WO2009100854A2

WO2009100854A2 - Method for producing acetals

Info

Publication number: WO2009100854A2
Application number: PCT/EP2009/000822
Authority: WO
Inventors: Matthias Beller; Udo Kragl; Eckhard Paetzold; Lorenz Neubert; Patrick Kollmorgen
Original assignee: Cognis Ip Management Gmbh
Priority date: 2008-02-14
Filing date: 2009-02-06
Publication date: 2009-08-20
Also published as: DE102008009103A1

Abstract

The invention relates to a method for producing acetals from polyols by the succession of two reactions in a one-pot process, namely firstly hydroformylation of olefins with transition metal phosphine complex catalysts in multiphase systems, the catalytic C-C linking reaction being carried out in the multiphase mixture in the presence of phosphines and diphosphines with sub-group elements such as cobalt or rhodium at temperatures between 0 and 200°C, and the molar transition metal/phosphine rations for the complex catalysts being between 1 : 0.5 and 1 : 100, and secondly acetals are produced in the one-pot process by the secondary reaction of the synthesized aldehydes with polyols under acidic conditions, an extension of the carbon chain of the olefin by more than one C atoms as the polyol leading to an increase of the gross calorific value of the products and to a reduction of the evaporation temperature with respect to the polyol. The invention also relates to the use of the acetals as fuels or fuel additives, as solvents or as detergents. The use of olefins > C3 during hydroformylation allows results to be obtained especially for the acetalizing of glycerol that meet industrial requirements.

Description

Process for the preparation of acetals

The invention relates to a process for the preparation of acetals and their use as fuels or as fuel additives, as solvents or as detergents.

Approximately 9 million t of hydroformylation products are produced worldwide annually using cobalt or rhodium compounds as catalysts. Through the formation of different transition states, different complex ligands strongly influence the activity and selectivity of the products. The phosphines and phosphites are used to control activity and selectivity in the complex catalysts to form aldehydes. Predominantly, the aldehydes are used for the synthesis of plasticizers of PVC products.

Polylols are characterized by multiple hydroxy groups. Glycol, glycerol, erythritol, 1,2- and 1,3-propanediol are to serve as examples of polyols (no sugars). The currently most important polyol glycerine is obtained from the saponification of natural fats and oils and in biodiesel production to a greatly increasing extent. There is an urgent need to identify variants for the sustained cost-effective application of the expected overproduction of glycerol (Plagliaro, M. et al., Angew Chem., 2007, 119, 4516-4522).

There are two principal ways to convert glycerol catalytically: First, the decomposition in synthesis gas and second, the conversion of one or more hydroxy groups to new functional groups. The conversion of the hydroxy groups can be carried out biologically or chemically. Since glycerol is a multi-million-tonne resource, one goal of the material transformation is to be the bulk product of making low-cost consumer goods. The glycerol conversion situation is described by M. Pagliaro et al. Angew. Chem., 2007, 119, 4516 - 4522 illuminated.

Glycerol, CH ₂ OH-CHOH-CH ₂ OH, characterized by its extremely high hydrophilicity, can not be significantly higher in its previous applications. Glycerol itself can not be used as fuel for engines (high temperature polymerization, high boiling point, lower)

Calorific value, etc.). However, there is a constant need for high-quality fuels for petrol and diesel engines. The conversion of glycerol to high-energy products with significantly lower boiling points compared to glycerol is a necessary prerequisite.

Analogous to methyl t-butyl ether, an additive for improving the knock resistance of carburetor fuels, the variant glycerol is to implement with olefins or olefin mixtures. One possibility of this type is the reaction with isobutene and the formation of monomeric and higher glycerol t-butyl ethers. The use of other polyols or

Olefins / olefin mixtures is also known. (Behr, A., et al., Chem. Ing. Techn., 2007, 79,

621-3636, K. Klepacova et al., Appl. Catal., A: General., 2005, 294, 141-147, R.S. Karinen et al., Appl. Catal., A: General., 2006, 306, 128-133, J. Kijenski et al., Pol.

Przemysl Chem., 2006, 85, 594-597, R. Westendorf et al., EP 501 411 A1).

The reactions between polyols with aldehydes to acetals are known. In acidic medium, short-chain aldehydes can react with polyols to form acetals with exclusion of moisture at room temperature. This type of reaction is particularly simple if the water formed is discharged by means of a so-called tractor.

Hydroformylation is the most important industrially used homogeneous catalytic synthesis for the preparation of aldehydes (about 9 - 10 milliliters t / a predominantly for PVC plasticizers). The most commonly used alkene is propene and only the 1-butanal can be used for plasticizer main application. The isobutanal also obtained in the hydroformylation is a difficult-to-sell by-product. Longer chain aldehydes are more costly and have limited availability. Isobutanal reacts with glycol, 1,2-propanediol, 1,3-propanediol, glycerol, erythritol to form acetals to synthesize 5-, 6- and 7-ring acetals, preferably 5- and 6-membered rings (Scheme 1). The C chain of the glycerol product after the reaction to the monoacetal is in the simplest case seven C atoms long. In addition, product formation is possible even with complete conversion of all three hydroxy groups to acetals when working with an excess of aldehyde, forming the products from two glycerol molecules and three aldehydes.

glycol

erythritol

monoacetals

+

Biacetale

glycerin

Scheme 1

The disadvantage of the known processes is that a promising reaction of polyols with alkenes leads only to ethers under medium pressures or the alkanals as starting materials to products, which is exactly extended by the C chain length of the respective educts.

It was therefore the object of the invention to design an economical conversion of the material by means of an effective reaction procedure such that the use of

Transition metal complex catalysts an extension by one carbon atom of the olefins while increasing their reactivity occurs and then synthesized aldehydes then allow a reaction with polyols to acetals. In a one-pot process, aldehydes are synthesized by means of an upstream hydroformylation with transition-metal complex catalysts, which are acetalized in a subsequent reaction with polyols under acidic conditions.

A first subject of the present application relates to a process for the preparation of acetals from polyols, wherein hydroformylated olefins in the presence of transition metal-phosphine or -phosphite complex catalysts in a multiphase systems to aldehydes and the resulting aldehydes with polyols under acidic conditions in acetals wherein the reaction is carried out at temperatures between 25 and 200 ° C, and for the complex catalysts, the molar Transition metal / phosphorus ratios between 1: 0.5 and 1: 100, characterized in that the steps (a) and (b) takes place in a reaction vessel without separation of intermediates. An essential element of the process according to the invention is that steps (a) and (b) are carried out in a reaction vessel without separation of intermediates. The process thus results in a combination of both reactions in a one-pot synthesis process, so that both reactions can be carried out one behind the other in a reaction vessel.

If one uses butenes as olefin for the first reaction of the transition metal-catalyzed hydroformylation, so n- and iso-pentanals are produced, which in the subsequent reaction z. B. with glycerol H ⁺ -catalyzed to monoactal. There is an extension of the carbon chain by four C-atoms on product with a total of eight carbon atoms seen through both reactions. This will be compared to the glycerol a significant increase in the

Calorific value and a lowering of the boiling point achieved by reducing the hydroxy groups by two. Cs units are extremely important for carburetor fuels, but also for

Solvent or other technical additives.

Are z. B. hexenes used as the olefin for the first reaction of the transition metal-catalyzed hydroformylation, so n- and iso-heptanals are produced, which in the subsequent reaction z. B. with glycerol H ⁺ -catalyzed to monoactal. There is an extension of the carbon chain by four C-atoms on product with a total of ten carbon atoms seen through both reactions. As a result, a significant increase in the calorific value and a reduction in the boiling point by the reduction of the hydroxy groups are achieved by two compared to the glycerol. C ₁₀ units are extremely important for diesel fuels (Scheme 2), but also for solvents or other technical additives. Are z. B. Octene used as the olefin for the first reaction of the transition metal-catalyzed hydroformylation, so n- and iso-nonanals are produced, which in the subsequent reaction z. B. with glycerol H ⁺ -catalyzed to monoactal. There is an extension of the carbon chain by four C-atoms on product with a total of eight carbon atoms seen through both reactions. As a result, a substantial increase in the calorific value and a reduction in the boiling point by the reduction of the hydroxy groups are achieved by two compared to the glycerol. Ci ₂ units are extremely important components of diesel fuels but also for solvents or other technical additives and detergents. From 1-olefins aldehydes are hydroformylated, which in the subsequent reaction with polyols z. B. form acetals with polyols. These products have their significance as gasoline or diesel fuels, detergents, cosmetics and additives for lubricants. Furthermore, as solvents, plasticizers, stabilizers, pharmaceuticals, fungicides and microbicides, flavorings, intermediates and as additives for various applications.

The transition metal complexes of the eighth subgroup can be used according to the invention as catalysts. The elements cobalt and rhodium can be used in different oxidation states as cobalt (I), cobalt (II) - or as rhodium (I) -, rhodium (II) - and rhodium (III) compound. The use of cobalt (I) and rhodium (I) complexes as precursors for the catalyst species of the valence state +1 forming during the reaction is particularly favorable.

The molar concentration of the transition metal to the olefin should be between 1 to 10 to 1 to 1 000 000, preferably between 1 to 100 to 1 to 100 000.

+

+

+

Scheme 2: Hydroformylation of 1-hexene and acetalization with glycerol

According to the invention, the phosphines for the catalytic reaction may be all known from the relevant literature chiral and achiral, hydrophilic and hydrophobic phosphines and diphosphines, especially all alkyl, alkenyl, alkoxy, aryl, substituted

Aryl, heteroaryl, etc. phosphines, arylalky-phosphines of the general formula: RR) 2rR> 3 _T P and diphosphines of the general formula: R ¹ R ^{2 may be} P- (B) -PR ³ R ⁴ where R ¹ = R ² = R ³ = R ⁴ , R ¹ - R ² = R ³ ≠ R ⁴ , R ¹ = R ² ≠ R ³ ≠ R ⁴ , R ¹ ≠ R ² ≠ R ³ ≠ R ⁴ , and R = alkyl = methyl, ethyl, propyl, iso-propyl, n-butyl, sec. Butyl, tert-butyl or R = aryl = phenyl, naphthyl and B = alkyl or aryl or arylalkyl or alkylaryl used. R = ligand = R ¹ , R ² , R ³ , R ⁴ (examples of phosphines and diphosphines see Scheme 3).

Scheme 3

Particularly preferred complex catalysts for step (a) are phosphines and diphosphines which contain one or more alkyl or arylsulfonic acids or their salts as hydrophilic species, and in particular sulfoaryl, sulfoarylalkyl and sulfoalkylphosphines such as TPPMS, TPPTS, bis-1, r -phenyl-2,2 '- [CH ₂ -P (Ph) (CH ₂ ) ₃ SO ₃ M] _2; bis-naphthyl-2,2 '- [CH ₂ -P (Ph) (CH ₂ ) ₃ SO ₃ M] ₂ PPh ₂ (2-SO ₃ M, 5-C ₁₂ H ₂₅ , -C ₆ H ₃ -) , Ph ₂ P (CH ₂ ) ₃ SO ₃ M, Ph ₂ P (CH ₂ ) ₄ SO ₃ M, Ph ₂ PCH ₂ C ₆ H ₄ -2-SO ₃ M, Ph ₂ P (CH ₂ ) ₂ S ( CH ₂ ) ₃ SO ₃ M, Ph ₂ P (CH ₂ ) ₂ S (CH ₂ ) ₂ SO ₃ M, Men ₂ P (CH ₂ ) ₄ SO ₃ M, Ph ₂ P (CH ₂ ) ₂ NHC * H ( COOM) CH ₂ SO ₃ M, Ph ₂ PCH ₂ C ₆ H ₄ SO ₃ M (o), where M = H, Li, Na, K.

According to the invention, the molar transition metal / phosphine ratios can be from 1: 0.5 to 1: 100, preferably between 1: 1 and 1: 20. According to the invention, multiphase systems in which the hydrofomylation can be carried out are polar / apolar multiphase solvent systems, especially with DMF, THF, diethyl ether, dimethyl ether, DMSO, methanol, ethanol, propanol, hexane, heptane, octane, decane, benzene, toluene, xylene , Petroleum benzine and mixtures, carbon tetrachloride, chloroform, dichloromethane, trichlorethylene, dichloroethane, acetone, acetonitrile and ethyl acetate, together with polyols and water, in application.

As catalysts for the acetal reaction (b) protonic acids, especially HCl, H ₂ SO ₃ , H ₂ SO ₄ , H ₃ PO ₄ but also ion exchangers, are used. The concentration of acids is between 1 wt .-% and 100 ppb, preferably between 0.01 wt .-% and 100 ppm.

The temperatures may be between 25 and 200 ⁰ C, preferably between 50 and 150 ° C, are. Preferred ranges are between 25 and 150 ° C, preferably between 30 and 100 ⁰ C and in particular between 35 and 80 ⁰ C. The method is preferably designed as a one-pot multiphase systems, wherein no further solvents must be used in the polar / apolar multiphase system. The procedure without solvent is thus preferred.

The reactions are preferably carried out under carbon monoxide / hydrogen atmosphere in a ratio CO: H ₂ of preferably 1:10 to 10: 1, preferably from 1: 3 to 3: 1. The total pressure can be between one and 300 bar, preferably between one and 100 bar, amount.

For the hydroformylation olefins and olefin mixtures of the C-chain C ₄ to C ig, especially for the recovery of energy rich substances olefins of C ₆ to Cj ₂ , are generally used under phase transfer conditions with phosphine-transition metal complexes. The products obtained are n- or iso-aldehydes.

Olefins in the narrower sense can be pure 1-olefins, pure internal olefins, internal olefins, especially as cis or trans isomeric olefins, but also technical olefin mixtures.

Ethylene glycol, 1, 2-propanediol, 1,3-propanediol, glycerol, erythritol and mixtures thereof are to be regarded as examples of polyols for the purposes of this invention, but no sugars. The solvent, the olefin and the polyol together with the catalyst system form at room temperature (= 21 ° C) two immiscible liquid phases, a polar and a non-polar phase, the presence of the solvent is not mandatory.

By the reaction sequence according to the invention, namely by the hydroformylation of olefins to aldehydes and their subsequent conversion to acetals, compounds can be prepared which are extended in the carbon chain an extension by one carbon from the hydroformylation and by the number of carbon atoms of the polyol. At the same time, acetal formation reduces the number of hydroxy groups by at least two. Products with lower boiling points and significantly higher calorific value than the polyol are synthesized.

Products relevant to the energy industry, which are produced from difficult-to-use polyols such as glycerol in a one-pot process, are of particular importance as fuels for a wide variety of engine types. Furthermore, the acetals so prepared can be used as solvents, detergents, in cosmetics or as other technical additives, e.g. in lubricants or hydraulic oils.

Another object of the application relates to the use of acetals, which have been prepared according to the method described above as a fuel for internal combustion engines or as an additive to fuels for internal combustion engines, preferably fuels based on hydrocarbons and in particular as an additive to gasoline or diesel fuels or in Kerosene, wherein use in biodiesel may be preferred. The acetals prepared according to the invention may be present in the fuels preferably in amounts of from 1 to 99% by weight, with amounts of from 5 to 60% by weight and in particular from 10 to 50% by weight being particularly preferred. Furthermore, the use of the acetals as solvents, detergents or in cosmetics, for example as an oil component or as an emulsifier claimed. Another object of the application relates to the use of acetals, prepared according to the above as a lubricant, or additive in lubricants and preferably as a so-called. Friction modifier. embodiments

example 1

In a 100 ml laboratory autoclave from Parr Instruments with magnetgekuppeltem Gaseintragsrührer the feed is made, seked, rinsed with synthesis gas, and at 50 bar CO / H ₂ = 1/1 and 100 ° C, hydroformylated for 24 hours and acetalized. Weighing: 16.0 ml of 1-octene (100 mmol), 1.2 ml of water, 4 ml of glycerol, 30 mg of p-toluenesulfonic acid,

22 mg [Rh (OAc) ₂ ] ₂ (0.05 mmol), 188 mg (0.50 mmol) Ph ₂ P (CH ₂ ) ₂ S (CH ₂ ) ₂ SO ₃ Na, olefin / Rh = 1000,

Yield: conversion: 90%, of which 91% acetals (GC)

Example 2

In a 100 ml laboratory autoclave Parr Instruments with magnetgekuppeltem Gaseintragsrührer the feed is made, seked, rinsed with synthesis gas, and hydroformylated and acetalized at 50 bar CO / H ₂ = 1/1 and 100 ° C for 5 hours.

Weighing: 16.0 ml 1-octene (100 mmol), 10 ml toluene, 4 ml glycerol, 25 mg p-

Toluenesulfonic acid,

3.1 mg [Rh (COD) acac] (0.01 mmol) and 13.1 mg (0.050 mmol) Ph ₃ P in 1 ml toluene, olefin / Rh = 10,000,

Yield: conversion: 99%, of which 60% acetals (GC)

Example 3

In a 100 ml laboratory autoclave Parr Instruments with magnetgekuppeltem Gaseintragsrührer the feed is made, seked, rinsed with synthesis gas, and at 50 bar CO / H ₂ = 1/1 and 120 ° C for 5 hours hydroformylated and acetalized.

Weighing: 16.0 ml 1-octene (100 mmol), 10 ml toluene, 4 ml glycerol, 25 mg p-

toluene sulfonic acid,

Yield: conversion: 99%, of which 63% acetals (GC) Example 4

In a 100 ml laboratory autoclave made by Parr Instruments with magnetically coupled

Gas entrainment is carried out the feed, seked, rinsed with synthesis gas, and at 50 bar CO / H ₂ = 1/1 and 140 ° C, 1 hydroformylated and acetalated the feed. Weighing: 16.0 ml 1-octene (100 mmol), 10 ml toluene, 4 ml glycerol, 10 mg p-

toluene sulfonic acid,

3.1 mg [Rh (COD) acac] (0.01 mmol) and 13.1 mg (0.050 mmol) Ph ₃ P in 1 ml toluene,

Olefin / Rh = 10,000,

Yield: conversion: 99%, of which 87% acetals (GC)

Example 5

Gas feed stirring, the feed is made, seked, rinsed with synthesis gas, and at 50 bar CO / H ₂ = 1/1 and 80 ° C, 1 hydroformylated and acetalized. Weighing: 16.0 ml 1-octene (100 mmol), 10 ml toluene, 4 ml glycerol, 25 mg p-

toluene sulfonic acid,

Olefin / Rh = 10,000,

Yield: Sales: 58%, of which 69% acetals (GC)

Example 6

Gas feed stirring, the feed is made, seked, rinsed with synthesis gas, and at 50 bar CO / H ₂ = 1/1 and 60 ° C, 1 hydroformylated and acetalized. Weighing: 12.4 ml 1-hexene (100 mmol), 10 ml toluene, 4 ml glycerol, 25 mg p-

toluene sulfonic acid,

Olefin / Rh = 10,000,

Yield: Sales: 20%, of which 94% acetals (GC) Example 7

Gas entrainment is carried out the feed, seked, rinsed with synthesis gas, and at 50 bar CO / H ₂ = 1/1 and 80 ° C, 5 hours hydroformylated and acetalized. Weighing: 12.4 ml 1-hexene (100 mmol), 10 ml toluene, 2 ml glycerol, 20 mg p-

toluene sulfonic acid,

Olefin / Rh = 10,000,

Yield: Sales: 78%, of which 88% acetals (GC)

Example 8

Gas entrainment is carried out the feed, seked, rinsed with synthesis gas, and at 50 bar CO / H ₂ = 1/1 and 90 ° C, 5 hours hydroformylated and acetalized. Weighing: 12.4 ml 1-hexene (100 mmol), 10 ml toluene, 2 ml glycerol, 30 mg p-

toluene sulfonic acid,

Olefin / Rh = 10,000,

Yield: conversion: 99%, of which 86% acetals (GC)

Example 9

Gas entrainment is carried out the feed, seked, flushed with synthesis gas, and at 50 bar CO / H ₂ = 1/1 and 100 ° C, 5 hours hydroformylated and acetalized.

Weighing: 12.4 ml 1-hexene (100 mmol), 10 ml toluene, 2 ml glycerol, 30 mg p-

toluene sulfonic acid,

Olefin / Rh = 10,000, Yield: conversion: 99%, of which 92% acetals (GC) Example 10

Gas feed stirring the feed is made, seked, rinsed with synthesis gas, and at 50 bar CO / H ₂ = 1/1 and 120 ° C, 5 hours hydroformylated and acetalized. Weighed: 12.4 ml of 1-hexene (100 mmol), 10 ml of toluene, 3 ml of glycerol, 30 mg of p-hexane.

toluene sulfonic acid,

Olefin / Rh = 10,000,

Yield: conversion: 99%, of which 90% acetals (GC)

Example 11

Gas entrainment is carried out the feed, seked, rinsed with synthesis gas, and at 50 bar CO / H ₂ = 1/1 and 140 ° C, 1 hydroformylated and acetalated the feed. Weighing: 12.4 ml of 1-hexene (100 mmol), 10 ml of toluene, 4 ml of glycerol, 30 mg of p-hexane.

toluene sulfonic acid,

Olefin / Rh = 10,000,

Yield: conversion: 99%, of which 79% acetals (GC)

Example 12

Gas entrainment is carried out the feed, seked, flushed with synthesis gas, and at 50 bar CO / H ₂ = 1/1 and 100 ° C, 5 hours hydroformylated and acetalized. Weighed: 12.4 ml 1-hexene (100 mmol), 10 ml toluene, 4 ml glycerol, 30 mg p-

toluene sulfonic acid,

0.75 mg [Rh (COD) acac] (0.0025 mmol) and 3.75 mg (0.0125 mmol) Ph ₃ P in 0.25 ml toluene,

Olefin / Rh - 40,000,

Yield: 97%, of which 92% are acetals (GC)

Example 13

Gas entrainment is carried out the feed, seked, flushed with synthesis gas, and at 50 bar CO / H ₂ = 1/1 and 100 ° C, 5 hours hydroformylated and acetalized. Weighing: 12.4 ml of 1-hexene (100 mmol), 10 ml of toluene, 4 ml of glycerol, 30 mg of p-toluenesulfonic acid,

0.31 mg of [Rh (COD) acac] (0.001 mmol) and 1.31 mg (0.005 mmol) of Ph ₃ P in 0.1 ml of toluene, olefin / Rh = 100,000, m.p .: 99%, thereof 79% acetals (GC)

Example 14

Weighing: 16.0 ml 1-octene (100 mmol), 10 ml toluene, 4 ml glycerol, 30 mg p-

toluene sulfonic acid,

1.55 mg [Rh (COD) acac] (0.005 mmol) and 6.55 mg (0.025 mmol) Ph ₃ P in 0.5 ml toluene,

Olefin / Rh = 10,000, Yield: conversion: 53%, thereof 86% acetals (GC)

Example 15

Weighing: 16.0 ml 1-octene (100 mmol), 10 ml toluene, 4 ml glycerol, 30 mg p-

toluene sulfonic acid,

Olefin / Rh = 10,000, Yield: conversion: 58%, of which 69% acetals (GC)

Example 16

In a 100 ml laboratory autoclave from Parr Instruments with magnetgekuppeltem Gaseintragsrührer the feed is made, seked, rinsed with synthesis gas, and at 50 bar CO / H ₂ = 1/1 and 120 ° C, 5 hours hydroformylated and acetalized.

Weighing: 10.0 ml of 3-methylbutene (90 mmol), 5 ml of water, 20 ml of toluene, 2 ml of glycerol, 30 mg of p-toluenesulfonic acid,

22 mg [Rh (OAc) ₂ ] ₂ (0.05 mmol), 188 mg (0.50 mmol) Ph ₂ P (CH ₂ ) ₂ S (CH ₂ ) ₂ SO ₃ Na, olefin / Rh

= 900 Yield: conversion: 95%, of which 75% acetals (GC)

Example 17

In a 100 ml laboratory autoclave from Parr Instruments with magnetgekuppeltem Gaseintragsrührer the feed is made, seked, rinsed with synthesis gas, and at 50 bar CO / H ₂ = 1/1 and 120 ° C, hydroformylated for 24 hours and acetalized.

Weighing: 20.0 ml 1-dodecene (90 mmol), 5 ml water, 2 ml glycerol, 50 mg p-

toluene sulfonic acid,

22 mg [Rh (OAc) ₂ ] ₂ (0.05 mmol), 188 mg (0.50 mmol) Ph ₂ P (CH ₂ ) ₂ S (CH ₂ ) ₂ SO ₃ Na, olefin / Rh = 900

Yield: conversion: 99%, of which 69% acetals (GC)

Example 18 In a 100 ml laboratory autoclave from Parr Instruments with magnetgekuppeltem Gaseintragsrührer the charging is performed and purged, flushed with synthesis gas, and hydroformylated at 50 bar CO / H ₂ = 1/1 and 120 ⁰ C, 5 hours and acetalized. Weighed: 7 ml of 1-pentene (64 mmol), 20 ml of toluene, 4 ml of glycerol, 30 mg of p-toluenesulfonic acid, 3.1 mg of [Rh (COD) acac] (0.01 mmol) and 13.1 mg (0.050 mmol) Ph ₃ P in 1 ml toluene, olefin / Rh = 6,400, Yield: conversion: 99%, of which 93% acetals (GC)

Example 19 In a 100 ml laboratory autoclave from Parr Instruments with a magnetically coupled gas introduction stirrer, the feed is carried out, centrifuged, flushed with synthesis gas and hydroformylated and acetalized at 50 bar CO / H ₂ = 1/1 and 120 ° C. for 5 hours. Weighed: 7 ml of 2-pentene (64 mmol), 20 ml of toluene, 4 ml of glycerol, 30 mg of p-toluenesulfonic acid, 3.1 mg of [Rh (COD) acac] (0.01 mmol) and 13.1 mg (0.050 mmol) Ph ₃ P in 1 ml toluene, olefin / Rh = 6,400, Yield: conversion: 99%, of which 75% acetals (GC) Example 20

Gas entrainment is carried out the feed, seked, rinsed with synthesis gas, and hydroformylated and acetalized at 50 bar CO / H ₂ = 1/1 and 120 ⁰ C ₅ 15 hours. Weighing: 8 ml 1-octene (50 mmol), 20 ml toluene, 4 ml glycerol, 25 mg p-

toluene sulfonic acid,

Olefin / Rh = 5,000,

Yield: conversion: 99%, of which 62% acetals (GC)

Example 21

Gas feed stirring, the feed is made, seked, rinsed with syngas, and hydroformylated and acetalized at 50 bar CO / H ₂ = 1/1 and 120 ° C for 5 hours. Sample weight: 16.0 ml 1-octene (100 mmol), 10 ml toluene, 8 ml 1,3-propanediol, 30 mg p

Toluenesulfonic acid,

Olefin / Rh = 10,000,

Yield: conversion: 39%, of which 90% acetals (GC)

Example 22

Gas feed stirring the feed is made, seked, rinsed with synthesis gas, and at 50 bar CO / H ₂ = 1/1 and 120 ° C, 5 hours hydroformylated and acetalized. Weighed: 12.4 ml of 1-hexene (100 mmol), 10 ml of toluene, 8 ml of 1,3-propanediol, 30 mg of p-hexane.

toluene sulfonic acid,

Olefin / Rh = 10,000,

Yield: conversion: 99%, of which 90% acetals (GC)

Example 23

Gas feed stirring the feed is made, seked, rinsed with synthesis gas, and at 50 bar CO / H ₂ = 1/1 and 120 ° C, 5 hours hydroformylated and acetalized. Weighing: 12.4 ml of 1-hexene (100 mmol), 10 ml of toluene, 4 ml of 1, 2-propanediol, 1 drop of sulfuric acid,

3.1 mg of [Rh (COD) acac] (0.01 mmol) and 13.1 mg (0.050 mmol) of Ph ₃ P in 1 ml of toluene, olefin / Rh = 10,000, m.p .: 99%, thereof 65% acetals (GC)

Example 24

Gas feed stirring, the feed was made, seked, rinsed with synthesis gas, and at 50 bar CO / H ₂ = 1/1 and 100 ⁰ C, hydroformylated and acetalated for 5 hours.

Weighed in: 16 ml of 1-octene (100 mmol), 10 ml of toluene, 4 ml of 1,2-propanediol, 1 drop

Sulfuric acid,

Olefin / Rh = 10,000, Yield: conversion: 99%, thereof 67% acetals (GC)

Example 25

Phosphoric acid,

Olefin / Rh = 10,000, Yield: conversion: 99%, thereof 59% acetals (GC)

Example 26

In a 100 ml laboratory autoclave Parr Instruments with magnetgekuppeltem Gaseintragsrührer the feed is made, seked, rinsed with synthesis gas, and at 50 bar CO / H ₂ = 1/1 and 100 ° C, 5 hours hydroformylated and acetalized.

Weighed: 12.4 ml of 1-hexene (100 mmol), 10 ml of toluene, 4 ml of 1,2-propanediol, 1 drop

Phosphoric acid,

Olefin / Rh = 10,000, Yield: conversion: 99%, of which 67% acetals (GC)

Example 27

In a 100 ml laboratory autoclave Parr Instruments with magnetgekuppeltem Gaseintragsrührer the feed is made, seked, rinsed with synthesis gas, and at 50 bar COZH ₂ = IZl and 100 ° C, 5 hours hydroformylated and acetalized. Sample weight: 16 ml of 1-octene (100 mmol), 10 ml of toluene, 4 ml of glycol, 1 drop of phosphoric acid, 3.1 mg of [Rh (COD) acac] (0.01 mmol) and 13.1 mg (0.050 mmol) Ph ₃ P in 1 ml toluene, olefin / Rh = 10,000, Yield: conversion: 99%, of which 90% acetals (GC)

Example 28

Gas feed stirring, the feed is made, seked, rinsed with syngas, and at 50 bar COZH ₂ = IZl and 100 ° C, 5 hours hydroformylated and acetalized.

Weighed: 12.4 ml of 1-hexene (100 mmol), 10 ml of toluene, 4 ml of glycol, 1 drop

Phosphoric acid,

OlefmZRh = 10,000, Yield: conversion: 99%, thereof 96% acetals (GC)

Example 29

Gaseintragsrührer the feed is made, seked, rinsed with synthesis gas, and hydroformylated and acetalized at 50 bar COZH ₂ = IZl and 100 ° C for 5 hours.

Weighed: 16.0 ml of 1-octene (100 mmol), 10 ml of toluene, 4 ml of glycerol, 200 mg

Ion exchange resin KPS,

Olefin / Rh = 10,000, Yield: conversion: 99%, of which 60% acetals (GC) Example 30

Gas feed stirring, the feed is made, seked, rinsed with syngas, and hydroformylated and acetalized at 50 bar CO / H ₂ = 1/1 and 100 ° C for 5 hours. Sample weight: 16.0 ml 1-hexene (100 mmol), 10 ml toluene, 4 ml glycerol, 200 mg

Ion exchange resin KPS,

Olefin / Rh = 10,000,

Yield: conversion: 99%, of which 84% acetals (GC)

Example 31

Gas feed stirring, the feed is made, seked, rinsed with syngas, and hydroformylated and acetalized at 50 bar CO / H ₂ = 1/1 and 100 ° C for 5 hours. Weighed: 16.0 ml of 1-octene (100 mmol), 10 ml of toluene, 1 drop of phosphoric acid, 3.7 g

erythritol,

3.1 mg [Rh (COD) acac] (0.01 mmol) and 10 mg (0.025 mmol) Ph ₂ PCH ₂ CH ₂ PPh ₂ in 1 ml

Dichloromethane, olefin / Rh = 10,000,

Yield: conversion: 91%, thereof 63% acetals (GC)

Example 32

Gas Einführsrührer the feed is made, rinsed with synthesis gas, and hydroformylated and acetalized at 50 bar CCVH ₂ = 1/1 and 100 ° C for 5 hours. Weighing: 5.0 ml of 3-methylbutene (45 mmol), 10 ml of toluene, 4 ml of glycerol, 25 mg of

toluene sulfonic acid,

Dichloromethane, olefin / Rh = 4,500,

Yield: Sales: 79%, of which 99% acetals (GC)

Example 33

Gas Einführsrührer the feed is made, rinsed with synthesis gas, and hydroformylated and acetalized at 50 bar CO / H ₂ = 1/1 and 100 ⁰ C for 5 hours. Weighing: 11.0 ml of 3-methylbutene (100 mmol), 10 ml of toluene, 4 ml of glycerol, 25 mg of p-toluenesulfonic acid,

3.1 mg of [Rh (COD) acac] (0.01 mmol) and 10 mg (0.025 mmol) of Ph ₂ PCH ₂ CH ₂ PPh ₂ in 1 ml of dichloromethane, olefin / Rh = 10 000, m.p .: conversion: 74 %, including 99% acetals (GC)

Example 34

The feed is carried out in a 2 l laboratory autoclave from Parr Instruments with a magnetically coupled stirrer, and the mixture is subjected to synthesis gas injection of 40 bar CO / H ₂ = 1/1 and 100 ° C. for 24 hours, repeatedly hydroformylated and acetalized.

Weighing: 612 ml of 1-hexene (5 mol), 400 ml of glycerol (5.4 mol), 2 g of p-toluenesulfonic acid,

31 mg of [Rh (COD) acac] (0.1 mmol) and 150 mg (0.025 mmol) of Ph ₃ P in 10 ml of toluene,

Olefin / Rh = 50,000,

After cooling, a phase separation is carried out and distilled in vacuo (Kp 0 _{, 1} 0 = 96 ° C)

Yield: conversion: 93%, of which 776.8 g (83% acetals)

Example 35

Gas Einführsrührer the feed is made, rinsed with synthesis gas, and hydroformylated and acetalized at 50 bar CO / H ₂ = 1/1 and 100 ° C for 5 hours. Weighing: 1.34 g of 4-methoxystyrene (10 mmol), 10 ml of toluene, 0.77 g of 1,2-propanediol, 5 mg of p-toluenesulfonic acid,

3.1 mg of [Rh (COD) acac] (0.01 mmol) and 13 mg (0.05 mmol) of Ph ₃ P in 1 ml of toluene,

Olefin / Rh = 1 000,

Yield: conversion: 98%, of which 95.5% acetals (GC)

Claims

claims

1. The invention relates to a process for the preparation of acetals from polyols, wherein (a) olefins in the presence of transition metal phosphine or phosphite

Hydroformylated complex catalysts in a multiphase system to give aldehydes; and (b) converting the resulting aldehydes with polyols under acidic conditions into acetals, wherein the reaction is carried out at temperatures between 25 and 200 ° C, and for the complex catalysts, the molar transition metal / phosphorus ratios between 1: 0.5 and 1: 100, characterized in that steps (a) and (b) take place in a reaction vessel without separation of intermediates.

2. The method according to claim 1, characterized in that as complex catalysts for step (a) hydrophilic or hydrophobic, chiral and achiral phosphines and diphosphines, aliphatic and aromatic phosphines and diphosphines, alkyl, alkenyl, alkoxy, aryl, substituted aryl , Heteroaryl, etc. phosphines, Arylalky- phosphines of the general formula: R ¹ R ² RP and diphosphines of the general formula R ¹ R ² P- (B) -PR ³ R ⁴ can be used.

3. The method according to at least one of claims 1 to 2, characterized in that as complex catalysts for the step (a) as ligands R hydrobes phosphines and diphosphines containing one or more alkyl or aryl groups such as alkyl, alkenyl, alkoxy, Aryl, substituted aryl, heteroaryl, etc. phosphines, Arylalky- phosphines of the general formula: RRRP and diphosphines of the general formula: R ¹ R ^{2 may be} P- (B) -PR ³ R ⁴ , wherein R ¹ = R ² = R ³ = R ⁴ , R ¹ = R ² = R ³ ≠ R ⁴ , R ¹ = R ² ≠ R ³ ≠ R ⁴ , R ¹ ≠ R ² ≠ R ³ ≠ R ⁴ , and R = alkyl - = methyl, ethyl, propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl or R = aryl = phenyl, naphthyl and B = alkyl or aryl or arylalkyl or alkylaryl used. R = ligand = R ¹ , R ² , R ³ , R ⁴ .

4. The method according to at least one of claims 1 to 3, characterized in that as complex catalysts for step (a) phosphines and diphosphines, the one or more alkyl or arylsulfonic acids or their salts as hydrophilic species, and in particular sulfoaryl, sulfoarylalkyl and sulfoalkylphosphines such as TPPMS, TPPTS, bis-l, r-phenyl-2,2 '- [CH ₂ -P (Ph ) (CH ₂ ) ₃ SO ₃ M] _2> bis-naphthyl-2,2 '- [CH ₂ -P (Ph) (CH ₂ ) ₃ SO ₃ M] _2, PPh ₂ (2-SO ₃ M, 5 - C ₁₂ H ₂₅₅ -C ₆ H ₃ -), Ph ₂ P (CH ₂ ) ₃ SO ₃ M, Ph ₂ P (CH ₂ ) ₄ SO ₃ M, Ph ₂ PCH ₂ C ₆ H ₄ -2 SO ₃ M,

Ph ₂ P (CH ₂ ) ₂ S (CH ₂ ) ₃ SO ₃ M, Ph ₂ P (CH ₂ ) ₂ S (CH ₂ ) ₂ SO ₃ M, Men ₂ P (CH ₂ ) ₄ SO ₃ M

Ph ₂ P (CH ₂ ) ₂ NHC * H (COOM) CH ₂ SO ₃ M, Ph ₂ PCH ₂ C ₆ H ₄ SO ₃ M (o), where M = H, Li, Na, K can be used ,

5. The method according to at least one of claims 1 to 4, characterized in that in the complex catalysts for step (a) the molar transition metal / phosphorus ratios between 1: 1 and 1: 20.

6. The method according to at least one of claims 1 to 5, characterized in that in the complex catalysts for step (a) as subgroup elements

Rhodium and cobalt are used and the concentrations of

Nebengruppenelementes in the transition metal complexes between 20 mol% and

10 ppb.

7. The method according to at least one of claims 1 to 6, characterized in that as a precursor for the complex catalysts for step (a) the element rhodium in different oxidation states as rhodium (I) -, rhodium (II) - and rhodium (III) compound as RhCl ₃ x n H ₂ O, Rh (OAc) _3, Rh (OAc) _2, [Rh (CO) ₂ acac], [Rh (COD) acac], [Rh (CO) ₂ Cl] _2, [ Rh (COD) Cl] ₂ , [Rh (COD) ₂ BF ₄ ], [Rh (NBD) acac], [Rh (NBD) Cl] ₂ , [Rh (NBD) ₂ BF ₄ ], [Rh (CH ₂ = CH ₂ ) ₂ acac] and [Rh (CH ₂ = CH ₂ ) ₂ Cl] _{2 is} used.

8. The method according to at least one of claims 1 to 7, characterized in that for the hydro-formylation reaction (a) olefins having C ₂ - to C ^ - atoms are used and the reactions under carbon monoxide

/ Hydrogen atmosphere in a molar ratio CO: H ₂ from 1:10 to 10: 1, preferably from 1: 3 to 3: 1, wherein the total pressure between 1 and 300 bar, and more preferably between 1 and 100 bar.

9. The method according to at least one of claims 1 to 8, characterized in that are used as olefins 1-Olefϊne, internal olefins, internal olefins as cis or trans isomers Olefϊne and / or technical olefin mixtures.

10. The method according to at least one of claims 1 to 9, characterized in that as polyols for step (b) ethylene glycol, 1, 2-propanediol, 1,3-propanediol, glycerol, erythritol and mixtures thereof are selected.

1 1. The method according to at least one of claims 1 to 10, characterized in that a multi-phase system in step (a) is formed from polar / apolar

Multiphase solvent systems, preferably selected from the group consisting of DMF, THF, diethyl ether, dimethyl ether, DMSO, methanol, ethanol, propanol, hexane, heptane, octane, decane, benzene, toluene, xylene, petroleum benzine and mixtures, carbon tetrachloride, chloroform, dichloromethane, trichlorethylene, Dichloroethane, acetone, acetonitrile and ethyl acetate, and polyols and water.

12. The method according to at least one of claims 1 to 1 1, characterized in that as catalysts for the acetalization (b) protonic acids, preferably p-toluenesulfonic acid, HCl, H ₂ SO ₃ , H ₂ SO ₄ , H ₃ PO ₄ and / or ion exchanger, preferably in concentrations of 1 wt .-% to 100 ppm, preferably between

0.01 wt .-% and 1000 ppm are applied.

13. The method according to at least one of claims 1 to 12, characterized in that the reaction temperature of the two steps between 25 and 150 ° C, preferably between 30 and 100 ° C and in particular between 35 and 80 ° C.

14. The method according to at least one of claims 1 to 13, characterized in that the reaction time of both steps depending on the temperature, the olefin, the polyol, the catalyst concentration and the cocatalyst concentration between one minute and 1000 hours, especially between

30 minutes and 24 hours.

15. The method according to claim 1 to 14, characterized in that formed from the nonpolar olefin and the polar polyol at room temperature, multiphase systems, it being preferred to work without further solvents.

16. Use of acetals prepared by the process according to claim 1 as

Fuel or as an ingredient of fuels, preferably as an ingredient in diesel oil, gasoline or kerosene.

17. Use of acetals prepared by the process according to claim 1 as solvents, detergents, or in cosmetics.

18. Use of acetals, prepared by the process according to claim 1 as a lubricant, or additive in lubricants and preferably as a friction modifier.