrylic acid which can be used according to the invention is preferably obtained via fractional condensation or by absorption in diphenyl ether-diphenyl phthalate ester mixtures.
- the usable crude (meth) acrylic acid obtained is the WOR.
- the process according to the invention consists of the following stages: 1. Pretreatment (optional)
- the crude acrylic acid or any other acetic or propionic acid-containing acrylic acid stream produced by any process used in the process according to the invention can contain, for example, the following components:
- a crude acrylic acid it is advantageous to use it in the esterification in the presence of an amine, a hydrazine or a hydrazine derivative, preferably a primary or secondary amine or hydrazine (derivatives) and particularly preferably a hydrazine, in amounts of 0, 5 - 2 mol / mol of carbonyl impurities, preferably 1 - 2 and more preferably, ' "l - 1/5 mol / mol and a temperature of 20 - 40 ° C for 0.1 - 10 hours, preferably 0.5 - 7 and particularly preferably 1 to 5 hours treated.
- Aminophenols, aminoguanidine and their salts e.g. Aminoguanidine bicarbonate, carboxylic acid hydrazides, e.g. Adipic acid dihydrazide, aniline, monoethanolamine, diethanolamine, hydrazine, hydrazine hydrate, phenylhydrazine, 4-nitrophenylhydrazine or 2,4-dinitrophenylhydrazine are used, particularly preferably hydrazine hydrate.
- the reaction is preferably carried out in the presence of 300-3000 pp of phenothiazine as a stabilizer, or an equivalent amount of another suitable stabilizer.
- Can order additional apparatuses to avoid the reaction for example in a storage tank or a quench or intermediate containers are guided by ⁇ , which is preferably with a circulation, stirring or a pumped circulation is provided.
- ⁇ which is preferably with a circulation, stirring or a pumped circulation is provided.
- the pretreatment can also be carried out in a tubular reactor which is optionally either heated, for example via a double jacket, or which is thermally insulated after heating in the entrance area, for example via a heat exchanger.
- an aldehyde-free acrylic acid-containing fraction with a carbonyl content below 50 ppm, preferably below 10 ppm, is used as the starting acid in the purification of crude acrylic acid in the production of pure acrylic acid, the pretreatment described can be omitted.
- pure acrylic acid can also be used for the process according to the invention, in which case no pretreatment is generally carried out.
- Such pure acrylic acid can have the following composition, for example:
- the acrylic acid-containing mixture which optionally comes from the pretreatment (stage 1), is reacted with the alcohol in a reaction zone b) in the presence of at least one acid catalyst.
- Suitable acid catalysts are sulfuric acid, para-toluenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic sulfonic acid or mixtures thereof, are also conceivable acidic Ionenaus ⁇ exchanger.
- Methanesulfonic acid used particularly preferably sulfuric acid.
- the catalyst concentration based on the reaction mixture is, for example, 1 to 20, preferably 5 to 15,% by weight.
- Suitable alcohols for the reaction are those which have 1 to 8 carbon atoms, preferably those with 1 to 4 and particularly preferably those with 1 to 3 carbon atoms.
- Methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol and 2-ethylhexanol are preferably used, particularly preferably methanol and ethanol.
- the alcohol can be supplied in liquid and / or gaseous form.
- the esterification takes place in at least one heatable reactor b1), with suitable measures ensuring thorough mixing. If several reactors are used, e.g. two to four, they can be arranged in a cascade.
- the reaction preferably takes place in a reactor.
- the reactor bl) is connected to at least one distillation unit, which preferably has 30-50 theoretical plates.
- the distillation unit b2) is preferably placed on the reactor bl).
- reactors can also be connected to one distillation unit.
- the reflux from the distillation unit is then preferably returned to the first reactor.
- the distillation unit is of a type known per se and has the usual internals.
- all common internals come into consideration as column internals, for example trays, packings and / or fillings.
- column internals for example trays, packings and / or fillings.
- bell bottoms, sieve bottoms, valve bottoms, Thormann bottoms and / or dual-flow bottoms are preferred; of the fillings are those with rings, spirals, saddle bodies, Raschig, Intos or Pall rings, Barrel or Intalox Saddling, Top-Pak etc. or braids preferred.
- the capacitor if any, is of conventional design.
- a preferred embodiment consists in that the bottom area and the evaporator of a distillation unit are used as reactor b1). If the alcohol is supplied in gaseous form (see below), the preferred dosing point is below the separating internals of the distillation unit b2) or in circulation.
- the reaction mixture is treated with a suitable stabilizer, e.g. Phenothiazine (0.05-0.5% with respect to the reaction mixture) stabilized against undesired polymerization, the stabilizer preferably being supplied with acrylic acid.
- a suitable stabilizer e.g. Phenothiazine (0.05-0.5% with respect to the reaction mixture) stabilized against undesired polymerization, the stabilizer preferably being supplied with acrylic acid.
- the reaction takes place at 120-150 ° C and ambient pressure, higher or reduced pressure can also be used, ambient pressure is preferred.
- the reaction time is usually 0.5 - 10 hours, preferably 1 - 6 hours.
- the starting materials acrylic acid and alcohol are usually in the stoichiometry 1: 0.7 - 3.0, preferably 1: 0.9 - 2.5. preferably 1: 1.0 - 2.0 and in particular 1: 1.0 - 1.5 metered.
- the target ester formed during the esterification, low boilers, the Michael addition products, among them preferably the alkoxypropionic acid ester, and the water of reaction formed are separated off as top product via column b2) connected to the esterification reactor bl) (top temperature 70-90 ° C. Head pressure 1 bar).
- the condensed top product (temperature usually 20 to 40 ° C) is stabilized with an inhibitor and consists essentially of target ester, unreacted alcohol, water, acetic acid ester, Michael addition product, such as alkoxypropionic acid ester, and various secondary components.
- the acrylic acid content in the top product is generally not more than 0.1%, preferably not more than 0.01%.
- Alkylphenols for example o-, m- or p-cresol (methylphenol), 2-tert-butyl-4-methylphenol, 6-tert-butyl-2, 4-dimethyl-phenol, 2, 6-di -ter. -Butyl-4-methylphenol, 2-ter. -Butylphenol, 4-tert. -Butylphenol, 2, 4-di-tert. -Butylphenol, 2-methyl-4-ter. -Butylphenol, 4-tert. -Butyl-2, 6-dimethylphenol, or 2, 2 '-methylene-bis- (6-tert-butyl-4-methylphenol),
- Hydroxyphenols for example hydroquinone, 2-methylhydroquinone, 2, 5-di-tert-butylhydroquinone, pyrocatechol (1, 2-dihydroxybenzene) or benzoquinone, aminophenols, such as, for example, para-a inophenol, nitrosophenols, such as, for example, para-nitrosophenol, Alkoxyphenols, for example 2-methoxyphenol (guaiacol, pyrocatechol monoethyl ether), 2-ethoxyphenol, 2-isopropoxyphenol, 4-methoxyphenol (hydroquinone monomethyl ether), mono- or di-tert-butyl-4-methoxy- phenol, tocopherols, such as, for example, ⁇ -tocopherol and 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran (2,2-dimethyl-7-hydroxycur ⁇ aran), N-oxyls, such as 4-hydroxy 2,2,6,6-tetramethyl-piperidine
- water-soluble stabilizers are preferred, particularly preferably N, N'-dialkyl-p-phenylenediamines, such as e.g. N, N '-di-iso-butyl-p-phenylenediamine or N, N' -di-is ⁇ -propyl-p-phenylenediamine, and N-oxyls, in particular para-phenylenediamine or 4-hydroxy-2, 2, 6, 6-tetramethyl-piperidine-N-oxyl.
- N, N'-dialkyl-p-phenylenediamines such as e.g. N, N '-di-iso-butyl-p-phenylenediamine or N, N' -di-is ⁇ -propyl-p-phenylenediamine
- N-oxyls in particular para-phenylenediamine or 4-hydroxy-2, 2, 6, 6-tetramethyl-piperidine-N-oxyl.
- the stabilizer is used in amounts of 10-1000 ppm, preferably 50 to 500 ppm, with respect to the distillate.
- an oxygen-containing gas preferably air or a mixture of air and nitrogen (lean air) can be present.
- This oxygen-containing gas is preferably metered into the bottom region of a column and / or into a circulation evaporator.
- condensation can also be dispensed with, in which case the distillate is passed essentially gaseously into the subsequent wash (stage 3).
- stage 3 largely alcoholic mixture acryl Acidester Anlagen cl
- the esterification is carried out so that the bottom max. 10% target and max. Contains 15% acrylic acid.
- a further process variant consists in carrying out the esterification in a heatable prereactor, if appropriate under pressure, and feeding the liquid reaction mixture obtainable in this way to a distillation unit consisting of a column, circulation evaporator and condenser. The reaction mixture is separated as described above. All or part of the bottom product containing the catalyst is returned to the reactor.
- stage 2 which consists essentially of acrylic acid ester (75 - 90%), alcohol (1 - 10%), water (7 - 13%), Michael addition product, especially alkyl alkoxypropionic acid ester, (0.5 - 2 , 5%), acetic acid ester (0.05 - 1%) and various low boilers, e.g. Propionic acid esters, aldehydes and ethers (0.5 - 3%) are, optionally with additional stabilizer, washed with a washing liquid.
- the amount of the washing liquid is 10-200% by weight, based on the distillate / condensate, preferably 40-150% by weight and particularly preferably 50-100% by weight.
- May be in the wash liquid is, for example, water to which, where appropriate, basic compounds such as sodium hydroxide, potassium hydroxide, Na riumhydrogencarbonat, sodium carbonate, potassium carbonate or Kaliu supplied ⁇ sets, preferably water is used.
- basic compounds such as sodium hydroxide, potassium hydroxide, Na riumhydrogencarbonat, sodium carbonate, potassium carbonate or Kaliu supplied ⁇ sets, preferably water is used.
- the wash liquid may be tap water, condensate or deionisier ⁇ tes water, optionally provided with the above additives, comparable applies to.
- a further embodiment consists in using or using the aqueous phases obtained in the process, for example from phase separators, for example those from stages 4 or 5, or water from vacuum units, for example water ring pumps, especially the aqueous fraction d2) from alcohol recovery (stage 4).
- washing of unreacted alcohol removes alcohol from the esterification and other by-products which are soluble in the washing liquid.
- washing processes and apparatuses are used, e.g. B. those described in Ullmann's Encyclopedia of Industrial Chemistry, 6th ed, 1999 Electronic Release, chapter: Liquid - Liquid Extraction - Appara - tus.
- these can be single-stage or multi-stage, preferably multi-stage extractions, as well as those in
- Sieve tray, packing or packed columns, stirred tanks or mixer-settlers, and 20 columns with rotating internals or pulsed columns are preferably used.
- a column with 70 to 150 theoretical plates is particularly preferably used. In principle come as column internals
- the distillate / condensate from step 2 is preferably at the lower end of the column, the washing liquid is preferably supplied at the top ⁇ leads.
- phase c2 The organic phase emerging at the top of the column is passed into a separation vessel known per se in order to separate off residual water as phase c2) and stabilized with an inhibitor.
- phase cl The largely alcohol-free ester phase cl), which is usually
- the distillation unit b2 has an alcohol content of not more than 0.1% by weight, preferably not more than 0.02%, is partly fed to the distillation unit b2) in stage 2 as reflux and partly to a further purification of the acrylic acid ester (stage 5) by distillation Ratio of 30:70 - 70:30, preferably in the ratio of
- the organic phase cl) is worked up by distillation without further washes or neutralizations.
- the aqueous phase c2) from the phase separator is preferably passed completely into the alcohol recovery (stage 4).
- Alkylphenols, alkoxyphenols, hydroxyphenols, aminophenols, tocopherols, N-oxyls, aromatic amines or phenylenediamines, hydroxylamines, phosphorus-containing compounds or sulfur-containing compounds may be used in combination with metal salts.
- Water-soluble stabilizers are preferred at this point, particularly preferably N, N'-dialkyl-para-phenylenediamines and N-oxyls, in particular N, N'-di-iso-butyl-para-phenylenediamine or 4-hydroxy-2,2,6 , 6-tetramethyl-piperidine-N-oxyl.
- the stabilizer is used in amounts of 10-1000 ppm, preferably 50 to 500 ppm, based on the organic phase emerging at the top of the column.
- the water phase c3) emerging at the lower end of the column which is generally 5-10% by weight alcohol, 3-7% by weight acrylic ester, 0.1-1% by weight Michael addition product such as alkoxypropionic acid alkyl ester and Contains 0.1 - 1 wt .-% low boilers, is processed in stage 4 (alcohol recovery) in whole or in part. Part of this water phase c3) can also be returned to the laundry as washing liquid.
- distillate consists of
- Stage 2 is not condensed, but is fed to stage 3 in gaseous form and quenched with the washing liquid.
- stage 3 In order to reduce the amount of wastewater, it may be advisable to bypass the washing (stage 3) in whole or in part, for example by wholly or partly by directing the distillate / condensate obtained at the top of column b2) to a distillative workup, for example the removal of low boilers (stage 5 ), whereby a phase separation vessel can optionally be connected upstream to separate the water formed in the reaction.
- the bottom product obtained in the working up by distillation, for example e3) can optionally be used in part as reflux for column b2). 4.
- the water phases c2) and c3) from the column and separation vessel obtained in stage 3 are optionally fed together with the water phases in stage 5 and with the water phases resulting from vacuum generation (water ring pumps) to a valuable product recovery of alcohol, acrylic ester and Michael addition products.
- the recovery unit preferably consists of a distillation column d) with an evaporator, a condenser of conventional design and a side draw.
- the column preferably has 30-70 theoretical plates, e.g. Soils, packs and / or fillings. Of the bottoms, bell bottoms, sieve bottoms, valve bottoms, Thormann bottoms and / or dual-flow bottoms are preferred; of the fillings are those with rings, spirals, saddle bodies, Raschig, Intos or Pall rings, Barrel or Intalox Saddling, Top-Pak etc. or braids preferred.
- the combined water phases are fed in at the upper end of the lower half of the column, the feed preferably being heated to 40-90.degree. C., preferably 60-90.degree. C. by heat exchange with the outlet of the alcohol recovery column. . ⁇
- the bottom temperature is 100-110 ° C, the top temperature 60-80 ° C at slightly reduced or atmospheric pressure, preferably at atmospheric pressure.
- the vapors emerging at the top of the column are condensed, stabilized with an inhibitor and partly fed back to column d) as reflux.
- the remaining part of the condensate dl) is fed directly to the esterification (stage 2).
- stage 2 may be the feed to level 2 if it is liquid, approximately in the middle of the column b2), in the reactor bl) or in the feed, or when it is shaped gas ⁇ , are dosed below the separating internals or in the circulation circuit ,
- the vapors consist essentially of alcohol (40 - 70%). and acrylic acid esters (30 - 50%).
- a ls inhibitors may also phenols, the above-mentioned alkyl phenols, hydroxy, amino phenols, tocopherols, N-oxyls, aromatic amines or phenylenediamines, hydroxylamine ine, phosphorus-containing compounds or sulfur-containing compounds, optionally tion in Kombina ⁇ be used with metal salts.
- Water-soluble stabilizers are preferred at this point, particularly preferably N, N'-dialkyl-para-phenylenediamines and N-oxyls, in particular N, N'-di-isobutyl-para-phenylenediamine or 4-hydroxy-2, 2.6 , 6-tetramethyl-piperidine-N-oxyl.
- the stabilizer is used in amounts of 10 to 500 ppm, preferably 50 to 300 ppm, based on the distillate.
- an oxygen-containing gas preferably air or a mixture of air and nitrogen (lean air) can be present.
- This acid containing gas is preferably metered into the bottom region of the column and / or into a circulation evaporator.
- a medium boiler fraction d3) in gaseous or liquid form is preferably discharged from the column via a side draw, which mainly contains Michael addition products, especially alkyl alkoxypropionic acid (5-10% by weight), alcohol (40- 60 wt .-%) and water.
- Michael addition products especially alkyl alkoxypropionic acid (5-10% by weight)
- alcohol 40- 60 wt .-%)
- water water
- the esterification (stage 2) is fed.
- the Michael addition products, especially alkyl alkoxypropionates are at least partially split back into alcohol and acrylic esters and the alcohol released in this way is esterified with the acrylic acid present.
- the water phase d2) obtained in the bottom of the recovery column d) is cooled, preferably by heat transfer to the column feed from d), in a heat exchanger, at least partially returned to the laundry (stage 3) and used there as washing liquid and partially discharged, preferably 1 - 50%, particularly preferably 5 - 40% and in particular 10 to 30%.
- the discharged part can be disposed of in a manner known per se, e.g. via a wastewater treatment plant.
- a further preferred embodiment consists in that the fresh alcohol required for the esterification is applied to the top of column d) as reflux and the vapors are fed directly, preferably in gaseous form, to reaction zone b) of the esterification (stage 2).
- the inflow is carried out as described above. 5.
- the low boiler removal is carried out in particular when crude acrylic acid is used as the starting material and / or a particularly low-boiler acrylic acid ester is to be prepared.
- a portion of the largely alcohol-free acrylic acid ester mixture (organic phase cl) of the phase separator from stage 3 obtained in stage 3 is converted into a low boiler fraction and into a distillation unit e), consisting of a distillation column, an evaporator and a condenser with a phase separation vessel, each of a customary type Bottom product e3), which contains the target ester, separated.
- a distillation unit e consisting of a distillation column, an evaporator and a condenser with a phase separation vessel, each of a customary type Bottom product e3, which contains the target ester, separated.
- the column preferably has 20-60 theoretical plates and the internals described in stage 4. , ...
- the feed is preferably above the middle of the column.
- the bottom temperature is between 80 and 100 ° C.
- the column is operated at normal pressure or slightly reduced pressure, for example 500 mbar - normal pressure, preferably 700 mbar - normal pressure and particularly preferably 800 mbar - normal pressure.
- the condensed low boiler fraction breaks down into a water phase e2), which is returned to the alcohol recovery stage (stage 4) and / or to the laundry (stage 3), and into an organic phase el), which mainly contains alkyl acetate, ether and alkyl acrylate.
- the organic phase el) is mixed with a stabilizer and partly applied as reflux to the top column bottom of column e) (reflux ratio 20-40) and can in part be fed to a further distillation unit (stage 6).
- the above-mentioned inhibitors can be Alkylphenols, alkoxyphenols, hydroxyphenols, aminophenols, tocopherols, N-oxyls, aromatic amines or N, N'-dialkyl-para-phenylenediamines, hydroxylamines, phosphorus-containing compounds or sulfur-containing compounds, if appropriate, can be used in combination with metal salts.
- an oxygen-containing gas preferably air or a mixture of air and nitrogen (lean air) can be present.
- This oxygen-containing gas is preferably metered into the bottom region of the column and / or into a circulation evaporator.
- the stage 5 capacitor is preferably charged with a solution of a partially water-soluble inhibitor in the target ester, preferably by spraying, in order to prevent polymerization from forming on the cooling surfaces.
- Preferred for this are p-phenylenediamines and N-oxyls, particularly preferably para-phenylenediamine or 4-hydroxy-2,2,6,6-tetramethyl-piperidine-N-oxyl.
- the low boiler reprocessing is carried out in particular when crude acrylic acid is used as the starting material and / or an especially low-boiler acrylic acid ester is to be prepared.
- the part of the organic phase el) of the low boiler fraction from stage 5 which is not used as reflux can, in a further distillation unit f) with a condenser and phase separation vessel of conventional design, be converted into a low boiler fraction f1), mainly comprising alkyl acetate and ether, and into a bottom product consisting essentially of alkyl acrylate f2) be separated.
- the condensate fl) is partly discharged and e.g. thermally recycled or saponified and partly, after stabilization analogously to stage 5, returned to the distillation column f) as reflux with a reflux ratio of, for example, 20-40: 1.
- the discharged Share may also be alkaline, for example with sodium hydroxide, are hydrolyzed to the information contained in acetate Alko ⁇ hol recover.
- the Verseifungsaustrag can then ⁇ example, the alcohol recovery d), respectively.
- the bottom f2) of the column which essentially contains acrylic acid esters is recycled to stage 5.
- the bottom f2) is a return in the distillation unit b2) of stage 2.
- the bottom temperature is 60 to 80 ° C
- the pressure is preferably normal pressure or slightly reduced pressure, for example 500 mbar - normal pressure, preferably 700 mbar - normal pressure and particularly preferably 800 mbar - normal pressure.
- a preferred embodiment consists in that a packing column with preferably 10-30 theoretical plates is used.
- stage 5 From the bottom product e3) obtained in stage 5, which generally has a purity of at least 98%, preferably at least 99%, or, if stages 5 and 6 have not been passed through, from the organic phase c1) isn distillation stage g) in a distillation column with preferably 5 - 20 theoretical plates and evaporators and condensers of conventional design at a bottom temperature between 40 and 80 ° C and a top pressure of 0.1 - 0.7 bar, preferably 0.2 - 0.6 bar, the target ester isolated as head product gl).
- a solution of a bearing stabilizer in the target ester is applied to the capacitor, and the stabilizer solution is preferably sprayed on.
- column internals for the column, for example trays, packings and / or fillings.
- Bell bottoms, sieve bottoms, valve bottoms, Thormann bottoms and / or dual flow bottoms are preferred of the bottoms, of the fillings are those with rings, spirals, saddle bodies, Raschig, Intos or Pall rings, Barrel or Intalox saddles, Top-Pak etc. or braids preferred.
- the above-mentioned inhibitors can be Alkylphenols, alkoxyphenols, hydroxyphenols, aminophenols, tocopherols, N-oxyls, aromatic amines or N, N '-dialkyl-para-phenylenediamines, optionally used in combination with metal salts.
- an oxygen-containing gas preferably air or a mixture of air and nitrogen (lean air) can be present.
- This oxygen-containing gas is preferably metered into the bottom region of the column and / or into a circulation evaporator.
- Hydroquinone onomethyl ether is preferably used as a storage stabilizer.
- the amount is adjusted so that the storage stabilizer content in the condensate is 10-20 ppm.
- Part of the target ester is mixed with the inhibitor mixture from stage 5 5 (see above), preferably with 50-100 ppm, and fed to the column as reflux (reflux ratio 0.1-1: 1, preferably 0.1-0.7: 1 , particularly preferably 0.1-0.5: 1).
- the bottom of column g2) which mainly contains alkyl acrylate and Michael addition product, especially alkyl alkoxypropionate, is preferably fed to reactor bl), where under the esterification conditions the Michael addition products are at least partially split back into alcohol and acrylate.
- the acrylic acid esters obtainable by the process according to the invention have a purity of at least 99%, preferably 99.5%, particularly preferably at least 99.8% and in particular at least 99.9% and have an alkyl propionate content of not more than 1000 ppm, preferably not more than
- the stream b3) from the esterification (stage 2) can optionally at least partially be subjected to high-boiling.
- stream b3) or, if appropriate, also streams d3) and / or g2) containing Michael addition products is fed to a reactor or a distillation apparatus which is optionally operated in a circuit and is treated there thermally and / or catalytically.
- the temperature in the cleavage is generally 110 to 220 ° C, preferably 120 to 200 ° C and particularly preferably 130 to 180 ° C.
- the separation of the remaining Acrylklareesters and thereby corresponds 0 standing cleavage products can be obtained by passing a under the reaction conditions in the substantially inert gas stream (stripping), such as nitrogen, water vapor, or preferably an oxygen-containing gas such as air, supported ⁇ the. 5
- the remaining residue can, for example, be partially discharged, distilled or subjected to further cleavage or used to obtain sulfuric acid.
- the gaseous stream obtained from the cleavage which may essentially contain acrylic acid ester, alcohol, acrylic acid and optionally ether and also stabilizer, can, if appropriate after condensation and / or further cooling, preferably in the esterification reactor b1) or below the separating internals of b2) or into the circulation of reaction zone b).
- stream b3 can also advantageously be used to obtain sulfuric acid.
- a sulfur-containing stream is converted into a stream containing sulfur oxide in a manner known per se and e.g. converted to sulfuric acid in a contact system.
- the crude acrylic acid was treated with hydrazine hydrate (1.5 mol / mol aldehyde) before the esterification at 23 ° C. (residence time 1 hour).
- the crude ester mixture was treated in a washing column (120 trays) with 10,000 parts / h of waste water from the methanol recovery, with the water phase of the phase separation vessel from the low boiler distillation (179 parts / h) and the waste water from the vacuum pumps (580 parts / h) being added were.
- the washed organic phase was mixed with 160 parts / h of stabilizer solution (see above) and partly (7000 parts / h) as reflux from the reactor column and partly (7242 parts / h) together with the bottom product of the Low boiler processing (86 parts / h) fed to the low boiler separation.
- the waste water from the washing column was heated to 40 ° C. and fed to the 25th tray of the methanol recovery column (60 dual-flow trays, external circulation evaporator, 105 ° C. bottom temperature).
- 2400 parts of methanol (99.9% by weight, fresh feed) as reflux and 100 parts of stabilizer solution (see above) were applied to the top of the column.
- the resulting distillate which mainly consisted of methanol (77.8%) and methyl acrylate (20.6%), was returned to the esterification gas.
- 400 parts / h of a fraction containing Michael addition product (6% methyl methoxypropionate, 48% methanol and 56% water) were discharged through a side draw (40th tray) and metered into the esterification reactor.
- the methanol-free wastewater was partly returned to the wash (10,000 parts / h) and partly discharged (2100 parts / h).
- the low boiler was separated off in a column with 52 dual-flow trays (feed to 32nd tray) and rotary evaporator at a bottom temperature of 88 ° C.
- the low boiler fraction discharged at the top of the column disintegrated into a water phase (179 parts / h), which was fed to the extraction column, and an organic phase, which was partly returned to the column as reflux (2000 parts / h) and partly ( 60 parts / h) was fed to the low boiler workup.
- the capacitor was charged with 200 parts / h stabilizer solution consisting of 0.2% phenothiazine and 0.1% N, N'-di-iso-butyl-p-phenylenediamine in methyl acrylate.
- the bottom product (7796 parts / h), consisting mainly of methyl acrylate (99%), was in the pure column in a top product, the target ester (7335 parts / h, 98.5% yield with respect to acrylic acid), and a bottom product, the consisted essentially of 89% methyl acrylate and 10.5% Michael addition product and fed back to the esterification, separated.
- the purifying distillation was carried out in a column with 15 dual-flow trays and an external circulating evaporator.
- the head temperature was 43 ° C (0.3 bar), the reflux ratio 0.3.
- 160 parts / h of a solution of 0.2% hydroquinone monoethyl ether in methyl acrylate were sprayed into the vapor tube and the condenser tube was sprayed with 100 parts / h of this solution.
- the return flow ratio was 0.3, the return was mixed with 120 parts of stabilizer mixture (see above).
- the low boiler was worked up in a packing column 5 (16 separation stages) at a bottom temperature of 72 ° C at atmospheric pressure and a reflux ratio of 25.
- the bottom product mainly methyl acrylate (94%), was returned to the low boiler removal, the top product not used as reflux (19th Parts / h) was removed.
- the return flow of column 10 was mixed with 50 parts / h of the stabilizer solution (see above).
- the methyl acrylate obtained had a purity of 99.96% and contained, as secondary components, 310 ppm methyl propionate, 15 25 ppm acrylic acid, 60 ppm water, less than 10 ppm methyl acetate and less than 1 ppm aldehydes.
- the system could be operated without malfunctions for at least 30 days.
- the purity of the product was 99.78%, it contained 1700 ppm 35 methyl acetate and 300 ppm methyl propionate.
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Abstract
Description
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE50209729T DE50209729D1 (de) | 2001-09-10 | 2002-09-03 | Verfahren zur herstellung von (meth)acrylsaeureestern |
EP02774555A EP1427692B1 (de) | 2001-09-10 | 2002-09-03 | Verfahren zur herstellung von (meth)acrylsaeureestern |
JP2003526871A JP2005502695A (ja) | 2001-09-10 | 2002-09-03 | (メタ)アクリル酸エステルの製造方法 |
US10/486,364 US20040236143A1 (en) | 2001-09-10 | 2002-09-03 | Method for producing (meth)acrylic acid esters |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE10144490.7 | 2001-09-10 | ||
DE10144490A DE10144490A1 (de) | 2001-09-10 | 2001-09-10 | Verfahren zur Herstellung von (Meth)acrylsäureestern |
Publications (1)
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WO2003022793A1 true WO2003022793A1 (de) | 2003-03-20 |
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ID=7698476
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Application Number | Title | Priority Date | Filing Date |
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PCT/EP2002/009814 WO2003022793A1 (de) | 2001-09-10 | 2002-09-03 | Verfahren zur herstellung von (meth)acrylsaeureestern |
Country Status (7)
Country | Link |
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US (1) | US20040236143A1 (de) |
EP (1) | EP1427692B1 (de) |
JP (1) | JP2005502695A (de) |
CN (1) | CN1318378C (de) |
AT (1) | ATE356794T1 (de) |
DE (2) | DE10144490A1 (de) |
WO (1) | WO2003022793A1 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1721886A1 (de) * | 2004-03-01 | 2006-11-15 | Mitsubishi Chemical Corporation | Verfahren zur verarbeitung einer methacrylsäureesterhaltigen lösung |
CN114450264A (zh) * | 2019-09-25 | 2022-05-06 | 罗姆化学有限责任公司 | 纯化甲基丙烯酸甲酯以除去低沸点组分的方法 |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102009058058A1 (de) | 2009-12-14 | 2011-06-16 | Basf Se | Verfahren zur Polymerisationsinhibierung von (Meth)acrylsäure und/oder Meth)acrylsäureestern |
FR3008971B1 (fr) | 2013-07-29 | 2016-08-19 | Arkema France | Procede de production en continu d'acrylates legers par esterification d'un acide acrylique de grade ester brut |
FR3024143B1 (fr) * | 2014-07-28 | 2016-07-15 | Arkema France | Procede perfectionne de fabrication de (meth)acrylates d'alkyle |
CN106699560B (zh) * | 2015-11-18 | 2020-08-14 | 上海浦景化工技术股份有限公司 | 一种含甲基丙烯酸甲酯的物流的分离设备与分离方法 |
US10308584B2 (en) * | 2016-02-25 | 2019-06-04 | 3M Innovative Properties Company | Methods of making (alk)acrylic esters in flow reactors |
TWI796324B (zh) * | 2017-03-09 | 2023-03-21 | 日商東亞合成股份有限公司 | (甲基)丙烯酸酯的製造方法 |
CN109678711B (zh) * | 2017-10-19 | 2021-08-27 | 山东开泰石化股份有限公司 | 一种从丙烯酸甲酯废油中提取甲氧基丙酸甲酯的系统和方法 |
FR3083233B1 (fr) * | 2018-06-27 | 2020-05-29 | Arkema France | Procede de purification d'acrylates legers. |
US20220162149A1 (en) * | 2019-04-16 | 2022-05-26 | Rohm And Haas Company | Acid catalyzed synthesis of methyl acrylate from acrylic acid and methanol |
EP3956284B1 (de) | 2019-04-16 | 2023-03-29 | Rohm and Haas Company | Säurekatalysierte synthese von methylacrylat aus acrylsäure und methanol |
WO2022230916A1 (ja) | 2021-04-28 | 2022-11-03 | 三菱ケミカル株式会社 | メタクリル酸メチル含有組成物及びメタクリル酸メチル重合体の製造方法 |
WO2022230913A1 (ja) | 2021-04-28 | 2022-11-03 | 三菱ケミカル株式会社 | メタクリル酸メチル含有組成物及びメタクリル酸メチル重合体の製造方法 |
BR112023022409A2 (pt) | 2021-04-28 | 2023-12-26 | Mitsubishi Chem Corp | Composição contendo metacrilato de metila e método de produção de polímero de metacrilato de metila |
WO2022230915A1 (ja) | 2021-04-28 | 2022-11-03 | 三菱ケミカル株式会社 | メタクリル酸メチル含有組成物及びメタクリル酸メチル重合体の製造方法 |
WO2022230914A1 (ja) | 2021-04-28 | 2022-11-03 | 三菱ケミカル株式会社 | メタクリル酸メチル含有組成物及びメタクリル酸メチル重合体の製造方法 |
WO2022238144A1 (de) * | 2021-05-10 | 2022-11-17 | Röhm Gmbh | Ungesättigte ester, enthaltend ein additiv zur reduktion und stabilisierung des gelbwertes |
WO2023100867A1 (ja) * | 2021-11-30 | 2023-06-08 | 三菱ケミカル株式会社 | メタクリル酸メチル含有組成物、メタクリル酸メチル含有組成物の保存方法及びメタクリル酸メチル重合体の製造方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5187309A (en) * | 1989-08-03 | 1993-02-16 | Elf Atochem S.A. | Process for the continuous preparation of lower acrylates |
DE19952449A1 (de) * | 1999-10-30 | 2001-05-03 | Metallgesellschaft Ag | Verfahren zur Herstellung von Estern der Acrylsäure oder Methacrylsäure |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3583963A (en) * | 1969-11-20 | 1971-06-08 | Du Pont | Use of hydrazine to inhibit vinyl polymerization |
JPS563338B2 (de) * | 1972-05-23 | 1981-01-24 | ||
DE2552987C2 (de) * | 1975-11-26 | 1983-09-29 | Hoechst Ag, 6230 Frankfurt | Verfahren zur kontinuierlichen Herstellung ätherfreier Acrylsäurealkylester |
US4076950A (en) * | 1976-07-19 | 1978-02-28 | Rohm And Haas Company | Process for manufacture of alkyl esters of aliphatic carboxylic acids |
US4464229A (en) * | 1981-07-09 | 1984-08-07 | Nippon Shokubai Kagaku Kogyo Co. Ltd. | Process for producing acrylic or methacrylic esters |
US5171888A (en) * | 1989-05-16 | 1992-12-15 | Betz Laboratories, Inc. | Methods and compositions for inhibiting (meth)acrylic acid polymerization |
DE19536179A1 (de) * | 1995-09-28 | 1997-04-03 | Basf Ag | Verfahren zur rektifikativen Abtrennung von ungesättigten Carbonsäuren aus Lösungsmitteln |
-
2001
- 2001-09-10 DE DE10144490A patent/DE10144490A1/de not_active Withdrawn
-
2002
- 2002-09-03 AT AT02774555T patent/ATE356794T1/de not_active IP Right Cessation
- 2002-09-03 DE DE50209729T patent/DE50209729D1/de not_active Expired - Lifetime
- 2002-09-03 WO PCT/EP2002/009814 patent/WO2003022793A1/de active IP Right Grant
- 2002-09-03 US US10/486,364 patent/US20040236143A1/en not_active Abandoned
- 2002-09-03 EP EP02774555A patent/EP1427692B1/de not_active Expired - Lifetime
- 2002-09-03 CN CNB028176979A patent/CN1318378C/zh not_active Expired - Fee Related
- 2002-09-03 JP JP2003526871A patent/JP2005502695A/ja not_active Ceased
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5187309A (en) * | 1989-08-03 | 1993-02-16 | Elf Atochem S.A. | Process for the continuous preparation of lower acrylates |
DE19952449A1 (de) * | 1999-10-30 | 2001-05-03 | Metallgesellschaft Ag | Verfahren zur Herstellung von Estern der Acrylsäure oder Methacrylsäure |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1721886A1 (de) * | 2004-03-01 | 2006-11-15 | Mitsubishi Chemical Corporation | Verfahren zur verarbeitung einer methacrylsäureesterhaltigen lösung |
EP1721886A4 (de) * | 2004-03-01 | 2007-05-09 | Mitsubishi Chem Corp | Verfahren zur verarbeitung einer methacrylsäureesterhaltigen lösung |
CN114450264A (zh) * | 2019-09-25 | 2022-05-06 | 罗姆化学有限责任公司 | 纯化甲基丙烯酸甲酯以除去低沸点组分的方法 |
Also Published As
Publication number | Publication date |
---|---|
EP1427692A1 (de) | 2004-06-16 |
DE10144490A1 (de) | 2003-03-27 |
EP1427692B1 (de) | 2007-03-14 |
CN1553889A (zh) | 2004-12-08 |
DE50209729D1 (de) | 2007-04-26 |
CN1318378C (zh) | 2007-05-30 |
JP2005502695A (ja) | 2005-01-27 |
US20040236143A1 (en) | 2004-11-25 |
ATE356794T1 (de) | 2007-04-15 |
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