HK1065740A - Double metal cyanide catalysts for the production of polyether polyols - Google Patents

Description

Double metal cyanide catalysts for preparing polyether polyols

The present application is a divisional application with application number 00815309.4(PCT/EP00/10550), application number 00815309.4 with application date of 2000-10-26, entitled "double metal cyanide catalyst for preparing polyether polyol".

Technical Field

The invention relates to novel Double Metal Cyanide (DMC) catalysts for producing polyether polyols by polyaddition of alkylene oxides to starter compounds containing active hydrogen atoms.

Background

Double Metal Cyanide (DMC) catalysts for the polyaddition of alkylene oxides to starter compounds containing active hydrogen atoms are known (see, for example, U.S. Pat. No. 3, 3404109, U.S. Pat. No. 3, 3829505, U.S. Pat. No. 3, 3941849 and U.S. Pat. No. 5158922). The use of these DMC catalysts for preparing polyether polyols makes it possible in particular to reduce the proportion of monofunctional polyethers having terminal double bonds, so-called monools, in comparison with conventional processes for preparing polyether polyols by means of alkali metal catalysts, such as alkali metal hydroxides. The polyether polyols thus obtained can be processed to high-grade polyurethanes (e.g.elastomers, foams, coatings). DMC catalysts are generally obtained by reacting aqueous solutions of metal salts with aqueous solutions of metal cyanide salts in the presence of organic complex ligands, such as ethers. For example, in a typical catalyst preparation method, an aqueous solution (excess) of zinc chloride is mixed with potassium hexacyanocobaltate and dimethoxyethane (glyme) is then added to the suspension formed, and once filtered and the catalyst washed with an aqueous solution of glyme, the catalyst having the general formula

Zn₃[Co(CN)₆]₂ xZncl₂ yH₂O z glyme (see, for example, EP-A700949).

From JP-A4145123, U.S. Pat. No. 3, 5470813, EP-A700949, EP-A743093, EP-A761708 and WO97/40086 DMC catalysts are disclosed which further reduce the proportion of monofunctional polyethers having terminal double bonds in the preparation of polyether polyols by using tert-butanol as organic complex ligand, alone or in combination with polyethers (EP-A700949, EP-A761708, WO 97/40086). Moreover, the use of these DMC catalysts also reduces the induction period for the polyaddition of alkylene oxides with suitable starter compounds and increases the activity of the catalysts.

Disclosure of Invention

It is an object of the present invention to provide further improved DMC catalysts for the polyaddition of alkylene oxides onto suitable starter compounds, which catalysts exhibit an increased catalyst activity in comparison with the catalyst types known hitherto. By shortening the alkoxylation time, the process for preparing polyether polyols is economically improved. The result of the increased activity is, ideally, that the catalyst concentration used subsequently (25ppm or less) is so low that separation of the catalyst and the product is no longer necessary with difficulty and the product can be used directly for the preparation of polyurethanes.

It has now surprisingly been found that DMC catalysts comprising three or more different complex-forming components have a significantly improved activity in the preparation of polyether polyols compared to a catalyst comprising only one complex-forming component.

Accordingly, the present invention provides a Double Metal Cyanide (DMC) catalyst comprising

a) One or more, preferably one double metal cyanide compound,

b) one or more, preferably one, organic complex ligand other than c), and

c) two or more, preferably two, components forming complexes from the class of compounds containing functionalized polymers selected from the group consisting of polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycol glycidyl ethers, polyacrylamides, poly (acrylamide-co-acrylic acid), polyacrylic acids, poly (acrylic acid-co-maleic acid), polyacrylonitriles, polyalkyl acrylates, polyalkyl methacrylates, polyvinyl methyl ethers, polyvinyl ethyl ethers, polyvinyl acetates, polyvinyl alcohols, poly-N-vinylpyrrolidone, poly (N-vinylpyrrolidone-co-acrylic acid), polyvinyl methyl ketones, poly (4-vinylphenol), poly (acrylic acid-co-styrene), poly (acrylamide-co-acrylic acid), poly (acrylic acid-co-styrene), poly (acrylic acid-co-acrylic acid), poly (vinyl, Oxazoline polymers, polyalkyleneimines, copolymers of maleic acid and maleic acid glycosides, hydroxyethylcellulose and polyacetals or from the group of glycidyl ethers, glycosides, carboxylic esters of polyhydric alcohols, bile acids or their salts, esters or amides, cyclodextrins, phosphorus compounds, alpha, beta-unsaturated carboxylic esters or ionic surface-or interface-active compounds.

The catalysts of the invention may optionally contain d) water, preferably from 1 to 10% by weight, and/or e) one or more water-soluble metal salts of the formula (I) M (X) n, preferably from 5 to 25% by weight, resulting from the preparation of the double metal cyanide compound a). In formula (I), M is selected from the metals Zn (II), Fe (II), Ni (II), Mn (II), Co (II), Sn (II), Pb (II), Fe (III), Mo (IV), Mo (VI), Al (III), V (V), V (IV), Sr (II), W (IV), W (VI), Cu (II) and Cr (III). Zn (II), Fe (II), Co (II) and Ni (II) are particularly preferred. X are identical or different, preferably identical and anionic, and are preferably selected from the group consisting of halides, hydroxides, sulfates, carbonates, cyanates, thiocyanates, isocyanates, isothiocyanates, carboxylates, oxalates or nitrates. The value of n is 1, 2 or 3.

The double metal cyanide compounds a) present in the catalyst according to the invention are reaction products of water-soluble metal salts with water-soluble metal cyanide salts.

Water-soluble metal salts suitable for preparing the double metal cyanide compounds a) preferably have the general formula (I) M (X) n, where M is selected from the metals Zn (II), Fe (II), Ni (II), Mn (II), Co (II), Sn (II), Pb (II), Fe (III), Mo (IV), Mo (VI), Al (III), V (V), V (IV), Sr (II), W (IV), W (VI), Cu (II) and Cr (III). Zn (II), Fe (II), Co (II) and Ni (II) are particularly preferred. The anions X are identical or different, preferably identical, and are preferably selected from halides, hydroxides, sulfates, carbonates, cyanates, thiocyanates, isocyanates, isothiocyanates, carboxylates, oxalates or nitrates. The value of n is 1, 2 or 3.

Examples of suitable water-soluble metal salts are zinc chloride, zinc bromide, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc nitrate, iron (II) sulfate, iron (II) bromide, iron (II) chloride, cobalt (II) thiocyanate, nickel (II) chloride and nickel (II) nitrate. Mixtures of various water-soluble metal salts may also be used.

Water-soluble metal cyanide salts which are suitable for preparing the double metal cyanide compounds a) preferably have the general formula (II), (Y)_aM′(CN)_b(A)_cWherein M' is selected from the metals Fe (II), Fe (III), Co (II), Co (III), Cr (II), Cr (III), Mn (II), Mn (III), Ir (III), Ni (II), Rh (III), Ru (II), V (IV) and V (V). M' is particularly preferably selected from the metals Co (II), Co (III), Fe (II), Fe (III), Cr (III), Ir (III) and Ni (II). The water-soluble metal cyanide salt may contain one or more of the above-mentioned metals. The cations Y are identical or different, preferably identical, and are selected from alkali metal ions and alkaline earth metal ions. The anions A are identical or different, preferably identical, and are selected from halides, hydroxides, sulfates, carbonates, cyanates, thiocyanates, isocyanates, isothiocyanates, carboxylates, oxalates or nitrates. a, b and c are integers, wherein the values of a, b and c are selected to ensure electroneutrality of the metal cyanide salt; a is preferably 1, 2, 3 or 4; b is preferably 4, 5 or 6; c is preferably 0. Examples of suitable water-soluble metal cyanide salts are potassium hexacyanocobaltate (III), potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), calcium hexacyanocobaltate (III) and lithium hexacyanocobaltate (III).

The double metal cyanide compounds a) present in the catalysts of the invention are preferably compounds of the formula (III)

M_x[M′_x′(CN)_y]_z，

Wherein M is as defined for formula (I), M 'is as defined for formula (II), and x, x', y and z are integers selected to ensure electroneutrality of the double metal cyanide compound.

Preferably x-3, x' -1, y-6 and z-2,

m ═ Zn (II), Fe (II), Co (II) or Ni (II) and

m ═ co (iii), fe (iii), cr (iii), or ir (iii).

Examples of suitable double metal cyanide compounds a) are zinc hexacyanocobaltate (III), zinc hexacyanocobaltate (III) and cobalt hexacyanocobaltate (III). Further examples of suitable double metal cyanide compounds can be found, for example, in U.S. Pat. No. 5,5158922. Zinc hexacyanocobaltate (III) is particularly preferably used.

The organic complex ligands b) present in the DMC catalysts of the present invention are known in principle and are described extensively in the prior art (for example U.S. Pat. No. 4, 5158922, 3404109, 3829505, 3941849,700949, EP 761708,4145123, 5470813, EP 743093 and WO 97/40086). Preferred organic complex ligands are water-soluble organic compounds having heteroatoms, such as oxygen, nitrogen, phosphorus or sulfur, which can form complexes with the double metal cyanide compounds a). Suitable organic complex ligands are, for example, alcohols, aldehydes, ketones, ethers, esters, amides, ureas, nitriles, sulfides and mixtures thereof. Preferred organic complex ligands are water-soluble aliphatic alcohols, such as ethanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol. Tert-butanol is particularly preferred.

The organic complex ligand may be added during the preparation of the catalyst or immediately after precipitation of the double metal cyanide compound a). The organic complex ligand is generally used in excess.

The DMC catalysts of the present invention contain the double metal cyanide compound a) in an amount of from 20 to 90% by weight, preferably from 25 to 80% by weight, based on the amount of final-forming (fertigen) catalyst, and the organic complex ligand b) in an amount of from 0.5 to 30% by weight, preferably from 1 to 25% by weight, based on the amount of final-forming (fertigen) catalyst. The DMC catalysts of the invention generally contain from 1 to 80% by weight, preferably from 1 to 40% by weight, of two or more complex-forming components c), relative to the amount of final-form (fertigen) catalyst.

Component c) suitable for preparing the complex-forming catalysts of the invention are the abovementioned functionalized polymers, glycidyl ethers, glycosides, carboxylic esters of polyols, bile acids or their salts, esters or amides, cyclodextrins, phosphorus compounds, alpha, beta-unsaturated carboxylic esters or ionic surface-or interface-active compounds.

Functionalized polymers suitable for preparing the catalysts of the invention are known in principle and are described in detail in EP-A700949, WO97/40086, WO98/16310 and German patent applications 19745120.9, 19757574.9, 19810269.0, 19834573.9 and 19842382.9. Suitable functionalized polymers are, for example, polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycol glycidyl ethers, polyacrylamides, poly (acrylamide-co-acrylic acid), polyacrylic acid, poly (acrylic acid-co-maleic acid), polyacrylonitrile, polyalkylacrylates, polyalkylmethacrylates, polyvinyl methyl ethers, polyvinyl ethyl ether, polyvinyl acetate, polyvinyl alcohol, poly-N-vinylpyrrolidone, poly (N-vinylpyrrolidone-co-acrylic acid), polyvinyl methyl ketone, poly (4-vinylphenol), poly (acrylic acid-co-styrene), oxazoline polymers, polyalkyleneimines, copolymers of maleic acid and maleic anhydride, hydroxyethylcellulose, and polyacetals.

The functionalized polymers preferably used are polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters and polyalkylene glycol glycidyl ethers.

Polyethers which are preferably used are those having 1 to 8, particularly preferably 1 to 3 hydroxyl functions and a number average molecular weight of 150 to 10⁷Particularly preferably 200 to 5.10⁴Polyether polyols in between. They are generally obtained by ring-opening polymerization of epoxides in the presence of suitable starter compounds containing active hydrogen atoms and having basic, acidic or complex catalytic activity, for example DMC catalytic activity. Suitable polyether polyols are, for example, poly (oxypropylene) polyols, poly (oxyethylene) polyols, EO-tipped poly (oxypropylene) polyols, mixed EO/PO polyols, butylene oxide polymers, copolymers of butylene oxide with ethylene oxide and/or propylene oxide and/or poly (oxytetramethylene) glycols.

The polyesters preferably used are linear and partially branched polyesters containing terminal hydroxyl groups and having an average molecular weight of less than 10000, which are described in more detail in German patent application 19745120.9. Particularly preferred polyesters used are those having an average molecular weight of 400 to 6000 and an OH number of 28 to 300mg (KOH/g) which are suitable for the preparation of polyureas. Suitable polyesters are, for example, poly (ethylene adipate), poly (diethylene glycol adipate), poly (dipropylene glycol adipate), trimethylolpropane-branched poly (diethylene glycol adipate) or poly (1, 4-butanediol adipate).

The polycarbonates preferably used are aliphatic polycarbonates having terminal hydroxyl groups and an average molecular weight of less than 12000, which are described in more detail in German patent application 19757574.9. Particular preference is given to using aliphatic polycarbonate diols having an average molecular weight of from 400 to 6000. Suitable polycarbonate diols are, for example, poly (1, 6-hexanediol) carbonate, poly (diethylene glycol) carbonate, poly (dipropylene glycol) carbonate, poly (triethylene glycol) carbonate, poly (1, 4-dimethylolcyclohexane) carbonate, poly (1, 4-butanediol) carbonate or poly (tripropylene glycol) carbonate.

The polyalkylene glycol sorbitan esters preferably used are polyethylene glycol sorbitan esters (polysorbates), which are described in more detail in German patent application 19842382.9. Particular preference is given to using polyethylene glycol sorbitan mono-, di-and triesters of fatty acids having from 6 to 18 carbon atoms and from 2 to 40 mol of ethylene oxide.

Preferred polyalkylene glycol glycidyl ethers used are mono-and diglycidyl ethers of polypropylene glycol and polyethylene glycol, which are described more fully in German patent application 19834573.9.

Glycidyl ethers of monomeric or polymeric (comprising at least two monomer units) aliphatic, aromatic or araliphatic mono-, di-, tri-, tetra-or polyfunctional alcohols are also preferably suitable for the preparation of the catalysts of the invention (component c)).

Preferred glycidyl ethers are those of mono-, di-, tri-, tetra-or polyfunctional aliphatic alcohols, such as butanol, hexanol, octanol, decanol, dodecanol, tetradecanol, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 2-dimethyl-1, 3-propanediol, 1, 2, 3-propanetriol, 1, 6-hexanediol, 1, 1, 1-tris (hydroxymethyl) ethane, 1, 1, 1-tris (hydroxymethyl) propane, tetrakis (hydroxymethyl) methane, sorbitol, polyethylene glycol and polypropylene glycol, not only mono-, di-, tri-, tetra-ethers but also polyethers are contemplated.

Particular preference is given to using butanol, hexanol, octanol, decanol, dodecanol, tetradecanol, ethylene glycol or 1, 4-butanediol and also mono-or diglycidyl ethers of polypropylene glycol or polyethylene glycol, in particular those having a degree of polymerization of from 2 to 1000 monomer units.

Glycidyl ethers are generally obtained by reaction of a mono-, di-, tri-, tetra-or polyfunctional alcohol with epichlorohydrin in the presence of a Lewis acid such as tin tetrachloride or boron trichloride to give the corresponding chlorohydrin and subsequent dehydrohalogenation with a base such as sodium hydroxide.

Processes for preparing glycidyl ethers are generally known and are described in detail, for example, in Kirk-Othmer, Encyclopedia of Chemical Technology, volume nine, fourth edition, 1994, page 739 and below, and Ullmann, Encyclopedia of Industrial Chemistry, volume A9, fifth edition, Weinheim, New York, 1987, page 552.

The glycidyl ethers used to prepare the catalysts of the invention may be present in the final catalyst in a form as originally introduced or chemically modified, e.g. hydrolyzed.

For component c), suitable glycosides are compounds synthesized from carbohydrates (sugars) and non-sugars (aglycones (Aglykone)), wherein the aglycone is linked to the hemiacetal carbon atom of the carbohydrate via a glycosidic bond via an oxygen atom, forming an acetal.

Suitable sugar components include monosaccharides such as glucose, galactose, mannose, fructose, arabinose, xylose or ribose; disaccharides, such as sucrose, maltose; and oligosaccharides or polysaccharides, such as starch.

A contemplated non-sugar component is C₁-C₃₀Such as aryl, aralkyl and alkyl residues, preferably aralkyl and alkyl residues, particularly preferably alkyl residues having 1 to 30 carbon atoms.

The glycosides preferably used are so-called alkyl polyglycosides, which are generally obtained by reaction of carbohydrates with alcohols, such as methanol, ethanol, propanol and butanol, or by transacetylation of short-chain alkyl glycosides with aliphatic alcohols having 8 to 20 carbon atoms in the presence of acids.

Particularly preferred alkyl polyglycosides are those having glucose as repeating unit in the chain and an alkyl chain length from C₈To C₁₆And an average degree of polymerization of between 1 and 2.

Methods for preparing glycosides are generally known and described in, for example, Kirk-Othmer, Encyclopedia of chemical Technology, volume 4, fourth edition, 1992, page 916 and below; r * mpp, Lexikon Chemie, Vol.two, tenth edition, Stuttgart/New York, 1996, p.1581 and the following: the process of the Angewandte Chemie,110page 1394-1412 (1998) is described in detail.

Suitable carboxylic acid esters of polyhydric alcohols are, for example, C₂-C₃₀Esters of carboxylic acids with aliphatic or cycloaliphatic alcohols having two or more hydroxyl groups per mole, e.g. ethylene glycol, 1, 2-propaneDiols, 1, 3-propanediol, diethylene glycol, triethylene glycol, 1, 2, 3-propanetriol (glycerol), 1, 3-butanediol, 1, 4-butanediol, butanetriol, 1, 6-hexanediol, 1, 1, 1-trimethylolethane, 1, 1, 1-trimethylolpropane, pentaerythritol, carbohydrates (sugars) or sugar alcohols, for example sorbitol or sorbitan. Suitable sugars are monosaccharides such as glucose, galactose, mannose, fructose, arabinose, xylose or ribose; disaccharides such as sucrose or maltose; and oligo-or polysaccharides, such as starch.

For example, a carboxylic acid component which may be considered is C₂-C₃₀Carboxylic acids, such as aryl, aralkyl and alkylcarboxylic acids, preferably aralkyl and alkylcarboxylic acids, particularly preferably alkylcarboxylic acids, such as acetic acid, butyric acid, isovaleric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid or linolenic acid.

The carboxylic esters of polyhydric alcohols preferably used are esters of 1, 2, 3-propanetriol (glycerol), 1, 1, 1-trimethylolpropane, pentaerythritol, maltose or sorbitan with C₂-C₁₈Esters of alkyl carboxylic acids.

Particularly preferred carboxylic acid esters of polyhydric alcohols are 1, 2, 3-glycerol (glycerol), pentaerythritol or sorbitan and C₂-C₁₈Mono-, di-, tri-or tetraesters of alkyl carboxylic acids.

Methods for preparing carboxylic esters of polyols or for isolating them from fats are generally known and are described, for example, in Kirk-Othmer, Encyclopedia of Chemical Technology, volume 9, third edition, 1980, page 795 and below, R * mpp, Lexikon Chemie, eighth edition, Stuttgart/New York, 1981; ullmann's Encyclopedia of Industrial chemistry, Vol.A 10, fifth edition, 1987, p.173-218 is described in detail.

Suitable bile acids for component C) are C₂₄Steroidal carboxylic acids, which are degradation products of cholesterol, are generally derived from 5 beta-cholestane (Cholan) -24 (die ure) -acid by introducing hydroxyl groups in the alpha positions of C-3, C-6, C-7 and C-12To do so.

Preferred bile acids have the formula

Wherein R is₁、R₂、R₃And R₄Each represents H or OH, R₅Represents OH, NH-CH₂-COOH、NH-CH₂-CH₂-SO₃H、NH-(CH₂)₃-N⁺(CH₃)₂-CH₂-CHOH-CH₂-SO₃ ^-Or NH- (CH)₂)₃-N⁺(CH₃)₂-(CH₂)₃-SO₃ ^-。

Also suitable are free acids or their salts, preferably alkali metal or alkaline earth metal salts, and esters thereof, preferably alkyl residues having from 1 to 30 carbon atoms and amides thereof, preferably alkyl residues having acid or salt form or sulfoalkyl, sulfoalkylaminoalkyl, sulfohydroxyalkylaminoalkyl and carboxyalkyl residues.

An example of a suitable bile acid or a salt, ester or amide thereof is cholic acid (3 α, 7 α, 12 α -trihydroxy-5 β -cholestane-24-acid; R₁＝R₃＝R₄＝R₅＝OH，R₂H), sodium cholate (sodium cholate), lithium cholate, potassium cholate, glycocholic acid (3 α, 7 α, 12 α -trihydroxy-5 β -cholane-24-oic acid N- [ carboxymethyl group)]-an amide; r₁＝R₃＝R₄＝OH，R₂＝H，R₅＝NH-CH₂-COOH), sodium glycocholate, taurocholic acid (3 α, 7 α, 12 α -trihydroxy-5 β -cholestane-24-oic acid N- [ 2-sulfoethyl group]-an amide; r₁＝R₃＝R₄＝OH，R₂＝H，R₅＝NH-CH₂-CH₂-SO₃H) Sodium taurocholate, deoxycholic acid (3 α, 12 α -dihydroxy-5 β -cholestane-24-oic acid; r₁＝R₄＝R₅＝OH，R₂＝R₃H), sodium deoxycholate, desaturationPotassium deoxycholate, lithium deoxycholate, glycodeoxycholic acid (3 alpha, 12 alpha-dihydroxy-5 beta-cholestane-24-oic acid N- [ carboxymethyl group)]-an amide; r₁＝R₄＝OH，R₂＝R₃＝H、R₅＝NH-CH₂-COOH), sodium glycodeoxycholate, taurodeoxycholic acid (3 α, 12 α -dihydroxy-5 β -cholestane-24-oic acid N- [ 2-sulfoethyl group]An amide; r₁＝R₄＝OH，R₂＝R₃＝H，R₅＝NH-CH₂CH₂-SO₃H) Sodium taurodeoxycholate, chenodeoxycholic acid (3 α, 12 α -dihydroxy-5 β -cholestane-24-oic acid; r₁＝R₃＝R₅＝OH，R₂＝R₄H), sodium chenodeoxycholate, glycochenodeoxycholic acid (3 alpha, 12 alpha-dihydroxy-5 beta-cholestane-24-oic acid N [ carboxymethyl group)]An amide; r₁＝R₃＝OH，R₂＝R₄＝H，R₅＝NH-CH₂-COOH), sodium glycochenodeoxycholate, taurochenodeoxycholic acid (3 alpha, 7 alpha-dihydroxy-5 beta-cholestane-24-oic acid N [ sulfoethyl group)]An amide; r₁＝R₃＝OH，R₂＝R₄＝H，R₅＝NH-CH₂-CH₂-SO₃H) Sodium taurochenodeoxycholate, lithocholic acid (3 α -hydroxy-5 β -cholestane-24-oic acid; r₁＝R₅＝OH，R₂＝R₃＝R₄H), lithocholic acid sodium, lithocholic acid potassium, hyocholic acid (3 α, 6 α, 7 α -trihydroxy-5 β -cholestane-24-acid; r₁＝R₂＝R₃＝R₅＝OH，R₄H), sodium hyocholate, lithium hyocholate, potassium hyocholate, hyodeoxycholic acid (3 α, 6 α -dihydroxy-5 β -cholestane-24-oic acid; r₁＝R₂＝R₅＝OH，R₃＝R₄H), sodium hyodeoxycholate, lithium hyodeoxycholate, potassium hyodeoxycholate, cholic acid methyl ester, cholic acid ethyl ester, deoxycholic acid ethyl ester and hyocholic acid methyl ester.

Particular preference is given to using the sodium, lithium or potassium or methyl or ethyl esters of cholic acid, glycocholic acid, taurocholic acid, deoxycholic acid, glycodeoxycholic acid, taurodeoxycholic acid, chenodeoxycholic acid, glycochenodeoxycholic acid, taurochenodeoxycholic acid, lithocholic acid, hyocholic acid, hyodeoxycholic acid or mixtures thereof.

Bile acids such as ursobile acid (Ursochol ure) (3 alpha, 7 beta, 12 alpha-trihydroxy-5 beta-cholane-24-oic acid), ursodeoxycholic acid (3 alpha, 7 beta-dihydroxy-5 beta-cholane-24-oic acid), 7-oxolithocholic acid (3 alpha-hydroxy-7-oxo-5 beta-cholane-24-oic acid), lithocholic acid 3-sulfate (3 alpha-hydroxy-5 beta-cholane-24-oic acid 3-sulfate), norcholic acid (nor-chol ure) and bisnorcholic acid, or salts, esters or amides thereof are also suitable.

Bile acids and their salts, esters or amides are generally known and described in nachr. chem. tech. lab.43(1995)1047, selchell et al: the Bile Acids, Vol.IV, Plenum, New York 1998 and R * mpp, Lexikon Nature stoffe, Stuttgart, New York 1997, page 248 and The following are described in detail.

Suitable cyclodextrins for component c) are, for example, unsubstituted cyclodextrins or esters thereof, alkyl ethers, hydroxyalkyl ethers, alkoxycarbonyl alkyl ethers and carboxyalkyl ether derivatives or salts thereof.

Cyclodextrins are cyclohexyl-, cycloheptyl-or cyclooctyl amylose having 6, 7 or 81, 4-cross-linked glucose units, which are formed by degrading starch by Paenibacillus macerans and Bacillus circulans with the aid of cyclodextrin glycosyltransferases, for example alpha-, beta-, gamma-or delta-cyclodextrins.

Suitable carboxylic acid components for the cyclodextrin esters are aryl, aralkyl and alkyl carboxylic acids having from 2 to 30 carbon atoms, preferably from 2 to 24 carbon atoms, particularly preferably from 2 to 20 carbon atoms, preferably aralkyl and alkyl carboxylic acids, particularly preferably alkyl carboxylic acids.

Straight-chain or branched alkyl radicals having from 1 to 30 carbon atoms, preferably from 1 to 24 carbon atoms, particularly preferably from 1 to 20 carbon atoms, are conceivable as alkyl components of cyclodextrin alkyl ethers, hydroxyalkyl ethers, alkoxycarbonyl alkyl ethers and carboxyalkyl ethers.

The cyclodextrins preferably used are α -, β -and γ -cyclodextrins and the mono-, di-and triethers, mono-, di-and triesters or monoesters/diesters thereof, generally obtained by etherification of α -, β -and γ -cyclodextrins with alkylating agents, such as dimethyl sulfate or alkyl halides having from 1 to 30 carbon atoms, for example methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, heptyl-, octyl-chloride, bromide or iodide and/or by esterification with acetic acid or succinic acid in the presence of acids.

Methyl-alpha-cyclodextrin, methyl-beta-cyclodextrin, methyl-gamma-cyclodextrin, ethyl-beta-cyclodextrin, butyl-alpha-cyclodextrin, butyl-beta-cyclodextrin, butyl-gamma-cyclodextrin, 2, 6-dimethyl-alpha-cyclodextrin, 2, 6-dimethyl-beta-cyclodextrin, 2, 6-dimethyl-gamma-cyclodextrin, 2, 6-diethyl-beta-cyclodextrin, 2, 6-dibutyl-beta-cyclodextrin, 2, 3, 6-trimethyl-alpha-cyclodextrin, 2, 3, 6-trimethyl-beta-cyclodextrin, 2, 3, 6-trimethyl-gamma-cyclodextrin, methyl-gamma-cyclodextrin, ethyl-beta-cyclodextrin, butyl-alpha-cyclodextrin, butyl-beta-cyclodextrin, 2, 6-dimethyl-beta-cyclodextrin, 2, 6-diethyl-beta-cyclodextrin, 2, 6-dibutyl-beta-cyclodextrin, 2, 2, 3, 6-trioctyl-alpha-cyclodextrin, 2, 3, 6-trioctyl-beta-cyclodextrin, 2, 3, 6-triacetyl-alpha-cyclodextrin, 2, 3, 6-triacetyl-beta-cyclodextrin, 2, 3, 6-triacetyl-gamma-cyclodextrin, (2-hydroxy) propyl-alpha-cyclodextrin, (2-hydroxy) propyl-beta-cyclodextrin, (2-hydroxy) propyl-gamma-cyclodextrin, partially or fully acetylated and succinylated alpha-, beta-and gamma-cyclodextrin, 2, 6-dimethyl-3-acetyl-beta-cyclodextrin or 2, 6-dibutyl-3-acetyl-beta-cyclodextrin.

Processes for preparing cyclodextrins are generally known and are described, for example, in R * mpp, Lexikon Chemie, tenth edition, Stuttgart/New York, 1997, page 845 and below and chemical reviews 98(1998)1743 are described in detail.

Phosphorus compounds suitable for component c) in the catalysts of the invention are organic phosphates, such as phosphoric acid mono-, di-or triesters, pyrophosphoric acid mono-, di-, tri-or tetraesters and polyphosphoric acid and mono-, di-, tri-, tetra-or polyesters of alcohols having from 1 to 30 carbon atoms.

Suitable organophosphites are mono-, di-or triesters of phosphorous acid and alcohols having 1 to 30 carbon atoms.

Suitable organic phosphonates for component c) are, for example, mono-or diesters of phosphonic acid, alkylphosphonic acids, arylphosphonic acids, alkoxycarbonylalkylphosphonic acids, alkoxycarbonylphosphonic acids, cyanoalkylphosphonic acids and cyanophosphonic acids or mono-, di-, tri-or tetraesters of alkylphosphonic acids with alcohols having from 1 to 30 carbon atoms.

The phosphonites more suitable for component c) are the diesters of phosphonous or arylphosphonous acids and alcohols having from 1 to 30 carbon atoms.

Phosphinic acid esters (component c)) suitable for the preparation of the catalysts of the invention are esters of phosphinic acids, alkylphosphinic acids, dialkylphosphinic acids or arylphosphinic acids with alcohols having from 1 to 30 carbon atoms.

The phosphinic acid esters (component c)) suitable for the preparation of the catalysts according to the invention are esters of alkyl, dialkyl or aryl phosphinic acids with alcohols having from 1 to 30 carbon atoms.

Suitable alcohol components are mono-or polyhydroxyl aryl, aralkyl, alkoxyalkyl and alkyl alcohols having 1 to 30 carbon atoms, preferably 1 to 24 carbon atoms, particularly preferably 1 to 20 carbon atoms, preferably aralkyl, alkoxyalkyl and alkyl alcohols, particularly preferably alkoxyalkyl and alkyl alcohols.

The organophosphates, phosphites, phosphonates, phosphonites, phosphinites or phosphinites used for the preparation of the catalysts of the invention are generally prepared by reacting phosphoric acid, pyrophosphoric acid, polyphosphoric acid, phosphonic acid, alkylphosphonic acids, arylphosphonic acids, alkoxycarbonylalkylphosphonic acids, alkoxycarbonylphosphonic acids, cyanoalkylphosphonic acids, cyanophosphonic acids, alkylphosphonic acids, phosphinic acids or their halogen derivatives or their phosphorus oxides with hydroxyl compounds having from 1 to 30 carbon atoms, for example methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, heptanol, octanol, nonanol, decanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, methoxymethanol, ethoxymethanol, propoxymethanol, butoxymethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, phenol, ethyl glycolate, propyl glycolate, ethyl hydroxypropionate, propyl hydroxypropionate, 1, 2-ethanediol, 1, 2-propanediol, 1, 2, 3-trihydroxypropane, 1, 1, 1-trimethylolpropane or pentaerythritol.

Triethyl phosphate, tributyl phosphate, trioctyl phosphate, tris (2-ethylhexyl) phosphate, tris (2-butoxyethyl) phosphate, dibutyl butyl phosphonate, dioctyl phenyl phosphonate, triethyl phosphonoformate, trimethyl phosphonoacetate, triethyl phosphonoacetate, trimethyl 2-phosphonopropionate, triethyl 2-phosphonopropionate, tripropyl2-phosphonopropionate, tributyl 2-phosphonopropionate, triethyl 3-phosphonopropionate, tributyl phosphite, trilauryl phosphite, tris (3-ethoxyethyl) -3-methyl) phosphite, and heptakis (dipropylene glycol) phosphite.

Methods for the preparation of phosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid, phosphinic acid esters are generally known and are described, for example, in Kirk-Othmer Encyclopedia of chemical technology, volume 18, fourth edition, 1996, page 737 and below; r * mpp, Lexikon Chemie, volume four, tenth edition, Stuttgart/New York, 1998, p 3280 and below; ullmann's Encyclopedia of Industrial Chemistry, volume A19, 5 th edition, 1991, p 545 and below; Houben-Weyl: methoden der organischen Chemie, volumes XII/1 and XII/2, Stuttgart 1963/1964, is described in detail.

Suitable α, β -unsaturated carboxylic acid esters (component c)) for preparing the catalysts of the invention are, for example, acrylic acid and mono-, di-, tri-or polyesters of alkyl-, alkoxy-, alkoxycarbonyl-and alkoxycarbonylalkylacrylic acids with alcohols having from 1 to 30 carbon atoms.

Suitable alcohol components are mono-, di-, tri-or polyhydroxyaryl, aralkyl, alkoxyalkyl and alkyl alcohols having 1 to 30 carbon atoms, preferably 1 to 24 carbon atoms, particularly preferably 1 to 20 carbon atoms, preferably aralkyl, alkoxyalkyl and alkyl alcohols, particularly preferably alkoxyalkyl and alkyl alcohols.

Suitable alcohol components are also polyalkylene glycols and polyalkylene glycol ethers, preferably polypropylene glycols and polyethylene glycols or ethers thereof, having molecular weights of from 200 to 10000, preferably from 300 to 9000, particularly preferably from 400 to 8000.

Alpha, beta-unsaturated carboxylic acids which may be considered are acrylic acid and alkyl, alkoxy and alkoxycarbonyl alkyl acrylic acids having 1 to 20 carbon atoms, such as 2-methacrylic acid (methacrylic acid), 3-methacrylic acid (crotonic acid), trans-2, 3-dimethylacrylic acid (tiglic acid), 3-dimethylacrylic acid (isopentenoic acid) or 3-methoxyacrylic acid, preferably acrylic acid, 2-methacrylic acid, 3-methacrylic acid and 3-methoxyacrylic acid, particularly preferably acrylic acid and 2-methacrylic acid.

The α, β -unsaturated carboxylic acid esters prepared by the catalysts used in the present invention are generally prepared by means of mono-, di-, tri-, tetra-or polyhydroxyl compounds having from 1 to 30 carbon atoms, such as methanol, ethanol, ethylene glycol, 1-propanol, 2-propanol, 1, 2-propanediol, 1, 3-propanediol, 1, 2, 3-propanetriol (glycerol), butanol, 2-butanol, i-butanol, 1, 2-butanediol, 1, 3-butanediol, 2, 3-butanediol, 1, 4-butanediol, 1, 2, 3-butanetriol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-hexadecanol, 1-heptadecanol, 9-octadecanol, 1, 1, 1-tris (hydroxymethyl) propane, pentaerythritol, methoxymethanol, ethoxymethanol, propoxymethanol, butoxymethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, methyl glycolate, ethyl glycolate, propyl glycolate, methyl hydroxypropionate, ethyl hydroxypropionate, propyl hydroxypropionate or polyether polyols, such as polyethylene glycol and polypropylene glycol, by esterification with suitable α, β -unsaturated carboxylic acids, optionally in the presence of a catalyst.

Preference is given to mono-, di-and triesters of acrylic acid and methacrylic acid with ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 2, 3-propanetriol, 1, 1, 1-tris (hydroxymethyl) propane ethoxylate, 1, 1, 1-tris (hydroxymethyl) propane propoxylate, polyethylene glycol and polypropylene glycol.

Particularly preferred alpha, beta-unsaturated carboxylic acid esters are polyethylene glycol acrylate, polyethylene glycol diacrylate, polyethylene glycol methacrylate, polyethylene glycol dimethacrylate, polypropylene glycol acrylate, polypropylene glycol diacrylate, polypropylene glycol methacrylate, polypropylene glycol dimethacrylate, 1, 2, 3-glycerol diacrylate, 1, 2, 3-glycerol dimethacrylate, 1, 2, 3-glycerol triacrylate, 1, 4-butanediol acrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, 1, 2, 3-glycerol propoxylate triacrylate, 1, 4-butanediol dimethacrylate, 1, 4-butanediol diacrylate, polypropylene glycol dimethacrylate, 2-hydroxypropyl methacrylate, 1, 1, 1-tris (hydroxymethyl) propane triacrylate, 1, 1, 1-tris (hydroxymethyl) propane ethoxylate trimethacrylate, 1, 1, 1-tris (hydroxymethyl) propane propoxylate triacrylate or 1, 1, 1-tris (hydroxymethyl) propane propoxylate trimethacrylate.

Methods for preparing α, β -unsaturated carboxylic acid esters are generally known and described in, for example, Kirk-Othmer: encyclopedia of Chemical Technology, volume 18, fourth edition, 1996, page 737 and below. (ii) a R * mpp, Lexikon Chemie, volume 4, tenth edition, Stuggart, New York, 1998, p 3286 and below; ullmann's Encyclopedia of Industrial Chemistry, volume A19, fifth edition, 1991, p 545 and below; Houben-Weyl; methoden der organischen Chemie, volumes XII/1 and XII/2, Stuttgart 1963/1964 is described in detail.

The structures of the ionic surface-or interface-active compounds suitable for preparing the catalysts of the invention are characterized by their amphiphilic molecular structure, that is to say that they comprise at least one hydrophilic group (or hydrophilic ionic part) and at least one hydrophobic group (or hydrophobic part). Examples of such ionic surface or interface-active compounds can be found in surfactants, soaps, emulsifiers, detergents and dispersants.

The hydrophilic ionic groups may be anionic, cationic or amphiphilic (amphoteric) in nature. Examples of anionic groups are carboxylate, sulfonate, sulfate, thiosulfate, phosphonate, phosphinate, phosphate or dithiophosphate groups. Examples of cations are ammonium, phosphonium or sulfonium groups. Examples of amphiphilic ionic groups are betaine, sulphobetaine or amine oxide groups.

The hydrophobic group is preferably C₂-C₅₀Hydrocarbon residues such as aryl, aralkyl and alkyl residues. But fluoroalkyl, silalkyl, thiaalkyl, oxaalkyl groups are also suitable.

Examples of suitable classes of compounds having hydrophilic anionic groups are carboxylates, such as alkyl carboxylates (soaps), ether carboxylates (carboxymethylated ethoxylates), polycarboxylates, such as malonates and succinates, bile salts, bile acid amides, such as in the form of salts, having sulfoalkyl and carboxyalkyl residues, amino acid derivatives, such as sarcosinates (alkanoylsarconates), sulfonamide carboxylates, sulfates, such as alkylsulfates, ether sulfates, such as aliphatic alcohol ether sulfates, aryl ether sulfates or amidoether sulfates, sulfated carboxylates, sulfated glycerol carboxylates, sulfated carboxylic esters, sulfated carboxylic amides, sulfonates, such as alkyl, aryl and alkylaryl sulfonates, sulfonated carboxylates, sulfonated carboxylic esters, sulfonated carboxylic acid amides, carboxylic ester sulfonates, such as alpha-sulfofatty acid esters, sulfonated carboxylic acid esters, sulfonated esters, and sulfonic acid esters, Carboxamide sulfonates, sulfosuccinates, ether sulfonates, thiosulfates, phosphates, such as alkyl phosphates or glycerophosphates, phosphonates, phosphinates and dithiophosphates.

Examples of suitable classes of compounds having hydrophilic cationic groups are primary, secondary, tertiary and quaternary ammonium salts having alkyl, aryl and aralkyl residues, alkoxylated ammonium salts, quaternary ammonium esters, benzylammonium salts, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, thiazolinium salts, amine oxide salts, sulfonium salts, quinolinium salts, isoquinolinium salts and  onium salts.

Examples of suitable classes of compounds having hydrophilic amphiphilic (amphoteric) groups are amine oxides, imidazolinium derivatives, such as imidazolinium carboxylates, betaines, such as alkyl-and amidopropyl betaines, sulphobetaines, aminocarboxylic acids and phospholipids, such as phosphatidylcholine (lecithin).

Of course, the ionic surface-or interface-active compound may also comprise two or more hydrophilic (anionic and/or cationic and/or amphiphilic) groups or moieties.

Methods suitable for preparing the ionic surface or interface-active compounds of the catalysts of the invention are generally known and are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, fifth edition, volume A25, page 747-.

The catalyst composition is conventionally analyzed by elemental analysis, thermogravimetric analysis, or extractive removal of complex-forming components followed by gravimetric determination.

The catalysts of the invention may be crystalline, partially crystalline or amorphous. The crystallinity is usually analyzed by powder X-ray diffraction.

Particularly preferred catalysts of the invention comprise:

a) zinc hexacyanocobaltate (III),

b) tert-butanol and

c) two or more of the above types of complex-forming components.

The DMC catalysts of the invention are usually prepared in aqueous solution by reacting metal salts, in particular of the formula (I), with metal cyanide salts, in particular of the formula (II), in the presence of organic complex ligands b), where the organic complex ligands b) are neither functionalized polymers, glycidyl ethers, glycosides, carboxylic esters of polyols, bile acids or their salts, esters or their amides, cyclodextrins, phosphorus compounds, α, β -unsaturated carboxylic esters, nor ionic surface-or interface-active compounds, and two or more complex-forming components c).

In this process, an aqueous solution of a metal salt (e.g. zinc chloride used in a stoichiometric excess (at least 50 mol% relative to the metal cyanide salt) and an aqueous solution of a metal cyanide salt (e.g. potassium hexacyanocobaltate) are preferably first reacted in the presence of an organic complex ligand b) (e.g. tert-butanol) wherein a suspension is formed comprising a double metal cyanide compound a) (e.g. zinc hexacyanocobaltate), water d), an excess of metal salt e), and an organic complex ligand b).

The organic complex ligands b) may here be present in aqueous solutions of metal salts and/or of metal cyanide salts or added directly to the suspension obtained after precipitation of the double metal cyanide compound a). It is advantageous to mix the aqueous solution with the organic complex ligand b) under vigorous stirring. The resulting suspension is then usually treated with a mixture of two or more complex-forming components c). Mixtures of two or more complex-forming components c) are preferably used here as mixtures of water and organic complex ligands b).

The catalyst is then separated from the suspension by known methods, such as centrifugation or filtration. In a variant of the preferred embodiment, the separated catalyst is then washed with an aqueous solution of the organic complex ligand b) (for example by resuspension followed by re-separation by filtration or centrifugation). In this way it is possible to remove, for example, water-soluble second products, such as potassium chloride, from the catalyst of the invention.

The amount of organic complex ligand b) in the aqueous washing solution is preferably from 40 to 80% by weight, based on the total solution. A small amount, preferably 0.5 to 5% by weight, relative to the total solution, of a mixture of two or more complex-forming components c) is added to the aqueous washing solution.

Furthermore, it is advantageous to wash the catalyst more than once. For example, the first washing operation may be repeated for this purpose. However, preference is given to carrying out further washing operations using nonaqueous solutions, for example mixtures of organic complex ligands and mixtures of two or more complex-forming components c).

The washed catalyst, optionally after being ground to powder, is dried at temperatures of generally from 20 to 100 ℃ and pressures of generally from 0.1 mbar to standard (1013 mbar).

The invention also provides for the use of the DMC catalysts of the invention in a process for preparing polyether polyols by polyaddition of alkylene oxides to starter compounds containing active hydrogen atoms.

Alkylene oxides which are preferably used are ethylene oxide, propylene oxide, butylene oxide and mixtures thereof. The synthesis of the polyether chains by alkoxylation can be carried out, for example, with only one monomeric epoxide or also with 2 or 3 different monomeric epoxides, either randomly or in blocks. For more details, see Ullmanns encyclopedia der industrillen Chemie, Vol.A 21, 1992, p.670 and below.

The starter compounds containing active hydrogen atoms are preferably compounds having a (number average) molecular weight of 18 to 2000 and 1 to 8 hydroxyl groups. Examples which may be mentioned are: ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propanediol, 1, 4-butanediol, hexamethylene glycol, bisphenol A, trimethylolpropane, glycerol, pentaerythritol, sorbitol, sucrose, degraded starch or water.

The starter compounds containing active hydrogen atoms which are preferably used are, for example, those which are prepared from the abovementioned low molecular weight starter compounds by conventional alkali metal catalysis and comprise oligomeric alkoxylation products having a (number average) molecular weight of from 200 to 2000.

The polyaddition of alkylene oxides onto starter compounds containing active hydrogen atoms is catalyzed by the catalysts of the invention and is generally carried out at from 20 to 200 ℃, preferably from 40 to 180 ℃ and particularly preferably from 50 to 150 ℃. The reaction is carried out at a total pressure of from 0.0001 to 20 bar. The polyaddition can be carried out without solvent or in inert organic solvents, for example toluene and/or THF. The amount of solvent is generally from 10 to 30% by weight, relative to the amount of polyether polyol produced.

The catalyst concentration is chosen such that the polyaddition reaction is kept under good control under the reaction conditions. The catalyst concentration is generally in the range from 0.0005 wt.% to 1 wt.%, preferably from 0.001 wt.% to 0.1 wt.%, particularly preferably from 0.001 wt.% to 0.0025 wt.%, relative to the amount of polyether polyol produced.

The (number average) molecular weight of the polyether polyols prepared using the process of the present invention is in the range from 500 to 100000g/mol, preferably from 1000 to 50000g/mol, particularly preferably from 2000 to 20000 g/mol.

The polyaddition can be carried out continuously or discontinuously, for example in a batch or semibatch process.

Due to the significantly improved activity, the catalysts of the invention can be used in very low concentrations (25ppm and below, relative to the amount of polyether polyol produced). If the polyether polyols prepared in the presence of the catalysts according to the invention are used in the preparation of polyurethanes (Kunststoffhandbuch, volume 7, Polyurethane, third edition, 1993, pages 25 to 32 and 57 to 67), the product quality of the polyurethanes obtained can also not be negatively influenced without removing the catalyst from the polyether polyols.

Detailed Description

Examples

Preparation of the catalyst

Example A

The DMC catalyst (catalyst A) was prepared using glycerol trihexanoate and triethyl 2-phosphonopropionate.

A solution of 12.5g (91.5mmol) of zinc chloride in 20ml of distilled water is added with vigorous stirring (24000rpm) to a solution of 4g (12mmol) of potassium hexacyanocobaltate in 70ml of distilled water. A mixture of 50g of tert-butanol and 50g of distilled water was then immediately added and the suspension obtained, which was then stirred vigorously for 10 minutes (24000 rpm). A mixture of 0.5g of glycerol trihexanoate and 0.5g of triethyl 2-phosphonopropionate, 1g of tert-butanol and 100g of distilled water was then added and stirred for 3 minutes (1000 rpm). The solid was separated by filtration and then stirred with a mixture of 70g of tert-butanol, 30g of distilled water, 0.5g of glycerol trihexanoate and 0.5g of triethyl 2-phosphonopropionate for 10 minutes (10000rpm) and filtered again. Finally, the product is stirred for a further 10 minutes (10000rpm) with a mixture of 100g of tert-butanol, 0.5g of glycerol trihexanoate and 0.5g of triethyl 2-phosphonopropionate. After filtration, the catalyst was dried to constant weight at 50 ℃ and standard pressure.

Yield of dried powdered catalyst: 5.8 g.

Elemental analysis, thermogravimetric analysis and extraction:

9.8 wt.% cobalt, 23.2 wt.% zinc, 3.0 wt.% tert-butanol, 11.4 wt.% glycerol trihexanoate, 16.9 wt.% triethyl 2-phosphonopropionate.

Example B

The DMC catalyst (catalyst B) was prepared using polypropylene glycol diglycidyl ether and triethyl 2-phosphonopropionate.

The same procedure as in example A was used, except that polypropylene glycol diglycidyl ether having an average molar mass of 640 and triethyl 2-phosphonopropionate were used instead of the glycerol trihexanoate and triethyl 2-phosphonopropionate.

Yield of dried powdered catalyst: 6.8 g.

Elemental analysis, thermogravimetric analysis and extraction:

10.3 wt.% cobalt, 23.4 wt.% zinc, 1.3 wt.% tert-butanol, 20.5 wt.% polypropylene glycol diglycidyl ether, 8.5 wt.% triethyl 2-phosphonopropionate.

Example C

The DMC catalyst (catalyst C) was prepared using polyester and sodium cholate salt.

The same procedure as in example A was used, except that the trihexanoic acid glyceride and the triethyl 2-phosphonopropionate were replaced by a polyester prepared from adipic acid and diethylene glycol and slightly branched with trimethylolpropane and having an average molar mass of 2300(OH number 50mg KOH/g) and by the sodium salt of cholic acid.

Yield of dried powdered catalyst: 4.8 g.

Elemental analysis, thermogravimetric analysis and extraction:

cobalt 12.7 wt.%, zinc 25.2 wt.%, tert-butanol 4.2 wt.%, polyester 12.8 wt.%, and sodium cholate 3.7 wt.%.

Example D (comparative example)

The DMC catalyst (catalyst D) was prepared using glycerol trihexanoate in the absence of triethyl 2-phosphonopropionate.

A solution of 12.5g (91.5mmol) of zinc chloride in 20ml of distilled water is added with vigorous stirring (24000rpm) to a solution of 4g (12mmol) of potassium hexacyanocobaltate in 75ml of distilled water. A mixture of 50g of tert-butanol and 50g of distilled water was then immediately added to the suspension obtained and stirred vigorously for 10 minutes (24000 rpm). A mixture of 1g of glycerol trihexanoate (Aldrich), 1g of tert-butanol and 100g of distilled water was then added and stirred for 3 minutes (10000 rpm). The solid was separated by filtration and then stirred with a mixture of 70g of tert-butanol, 30g of distilled water and 1g of the abovementioned glycerol trihexanoate for 10 minutes and filtered again. Finally, the product was stirred for a further 10 minutes (10000rpm) with a mixture of 100g of tert-butanol and 0.5g of glycerol trihexanoate. After filtration, the catalyst was dried to constant weight at 50 ℃ and standard pressure.

Yield of dried powdered catalyst: 5.3 g.

Elemental analysis, thermogravimetric analysis and extraction:

12.3 wt.% cobalt, 27.0 wt.% zinc, 7.2 wt.% tert-butanol and 3.7 wt.% glycerol trihexanoate.

Example E (comparative example)

The DMC catalyst (catalyst E) was prepared using triethyl 2-phosphonopropionate in the absence of glycerol trihexanoate.

The same procedure as in example D (comparative example) was used, except that triethyl 2-phosphonopropionate (Fluka) was used instead of the glycerol trihexanoate in example D.

Yield of dried powdered catalyst: 5.9 g.

Elemental analysis, thermogravimetric analysis and extraction:

10.2 wt.% cobalt, 23.5 wt.% zinc, 2.3 wt.% tert-butanol, 26.1 wt.% triethyl 2-phosphonopropionate.

Example F (comparative example)

The DMC catalyst (catalyst F) was prepared using polypropylene glycol diglycidyl ether in the absence of triethyl 2-phosphonopropionate.

The same procedure as in example D (comparative example) was used, except that polypropylene glycol diglycidyl ether (Aldrich) having an average molar mass of 640 was used in place of the glycerol trihexanoate in example D.

Yield of dried powdered catalyst: 6.0 g.

Elemental analysis, thermogravimetric analysis and extraction:

cobalt 8.7 wt.%, zinc 20.2 wt.%, tert-butanol 4.2 wt.%, and polypropylene glycol diglycidyl ether ligand 30.5 wt.%.

Example G (comparative example)

The DMC catalyst (catalyst G) was prepared using polyester in the absence of the sodium cholate salt.

The same procedure as in example D (comparative example) was used, except that the glycerol trihexanoate in example D was replaced by a polyester having an average molar mass of 2300(OH number 50mgKOH/g), prepared from adipic acid and diethylene glycol and slightly branched with trimethylolpropane.

Yield of dried powdered catalyst: 3.9 g.

Elemental analysis, thermogravimetric analysis and extraction:

12.2 wt.% cobalt, 25.7 wt.% zinc, 7.1 wt.% tert-butanol and 12.3 wt.% polyester.

Example H (comparative example)

The DMC catalyst (catalyst H) was prepared in the absence of polyester using the sodium salt of cholic acid.

The same procedure as in example D (comparative example) was used except that the glycerol trihexanoate in example D was replaced with the sodium salt of cholic acid.

Yield of dried powdered catalyst: 4.2 g.

Elemental analysis, thermogravimetric analysis and extraction:

12.6 wt.% cobalt, 27.3 wt.% zinc, 10.9 wt.% tert-butanol and 4.3 wt.% sodium cholate.

Preparation of polyether polyols

General procedure

50g of a polypropylene glycol starter compound (number-average molecular weight 1000g/mol) and 5mg of catalyst (25ppm, relative to the amount of polyether polyol prepared) were initially introduced under protective gas (argon) into a 500ml autoclave and heated to 105 ℃ with stirring. Propylene oxide (ca. 5g) was then added in one portion until the total pressure had risen to 2.5 bar. Propylene oxide was then not added in portions until an accelerated drop in pressure in the reactor was observed. This accelerated drop in pressure indicates that the catalyst has been activated. The remaining propylene oxide (145g) was then added in portions at a constant total pressure of 2.5 bar. When all the propylene oxide had been added and reacted at 105 ℃ for a further 2 hours, the volatile fractions were removed by distillation at 90 ℃ (1 mbar) and the temperature was then brought to room temperature.

The polyether polyols obtained were characterized by determining their OH number, double bond content and viscosity.

The course of the reaction is monitored by means of a time/conversion curve (consumption of propylene oxide [ g ] versus reaction time [ min ]). Induction time was determined by the intersection of the tangent to the steepest point of the time/transformation curve with the extended baseline of the curve. The propoxylation time, which is significant for the catalyst activity, corresponds to the period between the activation of the catalyst (end of the induction phase) and the completion of the propylene oxide addition. The total reaction time is the sum of the induction time and the propoxylation time.

Example 1

Preparation of polyether polyol with catalyst A (25ppm)

Induction time: 100min

Time of propoxylation: 40min

Total reaction time: 140min

Polyether polyol: OH number (mg KOH/g): 29.4

Double bond content (mmol/kg): 9

Viscosity, 25 ℃ (mPas): 845

Example 2

Preparation of polyether polyol with catalyst B (25ppm)

Induction time: 140min

Time of propoxylation: 37min

Total reaction time: 177min

Polyether polyol: OH number (mg KOH/g): 30.0

Double bond content (mmol/kg): 7

Viscosity, 25 ℃ (mpas): 821

Example 3

Preparation of polyether polyol with catalyst C (25ppm)

Induction time: 80min

Time of propoxylation: 27min

Total reaction time: 107min

Polyether polyol: OH number (mg KOH/g): 30.1

Double bond content (mmol/kg): 7

Viscosity, 25 ℃ (mPas): 863

If the catalyst is not removed, the metal content in the polyol is: zn is 5ppm and Co is 2ppm.

Example 4 (comparative example)

Preparation of polyether polyol with catalyst D (25ppm)

Induction time: 166min

Time of propoxylation: 291min

Total reaction time: 457min

Polyether polyol: OH number (mg KOH/g): 30.9

Double bond content (mmol/kg): 8

Viscosity, 25 ℃ (mPas): 874

Example 5 (comparative example)

Preparation of polyether polyol with catalyst E (25ppm)

Induction time: 99min

Time of propoxylation: 110mi n

Total reaction time: 209min

Polyether polyol: OH number (mg KOH/g): 29.9

Double bond content (mmol/kg): 10

Viscosity, 25 ℃ (mPas): 862

Example 6 (comparative example)

Preparation of polyether polyol with catalyst F (25ppm)

Induction time: 154min

Time of propoxylation: 37min

Total reaction time: 191min

Polyether polyol: OH number (mg KOH/g): 30.7

Double bond content (mmol/kg): 7

Viscosity, 25 ℃ (mPas): 809

Example 7 (comparative example)

Preparation of polyether polyol with catalyst G (25ppm)

Induction time: 130min

Time of propoxylation: 150min

Total reaction time: 280min

Polyether polyol: OH number (mg KOH/g): 29.5

Double bond content (mmol/kg): 5

Viscosity, 25 ℃ (mPas): 861

Example 8 (comparative example)

Preparation of polyether polyol with catalyst H (25ppm)

Induction time: 217min

Time of propoxylation: 33min

Total reaction time: 250min

Polyether polyol: OH number (mg KOH/g): 29.6

Double bond content (mmol/kg): 6

Viscosity, 25 ℃ (mPas): 855

Under the reaction conditions described above, catalysts A-C, which contained two complex-forming components other than t-butanol, exhibited higher activity than catalysts D-H, which contained only one complex ligand other than t-butanol.

Thus, catalyst A, which comprises glycerol trihexanoate and triethyl 2-phosphonopropionate as complex-forming components, exhibits an activity which is much higher than that of catalysts D or E, which comprise glycerol trihexanoate or triethyl 2-phosphonopropionate, respectively, as complex-forming components, especially in view of the propoxylation time.

Examples 1-3 show that, owing to their significantly increased activity, the novel DMC catalysts of the present invention can be used in the preparation of polyether polyols at such low concentrations that the catalyst can be dispensed with for removal from the polyol.

Claims (8)

1. Double Metal Cyanide (DMC) catalysts comprising

a) One or more double metal cyanide compounds,

b) one or more organic complex ligands other than c), and

c) two complex-forming components, one of which is selected from the group consisting of polyesters and the other is selected from the group consisting of bile acids or salts, esters or amides thereof.

2. The DMC catalyst of claim 1, further comprising d) water and/or e) a water-soluble metal salt.

3. The DMC catalyst as recited in claim 1, wherein the double metal cyanide compound is zinc hexacyanocobaltate (III).

4. The DMC catalyst of any of claims 1 to 3, wherein the organic complex ligand is tert-butanol.

5. The DMC catalyst of any of claims 1 to 4, wherein the catalyst comprises from 1 to 80 wt.% of a mixture of two or more complex-forming components c).

6. Method for preparing DMC catalyst, comprising the following steps

i) Reacting the following components in an aqueous solution

Alpha) metal salts and metal cyanide salts

Beta) organic complex ligands which are neither functionalized polymers, glycidyl ethers, glycosides, carboxylic esters of polyols, bile acids or salts, esters or amides thereof, cyclodextrins, phosphorus compounds, alpha, beta-unsaturated carboxylic esters, nor ionic surface-or interface-active compounds, and

γ) two complex-forming components c) according to claim 1,

ii) separating, washing and drying the catalyst obtained in step i).

7. Process for the preparation of polyether polyols by polyaddition of alkylene oxides to starter compounds containing active hydrogen atoms in the presence of one or more DMC catalysts as claimed in any of claims 1 to 5.

8. Use of one or more DMC catalysts according to any of claims 1 to 5 for the preparation of polyether polyols by polyaddition of alkylene oxides to starter compounds containing active hydrogen atoms.