DE102013021509A1 - Process for the preparation of 3-hydroxyalkanals - Google Patents

Abstract

The present invention relates to the preparation of 3-hydroxyalkanals by reacting two aldehydes in the presence of binary metal nitrides. In a preferred embodiment of the process according to the invention, the reaction of an aldehyde with at least one hydrogen atom on the α-position carbon atom takes place relative to the carbonyl group with formaldehyde.

Description

The present invention relates to a process for the preparation of 3-hydroxyalkanals in the presence of metal nitrides.

Polyhydric alcohols or polyols have a significant economic importance as a condensation component for the construction of polyesters or polyurethanes, synthetic resin paints, lubricants and plasticizers. Important intermediates for the preparation of polyols are 3-hydroxyalkanals, which can be prepared by aldol addition of two aldehydes. In this case, especially those polyhydric alcohols of interest, which are obtained by a mixed aldol addition of formaldehyde with iso- or n-butyraldehyde. In the aldol addition between formaldehyde and the corresponding butyraldehyde, an aldehydic intermediate first forms which subsequently has to be reduced to the polyhydric alcohol. Technically significant polyhydric alcohols obtainable by this process are neopentyl glycol [NPG, 2,2-dimethylpropanediol- (1,3)] from the mixed aldolization of formaldehyde and isobutyraldehyde (US Pat. Chemiker-Zeitung, 100th Year (1976) No. 12, pages 504-514 ; Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, 2003, Wiley VCH Verlag GmbH & Co. KGaA, Weinheim, vol. 2, pp. 50-52 ) or trimethylolpropane (TMP, 2-hydroxymethyl-2-methylpropanediol- (1,3)] from the mixed aldolization of formaldehyde and n-butyraldehyde ( Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition, 2003, Wiley VCH Verlag GmbH & Co. KGaA, Weinheim, Volume 2, pages 58-59 ).

As is known, in the aldol addition one aldehyde reacts as carbonyl component and the other aldehyde as methylene component to form a carbon-carbon bond. In order for the carbon-carbon bond to form, at least one aldehyde must carry at least one hydrogen atom in the α-position to the carbonyl group. This aldehyde then reacts as a methylene component. The aldol addition is catalyzed by both basic and acidic compounds.

In base catalysis, an anion | C (R) ₂ -C (H) = O first forms from the aldehyde having the α-position hydrogen atom, ie from the methylene component, according to reaction step (1), which is subsequently reacted with the carbonyl component R ' C (H) = O reacted to the addition product with liberation of the basic catalyst

The aldol addition is an equilibrium reaction and the location of the equilibrium depends on the base strengths of the reactants. In order for the formation of the 3-hydroxyalkanal to occur in step (2), the base strength of the alcoholate anion R'-C (H) (O ^- ) -C (R) ₂ -C (H) = O formed in the meantime must be greater than the base strength of the catalyst B | ^- .

Uniform aldol addition products are formed in the reaction of two structurally different aldehydes when one aldehyde component carries only one α-hydrogen atom and the other aldehyde component does not carry an α-hydrogen atom. In this combination of starting compounds it is clearly established which aldehyde reacts as the carbonyl component and which aldehyde as the methylene component. An economically significant process for this combination of the starting aldehydes is the reaction of formaldehyde with iso-butyraldehyde to hydroxypivalaldehyde (2,2-dimethyl-3-hydroxypropanal). If n-butyraldehyde is reacted with two α-hydrogen atoms to the carbonyl group with formaldehyde, usually formaldehyde in molar excess per α-hydrogen is used to urge the reaction in the direction of 2,2-dimethylolbutanal and the self-addition of n-butyraldehyde in to push the background.

It is known to carry out the aldol addition of two aldehydes in the presence of alkali metal or alkaline earth metal hydroxides as basic catalysts ( DE 15 18 784 A1 . US 2 400 724 ). An aqueous catalyst solution is usually used, bringing the organic phase into intimate contact with the aqueous catalyst phase. After the reaction has ended, the organic phase and the aqueous catalyst phase are separated from one another and the organic phase is processed further. A disadvantage of this method, however, is the high salt content and contamination of the resulting Aldoladditionsproduktes with alkali or Alkaline earth metal ions which interfere with the subsequent catalytic hydrogenation of the aldol addition product to the polyol for the metal catalyst (US Pat. DE 17 68 274 A1 . DE 19 57 591 A1 ).

In the meantime, the use of tertiary amines as a catalyst for the aldol addition reaction has become established in the art ( DE 19 57 591 A1 . US 4,855,515 . EP 0 522 368 A1 ). As tertiary amines are often used lower trialkylamines such as trimethylamine or triethylamine ( WO 2010/079187 A1 . EP 1 752 439 A1 ) or tri-n-propylamine ( DE 36 44 675 A1 ). In contrast to the use of aqueous alkaline solutions, the amine-catalyzed aldol addition reaction takes place in a homogeneous organic medium. Accordingly, a high distillation effort to operate for the separation and recycling of the amine catalyst. Also, in the subsequent hydrogenation to polyols, the tertiary alkylamines tend to form nitrogen-containing decomposition products, the presence of which, even in slight traces, massively affects the quality of the polyol for many subsequent applications. When working up the polyol, it is therefore necessary to ensure almost complete removal of nitrogen-containing contaminants.

In order to facilitate the separation of the basic catalyst from the organic reaction product, the use of solid, basic catalysts is also recommended. As such catalysts, for example, macroporous ion exchange resins are used which carry basic tertiary amino groups ( DE 19 57 591 A1 ). Both weakly and strongly basic ion exchange resins are described, which are preferably based on a styrene-divinylbenzene polymer matrix having tertiary amino groups as functional groups ( EP 0 948 476 B1 . US 2818443 ). Preferably, weakly basic ion exchange resins ( WO 98/29374 A1 ). However, ion exchange resins are not always convincing in terms of aldehyde conversion and their use is generally limited by their low stability.

The use of inorganic, basic solids is also described. According to WO 92/19579 A1 is used as a catalyst, a mixture of tertiary amines and metal oxides of the elements IB, IVA, IVB, VA, VB, VIB and VIII of the Periodic Table of the Elements, in particular titanium and chromium. Although the organic reaction product is easily filtered off from the oxidic solid, laborious work-up is required to sufficiently separate the nitrogen-containing compounds. To WO 00/00456 A1 Basic modified phyllosilicates can be used which show advantageous conversions and selectivities. However, quite long reaction times are needed. EP 1 205 463 A1 deals with the catalytic production of aldols in a microstructured reaction system, wherein a heterogeneous catalyst is incorporated into the microstructured system. As the heterogeneous catalyst, basic ion exchange resins, basic zeolites or metal oxides of Mo, W, Ca, Mg or Al can be used.

Due to the great importance of 3-hydroxyalkanals as intermediates for the preparation of polyols, there is a constant search for further improvements in alternative processes and alternative catalysts for the preparation of 3-hydroxyalkanals. The aldol addition should lead to the desired 3-hydroxyalkanal at high aldehyde conversion with high selectivity. Likewise, the aldolization catalyst used in the reaction medium should have a high stability in order to ensure a sufficiently long catalyst life.

The present invention therefore consists in a process for the preparation of 3-hydroxyalkanals by reacting an aldehyde of the general formula (I) R ¹ R ² HCC = (O) H with a further aldehyde of the general formula (II) R ³ -C = ( O) H to an addition product of general formula (III) [R ³ -C (OH) H] _x -C [R ¹ ] _a [R ² ] _b -C = (O) H in which R ¹ , R ² and R ^{3 are} each independently hydrogen or an aliphatic hydrocarbon group of 1 to 8 carbon atoms, x is an integer of 1 to 3, a is 0 or 1 and b is 0 or 1 and x + a + b is 3, thereby in that the reaction takes place in the presence of binary metal nitrides of the formula A ^{(m +)} _oN ^(3-) _p , in which o can assume the integer values 1 to 3, p independently of this can assume the integer values 1 to 4, m is an integer of 1 to 4, and the condition (m +) · o is satisfied equal to (3-) · p.

Out J. Mol. Catal. A: Chem., 2006, 247, pages 116-123 For example, the reaction of cyclopentanone with valeraldehyde on AlPON and ZrPON catalysts for the aldol condensation product is known, but it has surprisingly been found that binary metal nitrides are likewise suitable as solid catalysts in the aldol addition of two aldehydes. When solid metal nitrides are used, the aldolization catalyst can advantageously be separated off from the reaction mixture by filtration after completion of the reaction in a simple manner. Also, in the reaction of solid catalysts, the residence time of the reactants can be set very selectively on the catalyst surface over a process procedure in which the Aldolisierungskatalysator is dissolved homogeneously in the reaction mixture or dissolved in a separate aqueous phase, which is thoroughly mixed with the organic Eduktphase.

The metal nitrides used according to the invention are binary metal nitrides of the general formula A ^{(m +)} _o N ^(3-) _p , in which o the integer values from 1 to 3 and independently of these p can assume the integer values from 1 to 4, m is an integer of 1 to 4, and the condition (m +) · o is satisfied equal to (3-) · p.

Suitable metal nitrides are, for example, AlN, TiN, ZrN, HfN, VN, NbN, TaN, Si ₃ N ₄ , FeN, Fe ₂ N ₂ and CrN, either as individual substance or as mixtures. Mixtures of metal nitrides with other solids, such as carbides, transition metal oxides, silica, alumina, boron oxide or activated carbon can also be used in the process according to the invention.

The preparation of the binary metal nitrides used in the invention is carried out according to known methods, for example by nitriding of metal oxides under nitrogen or ammonia with the simultaneous presence of carbon or by reaction of metal chlorides or organometallic compounds with nitrogen / hydrogen mixtures or with ammonia ( Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, 2003, Wiley VCH Verlag GmbH & Co. KGaA, Weinheim, vol. 23, pp. 51-64 ). Suitable metal nitrides for the process according to the invention are both ionic nitrides, such as AlN, covalent nitrides, such as Si ₃ N ₄ , or transition metal nitrides of the formula AN, which are to be regarded as inclining compounds, for example TiN, TaN, FeN or CrN. AlN, TiN, TaN, Si ₃ N ₄ , FeN or CrN are particularly suitable for the process according to the invention.

The solid aldolization catalyst is used in an amount of 1 to 10 wt .-%, preferably 3 to 8 wt .-%, based on the total reaction mixture.

The practical implementation of the aldol addition is carried out in suspension in a stirred tank or in a stirred tank cascade, wherein a sufficient distribution of the solid in the reaction solution is ensured by intensive stirring. Likewise, the aldol addition can be carried out in a tubular reactor on a fixed catalyst bed, for example, in a microstructured reaction system in which the reaction chamber is lined with the solid catalyst. The procedure with fixed catalysts allows in a simple way to return from the discharged reaction mixture a partial flow as a circulation stream in the reactor. Otherwise, when using catalysts suspended in the reaction mixture, the catalyst is filtered off after the reaction has ended. The aldol addition can be carried out both continuously and batchwise.

The aldol addition is carried out at temperatures in the range of 0 to 200, preferably 40 to 170 ° C under autogenous pressure or under application of a foreign gas pressure, preferably an inert gas pressure such as nitrogen pressure or noble gas pressure to 5 MPa, preferably to 3 MPa.

In the aldehydes of the general formula (I) R ¹ R ² HCC = (O) H, R ¹ and R ^{2 are} each independently hydrogen or an aliphatic hydrocarbon radical of 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Particularly preferably, R ¹ and R ^{2 are} each hydrogen, methyl, ethyl, n-propyl and iso-propyl.

Particularly suitable acetaldehyde with R ¹ is R ² is hydrogen, propionaldehyde with R ¹ is methyl and R ² is hydrogen, n-butyraldehyde with R ¹ is ethyl and R ² is hydrogen, iso-butyraldehyde with R ¹ is R ² is methyl , n-pentanal with R ¹ is n-propyl and R ² is hydrogen, 2-methylbutanal with R ¹ is ethyl and R ² is methyl and 3-methylbutanal with R ¹ is iso-propyl and R ² is hydrogen.

In the aldehydes of general formula (II) R ³ -C = (O) H, R ^{3 is} hydrogen or an aliphatic hydrocarbon radical of 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. R ³ particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and 2-butyl.

Particularly preferably, R ^{3 is} hydrogen, so that the reaction of the aldehyde of the general formula (I) is carried out with formaldehyde. In particular, the reaction with acetaldehyde gives 1,1,1-trimethylolethanal, 2,2-dimethylolpropanal with propionaldehyde, 2,2-dimethylbutanal with n-butyraldehyde and 2,2-dimethyl-3-hydroxypropanal with isobutyraldehyde. Formaldehyde can be used in solid form, as paraformaldehyde, or in solution. It is expedient to use commercial aqueous formaldehyde solutions having a concentration of from 30 to 50% by weight. When using an aqueous formaldehyde solution is obtained a two-phase mixture which additionally contains the solid aldolization catalyst. After the reaction, the organic phase containing the 3-hydroxyalkanal is separated from the water and the metal nitride.

If the aldehydes of the general formula (I) and (II) are structurally identical aldehydes, the self-condensation product is formed in the aldol addition. For example, in the self-addition of n-butyraldehyde, 2-ethyl-3-hydroxyhexanal is formed, and in the self-addition of isobutyraldehyde, 2,4-dimethyl-3-hydroxypentanal is formed.

If the carbonyl carbon atom α-carbon atom still carries one hydrogen atom, the 3-hydroxyalkanal can be converted into an α, β-unsaturated alkenal with elimination of water. These α, β-unsaturated alkenals can be converted either by complete hydrogenation in the corresponding alcohols or by selective hydrogenation in the saturated aldehydes from which, for example, by subsequent oxidation carboxylic acids are accessible. Both the complete hydrogenation to alcohols and the selective hydrogenation with subsequent oxidation are known from the prior art ( Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition, 2003, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Volume 2, pages 24-25; Volume 6, pages 497-502 ). This further reaction of the aldol addition product to the aldol condensation product occurs when in the aldehyde of the general formula (I) R ¹ and / or R ² are hydrogen. Economically significant is the self-addition with subsequent condensation of n-butyraldehyde, in which both the aldehyde of the general formula (I) and the aldehyde of the general formula (II) mean n-butyraldehyde. It initially forms 2-ethyl-3-hydroxyhexanal, which passes with elimination of water in 2-ethylhexenal. If the aldehyde of the general formula (I) is identical to the general formula (II) is n-pentanal, initially 2-propyl-3-hydroxyheptanal is formed, which is converted into 2-propylheptenal with elimination of water.

The obtained 3-hydroxyalkanals are important intermediates for the preparation of polyols, for example of 1,3-diols. The hydrogenation of 3-hydroxyalkanals, for example of 2,2-dimethyl-3-hydroxypropanal to neopentyl glycol, is known per se and is technically implemented in the form of gas phase or liquid phase hydrogenation on the metal contact.

In the gas-phase variant, the 3-hydroxyalkanal, for example 2,2-dimethyl-3-hydroxypropanal, is first freed from high boilers in an evaporator upstream of the hydrogenation stage. The subsequent hydrogenation is preferably carried out in the presence of Raney nickel catalysts or supported catalysts based on nickel, which may additionally contain other active metals such as copper or chromium and moreover activators. For example, in the gas phase variant EP 0 278 106 A1 ; US 4,094,014 ; Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, 2003, Wiley VCH Verlag GmbH & Co. KGaA, Weinheim, vol. 2, pp. 50-52 ; Chemiker-Zeitung, 100th Year (1976), No. 12, pages 504-514 received.

The hydrogenation in the liquid phase is often described, for example in the EP 0 484 800 A2 using catalysts based on copper, zinc and zirconium. Frequently, the liquid phase hydrogenation of 2,2-dimethyl-3-hydroxypropanal in the presence of Kupferchromit catalysts. Copper chromite catalysts often contain other metals as activators, for example barium, cadmium, magnesium, manganese and / or a rare earth metal. According to US 4,855,515 In particular, manganese-doped copper chromite catalysts are distinguished in the hydrogenation of the aldolization product from the reaction of formaldehyde with isobutyraldehyde. WO 98/29374 A1 discloses the use of a barium-doped copper chromite catalyst for the hydrogenation of 2,2-dimethyl-3-hydroxypropanal in a methanolic solution. Also EP 0 522 368 A1 recommends the use of copper chromite catalysts in liquid phase hydrogenation in the presence of a lower alcohol and water.

Other copper-containing hydrogenation catalysts are, for example, in WO 95/32171 or WO 98/29374 described.

3-Hydroxyalkanals can also be reduced in the presence of stoichiometric amounts of a base and formaldehyde following the Cannizzaro reaction to the polyols. This variant of the method is known per se and is technically operated ( WO 01/51438 A1 . EP 2 341 041 A1 . US 5,948,943 ). Appropriately used as the base are aqueous solutions of alkali metal or alkaline earth metal hydroxides, for example aqueous solutions of sodium hydroxide, potassium hydroxide or calcium hydroxide. Due to the reduction of the aldehyde function, formaldehyde is oxidized to formic acid and the corresponding formates, such as sodium formate, potassium formate or calcium formate, are obtained as by-products.

Examples:

The investigation of the catalytic activity of various metal nitrides in the aldol addition of isobutyraldehyde with formaldehyde was carried out in a 50 ml digestion autoclave. To this was added 9 ml of an aqueous formaldehyde solution (37% strength by weight) and 12 ml of isobutyraldehyde, corresponding to a 10 mol% excess of isobutyraldehyde, based on formaldehyde, with 5% by weight of metal nitride to the reaction mixture, corresponding to 0.96 grams, added. The reaction was carried out under an argon atmosphere at 150 ° C and the pressure to be set under intensive stirring over a period of 1.5 hours.

Subsequently, the batch was cooled to room temperature, relaxed and removed. The results of the gas chromatographic examination (% by weight) of the reaction mixture are summarized in Table 1 below. Table 1: Gas chromatographic analysis of the aldol addition product of isobutyraldehyde with formaldehyde in the presence of metal nitride catalysts attempt metal nitride Conversion of isobutyraldehyde [%] Selectivity to 2,2-dimethyl-3-hydroxypropanal [%] Yield to 2,2-dimethyl-3-hydroxypropanal [%] 1 AlN 81.8 53.9 44.1 2 TLN 42.5 50.4 21.4 3 * TiN / TiC 52.7 45.4 23.9 4 TaN 13.1 60.6 8.0 5 ** Si ₃ N ₄ (M9) 22.9 65.8 15.1 6 *** Si ₃ N ₄ (M11) 35.8 57.9 20.7 * TiC / TiN in the mass ratio of 1: 1
** M9: 95.70 weight% α-Si ₃ N ₄ , C 1779 ppm, O 1.12%, Al 375 ppm, Ca 38 ppm, Fe 30 ppm; Remainder to 100% by weight of further X-ray amorphous Si / N compounds
M11: 90.8% by weight of α-Si ₃ N ₄ , C 0.2%, O 1.5%, Al 0.01%, Fe 0.002%; Remainder to 100% by weight of further X-ray amorphous Si / N compounds

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 1518784 A1 [0007]
• US 2400724 [0007]
• DE 1768274 A1 [0007]
• DE 1957591 A1 [0007, 0008, 0009]
• US 4855515 [0008, 0028]
• EP 0522368 A1 [0008, 0028]
• WO 2010/079187 A1 [0008]
• EP 1752439 A1 [0008]
• DE 3644675 A1 [0008]
• EP 0948476 B1 [0009]
• US Pat. No. 2,818,444 [0009]
• WO 98/29374 A1 [0009, 0028]
• WO 92/19579 A1 [0010]
• WO 00/00456 A1 [0010]
• EP 1205463 A1 [0010]
• EP 0278106 A1 [0027]
• US 4094014 [0027]
• EP 0484800 A2 [0028]
• WO 95/32171 [0029]
• WO 98/29374 [0029]
• WO 01/51438 A1 [0030]
• EP 2341041 A1 [0030]
• US 5948943 [0030]

Cited non-patent literature

• Chemiker-Zeitung, 100th Year (1976) No. 12, pages 504-514 [0002]
• Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, 2003, Wiley VCH Verlag GmbH & Co. KGaA, Weinheim, vol. 2, pp. 50-52 [0002]
• Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition, 2003, Wiley VCH Verlag GmbH & Co. KGaA, Weinheim, Volume 2, pages 58-59 [0002]
• J. Mol. Catal. A: Chem., 2006, 247, pages 116-123 [0013]
• Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, 2003, Wiley VCH Verlag GmbH & Co. KGaA, Weinheim, vol. 23, pp. 51-64 [0016]
• Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition, 2003, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Volume 2, pages 24-25; Volume 6, pages 497-502 [0025]
• Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, 2003, Wiley VCH Verlag GmbH & Co. KGaA, Weinheim, Volume 2, pages 50-52 [0027]
• Chemiker-Zeitung, 100th Year (1976), No. 12, pages 504-514 [0027]

Claims (11)

A process for the preparation of 3-hydroxyalkanals by reacting an aldehyde of the general formula (I) R ¹ R ² HCC = (O) H with a further aldehyde of the general formula (II) R ³ -C = (O) H to an addition product of general formula (III) [R ³ -C (OH) H] _x -C [R ¹ ] _a [R ² ] _b -C = (O) H, in which R ¹ , R ² and R ^{3 are} each independently hydrogen or an aliphatic hydrocarbon radical of 1 to 8 carbon atoms, x is an integer from 1 to 3, a is 0 or 1 and b is 0 or 1 and x + a + b is 3, characterized in that the reaction in the presence of binary metal nitrides of the formula A ^{(m +)} _oN ^(3-) p, in which o can assume the integer values 1 to 3, p independently of the integer values can assume 1 to 4, m an integer of 1 to 4 means and the condition (m +) · o is equal to (3-) · p satisfied. A method according to claim 1, characterized in that A is aluminum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, iron or silicon. A method according to claim 1 or 2, characterized in that the binary metal nitrides are selected from the group of AlN, TiN, TaN, Si ₃ N ₄ , CrN, FeN. Process according to one or more of Claims 1 to 3, characterized in that the aldehyde of the general formula (I) is acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-pentanal, 2-methylbutanal or 3-methylbutanal. Method according to one or more of claims 1 to 4, characterized in that in the general formula (II) R ^{3 is} hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl or 2-butyl stands. Method according to one or more of claims 1 to 5, characterized in that the reaction at a temperature of 0 to 200 ° C, preferably from 40 to 170 ° C, is performed. Method according to one or more of claims 1 to 6, characterized in that the reaction under autogenous pressure or under application of a foreign gas pressure to 5 MPa, preferably to 3 MPa is performed. Method according to one or more of claims 1 to 7, characterized in that the reaction takes place in the presence of suspended or fixed binary metal nitrides. Method according to one or more of claims 1 to 8, characterized in that the reaction takes place in a tubular reactor. Process according to one or more of Claims 1 to 9, characterized in that the aldehyde of the general formula (I) is acetaldehyde, propionaldehyde, n-butyraldehyde or isobutyraldehyde and the aldehyde of the general formula (II) is formaldehyde. Method according to one or more of claims 1 to 9, characterized in that the reaction is continued for aldehydes of the general formula (I) with R ¹ and / or R ² is hydrogen, with elimination of water to Aldolkondensationsprodukt.