EP2097363A1

EP2097363A1 - Process for preparing 3-alkoxypropan-1-ols

Info

Publication number: EP2097363A1
Application number: EP07822482A
Authority: EP
Inventors: Jens Heimann; Markus Rösch; Ellen Dahlhoff; Steffen Maas
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2006-11-27
Filing date: 2007-11-12
Publication date: 2009-09-09
Also published as: WO2008064991A1; CN101541721A; JP2010511006A; US20100069681A1

Abstract

The present invention relates to a process for preparing 3-alkoxy-propan-1-ols of the general formula (I) by catalytic hydrogenation of esters of the general formula (II), where the radicals R1 and R2 and R3, R4 and R5 can be, independently of one another, straight chain or branched, C1-C20-alkyl radicals which may be substituted by one or more C1-C20-alkoxy groups or interrupted by one or more oxygen atoms in the chain, C6-C20-aryl, C7-C20-arylalkyl which may be substituted by one or more C1-C20-alkoxy groups or interrupted by one or more oxygen atoms in the alkyl chain, C7-C20-alkylaryl which may be substituted by one or more C1-C20-alkoxy groups or interrupted by one or more oxygen atoms in the alkyl chain, C7-C20-cycloalkyl radicals which may be substituted by one or more C1-C20-alkoxy groups and R2, R3 and R4 can, independently of one another, also be hydrogen, over chromium and nickel-free catalysts.

Description

Process for the preparation of 3-alkoxypropan-1-ols

description

The present invention relates to processes for the preparation of 3-alkoxypropan-1-ols of general formula I.

I by catalytic hydrogenation of esters of general formula II,

in which the radicals R 1 and R 2 and R 3, R 4 and R 5 independently of one another denote straight-chain or branched C 1 - to C 20 -alkyl radicals which are optionally mono- or polysubstituted to C 20 -alkoxy-substituted or interrupted by one or more oxygen atoms in the chain; C 8 - to C 20 -aryl, optionally mono- or polysubstituted to C 20 -alkoxy-substituted or interrupted by or one or more oxygen atoms in the alkyl chain, C 7 - to C 20 -arylalkyl, optionally mono- or polysubstituted to C 20 -alkoxy substituted or interrupted by or one or more oxygen atoms in the alkyl chain C7 to C20 alkylaryl, optionally mono- or polysubstituted to C20 alkoxy-substituted C7 to C2o-cycloalkyl and R2, R3 and R4 are each independently hydrogen mean, on chromium and nickel-free catalysts.

3-alkoxypropanols are sought solvents and also versatile as building blocks for active ingredients.

For the preparation of 3-alkoxypropanols, various processes, which are generally based on a C3 building block, are known.

JP-A-2001247503 discloses the ZrO ₂ -catalyzed addition of alcohols to allyl alcohol, which, however, proceeds with only unsatisfactory conversion and unsatisfactory selectivity. The etherification of the corresponding diols described in J PA-2004196783 requires either stoichiometric amounts of base or conversion and selectivity to the monoether are not satisfactory.

Acrolein is also known in the presence of a catalyst first to alkoxylie- Ren, wherein 3-alkoxypropionadehyde is formed, and then to hydrogenate the aldehyde in the presence of hydrogenation catalysts to 3-alkoxypropanol. For this hydrogenation, nickel catalysts are recommended to be particularly effective and inexpensive, for example in EP-A 1 085 003. These processes have the disadvantage that the catalytically active element, in particular when using Raney nickel catalysts, in small amounts in the form of soluble compounds contaminates the product stream and thus additional workup steps are required. There are additional concerns about the use of nickel catalysts and acrolein due to the toxicity of the substances. For production on an industrial scale special safety precautions are necessary.

Although the catalytic hydrogenation of optionally substituted 1,3-dioxane described in EP-A 810 194 does not require the use of nickel catalysts, it can not satisfy the achievable conversions and selectivities.

Furthermore, Mozingo and Folkers in J. Am. Chem. Soc. 1948, 70, 227-229 the hydrogenation of 3-Ethoxypropionsäureethylester in methanol on a Kupferchro- with catalyst at 290 - 438 bar to 3-ethoxypropanol and ethanol. Both the high investment costs requiring high reaction pressure, as well as the use of a known as toxic chromium catalyst are disadvantageous.

Based on this prior art, the present invention, the object of the invention to provide a method with the 3-Alkoxypropan1-ole without the use of toxicologically problematic substances technically easy to implement and generally applicable, that is also in large-scale multi-pupose systems feasible, with good turnover and good selectivity can be produced without the disadvantages mentioned above occur.

There has now been a process for the preparation of 3-alkoxypropane-1-oils of the general formula I.

by catalytic hydrogenation of esters of general formula II,

in which the radicals R 1 and R 2 and R 3, R 4 and R 5 independently of one another denote straight-chain or branched C 1 - to C 20 -alkyl radicals which are optionally mono- or polysubstituted to C 20 -alkoxy-substituted or interrupted by one or more oxygen atoms in the chain; C 8 - to C 20 -aryl, optionally mono- or polysubstituted to C 20 -alkoxy-substituted or interrupted by or one or more oxygen atoms in the alkyl chain, C 7 - to C 20 -arylalkyl, optionally mono- or polysubstituted to C 20 -alkoxy substituted or interrupted by or one or more oxygen atoms in the alkyl chain C7 to C20 alkylaryl, optionally mono- or polysubstituted to C20 alkoxy-substituted C7 to C2o-cycloalkyl and R2, R3 and R4 independently of one another additionally hydrogen mean, on chromium and nickel-free catalysts.

The inventive method allows the selective conversion of the corresponding, accessible by addition of alcohols to acrylic esters ester of the general formula II in 3-alkoxypropan-1-ols with good conversion. The procedure is suitable without special safety precautions also in large-scale plants, which are used for the production of changing products.

Catalysts for the hydrogenation according to the invention may be homogeneous or heterogeneous metal-containing catalysts, the metal being present elementally or in the form of a compound; Chrome and nickel are not included.

The catalysts which can be used preferably contain at least one metal from the 7th, the 8th, the 9th, the 10th, the 11th or the 14th group of the Periodic Table of the Elements. The catalysts which can be used according to the invention more preferably contain at least one element selected from the group consisting of Re, Fe, Ru, Co, Rh, Ir, Pd, Pt, Cu and Au. In particular, the catalysts which can be used according to the invention particularly preferably contain at least one element selected from the group consisting of Pd, Pt, Ru and Cu. The catalysts which can be used according to the invention particularly preferably comprise Cu as the hydrogenation-active component. Particularly preferred catalysts containing Cu as the hydrogenation-active component can be prepared according to the disclosure of US Pat. No. 5,403,962 or WO 2004/85356, which is expressly incorporated herein by reference.

Particular preference is therefore given to using the shaped catalyst bodies which are known from WO 2004/85356 and can be prepared by a process in which

(i) an oxidic material comprising copper oxide, alumina and at least one of the oxides of lanthanum, tungsten, molybdenum, titanium or zirconium is provided;

(ii) powdered metallic copper, copper flakes, powdered cement or graphite or a mixture thereof may be added to the oxidic material, and

(iii) the mixture resulting from (ii) is shaped into a shaped article.

Of the oxides of lanthanum, tungsten, molybdenum, titanium or zirconium, lanthanum oxide is preferred.

Particular preference is given to catalysts according to the disclosure of WO 2004/85356, which is expressly to be included here, in which the oxidic material

(a) copper oxide in a proportion in the range of 50 <x <80, preferably 55 <x <75 wt .-%,

(b) alumina in a proportion in the range of 15 <y <35, preferably 20 <y <30 wt .-% and

(c) at least one of the oxides of lanthanum, tungsten, molybdenum, titanium or zirconium in an amount in the range of 2 <z <20, preferably 3 <z <15 wt%,

in each case based on the total weight of the oxidic material after calcination, where: 80 <x + y + z <100, in particular 95 <x + y + z <100.

Also suitable are homogeneous catalysts comprising at least one element of the 8th, 9th or 10th group, with the exception of nickel. More preferred are homogeneous catalysts containing Ru, Rh, and / or Ir. If compounds of the abovementioned elements are used, salts such as, for example, halides, oxides, nitrates, sulfates, carbonates, alkoxides and aryloxides, carboxylates, acetylacetonates or acetates of the particular metal are suitable. Furthermore, these salts may be modified with complexing ligands. The catalysts used according to the invention preferably contain one or more oxygen, sulfur, nitrogen or phosphorus-containing complexing ligands. The catalyst is preferably selected from halides, oxides, nitrates, sulfates, carbonates, alkoxides, aryloxides, carboxylates, acetylacetonates and acetates of the respective metal and the compounds of the metal containing CO, CS, an optionally organyl-substituted amino ligand, an optionally organyl-substituted phosphine. ligand, an alkyl, allyl, cyclopentadienyl and / or olefin ligand.

For example, here are about RhCI (TPP) 3 θder Ru ₄ H ₄ (CO) -I ₂ call. Particularly preferred are those homogeneous catalysts containing Ru. For example, homogeneous catalysts are used, as described in US 5,180,870,

Chem. 38 (1973) pp. 80-87, the disclosure of which is incorporated herein by reference in the context of the present application in its entirety. US Pat. Nos. 5,321,176, 5,177,278, 3,804,914, 5,210,349, 5,128,296 and DR Fahey , Such catalysts are about (TPP) ₂ (CO) ₃ Ru, [Ru (CO) ₄ J ₃ , (TPP) ₂ Ru (CO) ₂ Cl ₂ , (TPP) ₃ (CO) RuH ₂ , (TPP) ₂ ( CO) ₂ RuH ₂ , (TPP) ₂ (CO) ₂ RUCIH or (TPP) ₃ (CO) RuCl ₂ .

In particular, at least one heterogeneous catalyst is suitable, wherein at least one of the abovementioned metals can be used as such, as a Raney catalyst and / or applied to a conventional support. Preferred support materials are, for example, activated carbons or oxides such as, for example, aluminum oxides, silicon oxides, titanium oxides or zirconium oxides. Also to be mentioned among other things as support materials bentonites. If two or more metals are used, they may be present separately or as an alloy. In this case, it is possible to use at least one metal as such and at least one other metal as Raney catalyst or at least one metal as such and at least one other metal applied to at least one support, or at least one metal as Raney catalyst and at least one another metal applied to at least one support, or at least one metal as such and at least one metal other than Raney catalyst and at least one other metal applied to at least one support.

The catalysts used may, for example, also be so-called precipitation catalysts. Such catalysts can be prepared by reacting their catalytically active components from their salt solutions, in particular from the solutions of their nitrates and / or acetates, for example by adding solutions of alkali metal and / or alkaline earth metal hydroxide and / or carbonate. Solutions, for example, sparingly soluble hydroxides, oxide hydrates, basic salts or carbonates. precipitates, and then calcined by calcination at generally 300 to 700 ⁰ C, in particular 400 to 600 ⁰ C in the corresponding oxides, mixed oxides and / or mixed-valent oxides, by treatment with hydrogen or with hydrogen containing gases in the range of generally 50 to 700 ° C, especially 100 to 400 ⁰ C to the respective metals and / or oxidic compounds lower oxidation state reduced and converted into the actual catalytically active form. This is usually reduced until no more water is formed. In the preparation of precipitation catalysts containing a support material, the precipitation of the catalytically active components can be carried out in the presence of the relevant support material. The catalytically active components can advantageously be precipitated simultaneously with the carrier material from the relevant salt solutions.

Hydrogenation catalysts which contain the metals or metal compounds catalyzing the hydrogenation on a carrier material are preferably used.

In addition to the precipitation catalysts mentioned above, which additionally contain a carrier material in addition to the catalytically active components, those carrier materials in which the catalytic hydrogenating component has been applied to a carrier material, for example by impregnation, are generally suitable for the process according to the invention ,

The manner of applying the catalytically active metal to the support is usually not critical and can be accomplished in various ways. The catalytically active metals can be supported on these support materials, for example by impregnation with solutions or suspensions of the salts or oxides of the relevant elements, drying and subsequent reduction of the metal compounds to the respective metals or compounds of lower oxidation state by means of a reducing agent, preferably with hydrogen or complex hydrides. be applied. Another possibility for applying the catalytically active metals to these carriers is to impregnate the carrier with solutions of thermally easily decomposable salts, for example with nitrates or thermally easily decomposable complex compounds, for example carbonyl or hydrido complexes of the catalytically active metals, and the like impregnated carrier for thermal decomposition of the adsorbed metal compounds to temperatures in the range of 300 to 600 ° C to heat. This thermal decomposition is preferably carried out under a protective gas atmosphere. Suitable shielding gases are, for example, nitrogen, carbon dioxide, hydrogen or the noble gases. Furthermore, the catalytically active metals can be deposited on the catalyst support by vapor deposition or by flame spraying. The content of these supported catalysts on the catalytically active metals is in principle not critical to the success of the process according to the invention. In space- In general, higher levels of catalytically active metals of these supported catalysts result in higher space-time conversions than lower levels.

In general, supported catalysts are used whose content of catalytically active metals in the range of 0.1 to 90 wt .-%, preferably in the range of 0.5 to 80 wt .-% based on the total weight of the catalyst. Since these content data refer to the entire catalyst including carrier material, but the different carrier materials have very different specific weights and specific surface areas, it is also conceivable that these data can be exceeded or exceeded, without adversely affecting the result of the process according to the invention. Of course, several of the catalytically active metals may be applied to the respective carrier material. Furthermore, the catalytically active metals can be applied to the support, for example, by the process of DE-OS 25 19 817 or EP 0 285 420 A1. In the catalysts according to the above-mentioned documents, the catalytically active metals are present as alloys which are obtained by thermal treatment and / or reduction of e.g. by impregnation of the carrier material with a salt or complex of the aforementioned metals.

Both the activation of the precipitation catalysts and of the supported catalysts can also be carried out in situ at the beginning of the reaction by the hydrogen present. Preferably, these catalysts are activated separately before use. As carrier materials, in general, the oxides of zinc, aluminum and titanium, zirconium dioxide, silicon dioxide, lanthanum oxide, clays such as montmorillonites, silicates such as magnesium or aluminum silicates, zeolites such as the structural types ZSM-5 or ZSM-10, or activated carbon be used. Preferred support materials are aluminas, titanium dioxides, silica, zirconia, lanthana and activated carbon. Of course, it is also possible to use mixtures of different carrier materials as carriers for catalysts which can be used in the process according to the invention. As admixtures for the targeted adjustment of the acidic, especially basic properties of the catalyst and alkali and / or alkaline earth-containing compounds, preferably as oxides, may be included. Possible catalysts are also those which contain zinc oxide or zirconium oxide as the active component.

In the process according to the invention, the heterogeneous catalyst can be used, for example, as a suspension catalyst and / or as a fixed bed catalyst.

If, for example, in the context of the process according to the invention the hydrogenation is carried out with at least one suspension catalyst, preference is given in at least one stirred reactor or in at least one bubble column or in at least one hydrogenated a packed bubble column or in a combination of two or more identical or different reactors.

The term "different reactors" in the present case denotes both different types of reactors and reactors of the same type, which differ, for example, by their geometry, such as, for example, their volume and / or their cross-section and / or by the hydrogenation conditions in the reactors.

If, for example, a heterogeneous catalyst is used as catalyst in the hydrogenation as suspension catalyst, it is preferably separated off in the context of the present invention by at least one filtration step. The thus separated catalyst can be recycled to the hydrogenation or fed to at least one of any other method. It is also possible to work up the catalyst in order, for example, to recover the metal contained in the catalyst.

In the context of the process according to the invention, the hydrogenation is particularly preferably carried out with at least one fixed catalyst. For this purpose, preferably at least one tubular reactor, such as at least one shaft reactor and / or at least one tube bundle reactor is used, it being possible to operate a single reactor in bottom or trickle mode. If two or more reactors are used, at least one can be operated in a sump mode and at least one in a trickle mode.

In one embodiment, the solution to be hydrogenated is pumped in a straight pass over the catalyst bed. In another embodiment of the method according to the invention, a portion of the product is withdrawn continuously after passing through the reactor as a product stream and optionally passed through a second reactor. The other part of the product (circulation amount) is fed together with fresh starting material (feed quantity) to the reactor again. Among other things, this liquid circuit is used for heat dissipation. This procedure is also referred to as circulation mode. In the process according to the invention, a weight ratio of feed to circulation amount of from 3: 1 to 1:40, more preferably from 2: 1 to 1:10, is preferably set.

Optionally, in addition to the liquid circulation amount and a portion of the gas phase of the discharge after phase separation recycled, that is mixed with the inlet and the fresh gas hydrogen at any point in front of the reactor inlet. This can be realized either after separation of the liquid phase of the discharge via a second separate pump or together with the liquid circuit via a pump. Particularly preferred is a recycling of the gas phase (circulating gas) for heat removal in the case of the particularly preferred small liquid circulating amounts of feed: circulating amount = 3: 1 to 1:10.

Before use in any process, for example before being returned to the process according to the invention, both the at least one homogeneous and the at least one heterogeneous catalyst can, if necessary, be regenerated by at least one suitable process.

Heterogeneous catalysts which are present in shaped articles in the form of tablets, rings, cylinders, spheres, trilobes or strands are preferred for the hydrogenation.

Heterogeneous catalysts are, if necessary, generally activated prior to their use, preferably with hydrogen. The methods for this are known to the person skilled in the art.

The catalytic hydrogenation according to the invention is at 10 to 400 bar, preferably at 120 to 280 bar and more preferably at 130 to 250 bar and at a temperature of 100 to 300 ⁰ C, preferably 120 to 200 ⁰ C and particularly preferably 130 to 190 ° C performed.

The ester II, which serves as starting material for the hydrogenation according to the invention, can be prepared by processes known per se. Thus, the ester II can be prepared, for example, by addition of alcohols of the formula R1-OH to acrylic esters of the formula III,

in which the radicals R 1 and R 2 and R 3, R 4 and R 5 are independently straight-chain or branched, optionally mono- or poly-C 1 -C 20 -alkoxy, substituted or interrupted by or one or more oxygen atoms in the chain d- to C 20 -alkyl radicals , Cβ- to C 2 O -aryl, optionally mono- or polysubstituted to C 2 -alkoxy-substituted or interrupted by or one or more oxygen atoms in the alkylene chain, C 7 - to C 2 -alkyl-arylalkyl, optionally mono- or polysubstituted Alkoxy-substituted or interrupted by or one or more oxygen atoms in the alkyl chain C7 to C30 alkylaryl, optionally mono- or polysubstituted to C20 alkoxy-substituted C7 to C2o-cycloalkyl and R2, R3 and R4 are each independently hydrogen can mean. The addition of the alcohol to the acrylic ester can be carried out in an inert solvent such as. B. tetrahydrofuran or ethylene glycol dimethyl ether can be performed. This is necessary in particular when the alcohol R1-OH or the acrylate III used is not liquid under the conditions of the additions.

In a preferred variant for the preparation of the reactants II for the hydrogenation according to the invention for the addition 0.001 to 10 mol%, based on the amount of acrylic ester, soluble in the reaction mixture of metal alkoxides, eg. As sodium methylate, used as a catalyst. In a particularly preferred embodiment, the anion of the metal alcoholate corresponds to the anion of the alcohol R1-OH to be added.

In a further preferred embodiment, the acrylic acid ester III and the alcohol R1-OH are chosen so that R5 and R1 represent the same radical. Thus, a reduction in the yield of Il by transesterification and consequent release of alcohol R5-OH can be avoided.

In a preferred variant of the invention, the ester II but not with known per se methods for the purification of substances such. B. distillation, but the reaction mixture from the addition after separation or neutralization of the addition catalyst without further purification of the ester II used directly in the hydrogenation.

If homogeneous basic or acidic catalysts were used to prepare the ester II, they are preferably neutralized and / or neutralized with an organic or inorganic acid such as, for example, formic acid, acetic acid or another mono- or dicarboxylic acid or an organic or inorganic base optionally filtered off. Furthermore, the catalyst used for the addition can also be removed by means of a suitable ion exchanger, in particular a commercially available anion or cation exchange resin.

If a heterogeneous catalyst was used, the reaction mixture must be filtered before use as starting material in the hydrogenation according to the invention.

In addition to the alkoxypropan-1-ol I, in the hydrogenation process according to the invention, especially n-propanol is formed as a by-product by hydrogenation of acrylic ester formed by cleavage, which can easily be separated off by distillation and either reused or otherwise recycled.

The invention is explained in more detail by the following examples, but not restricted. Examples

Example 1: Preparation of 6-ethyl-4-oxadecan-1-ol

At 60 ⁰ C 1670 g of 2-ethylhexanol were reacted with 640 mg of sodium. After a homogeneous solution had formed, 1160 g of 2-ethylhexyl acrylate were added within 6 hours. After a further 6 hours at 60 ⁰ C, the reaction mixture over a fresh with 2 N sulfuric acid regenerated and washed with methanol and then with 2-ethylhexanol acidic cation exchanger (Amberlite IR-120 from Merck, Darmstadt) was added. A 67% strength by weight solution of 2-ethylhexyl [6-ethyl-4-oxadecanoate] in 2-ethylhexanol was obtained (yield 96%). 80 g of copper catalyst of composition 57% CuO / 28.5% Al ₂ O ₃ / 9.5% La ₂ O ₃ /5% Cu in 3 x 3 mm tablets, prepared according to Example 1 of WO -A 2004/85356, were reduced in a hydrogen stream at 180 ⁰ C. Subsequently, at 180 ⁰ C, 200 bar, an inlet of 12 g / h of the above-prepared 2-ethylhexyl [6-ethyl-4-oxadecanoate] containing reaction mixture, return of the discharge to the reactor inlet in an amount of 80 g / h and hydrogenation of 40 NL / h hydrogenated. The effluent contained 99% conversion: 68% by weight of 2-ethylhexanol, 24% by weight of 6-ethyl-4-oxadecan-1-ol (yield 59%), 5% by weight of propanol, 1% by weight. % 2-ethylhexyl [6-ethyl-4-oxadecanoate] and in total 2% by weight of other compounds. Example 2: Preparation of 3-methoxypropan-1-ol

At 60 ⁰ C 1 160 g of methanol and 5 g of a 30% solution of sodium methylate in methanol were added within 6 hours with 1160 g of methyl acrylate and then further stirred at 60 ⁰ C for two hours. Gas chromatography showed a methyl acetate conversion of more than 99%, corresponding to a yield of 99%). It was neutralized with one equivalent of acetic acid based on the amount of sodium methylate at room temperature and the reaction solution was used directly as feed for the continuous hydrogenation.

80 g of copper catalyst of composition 57% CuO / 28.5% Al ₂ O ₃ / 9.5% La ₂ O ₃ /5% Cu in 3 x 3 mm tablets, prepared according to Example 1 of WO-A 2004/85356 were in a hydrogen stream at 180 ⁰ C reduced. The plant was then operated under the following conditions: temperature in the reactor 170 ^° C., pressure 200 bar, feed 16 g / h of the ester-containing reaction mixture prepared above, return of the discharge to the reactor inlet in an amount of 80 g / h and a hydrogen feed of 40 NL / h. The effluent contained at 99% conversion: 57 wt .-% methanol, 27 wt .-% of 3-methoxypropan-1-ol, corresponding to a yield of 51%, 14 wt .-% propanol, 1 wt .-% 3-Methoxypropionsäuremethylester and in total 1% by weight of other esters.

Claims

claims

1. A process for the preparation of 3-alkoxypropan-1-ols of the general formula I.

I by catalytic hydrogenation of esters of general formula II,

in which the radicals R1 and R2 and R3, R4 and R5 independently of one another straight-chain or branched, optionally mono- or polysubstituted to C2o-alkoxy-substituted or interrupted by or one or more oxygen atoms in the chain Cr to C2o-alkyl radicals , Cβ- to C 2o-aryl, optionally mono- or polysubstituted to C 20 -alkoxy-substituted or interrupted by or one or more oxygen atoms in the AI alkyl chain C7 to C 2o-arylalkyl, optionally one or more times d- to C 2o Alkoxy-substituted or interrupted by or one or more oxygen atoms in the alkyl chain C7 to C20 alkylaryl, optionally mono- or polysubstituted to C2o-alkoxy-substituted C7 to C20 cycloalkyl radicals and R2, R3 and R4 independently of one another Hydrogen on chromium and nickel-free catalysts.

2. The method according to claim 1, characterized in that a homogeneous catalyst is used, the containing a salt and / or one or more oxygen, sulfur, nitrogen or phosphorus-containing complexing ligand-containing compound of a metal of groups 8., 9th and 10th of the periodic table with the exception of nickel.

3. The method according to claim 1, characterized in that a heterogeneous catalyst is used, which contains at least one metal selected from the groups 7, 8, 9, 10 with the exception of nickel, 11 and 14 of the Periodic Table of the Elements.

4. The method according to claim 3, characterized in that a shaped body is used as the catalyst which can be produced according to a method in which (i) an oxidic material comprising copper oxide, alumina and at least one of the oxides of lanthanum, tungsten, molybdenum, titanium or zirconium,

(ii) adding powdered metallic copper, copper flakes, powdered cement, graphite or a mixture thereof to the oxidic material, and

(iii) the mixture resulting from (ii) is shaped into a shaped article.

5. The method according to claim 4, characterized in that the oxidic material

in each case based on the total weight of the oxidic material after calcination, where: 80 <x + y + z <100, in particular 95 <x + y + z <100, where cement is not attributed to the oxidic material in the above sense - sums up.

6. The method according to any one of claims 1 to 5, characterized in that is hydrogenated at a pressure of 100 to 400 bar and a temperature of 100 to 300 ⁰ C in the liquid phase.

7. The method according to any one of claims 1 to 6, characterized in that the process is operated in circulation mode with a ratio of circulation: feed from 1: 3 to 40: 1.

8. The method according to any one of claims 1 to 7, characterized in that the starting material used is a reaction mixture prepared by addition of alcohols of the formula R 1 -OH to acrylic acid esters of the formula III and containing the ester of the general formula II,

in which the radicals R 1 and R 2 and R 3, R 4 and R 5 independently of one another denote straight-chain or branched C 1 to C 2 o radicals which are optionally mono- or polysubstituted to C 20 -alkoxy, substituted or interrupted by or one or more oxygen atoms in the chain. Alkyl radicals, Cβ- to C 2o-aryl, optionally mono- or polysubstituted to C 20 -alkoxy-substituted or interrupted by one or more oxygen atoms in the alkylene chain C7 to C 2o-arylalkyl, optionally one or more times Ci -C 2o-alkoxy-substituted or by or one or more oxygen atoms in the AI alkyl chain interrupted C7 to C 20 alkylaryl, optionally mono- or polysubstituted to C 20 -alkoxy-substituted C 7 to C 20 cycloalkyl radicals and R 2, R 3 and R4 independently of one another may additionally denote hydrogen.

9. The method according to claim 8, characterized in that the addition of the alcohols R1-OH to acrylic acid ester of the formula III is carried out in the presence of catalytic amounts of a metal alcoholate.

10. The method according to any one of claims 8 or 9, characterized in that the metal alkoxide is chosen so that its anion corresponds to the anion of the alcohol to be added R1-OH.

1 1. A method according to any one of claims 8 to 10, characterized in that an acrylic acid ester of formula III and an alcohol of the formula R1-OH are used, in which the radicals R5 and R1 are the same.

12. The method according to any one of claims 8 to 1 1, characterized in that the reaction mixture containing the ester Il is not purified before use in the hydrogenation according to the invention according to claims 1 to 5.

13. The method according to any one of claims 8 to 12, characterized in that the reaction mixture containing the ester Il before use in the hydrogenation according to the invention according to claims 1 to 5 treated with a cation exchanger or neutralized with an organic or inorganic acid.