Double metal cyanide catalysts for the preparation of polyetherpolyols

The invention relates to new double metal cyanide (DMC) catalysts for the production of polyether polyols by polyaddition of alkylene oxides onto starter compounds having active hydrogen atoms.

Double metal cyanide (DMC) catalysts for the polyaddition of alkylene oxides to starter compounds having active hydrogen atoms are known (see, for example, US Pat. Nos. 3,440,109, 3,829,505, 3,941,849 and 5,158,922). The use of these DMC catalysts for the production of polyether polyols leads in particular to a reduction in the proportion of monofunctional polyethers with terminal double bonds, so-called monools, compared to the conventional production of polyether polyols using alkali catalysts, such as alkali metal hydroxides. The polyether polyols thus obtained can be processed to high-quality polyurethanes (eg elastomers, foams, coatings). DMC catalysts are usually obtained by reacting an aqueous solution of a metal salt with the aqueous solution of a metal cyanide salt in the presence of an organic complex ligand, for example an ether. In a typical catalyst preparation, for example, aqueous solutions of zinc chloride (in excess) and potassium hexacyanocobaltate are mixed and then dimethoxyethane (glyme) is added to the suspension formed. After filtration and washing the catalyst with aqueous glyme solution, an active catalyst of the general formula         Zn₃[Co (CN)₆]₂   x ZnCl₂   yH₂O z Glyme obtained (see for example EP-A 700 949).

DMC catalysts are known from JP-A 4 145 123, US-A 5 470 813, EP-A 700 949, EP-A 743 093, EP-A 761 708 and WO 97/40086. Butanol as an organic complex ligand (alone or in combination with a polyether (EP-A 700 949, EP-A 761 708, WO 97/40086)) further reduce the proportion of monofunctional polyethers with terminal double bonds in the production of polyether polyols. In addition, the use of these DMC catalysts reduces the induction time in the polyaddition reaction of the alkylene oxides with corresponding starter compounds and increases the catalyst activity.

The object of the present invention was to provide further improved DMC catalysts for the polyaddition of alkylene oxides to corresponding starter compounds which have increased catalyst activity in relation to the types of catalysts known hitherto. By reducing the alkoxylation times, this leads to improved economy of the manufacturing process for polyether polyols. Ideally, due to the increased activity, the catalyst can then be used in such low concentrations (25 ppm or less) that the very complex separation of the catalyst from the product is no longer necessary and the product can be used directly for the production of polyurethane.

Surprisingly, it has now been found that DMC catalysts which contain two or more different complex-forming components have a greatly increased activity in the production of polyether polyols in comparison with catalysts which contain only one complex-forming component.

The present invention therefore relates to a double metal cyanide (DMC) catalyst comprising<ul id="ul0001" list-style="none"><li>a) one or more, preferably a double metal cyanide compound,</li><li>b) an organic complex ligand which is neither a polyether, polyester, polycarbonate, polyalkylene glycol sorbitan ester, polyalkylene glycol glycidyl ether, polyacrylamide, a poly (acrylamide-co-acrylic acid), polyacrylic acid, poly (acrylic acid-co-maleic acid), a polyacrylonitrile, polyalkylacrylate, polyalkyl methacrylate, polyvinyl methyl ether , Polyvinyl ethyl ether, polyvinyl acetate, polyvinyl alcohol, poly-N-vinylpyrrolidone, a poly (N-vinylpyrrolidone-coacrylic acid), a polyvinyl methyl ketone, Poly (4-vinylphenol), poly (acrylic acid co-styrene), oxazoline polymer, polyalkyleneimine, maleic acid or maleic anhydride copolymer, a hydroxyethyl cellulose, a polyacetal, glycidyl ether, glycoside, carboxylic acid ester of polyhydric alcohols, a bile acid or a bile acid salt, bile acid esters, cyclodinic acid esters or cyclodinic acid esters or cyclodinic acid salts Phosphorus compound, an α, β-unsaturated carboxylic acid ester is still an ionic surface or surface-active compound,</li><li>c) two different complex-forming components, each selected from the group comprising: Polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycol glycidyl ethers, polyacrylamide, poly (acrylamide-co-acrylic acid), polyacrylic acid, poly (acrylic acid-co-maleic acid), polyacrylonitrile, polyalkyl acrylates, polyalkyl methacrylates, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl acetate, polyvinyl acetate, polyvinyl acetate vinyl pyrrolidone, poly (N-vinyl pyrrolidone-co-acrylic acid), polyvinyl methyl ketone, poly (4-vinylphenol), poly (acrylic acid-co-styrene), oxazoline polymers, Polyalkyleneimines, maleic acid and maleic anhydride copolymers, hydroxyethyl cellulose, polyacetals, glycidyl ethers, glycosides, carboxylic acid esters of polyhydric alcohols, bile acids and their salts, esters or amides, cyclodextrins, phosphorus compounds, α, β-unsaturated carboxylic acid esters and ionic surface or component compounds, where each belongs to another connection class from the group mentioned.</li></ul>

In the catalyst according to the invention, d) water, preferably 1 to 10% by weight and / or e) one or more water-soluble metal salts, preferably 5 to 25% by weight, of the formula (I) M (X)_n from the preparation of the double metal cyanide compounds 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 the same or different, preferably the same and an anion, preferably selected from the group of halides, hydroxides, sulfates, carbonates, cyanates, thiocyanates, isocyanates, isothiocyanates, carboxylates, oxalates or nitrates. The value for n is 1, 2, or 3.

The double metal cyanide compounds a) contained in the catalysts according to the invention are the reaction products of water-soluble metal salts and water-soluble metal cyanide salts.

Water-soluble metal salts suitable for the preparation of 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 the same or different, preferably the same and are preferably selected from the group of halides, hydroxides, sulfates, carbonates, cyanates, thiocyanates, isocyanates, isothiocyanates, carboxylates, oxalates or nitrates. The value for 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) chloride, cobalt (II) thiocyanate, nickel ( II) chloride and nickel (II) nitrate. Mixtures of various water-soluble metal salts can also be used.

Water-soluble metal cyanide salts suitable for the preparation of double metal cyanide compounds a) preferably have the general formula (II) (Y)_a M '(CN)_b (A)_c, where 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 can contain one or more of these metals. The cations Y are the same or different, preferably the same, and are selected from the group consisting of alkali metal ions and alkaline earth metal ions. The anions A are the same or different, preferably the same, and are selected from the group of halides, hydroxides, sulfates, carbonates, cyanates, thiocyanates, isocyanates, isothiocyanates, carboxylates, oxalates or nitrates. Both a and b and c are integers, the values ​​for a, b and c being chosen such that the electroneutrality of the metal cyanide salt is given; a is preferably 1, 2, 3 or 4; b is preferably 4, 5 or 6; c preferably has the value 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).

Preferred double metal cyanide compounds a) which are contained in the catalysts according to the invention are compounds of the general formula (III)         M_x[M '_x, (CN)_y]_e.g., where M is as in formula (I) and M 'is as defined in formula (II), and x, x ', y and z are integers and are selected so that the electroneutrality of the double metal cyanide compound is given.

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 hexacyanoiridate (III), zinc hexacyanoferrate (III) and cobalt (II) hexacyanocobaltate (III). Further examples of suitable double metal cyanide compounds can be found, for example, in US Pat. No. 5,158,922. Zinc hexacyanocobaltate (III) is particularly preferably used.

The organic complex ligands b) contained in the DMC catalysts according to the invention are known in principle and are described in detail in the prior art (for example in US Pat. No. 5,158,922, US Pat. No. 3,404,109, US Pat. No. 3,829,505, US Pat 3 941 849, EP-A 700 949, EP-A 761 708, JP-A 4 145 123, US-A 5 470 813, EP-A 743 093 and WO 97/40086). Preferred organic complex ligands are water-soluble, organic compounds with heteroatoms, such as oxygen, nitrogen, phosphorus or sulfur, which can form complexes with the double metal cyanide compound 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, iso-butanol, sec-butanol and tert-butanol. Tert-butanol is particularly preferred.

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

The DMC catalysts according to the invention contain the double metal cyanide compounds a) in amounts of 20 to 90% by weight, preferably 25 to 80% by weight, based on the amount of the finished catalyst, and the organic complex ligands b) in amounts of 0 , 5 to 30 wt .-%, preferably 1 to 25 wt .-%, based on the amount of the finished catalyst. The DMC catalysts according to the invention usually contain 1 to 80% by weight, preferably 1 to 40% by weight, based on the amount of the finished catalyst, of a mixture of the complex-forming components c).

Complex-forming components c) suitable for the preparation of the catalysts according to the invention are the aforementioned functionalized polymers, glycidyl ethers, glycosides, carboxylic acid esters of polyhydric alcohols, bile acids or their salts, esters or amides, cyclodextrins, phosphorus compounds, α, β-unsaturated carboxylic acid esters or ionic surface or surfactant compounds.

Functionalized polymers suitable for the preparation of the catalysts according to the invention as component c) are known in principle and are described in detail in EP-A700949, WO 97/40086, WO 98/16310, and German patent applications 197 45 120.9, 197 57 574.9, 198 10 269.0 , 198 34 573.9 and 198 42 382.9. Suitable functionalized polymers are, for example Polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycol glycidyl ethers, polyacrylamide, poly (acrylamide-co-acrylic acid), polyacrylic acid, poly (acrylic acid-co-maleic acid), polyacrylonitrile, polyalkyl acrylates, polyalkyl methacrylates, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl acetate, polyvinyl acetate, polyvinyl acetate vinyl pyrrolidone, poly (N-vinyl pyrrolidone-co-acrylic acid), polyvinyl methyl ketone, poly (4-vinylphenol), poly (acrylic acid-co-styrene), oxazoline polymers, Polyalkyleneimines, maleic acid and maleic anhydride copolymers, hydroxyethyl cellulose and polyacetals.

Functionalized polymers used with preference are polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters and polyalkylene glycol glycidyl ethers.

Polyethers preferably used in component c) are polyether polyols with hydroxy functionalities from 1 to 8, particularly preferably from 1 to 3, and number average molecular weights between 150 and 10⁷, particularly preferably between 200 and 5 · 10⁴. They are generally obtained by ring-opening polymerization of epoxides in the presence of corresponding starter compounds having active hydrogen atoms under basic, acidic or coordinative catalysis (for example DMC catalysis). Suitable polyether polyols are, for example Poly (oxypropylene) polyols, poly (oxyethylene) polyols, EO-typed poly (oxypropylene) polyols, mixed EO / PO polyols, butylene oxide polymers, butylene oxide copolymers with ethylene oxide and / or propylene oxide and poly (oxytetramethylene) glycols

Polyesters preferably used in component c) are linear and partially branched polyesters having hydroxyl end groups and having average molecular weights below 10,000, which are described in more detail in German patent application 197 45 120.9. Polyesters with average molecular weights of 400 to 6000 and OH numbers of 28 to 300 mg KOH / g, which are suitable for the production of polyurethanes, are particularly preferably used. Suitable polyesters are, for example Poly (ethylene glycol adipate), poly (diethylene glycol adipate), poly (dipropylene glycol adipate), poly (diethylene glycol adipate) branched with trimethylol propane, poly (tetramethylene glycol adipate) or poly (2-methyl-1,3-propylene glutarate).

Polycarbonates preferably used in component c) are hydroxyl-terminated aliphatic polycarbonates with average molecular weights below 12,000, which are described in more detail in German patent application 197 57 574.9. Aliphatic polycarbonate diols with average molecular weights of 400 to 6000 are particularly preferably used. 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-bishydroxymethylcyclohexane) carbonate, poly (1,4-butanediol) carbonate or Poly (tripropylene glycol) carbonate.

Polyalkylene glycol sorbitan esters preferably used in component c) are polyethylene glycol sorbitan esters (polysorbates), which are described in more detail in EP 1 115 489 (WO 00/15 336). Polyethylene glycol sorbitan mono-, di- and triesters of fatty acids having 6 to 18 carbon atoms and 2 to 40 moles of ethylene oxide are particularly preferred.

Polyalkylene glycol glycidyl ethers preferably used in component c) are mono- and diglycidyl ethers of polypropylene glycol and polyethylene glycol, which are described in more detail in German patent application 198 34 573.9.

Also preferred for the preparation of the catalysts of the invention (component c)) are glycidyl ethers of monomeric or polymeric (with at least two monomer units) aliphatic, aromatic or araliphatic, mono-, di-, tri-, tetra- or polyfunctional alcohols.

Glycidyl ethers of mono-, di-, tri-, tetra- or polyfunctional aliphatic alcohols such as butanol, hexanol, octanol, decanol, dodecanol, tetradecanol, ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4- Butanediol, 2,2-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, both mono-, di-, tri-, Tetra as well as polyethers come into question.

Mono- or diglycidyl ethers of butanol, hexanol, octanol, decanol, dodecanol, tetradecanol, ethanediol or 1,4-butanediol and polypropylene glycol or polyethylene glycol, in particular with degrees of polymerization of 2 to 1000 monomer units, are particularly preferably used.

The glycidyl ethers are generally obtained by reacting mono-, di-, tri-, tetra- or polyfunctional alcohols with epichlorohydrin in the presence of a Lewis acid such as tin tetrachloride or boron trifluoride to give the corresponding chlorohydrins and subsequent dehydrohalogenation with base (eg sodium hydroxide).

Methods for the preparation of glycidyl ethers are generally well known and are described in detail, for example, in "Kirk-Othmer, Encyclopedia of Chemical Technology", volume 9, 4th edition, 1994, p. 739 ff. And "Ullmann, Encyclopedia of Industrial Chemistry", volume A9, 5th edition, Weinheim / New York, 1987, p. 552.

The glycidyl ether used to produce the catalyst according to the invention can be present in the finished catalyst in the form originally used or in chemically modified, for example hydrolyzed, form.

Suitable glycosides for component c) are compounds made up of carbohydrates (sugars) and non-sugars (aglycons) in which the aglycon is bonded to the full acetal by an oxygen atom via a glycosidic bond with a hemiacetal carbon atom of the carbohydrate.

Suitable sugar components 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.

The non-sugar component is C₁-C₃₀Hydrocarbon residues such as aryl, aralkyl and alkyl residues, preferably aralkyl and alkyl residues, particularly preferably alkyl residues with 1 to 30 carbon atoms in question.

Preferred glycosides are the so-called alkyl polyglycosides, which are generally obtained by reaction of carbohydrates with alcohols such as methanol, ethanol, propanol and butanol or by transacetalization of short-chain alkyl glycosides with fatty alcohols with 8 to 20 C atoms in the presence of acids.

Alkylpolyglycosides with glucose as the repeating unit in the chain and with alkyl chain lengths of C are particularly preferred₈ to C₁₆ and average degrees of polymerization between 1 and 2.

Methods for producing glycosides are generally well known and are described, for example, in detail in "Kirk-Othmer, Encyclopedia of Chemical Technology", Volume 4, 4th edition, 1992, pp. 916 ff .; "Römpp, Lexikon Chemie", Vol. 2, 10.

Edition, Stuttgart / New York, 1996 pp. 1581 ff .; applied Chemistry<u>110</u>, Pp. 1394-1412 (1998).

Suitable carboxylic acid esters of polyhydric alcohols for component c) are, for example, esters of C.₂-C₃₀Carboxylic acids with aliphatic or alicyclic alcohols with two or more hydroxyl groups per molecule, such as ethylene glycol, 1,2-propanediol, 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-trimethylol-propane, pentaerythritol, carbohydrates (sugars) or sugar alcohols such as sorbitol or sorbitan. Suitable sugars are monosaccharides such as glucose, galactose, mannose, fructose, arabinose, xylose or ribose, disaccharides such as sucrose or maltose and oligosaccharides or polysaccharides such as starch.

Examples of suitable carboxylic acid components are C₂-C₃₀Carboxylic acids such as aryl, aralkyl and alkyl carboxylic acids, preferably aralkyl and alkyl carboxylic acids, particularly preferably alkyl carboxylic 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.

Preferred carboxylic acid esters of polyhydric alcohols are esters of 1,2,3-propanetriol (glycerol), 1,1,1-trimethylolpropane, pentaerythritol, maltose or sorbitan with C.₂-C₁₈-Alkyl carboxylic acids.

Particularly preferred carboxylic acid esters of polyhydric alcohols are mono-, di-, tri- or tetraesters of 1,2,3-propanetriol (glycerol), pentaerythritol or sorbitan with C.₂-C₁₈-Alkyl carboxylic acids.

Methods for the preparation of carboxylic acid esters of polyhydric alcohols or their isolation from fats are generally well known and are described in detail, for example, in "Kirk-Othmer, Encyclopedia of Chemical Technology", Volume 9, 3rd edition, 1980, pp. 795 ff .; "Römpp, Lexikon Chemie", 8th edition, Stuttgart / New York, 1981; "Ullmann's Encyclopedia of Industrial Chemistry", Volume A10, 5th Edition, 1987, pp. 173 to 218.

Suitable bile acids for component c) are C₂₄Steroid carboxylic acids, which are cholesterol breakdown products, and which are generally derived from 5β-cholan-24-acid by introducing α-terminal hydroxyl groups at C-3, C-6, C-7 and C-12 .

Preferred bile acids have the general formula<chemistry id="chem0001" num="0001"><img file="EP1258291A2_D0001.tif" /></chemistry> where R₁, R₂, R₃ and R₄ independently of one another H or OH and R.₅ OH, NH-CH₂-COOH, NH-CH₂-CH₂-SO₃H, NH- (CH₂)₃-N⁺(CH₃)₂-CH₂-CHOH-CH₂-SO₃^- or NH- (CH₂)₃-N⁺(CH₃)₂- (CH₂)₃-SO₃^- mean.

Suitable are the free acids or their salts, preferably alkali or alkaline earth metal salts, and their esters, preferably with alkyl radicals having 1 to 30 carbon atoms, and their amides, preferably with alkyl radicals or sulfoalkyl, sulfoalkylaminoalkyl, sulfohydroxyalkylaminoalkyl and carboxyalkyl radicals in the acid - or salt form.

Examples of suitable bile acids or their salts, esters or amides are cholic acid (3α, 7α, 12α-trihydroxy-5β-cholan-24-acid; R₁ = R₃ = R₄ = R₅ = OH, R₂ = H), sodium cholate (sodium cholate), lithium cholate, potassium cholate, glycol cholic acid (3α, 7α, 12α-trihydroxy-5β-cholan-24-acid-N- [carboxymethyl] amide; R₁ = R₃ = R₄ = OH, R₂ = H, R₅ = NH-CH₂-COOH), sodium glycocholate, taurocholic acid (3α, 7α, 12α-trihydroxy-5β-cholan-24-acid-N- [2-sulfoethyl] amide; R₁ = R₃ = R₄ = OH, R₂ = H, R₅ = NH-CH₂-CH₂-SO₃H), sodium taurocholate, deoxycholic acid (3α, 12α-dihydroxy-5β-cholan-24-acid; R₁ = R₄ = R₅ = OH, R₂ = R₃ = H), sodium deoxycholate, potassium deoxycholate, lithium deoxycholate, glycodeoxycholic acid (3α, 12α-dihydroxy-5β-cholan-24-acid-N- [carboxymethyl] amide; R₁ = R₄ = OH, R₂ = R₃ = H, R₅ = NH-CH₂-COOH), sodium glycodeoxycholate, taurodeoxycholic acid (3α, 12α-dihydroxy-5β-cholan-24-acid-N- [2-sulfoethyl] amide; R₁ = R₄ = OH, R₂ = R₃ = H, R₅ = NH-CH₂-CH₂-SO₃H), sodium taurodeoxycholate, chenodeoxycholic acid (3α, 7α-dihydroxy-5β-cholan-24-acid; R₁ = R₃ = R₅ = OH, R₂ = R₄ = H), sodium chenodeoxycholate, glycochenodeoxycholic acid (3α, 7α-dihydroxy-5β-cholan-24-acid-N- [carboxymethyl] amide; R₁ = R₃ = OH, R₂ = R₄ = H, R₅ = NH-CH₂-COOH), sodium glycochnodeoxycholate, taurochenodeoxycholic acid (3α, 7α-dihydroxy-5β-cholan-24-acid-N- [2-sulfoethyl] amide; R₁ = R₃ = OH, R₂ = R₄ = H, R₅ = NH-CH₂-CH₂-SO₃H), sodium taurochenodeoxycholate, lithocholic acid (3α-hydroxy-5β-cholan-24-acid; R₁ = R₅ = OH, R₂ = R₃ = R₄ = H), sodium lithocholate, potassium lithocholate, hyocholic acid (3α, 6α, 7α-trihydroxy-5β-cholan-24-acid; R₁ = R₂ = R₃ = R₅ = OH, R₄ = H), sodium hyocholate, lithium hyocholate, potassium hyocholate, hyodeoxycholic acid (3α, 6α-dihydroxy-5β-cholan-24-acid; R₁ = R₂ = R₅ = OH; R₃ = R₄ = H), sodium hyodeoxycholate, lithium hyodeoxycholate, potassium hyodeoxycholate, methyl cholic acid, ethyl cholic acid, ethyl deoxycholic acid and methyl hyocholic acid.

The sodium, lithium or potassium salts or the methyl or ethyl esters of cholic acid, glycocholic acid, taurocholic acid, deoxycholic acid, glycodeoxycholic acid, taurodeoxycholic acid, chenodeoxycholic acid, glycochnodeoxycholic acid, taurochenodeoxycholic acid, lithocholic acid or hyodicholic acid, hyocholic acid, their hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid, hyocholic acid and their hyocholic acid, hyocholic acid, hyocholic acid, for example.

Bile acids such as ursocholic acid (3α, 7β, 12α-trihydroxy-5β-cholan-24-acid), ursodeoxycholic acid (3α, 7β-dihydroxy-5β-cholan-24-acid), 7-oxo-lithocholic acid (3α-hydroxy -7-oxo-5β-cholan-24-acid), lithocholic acid-3-sulfate (3α-hydroxy-5β-cholan-24-acid-3-sulfate), nor-cholic acid and bisnor-cholic acid, or their salts, esters or amides.

The bile acids and their salts, esters or amides are generally well known and are described, for example, in detail in Nachr. Chem. Tech. Lab.<u>43</u> (1995) 1047, Setchell et al .: "The Bile Acids", Vol. 4, Plenum, New York 1998 and "Römpp, Lexikon Naturstoffe", Stuttgart, New York 1997, pp. 248ff.

Suitable cyclodextrins for component c) are, for example, unsubstituted cyclodextrins or their ester, alkyl ether, hydroxyalkyl ether, alkoxycarbonylalkyl ether and carboxyalkyl ether derivatives or their salts.

Cyclodextrins are cyclohexa-, cyclohepta- or cyclooctaamyloses with 6, 7 or 8 1,4-linked glucose units, which arise when starch is broken down by Bacillus macerans or Bacillus circulans under the action of cyclodextrin cosyl transferase, such as α-, β-, γ - or δ-cyclodextrin.

Aryl, aralkyl and alkyl carboxylic acids having 2 to 30 carbon atoms, preferably 2 to 24 carbon atoms, particularly preferably 2 to 20 carbon atoms, preferably aralkyl and alkyl carboxylic acids, particularly preferably alkyl carboxylic acids are suitable for the cyclodextrin esters as the carboxylic acid component.

Linear or branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 24 carbon atoms, particularly preferably 1 to 20 carbon atoms, are suitable as the alkyl component for the cyclodextrin alkyl ethers, hydroxyalkyl ethers, alkoxycarbonylalkyl ethers and carboxyalkyl ethers.

Cyclodextrins which are preferably used are α-, β- and γ-cyclodextrins and their mono-, di- and triether, mono-, di- and triesters or monoesters / diethers, which are generally obtained by etherification of α-, β- and γ- Cyclodextrins with alkylating agents such as dimethyl sulfate or alkyl halides with 1 to 30 C atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl chloride, bromide or iodide and / or esterification with acetic acid or succinic acid in the presence of acids.

Methyl-α-cyclodextrin, methyl-β-cyclodextrin, methyl-γ-cyclodextrin, ethyl-β-cyclodextrin, butyl-α-cyclodextrin, butyl-β-cyclodextrin, butyl-γ-cyclodextrin, 2,6-dimethyl are particularly preferred -α-cyclodextrin, 2,6-dimethyl-β-cyclodextrin, 2,6-dimethyl-γ-cyclodextrin, 2,6-diethyl-β-cyclodextrin, 2,6-dibutyl-β-cyclodextrin, 2,3,6 Trimethyl-α-cyclodextrin, 2,3,6-trimethyl-β-cyclodextrin, 2,3,6-trimethyl-γ-cyclodextrin, 2,3,6-trioctyl-α-cyclodextrin, 2,3,6-trioctyl -β-cyclodextrin, 2,3,6-triacetyl-α-cyclodextrin, 2,3,6-triacetyl-β-cyclodextrin, 2,3,6-triacetyl-γ-cyclodextrin, (2-hydroxy) propyl-α-cyclodextrin, (2- Hydroxy) propyl-β-cyclodextrin, (2-hydroxy) -propyl-γ-cyclodextrin, partially or completely acetylated and succinylated α-, β- or γ-cyclodextrin, 2,6-dimethyl-3-acetyl-β-cyclodextrin or 2,6-dibutyl-3-acetyl-β-cyclodextrin.

Methods for the preparation of cyclodextrins are generally well known and are described, for example, in detail in "Römpp, Lexikon Chemie", 10th edition, Stuttgart / New York 1997, pp. 845 ff and Chemical Reviews <u>98</u> (1998) 1743.

Phosphorus compounds suitable as component c) of the catalyst according to the invention are organic phosphates such as, for example, mono-, di- or triesters of phosphoric acid, mono-, di-, tri- or tetraesters of pyrophosphoric acid and mono-, di-, tri-, tetra- or polyester of polyphosphoric acid and alcohols with 1 to 30 carbon atoms.

Suitable organic phosphites are mono-, di- or triesters of phosphoric acid and alcohols with 1 to 30 C atoms.

Suitable organic phosphonates 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 alkyldiphosphonic acids and alcohols with 1 to 30 carbon atoms.

Suitable phosphonites are diesters of phosphonous acid or arylphosphonous acid and alcohols with 1 to 30 carbon atoms.

Suitable phosphinates are esters of phosphinic acid, alkylphosphinic acids, dialkylphosphinic acids or arylphosphinic acids and alcohols with 1 to 30 carbon atoms.

Suitable phosphinites are esters of alkylphosphinous acid, dialkylphosphinous acid or arylphosphinous acid and alcohols with 1 to 30 carbon atoms.

Suitable alcohol components are mono- or polyvalent 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 organic phosphates, phosphites, phosphonates, phosphonites, phosphinates or phosphinites used to prepare the catalysts according to the invention are generally obtained by reacting phosphoric acid, pyrophosphoric acid, polyphosphoric acids, phosphonic acid, alkylphosphonic acids, arylphosphonic acids, alkoxycarbonylalkylphosphonic acids, alkoxycarbonylphosphonic acids, cyanoalkylphosphonic acids, cyanoalkylphosphonic acids, cyanoalkylphosphonic acids, Phosphoric acid, phosphinic acid, Phosphinic acid or its halogenated derivatives or phosphorus oxides with hydroxy compounds with 1 to 30 C atoms such as methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, heptanol, octanol, nonanol, decanol, dodekanol, tridekanol, tetradekanol, pentadekanol, hexadekanol, Heptadekanol, octadekanol, nonadekanol, methoxymethanol, ethoxymethanol, propoxymethanol, butoxymethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, phenol, ethyl hydroxyacetate, Hydroxyacetic acid propyl ester, hydroxypropionic acid ethyl ester, hydroxypropionic acid propyl ester, 1,2-ethanediol, 1,2-propanediol, 1,2,3-trihydroxypropane, 1,1,1-trimethylolpropane or pentaerythritol.

Phosphoric acid triethyl ester, Phosphoric acid tributyl ester, Phosphorsäuretrioctylester, Phosphorsäuretris (2-ethylhexyl) ester, Phosphorsäuretris- (2-butoxyethyl) ester, Butylphosphonsäuredibutylester, Phenylphosphonsäuredioctylester, Phosphonoameisensäuretriethylester, phosphonoacetate, triethyl phosphonoacetate, 2-Phosphonopropionsäuretrimethylester, 2-phosphonopropionic acid, 2-Phosphonopropionsäuretripropylester, 2-Phosphonopropionsäuretributylester are preferred , 3-phosphonopropionic acid triethyl ester, tributyl phosphite, trilauryl phosphite, tris (3-ethyloxethanyl-3-methyl) phosphite and heptakis (dipropylene glycol) phosphite.

Methods for the preparation of phosphoric, phosphoric, phosphonic, phosphonous, phosphinic and phosphinous esters are known and are described in detail in Kirk-Othmer: "Encyclopedia of Chemical Technology", Volume 18, 4th edition, 1996, p. 737 ff .; "Römpp, Lexikon Chemie", Volume 4, 10th edition, Stuttgart / New York, 1998, pp. 3280 ff .; "Ullmann's Encyclopedia of Industrial Chemistry", Volume A19, 5th edition, 1991, p. 545 ff., "Houben-Weyl: Methods of Organic Chemistry", Volumes XII / 1 and XII / 2, Stuttgart 1963/1964.

Α, β-Unsaturated carboxylic acid esters suitable for the preparation of the catalysts (component c)) according to the invention are, for example, mono-, di-, tri- or polyesters of acrylic acid and alkyl-, alkoxy-, alkoxycarbonyl and alkoxycarbonylalkylacrylic acids with alcohols with 1 to 30 C- Atoms or polyether polyols.

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

Also suitable as alcohol components are polyalkylene glycols and polyalkylene glycol ethers, preferably polypropylene glycols and polyethylene glycols or their ethers with molecular weights from 200 to 10,000, preferably 300 to 9000, particularly preferably 400 to 8000.

The α, β-unsaturated carboxylic acids are acrylic acid and alkyl, alkoxy and alkoxycarbonylalkylacrylic acids with 1 to 20 carbon atoms, such as 2-methylacrylic acid (methacrylic acid), 3-methylacrylic acid (crotonic acid), trans-2,3-dimethylacrylic acid (tiglinic acid), 3,3-dimethylacrylic acid (senecioic acid) or 3-methoxyacrylic acid, preferably acrylic acid, 2-methylacrylic acid, 3-methylacrylic acid and 3-methoxyacrylic acid, particularly preferably acrylic acid and 2-methylacrylic acid.

The α, β-unsaturated carboxylic acid esters used to prepare the catalysts according to the invention are generally obtained by esterification of mono-, di-, tri-, tetra- or polyhydroxy compounds having 1 to 30 carbon atoms, such as methanol, ethanol, ethanediol (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-dodekanol, 1-tridekanol, 1-tetradekanol, 1-hexadekanol, 1-heptadekanol, 9-octadekanol, 1,1,1-tris (hydroxymethyl ) -propane, pentaerythritol, methoxymethanol, ethoxymethanol, propoxymethanol, butoxymethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, methyl hydroxy ester, ethyl hydroxyacetate, propyl hydroxyacetate, methyl hydroxypropionate, hydroxypropionate Hydroxypropionic acid propyl ester or polyether polyols such as polyethylene glycols and polypropylene glycols with the corresponding α, β-unsaturated carboxylic acids, optionally in the presence of catalysts.

Mono-, di- and triesters of acrylic acid and methacrylic acid with ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,2,3-propanetriol, 1, 1,1-tris (hydroxymethyl) propane, 1,1,1-tris (hydroxymethyl) propane ethoxylates, 1,1,1-tris (hydroxymethyl) propane propoxylates, polyethylene glycols and polypropylene glycols.

Particularly preferred α, β-unsaturated carboxylic acid esters are polyethylene glycol acrylic acid esters, polyethylene glycol diacrylic acid esters, polyethylene glycol methacrylic acid esters, polyethylene glycol dimethacrylic acid esters, polypropylene glycol acrylic acid esters, polypropylene glycol diacrylic acid esters, polypropylene glycol methacrylic acid esters, polypropylene glycol dimethane tranethanoic acid, 1,2,3-triethanoic acid triacrylate, 1,2,3-triethane triacid, 1,2,3, 1,2,3-propanetriol-1,3- (2-hydroxypropoxylate) diacrylic acid ester, 1,2,3-propanetriol propoxylate triacrylic acid ester, 1,4-butanediol acrylic acid ester, 1,4-butanediol dimethacrylic acid ester, 1,6-hexanediol diacrylic acid ester, 2-hydroxypropyl methacrylic acid ester , 1,1,1-tris (hydroxymethyl) propane-triacrylic acid ester, 1,1,1-tris (hydroxymethyl) propane-ethoxylate-triacrylic acid ester, 1,1,1-tris (hydroxymethyl) propane-ethoxylate-trimethacrylic acid ester, 1,1,1-tris (hydroxymethyl) propane-propoxylate-triacrylic acid ester or 1,1,1-tris (hydroxymethyl) propane-propoxylate-trimethacrylic acid ester.

Methods for producing α, β-unsaturated carboxylic acid esters are generally well known and are described, for example, in detail in "Kirk-Othmer: Encyclopedia of Chemical Technology", Volume 18, 4th Edition, 1996, pp. 737ff .; "Römpp, Lexikon Chemie", Volume 4, 10th edition, Stuttgart / New York 1998, pp. 3286ff .; "Ullmanns Encyclopedia of Industrial Chemistry", volume A19, 5th edition, 1991, pp. 545ff., "Houben-Weyl: Methods of Organic Chemistry, volumes XII / 1 and XII / 2, Stuttgart 1963/1964.

The structural feature of the ionic surface or surface-active compounds suitable as component c) for the preparation of the catalysts according to the invention is their amphiphilic molecular structure, ie they contain at least one hydrophilic ionic group (or a hydrophilic ionic part of the molecule) and at least one hydrophobic group (or one hydrophobic part of the molecule). Examples of such ionic surface or Surfactant compounds can be found in the group of surfactants, soaps, emulsifiers, detergents and dispersants.

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

The hydrophobic groups are preferably C₂-C₅₀-Hydrocarbon residues such as aryl, aralkyl and alkyl residues. However, fluoroalkyl, silaalkyl, thiaalkyl or oxaalkyl groups are also suitable.

Examples of suitable classes of compounds with hydrophilic anionic groups are carboxylates such as alkyl carboxylates (soaps), ether carboxylates (carboxymethylated ethoxylates), polycarboxylates such as malonates and succinates, bile acid salts, for example bile acid amides with sulfoalkyl and carboxyalkyl radicals in the salt form, amino acid derivatives such as sarcosocides (alkanolysulfate amide sulfate amide sulfates), alkoxylate sulfate amides such as alkyl sulfates, ether sulfates, for example Fatty alcohol ether sulfates, aryl ether sulfates or amido ether sulfates, sulfated carboxylates, sulfated carboxylic acid glycerides, sulfated carboxylic acid esters, sulfated carboxylic acid amides, sulfonates, for example alkyl, aryl and alkylarylsulfonates, sulfonated carboxylates, sulfonated carboxylic acid esters, sulfonated carboxylic acid sulfate, sulfonate sulfate, sulfonate sulfates, sulfonate sulfate acid, sulfonate sulfates, Phosphates, e.g. Alkyl phosphates or glycerol phosphates, phosphonates, phosphinates and dithiophosphates.

Examples of suitable classes of compounds with hydrophilic cationic groups are primary, secondary, tertiary and quaternary ammonium salts with alkyl, aryl and aralkyl radicals, alkoxylated ammonium salts, quaternary Ammoniumester, benzylammonium, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, thiazolinium salts, salts of amine oxides, sulfonium salts, quinolinium , Isoquinolinium salts and tropylium salts.

Examples of suitable classes of compounds with a hydrophilic zwitterionic (amphoteric) group are amine oxides, imidazolinium derivatives such as imidazolinium carboxylates, betaines, for example alkyl and amidopropylbetaines, sulfobetaines, aminocarboxylic acids and phospholipids, for example phosphatidylcholine (lecithin).

Of course, the ionic surface or surface-active compounds can also contain several hydrophilic (anionic and / or cationic and / or zwitterionic) groups or parts of molecules.

The ionic surface or surface-active compounds suitable for the preparation of the catalysts according to the invention are generally well known and are described, for example, in detail in "Ullmann's Encyclopedia of Industrial Chemistry", 5^th Edition, Vol. A25, pp. 747-817, VCH, Weinheim, 1994, "Kirk-Othmer, Encyclopedia of Chemical Technology", 4^th Edition, Vol. 23, pp. 477-541, John Wiley &amp; Sons, New York, 1997, "Tensid-Taschenbuch", 2nd edition, H. Stache (ed.), Carl Hanser Verlag, Munich, 1982, " Surfactant Science Series ", Vol. 1-74, MJ Schick (Consulting Editor), Marcel Decker, New York, 1967-1998," Methods in Enzymology ", Vol. 182, MP Deutscher (Ed.), S.239-253 , Academic Press, San Diego, 1990.

The catalysts according to the invention contain, as component c), complex-forming components from two different of the compound classes described above.

Preferred embodiments are catalysts which contain a combination of phosphorus compounds with α, β-unsaturated carboxylic acid esters, of phosphorus compounds with cyclodextrins, of phosphorus compounds with polyesters, phosphorus compounds with glycosides, or of phosphorus compounds with bile acids or their salts, esters or amides. Particularly preferred are those which contain a combination of phosphorus compounds with α, β-unsaturated carboxylic acid esters, of phosphorus compounds with polyesters, phosphorus compounds with glycosides, or of phosphorus compounds with bile acids or their salts, esters or amides.

Further preferred embodiments are catalysts which are a combination of carboxylic acid esters of polyhydric alcohols with α, β-unsaturated carboxylic acid esters, of carboxylic acid esters of polyhydric alcohols with cyclodextrins, of carboxylic acid esters of polyhydric alcohols with polyesters, of carboxylic acid esters of polyhydric alcohols with glycosides, of carboxylic acid esters of polyhydric alcohols with glycidyl ethers Carboxylic acid esters of polyhydric alcohols with bile acids or their salts, esters or amides, or carboxylic acid esters of polyhydric alcohols with phosphorus compounds. Particularly preferred are those which are a combination of carboxylic acid esters of polyhydric alcohols with α, β-unsaturated carboxylic acid esters, of carboxylic acid esters of polyhydric alcohols with polyesters, of carboxylic acid esters of polyhydric alcohols with glycosides, of carboxylic acid esters of polyhydric alcohols with glycidyl ethers, or of carboxylic acid esters of polyhydric alcohols with bile acids or contain their salts, esters or amides.

Further preferred embodiments are catalysts which are a combination of α, β-unsaturated carboxylic acid esters with cyclodextrins, of α, β-unsaturated carboxylic acid esters with polyesters, of α, β-unsaturated carboxylic acid esters with glycosides, of α, β-unsaturated carboxylic acid esters with bile acids or their salts, esters or amides, of α, β-unsaturated carboxylic acid esters with phosphorus compounds or of α, β-unsaturated carboxylic acid esters with carboxylic acid esters of polyhydric alcohols. Particularly preferred are those which contain a combination of α, β-unsaturated carboxylic acid esters with glycosides, of α, β-unsaturated carboxylic acid esters with bile acids or their salts, esters or amides, or of α, β-unsaturated carboxylic acid esters with phosphorus compounds.

Further preferred embodiments are catalysts which contain a combination of cyclodextrins with glycidyl ethers, cyclodextrins with bile acids or their salts, esters or amides, cyclodextrins with phosphorus compounds, cyclodextrins with carboxylic acid esters of polyhydric alcohols or cyclodextrins with α, β-unsaturated carboxylic acid esters. Those which contain a combination of cyclodextrins with glycidyl ethers, of cyclodextrins with bile acids or their salts, esters or amides or of cyclodextrins with α, β-unsaturated carboxylic acid esters are particularly preferred.

Further preferred embodiments are catalysts which contain a combination of polyesters with phosphorus compounds, of polyesters with carboxylic acid esters of polyhydric alcohols or of polyesters with α, β-unsaturated carboxylic acid esters.

Further preferred embodiments are catalysts which contain a combination of glycosides with glycidyl ethers, of glycosides with bile acids or their salts, esters or amides, of glycosides with phosphorus compounds, of glycosides with carboxylic acid esters of polyhydric alcohols or of glycosides with α, β-unsaturated carboxylic acid esters.

Further preferred embodiments are catalysts which are a combination of glycidyl ethers with bile acids or their salts, esters or amides, of glycidyl ethers with phosphorus compounds, of glycidyl ethers with carboxylic acid esters of polyhydric alcohols, of glycidyl ethers with α, β-unsaturated carboxylic acid esters, of glycidyl ethers with cyclodextrins or of Contain glycidyl ethers with glycosides.

Further preferred embodiments are catalysts which combine bile acids or their salts, esters or amides with phosphorus compounds, bile acids or their salts, esters or amides with carboxylic acid esters of polyhydric alcohols, bile acids or their salts, esters or amides with α, β-unsaturated carboxylic acid esters, of bile acids or their salts, esters or amides with cyclodextrins, of bile acids or their salts, esters or amides with glycosides, or of bile acids or their salts, esters or amides with glycidyl ethers.

The analysis of the catalyst composition is usually carried out by means of elemental analysis, thermogravimetry or extractive removal of the complex-forming components with subsequent gravimetric determination.

The catalysts of the invention can be crystalline, semi-crystalline or amorphous. The crystallinity is usually analyzed by powder X-ray diffractometry.

Catalysts according to the invention are preferred which contain zinc hexacyanocobaltate (III) as component a) and tert-butanol as component b).

The DMC catalysts according to 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) which are neither functionalized polymers, glycidyl ethers, glycosides , Carboxylic acid esters of polyhydric alcohols, bile acids or their salts, esters or amides, cyclodextrins, phosphorus compounds, α, β-unsaturated carboxylic acid esters or ionic surface or surface-active compounds are and the complex-forming components c).

The aqueous solutions of the metal salt (eg zinc chloride, used in a stoichiometric excess (at least 50 mol% based on the metal cyanide salt)) and of the metal cyanide salt (eg potassium hexacyanocobaltate) in the presence of the organic complex ligand b) (eg tert-butanol) are preferred. implemented, forming a suspension that the double metal cyanide compound a) (eg Zinc hexacyanocobaltate), water d), excess metal salt e), and the organic complex ligand b).

The organic complex ligand b) can be present in the aqueous solution of the metal salt and / or the metal cyanide salt, or it is added directly to the suspension obtained after precipitation of the double metal cyanide compound a). It has proven to be advantageous to mix the aqueous solutions and the organic complex ligand b) with vigorous stirring. The suspension formed is then usually treated with a mixture of the complex-forming components c). The mixture of the complex-forming components c) is preferably used in a mixture with water and organic complex ligand b).

The catalyst is then isolated from the suspension by known techniques, such as centrifugation or filtration. In a preferred embodiment, the isolated catalyst is then washed with an aqueous solution of the organic complex ligand b) (for example by resuspending and then isolating again by filtration or centrifugation). In this way, for example, water-soluble by-products such as potassium chloride can be removed from the catalyst according to the invention.

The amount of the organic complex ligand b) in the aqueous washing solution is preferably between 40 and 80% by weight, based on the total solution. It is also advantageous to add a small amount of the mixture of the complex-forming components c) to the aqueous washing solution, preferably 0.5 to 5% by weight, based on the total solution.

It is also advantageous to wash the catalyst more than once. For this purpose, the first washing process can be repeated, for example. However, it is preferred to use non-aqueous solutions for further washing processes, for example a mixture of organic complex ligands and the mixture of the complex-forming components c).

The washed catalyst is then dried, if appropriate after pulverization, at temperatures of generally 20-100 ° C. and at pressures generally from 0.1 mbar to normal pressure (1013 mbar).

The present invention furthermore relates to the use of the DMC catalysts according to the invention in a process for the preparation of polyether polyols by polyaddition of alkylene oxides onto starter compounds having active hydrogen atoms.

Preferred alkylene oxides are ethylene oxide, propylene oxide, butylene oxide and mixtures thereof. The construction of the polyether chains by alkoxylation can, for example, only be carried out with one monomeric epoxide or also statistically or in blocks with 2 or 3 different monomeric epoxides. More details can be found in "Ullmann's Encyclopedia of Industrial Chemistry", Volume A21, 1992, p. 670f.

As starter compounds having active hydrogen atoms, compounds with (number average) molecular weights of 18 to 2,000 and 1 to 8 hydroxyl groups are preferably used. Examples include: ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-butanediol, hexamethylene glycol, bisphenol A, trimethylolpropane, glycerin, pentaerythritol, sorbitol, cane sugar, degraded starch or water.

Advantageously, such starter compounds containing active hydrogen atoms are used which were prepared, for example, by conventional alkali catalysis from the aforementioned low molecular weight starters and which are oligomeric alkoxylation products with (number average) molecular weights of 200 to 2,000.

The polyaddition of alkylene oxides to starter compounds having active hydrogen atoms, which is catalyzed by the catalysts according to the invention, generally takes place at temperatures from 20 to 200 ° C., preferably in the range from 40 to 180 ° C., particularly preferably at temperatures from 50 to 150 ° C. The reaction can be carried out at total pressures of 0.0001 to 20 bar. The polyaddition can be carried out in bulk or in an inert, organic solvent, such as toluene and / or THF. The amount of solvent is usually 10 to 30% by weight, based on the amount of the polyether polyol to be produced.

The catalyst concentration is chosen so that a good mastery of the polyaddition reaction is possible under the given reaction conditions. The catalyst concentration is generally in the range from 0.0005% by weight to 1% by weight, preferably in the range from 0.001% by weight to 0.1% by weight, particularly preferably in the range from 0.001 to 0.0025 % By weight, based on the amount of the polyether polyol to be produced.

The (number average) molecular weights of the polyether polyols produced by the process according to the invention are in the range from 500 to 100,000 g / mol, preferably in the range from 1,000 to 50,000 g / mol, particularly preferably in the range from 2,000 to 20,000 g / mol.

The polyaddition can be carried out continuously or batchwise, for example in a batch or semi-batch process.

Because of their significantly increased activity, the catalysts according to the invention can be used in very low concentrations (100 ppm and less, based on the amount of the polyether polyol to be prepared). Are the polyether polyols produced in the presence of the catalysts according to the invention used for the production of polyurethanes (Kunststoff Handbuch, Vol. 7, Polyurethane, 3rd ed. 1993, p. 25-32 and 57-67), there is no need to remove the catalyst from the polyether polyol without adversely affecting the product qualities of the polyurethane obtained.

<u>Examples</u>

<u>Catalyst preparation</u>

<u>example 1</u>

DMC catalyst containing phosphorus compound and α, β-unsaturated carboxylic acid ester (catalyst I).

A solution of 12.5 g (91.5 mmol) of zinc chloride in 20 ml of distilled water was added to a solution of 4 g (12 mmol) of potassium hexacyanocobaltate in 70 ml of distilled water with vigorous stirring (24,000 rpm). Immediately afterwards, a mixture of 50 g of tert-butanol and 50 g of distilled water was added to the suspension formed and then stirred vigorously for 10 minutes (24,000 rpm). Then a mixture of 0.5 g of polyethylene glycol diacrylate (M_n 575 g / mol) and 0.5 g of 2-phosphonopropionic acid triethyl ester, 1 g of tert-butanol and 100 g of distilled water were added and the mixture was stirred for 3 minutes (1,000 rpm). The solid was isolated by filtration, then stirred for 10 min with a mixture of 70 g tert-butanol, 30 g distilled water, 0.5 g glycerol tricapronate and 0.5 g 2-phosphonopropionic acid triethyl ester (10,000 rpm) and filtered again . Finally, another 10 min with a mixture of 100 g of tert-butanol, 0.5 g of polyethylene glycol diacrylate (M._n 575 g / mol) and 0.5 g of 2-phosphonopropionic acid triethyl ester (10,000 rpm). After filtration, the catalyst was dried to constant weight at 50 ° C. and normal pressure. Yield of dried powdery catalyst: 6.0 g Elemental analysis: Cobalt = 10.9% by weight, zinc = 24.9% by weight

<u>Example 2</u>

DMC catalyst containing phosphorus compound and cyclodextrin (catalyst II).

The procedure was as in Example 1, but instead of polyethylene glycol diacrylate and 2-phosphonopropionic acid triethyl ester as complex-forming components 2,6-dimethyl-β-cyclodextrin (Beta W 7 M 1.8, Wacker-Chemie GmbH, D-81737 Munich) and triethyl 2-phosphonopropionate are used. Yield of dried powdery catalyst: 4.8 g Elemental analysis: Cobalt = 10.7% by weight, zinc = 24.3% by weight.

<u>Example 3</u>

DMC catalyst containing phosphorus compound and polyester (catalyst III).

The procedure was as in Example 1, but instead of polyethylene glycol diacrylate and triethyl 2-phosphonopropionate, poly (2-methyl-1,3-propylene glutarate) (M._n 1020) and 2-phosphonopropionic acid triethyl ester. Yield of dried powdery catalyst: 4.4 g Elemental analysis: Cobalt = 9.9% by weight, zinc = 23.4% by weight.,

<u>Example 4</u>

DMC catalyst containing phosphorus compound and glycoside (catalyst IV).

The procedure was as in Example 1, but alkyl polyglycoside (Glucopon® 650 EC, Henkel KGaA, D-40589 Düsseldorf) and 2-phosphonopropionic acid triethyl ester were used as complex-forming components instead of polyethylene glycol diacrylate and 2-phosphonopropionic acid triethyl ester. Yield of dried powdery catalyst: 4.3 g Elemental analysis: Cobalt = 11.2% by weight, zinc = 25.2% by weight.

<u>Example 5</u>

DMC catalyst containing phosphorus compound and bile acid derivative (catalyst V).

The procedure was as in Example 1, but instead of polyethylene glycol diacrylate and 2-phosphonopropionic acid triethyl ester, cholic acid sodium salt and 2-phosphonopropionic acid triethyl ester were used as complex-forming components. Yield of dried powdery catalyst: 5.7 g Elemental analysis: Cobalt = 14.0% by weight, zinc 32.0% by weight.

<u>Example 6</u>

DMC catalyst containing carboxylic acid esters of polyhydric alcohols and α, β-unsaturated carboxylic acid esters (catalyst VI).

The procedure was as in Example 1, but instead of polyethylene glycol diacrylate and 2-phosphonopropionic acid triethyl ester as complex-forming components, polyethylene glycol sorbitan monooleate (Disponil® SMO 120, Henkel KG aA, 40589 Düsseldorf) and polyethylene glycol diacrylate (M_n 575 g / mol) used. Yield of dried powdery catalyst: 5.2 g Elemental analysis: Cobalt = 9.6% by weight, zinc = 21.9% by weight.

<u>Example 7</u>

DMC catalyst containing carboxylic acid esters of polyhydric alcohols and cyclodextrin (catalyst VII).

The procedure was as in Example 1, but instead of polyethylene glycol diacrylate and 2-phosphonopropionic acid triethyl ester as complex-forming components, polyethylene glycol sorbitan monooleate (Disponil® SMO 120) and 2,6-dimethyl-β-cyclodextrin (Beta W 7 M 1.8) used. Yield of dried powdered catalyst: 4.6 g Elemental analysis, thermogravimetric analysis and extraction: Cobalt = 10.1% by weight, zinc = 22.1% by weight.

<u>Example 8</u>

DMC catalyst containing carboxylic acid esters of polyhydric alcohols and polyester (catalyst VIII).

The procedure was as in Example 1, but instead of polyethylene glycol diacrylate and 2-phosphonopropionic acid triethyl ester as complex-forming components glycerol tricapronate and poly (2-methyl-1,3-propylene glutarate) (M._n 1020) used. Yield of dried powdery catalyst: 5.2 g Elemental analysis: Cobalt = 10.1% by weight, zinc = 23.8% by weight.

<u>Example 9</u>

DMC catalyst containing carboxylic acid esters of polyhydric alcohols and glycoside (catalyst IX).

The procedure was as in Example 1, but instead of polyethylene glycol diacrylate and triethyl 2-phosphonopropionate, glycerol tricapronate and alkyl polyglycoside (Glucopon® 650 EC) were used as complex-forming components. Yield of dried powdery catalyst: 3.8 g Elemental analysis: Cobalt = 10.2% by weight, zinc = 24.7% by weight.

<u>Example 10</u>

DMC catalyst containing carboxylic acid esters of polyhydric alcohols and glycidyl ether (catalyst X).

The procedure was as in Example 1, but instead of polyethylene glycol diacrylate and 2-phosphonopropionic acid triethyl ester as complex-forming components glycerol tricapronate and polypropylene glycol diglycidyl ether (M._n 640 g / mol) used. Yield of dried powdered catalyst: 5.4 g Elemental analysis: Cobalt = 11.1% by weight, zinc = 24.9% by weight.

<u>Example 11</u>

DMC catalyst containing carboxylic acid esters of polyhydric alcohols and bile acid derivative (catalyst XI).

The procedure was as in Example 1, but instead of polyethylene glycol diacrylate and triethyl 2-phosphonopropionate, glycerol tricapronate and sodium cholic acid were used as complex-forming components. Yield of dried powdered catalyst: 4.5 g Elemental analysis: Cobalt = 13.0% by weight, zinc = 30.0% by weight.

<u>Example 12</u>

DMC catalyst containing α, β-unsaturated carboxylic acid ester and cyclodextrin (catalyst XII).

The procedure was as in Example 1, but instead of polyethylene glycol diacrylate and 2-phosphonopropionic acid triethyl ester as complex-forming components, polyethylene glycol diacrylate (M._n 575 g / mol) and 2,6-dimethyl-β-cyclodextrin (Beta W 7 M 1.8). Yield of dried powdery catalyst: 4.7 g Elemental analysis: Cobalt = 10.5% by weight, zinc = 23.5% by weight.

<u>Example 13</u>

DMC catalyst containing α, β-unsaturated carboxylic acid ester and polyester (catalyst XIII).

The procedure was as in Example 1, but instead of polyethylene glycol diacrylate and 2-phosphonopropionic acid triethyl ester as complex-forming components, polyethylene glycol diacrylate (M._n 575 g / mol) and poly (2-methyl-1,3-propylene glutarate (M._n 1020) used. Yield of dried powdered catalyst: 5.6 g Elemental analysis: Cobalt = 11.3% by weight, zinc = 25.6% by weight.

<u>Example 14</u>

DMC catalyst containing α, β-unsaturated carboxylic acid ester and glycoside (catalyst XIV).

The procedure was as in Example 1, but instead of polyethylene glycol diacrylate and 2-phosphonopropionic acid triethyl ester as complex-forming components, polyethylene glycol diacrylate (M._n 575 g / mol) and alkyl polyglycoside (Glucopon® 650 EC). Yield of dried powdery catalyst: 4.7 g Elemental analysis, thermogravimetric analysis and extraction: Cobalt = 9.5% by weight, zinc = 21.9% by weight.

<u>Example 15</u>

DMC catalyst containing α, β-unsaturated carboxylic acid ester and glycidyl ether (catalyst XV).

The procedure was as in Example 1, but instead of polyethylene glycol diacrylate and 2-phosphonopropionic acid triethyl ester as complex-forming components, polyethylene glycol diacrylate (M._n 575 g / mol) and polypropylene glycol diglycidyl ether (M_n 640 g / mol) used. Yield of dried powdered catalyst: 5.3 g Elemental analysis: Cobalt = 8.4% by weight, zinc = 20.4% by weight.

<u>Example 16</u>

DMC catalyst containing α, β-unsaturated carboxylic acid ester and bile acid derivative (catalyst XVI).

The procedure was as in Example 1, but instead of polyethylene glycol diacrylate and 2-phosphonopropionic acid triethyl ester as complex-forming components, polyethylene glycol diacrylate (M._n 575 g / mol) and cholic acid sodium salt used. Yield of dried powdered catalyst: 5.6 g Elemental analysis: Cobalt = 11.5% by weight, zinc = 26.4% by weight.

<u>Example 17</u>

DMC catalyst containing cyclodextrin and glycidyl ether (catalyst XVII).

The procedure was as in Example 1, but instead of polyethylene glycol diacrylate and 2-phosphonopropionic acid triethyl ester as complex-forming components polypropylene glycol diglycidyl ether (M._n 640 g / mol) and 2,6-dimethyl-β-cyclodextrin (Beta W 7 M 1.8). Yield of dried powdery catalyst: 5.1 g Elemental analysis: Cobalt = 9.4% by weight, zinc = 22.4% by weight.

<u>Example 18</u>

DMC catalyst containing cyclodextrin and bile acid derivative (catalyst XVIII).

The procedure was as in Example 1, but instead of polyethylene glycol diacrylate and triethyl 2-phosphonopropionate, 2,6-dimethyl-β-cyclodextrin (Beta W 7 M 1.8) and sodium cholic acid were used as complex-forming components. Yield of dried powdery catalyst: 4.3 g Elemental analysis: Cobalt = 11.4% by weight, zinc = 26.7% by weight.

<u>Example 19</u>

DMC catalyst containing glycoside and glycidyl ether (catalyst XIX).

The procedure was as in Example 1, but instead of polyethylene glycol diacrylate and 2-phosphonopropionic acid triethyl ester as complex-forming components alkyl polyglycoside (Glucopon® 650 EC) and polypropylene glycol diglycidyl ether (M_n 640 g / mol) used. Yield of dried powdered catalyst: 6.3 g Elemental analysis: Cobalt = 10.0% by weight, zinc = 22.6% by weight.

<u>Example 20</u>

DMC catalyst containing glycoside and bile acid derivative (catalyst XX).

The procedure was as in Example 1, but instead of polyethylene glycol diacrylate and 2-phosphonopropionic acid triethyl ester, the complex-forming components used were alkyl polyglycoside (Glucopon® 650 EC) and cholic acid sodium salt. Yield of dried powdery catalyst: 4.4 g Elemental analysis: Cobalt = 11.6% by weight, zinc = 27.8% by weight.

<u>Example 21</u>

DMC catalyst containing glycidyl ether and bile acid derivative (catalyst XXI).

The procedure was as in Example 1, but instead of polyethylene glycol diacrylate and 2-phosphonopropionic acid triethyl ester as complex-forming components polypropylene glycol diglycidyl ether (M._n 640 g / mol) and cholic acid sodium salt used. Yield of dried powdery catalyst: 6.6 g Elemental analysis: Cobalt = 9.0% by weight, zinc = 21.4% by weight.

<u>Example 22</u>

DMC catalyst containing phosphorus compound and α, β-unsaturated carboxylic acid ester (catalyst XXII).

The procedure was as in Example 1, but instead of polyethylene glycol diacrylate and 2-phosphonopropionic acid triethyl ester, trimethylolpropane ethoxylate (14/3 EO / OH) triacrylate and 2-phosphonopropionic acid triethyl ester were used as complex-forming components. Yield of dried powdered catalyst: 6.3 g Elemental analysis: Cobalt = 9.2% by weight, zinc = 21.2% by weight.

<u>Example 23 (comparison)</u>

DMC catalyst containing carboxylic acid of polyhydric alcohols (catalyst XXIII)

A solution of 12.5 g (91.5 mmol) of zinc chloride in 20 ml of distilled water was added to a solution of 4 g (12 mmol) of potassium hexacyanocobaltate in 75 ml of distilled water with vigorous stirring (24,000 rpm). Immediately afterwards, a mixture of 50 g of tert-butanol and 50 g of distilled water was added to the suspension formed and then stirred vigorously for 10 minutes (24,000 rpm). A mixture of 1 g of glycerol tricapronate, 1 g of tert-butanol and 100 g of distilled water was then added and the mixture was stirred for 3 minutes (10,000 rpm). The solid was isolated by filtration, then stirred for 10 min with a mixture of 70 g of tert-butanol, 30 g of distilled water and 1 g of glycerol tricapronate and filtered again. Finally, the mixture was stirred again for 10 minutes with a mixture of 100 g of tert-butanol and 0.5 g of glycerol tricapronate (10,000 rpm). After filtration, the catalyst was dried to constant weight at 50 ° C. and normal pressure. Yield of dried powdered catalyst: 5.3 g Elemental analysis, thermogravimetric analysis and extraction: Cobalt = 12.3% by weight, zinc = 27.0% by weight, tert-butanol = 7.2% by weight, glycerol tricapronate = 3.7% by weight.

<u>Example 24 (comparison)</u>

DMC catalyst containing phosphorus compound (catalyst XXIV)

The procedure was as in Example 23, but triethyl 2-phosphonopropionate was used instead of the glycerol tricapronate. Yield of dried powdery catalyst: 5.9 g Elemental analysis, thermogravimetric analysis and extraction: Cobalt = 10.2% by weight, zinc = 23.5% by weight, tert-butanol = 2.3% by weight, 2-phosphonopropionic acid triethyl ester = 26.1% by weight.

<u>Example 25 (comparison)</u>

DMC catalyst containing glycidyl ether (catalyst XXV)

The procedure was as in Example 23 (comparison), but polypropylene glycol diglycidyl ether with an average molecular weight of 640 was used instead of the glycerol tricapronate. Yield of dried powdery catalyst: 6.0 g Elemental analysis, thermogravimetric analysis and extraction: Cobalt = 8.7% by weight, zinc = 20.2% by weight, tert-butanol = 4.2% by weight, polypropylene glycol diglycidyl ether ligand = 30.5%.

<u>Example 26 (comparison)</u>

DMC catalyst containing polyester (catalyst XXVI)

The procedure was as in Example 23, but a polyester of adipic acid and diethylene glycol with a medium molecular weight 2300 (OH number = 50 mg KOH / g) which was weakly branched by trimethylolpropane was used instead of the glycerol tricapronate from Example 23. Yield of dried powdery catalyst: 3.9 g Elemental analysis and thermogravimetric analysis: Cobalt = 12.2% by weight, zinc = 25.7% by weight, tert-butanol = 7.1% by weight, polyester = 12.3% by weight.

<u>Example 27 (comparison)</u>

DMC catalyst containing bile acid derivative (catalyst XXVII)

The procedure was as in Example 23, but cholic acid sodium salt was used instead of the glycerol tricapronate. Yield of dried powdery catalyst: 4.2 g Elemental analysis, thermogravimetric analysis and extraction: Cobalt = 12.6% by weight, zinc = 27.3% by weight, tert-butanol = 10.9% by weight, cholic acid sodium salt = 4.3% by weight

<u>Manufacture of polyether polyols</u>

General implementation

50 g of polypropylene glycol starter (number average molecular weight = 1,000 g / mol) and 20 mg of catalyst (100 ppm, based on the amount of the polyether polyol to be prepared) were placed in a 500 ml pressure reactor under protective gas (argon) and with stirring to 105 ° C. heated up. Then propylene oxide (approx. 5 g) was metered in at one time until the total pressure had risen to 2.5 bar. Further propylene oxide was only metered in again when an accelerated pressure drop in the reactor was observed. This accelerated pressure drop indicates that the catalyst is activated. The remaining propylene oxide (145 g) was then metered in continuously at a constant total pressure of 2.5 bar. After complete metering of propylene oxide and a reaction time of 2 hours at 105 ° C., volatile constituents were distilled off at 90 ° C. (1 mbar) and the reaction mixture was then cooled to room temperature.

The polyether polyols obtained were characterized by determining the OH numbers, the double bond contents and the viscosities.

The course of the reaction was followed using time-conversion curves (propylene oxide consumption [g] vs. reaction time [min]). The induction time was determined from the point of intersection of the tangent to the steepest point of the time-turnover curve with the extended baseline of the curve. The propoxylation times relevant for the catalyst activity correspond to the period between catalyst activation (end of the induction period) and the end of the propylene oxide metering. The total reaction time is the sum of the induction and propoxylation times.

<u>Example 28</u>

Preparation of polyether polyol with catalyst I (100 ppm)

<tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="3" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Induction time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">251 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Propoxylation time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">27 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Total response time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">278 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Polyether polyol</entry><entry namest="col2" nameend="col2" align="left">OH number (mg KOH / g)</entry><entry namest="col3" nameend="col3" align="right">29,2</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">Double bond content (mmol / kg)</entry><entry namest="col3" nameend="col3" align="right">7</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">Viscosity 25 ° C (mPas)</entry><entry namest="col3" nameend="col3" align="right">871</entry></row></tbody></tgroup></table></tables>

<u>Example 29</u>

Preparation of polyether polyol with catalyst III (25 ppm)

<tables id="tabl0002" num="0002"><table frame="all"><tgroup cols="3" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Induction time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">126 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Propoxylation time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">50 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Total response time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">176 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Polyether polyol</entry><entry namest="col2" nameend="col2" align="left">OH number (mg KOH / g)</entry><entry namest="col3" nameend="col3" align="right">29,9</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">Double bond content (mmol / kg)</entry><entry namest="col3" nameend="col3" align="right">9</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">Viscosity 25 ° C (mPas)</entry><entry namest="col3" nameend="col3" align="right">878</entry></row></tbody></tgroup></table></tables>

<u>Example 30</u>

Preparation of polyether polyol with catalyst IV (25 ppm)

<tables id="tabl0003" num="0003"><table frame="all"><tgroup cols="3" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Induction time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">163 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Propoxylation time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">52 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Total response time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">215 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Polyether polyol</entry><entry namest="col2" nameend="col2" align="left">OH number (mg KOH / g)</entry><entry namest="col3" nameend="col3" align="right">30,1</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">Double bond content (mmol / kg)</entry><entry namest="col3" nameend="col3" align="right">7</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">Viscosity 25 ° C (mPas)</entry><entry namest="col3" nameend="col3" align="right">821</entry></row></tbody></tgroup></table></tables>

<u>Example 31</u>

Preparation of polyether polyol with catalyst V (100 ppm)

<tables id="tabl0004" num="0004"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Induction time</entry><entry namest="col2" nameend="col2" align="right">165 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Propoxylation time</entry><entry namest="col2" nameend="col2" align="right">10th min</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Total response time</entry><entry namest="col2" nameend="col2" align="right">175 min</entry></row></tbody></tgroup></table></tables>

<u>Example 32</u>

Preparation of polyether polyol with catalyst VI (100 ppm)

<tables id="tabl0005" num="0005"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Induction time</entry><entry namest="col2" nameend="col2" align="right">160 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Propoxylation time</entry><entry namest="col2" nameend="col2" align="right">10th min</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Total response time</entry><entry namest="col2" nameend="col2" align="right">170 min</entry></row></tbody></tgroup></table></tables>

<u>Example 33</u>

Preparation of polyether polyol with catalyst VII (100 ppm)

<tables id="tabl0006" num="0006"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Induction time</entry><entry namest="col2" nameend="col2" align="right">240 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Propoxylation time</entry><entry namest="col2" nameend="col2" align="right">5 min</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Total response time</entry><entry namest="col2" nameend="col2" align="right">245 min</entry></row></tbody></tgroup></table></tables>

<u>Example 34</u>

Preparation of polyether polyol with catalyst VIII (100 ppm)

<tables id="tabl0007" num="0007"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Induction time</entry><entry namest="col2" nameend="col2" align="right">165 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Propoxylation time</entry><entry namest="col2" nameend="col2" align="right">10th min</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Total response time</entry><entry namest="col2" nameend="col2" align="right">175 min</entry></row></tbody></tgroup></table></tables>

<u>Example 35</u>

Preparation of polyether polyol with catalyst IX (100 ppm)

<tables id="tabl0008" num="0008"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Induction time</entry><entry namest="col2" nameend="col2" align="right">100 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Propoxylation time</entry><entry namest="col2" nameend="col2" align="right">10th min</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Total response time</entry><entry namest="col2" nameend="col2" align="right">110 min</entry></row></tbody></tgroup></table></tables>

<u>Example 36</u>

Preparation of polyether polyol with catalyst X (100 ppm)

<tables id="tabl0009" num="0009"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Induction time</entry><entry namest="col2" nameend="col2" align="right">150 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Propoxylation time</entry><entry namest="col2" nameend="col2" align="right">10th min</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Total response time</entry><entry namest="col2" nameend="col2" align="right">160 min</entry></row></tbody></tgroup></table></tables>

<u>Example 37</u>

Preparation of polyether polyol with catalyst XI (100 ppm)

<tables id="tabl0010" num="0010"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Induction time</entry><entry namest="col2" nameend="col2" align="right">155 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Propoxylation time</entry><entry namest="col2" nameend="col2" align="right">10th min</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Total response time</entry><entry namest="col2" nameend="col2" align="right">165 min</entry></row></tbody></tgroup></table></tables>

<u>Example 38</u>

Preparation of polyether polyol with catalyst XII (100 ppm)

<tables id="tabl0011" num="0011"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Induction time</entry><entry namest="col2" nameend="col2" align="right">320 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Propoxylation time</entry><entry namest="col2" nameend="col2" align="right">5 min</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Total response time</entry><entry namest="col2" nameend="col2" align="right">325 min</entry></row></tbody></tgroup></table></tables>

<u>Example 39</u>

Preparation of polyether polyol with catalyst XIII (25 ppm)

<tables id="tabl0012" num="0012"><table frame="all"><tgroup cols="3" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Induction time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">106 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Propoxylation time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">43 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Total response time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">149 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Polyether polyol</entry><entry namest="col2" nameend="col2" align="left">OH number (mg KOH / g)</entry><entry namest="col3" nameend="col3" align="right">29,3</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">Double bond content (mmol / kg)</entry><entry namest="col3" nameend="col3" align="right">6</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">Viscosity 25 ° C (mPas)</entry><entry namest="col3" nameend="col3" align="right">835</entry></row></tbody></tgroup></table></tables>

<u>Example 40</u>

Preparation of polyether polyol with catalyst XIV (100 ppm)

<tables id="tabl0013" num="0013"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Induction time</entry><entry namest="col2" nameend="col2" align="right">205 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Propoxylation time</entry><entry namest="col2" nameend="col2" align="right">5 min</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Total response time</entry><entry namest="col2" nameend="col2" align="right">210 min</entry></row></tbody></tgroup></table></tables>

<u>Example 41</u>

Preparation of polyether polyol with catalyst XV (100 ppm)

<tables id="tabl0014" num="0014"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Induction time</entry><entry namest="col2" nameend="col2" align="right">320 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Propoxylation time</entry><entry namest="col2" nameend="col2" align="right">10th min</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Total response time</entry><entry namest="col2" nameend="col2" align="right">330 min</entry></row></tbody></tgroup></table></tables>

<u>Example 42</u>

Preparation of polyether polyol with catalyst XVI (25 ppm)

<tables id="tabl0015" num="0015"><table frame="all"><tgroup cols="3" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Induction time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">160 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Propoxylation time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">43 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Total response time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">203 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Polyether polyol</entry><entry namest="col2" nameend="col2" align="left">OH number (mg KOH / g)</entry><entry namest="col3" nameend="col3" align="right">29,5</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">Double bond content (mmol / kg)</entry><entry namest="col3" nameend="col3" align="right">8</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">Viscosity 25 ° C (mPas)</entry><entry namest="col3" nameend="col3" align="right">842</entry></row></tbody></tgroup></table></tables>

<u>Example 43</u>

Preparation of polyether polyol with catalyst XVII (100 ppm)

<tables id="tabl0016" num="0016"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Induction time</entry><entry namest="col2" nameend="col2" align="right">265 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Propoxylation time</entry><entry namest="col2" nameend="col2" align="right">5 min</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Total response time</entry><entry namest="col2" nameend="col2" align="right">270 min</entry></row></tbody></tgroup></table></tables>

<u>Example 44</u>

Preparation of polyether polyol with catalyst XVIII (100 ppm)

<tables id="tabl0017" num="0017"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Induction time</entry><entry namest="col2" nameend="col2" align="right">250 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Propoxylation time</entry><entry namest="col2" nameend="col2" align="right">5 min</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Total response time</entry><entry namest="col2" nameend="col2" align="right">255 min</entry></row></tbody></tgroup></table></tables>

<u>Example 45</u>

Preparation of polyether polyol with catalyst XIX (100 ppm)

<tables id="tabl0018" num="0018"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Induction time</entry><entry namest="col2" nameend="col2" align="right">105 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Propoxylation time</entry><entry namest="col2" nameend="col2" align="right">10th min</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Total response time</entry><entry namest="col2" nameend="col2" align="right">115 min</entry></row></tbody></tgroup></table></tables>

<u>Example 46</u>

Preparation of polyether polyol with catalyst XX (100 ppm)

<tables id="tabl0019" num="0019"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Induction time</entry><entry namest="col2" nameend="col2" align="right">265 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Propoxylation time</entry><entry namest="col2" nameend="col2" align="right">5 min</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Total response time</entry><entry namest="col2" nameend="col2" align="right">270 min</entry></row></tbody></tgroup></table></tables>

<u>Example 47</u>

Preparation of polyether polyol with catalyst XXI (100 ppm)

<tables id="tabl0020" num="0020"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Induction time</entry><entry namest="col2" nameend="col2" align="right">135 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Propoxylation time</entry><entry namest="col2" nameend="col2" align="right">5 min</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Total response time</entry><entry namest="col2" nameend="col2" align="right">140 min</entry></row></tbody></tgroup></table></tables>

<u>Example 48</u>

Preparation of polyether polyol with catalyst XXII (100 ppm)

<tables id="tabl0021" num="0021"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Induction time</entry><entry namest="col2" nameend="col2" align="right">135 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Propoxylation time</entry><entry namest="col2" nameend="col2" align="right">10th min</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Total response time</entry><entry namest="col2" nameend="col2" align="right">145 min</entry></row></tbody></tgroup></table></tables>

<u>Example 49 (comparison)</u>

Preparation of polyether polyol with catalyst XXIII (100 ppm)

<tables id="tabl0022" num="0022"><table frame="all"><tgroup cols="3" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Induction time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">133 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Propoxylation time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">50 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Total response time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">183 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Polyether polyol</entry><entry namest="col2" nameend="col2" align="left">OH number (mg KOH / g)</entry><entry namest="col3" nameend="col3" align="right">30,0</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">Double bond content (mmol / kg)</entry><entry namest="col3" nameend="col3" align="right">6</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">Viscosity 25 ° C (mPas)</entry><entry namest="col3" nameend="col3" align="right">845</entry></row></tbody></tgroup></table></tables>

<u>Example 50 (comparison)</u>

Preparation of polyether polyol with catalyst XXIV (25 ppm)

<tables id="tabl0023" num="0023"><table frame="all"><tgroup cols="3" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Induction time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">99 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Propoxylation time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">110 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Total response time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">209 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Polyether polyol</entry><entry namest="col2" nameend="col2" align="left">OH number (mg KOH / g)</entry><entry namest="col3" nameend="col3" align="right">29,9</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">Double bond content (mmol / kg)</entry><entry namest="col3" nameend="col3" align="right">10</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">Viscosity 25 ° C (mPas)</entry><entry namest="col3" nameend="col3" align="right">862</entry></row></tbody></tgroup></table></tables>

<u>Example 51 (comparison)</u>

Preparation of polyether polyol with catalyst XXV (25 ppm)

<tables id="tabl0024" num="0024"><table frame="all"><tgroup cols="3" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Induction time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">154 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Propoxylation time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">37 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Total response time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">191 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Polyether polyol</entry><entry namest="col2" nameend="col2" align="left">OH number (mg KOH / g)</entry><entry namest="col3" nameend="col3" align="right">30,7</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">Double bond content (mmol / kg)</entry><entry namest="col3" nameend="col3" align="right">7</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">Viscosity 25 ° C (mPas)</entry><entry namest="col3" nameend="col3" align="right">809</entry></row></tbody></tgroup></table></tables>

<u>Example 52 (comparison)</u>

Preparation of polyether polyol with catalyst XXVI (25 ppm)

<tables id="tabl0025" num="0025"><table frame="all"><tgroup cols="3" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Induction time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">130 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Propoxylation time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">150 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Total response time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">280 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Polyether polyol</entry><entry namest="col2" nameend="col2" align="left">OH number (mg KOH / g)</entry><entry namest="col3" nameend="col3" align="right">29,5</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">Double bond content (mmol / kg)</entry><entry namest="col3" nameend="col3" align="right">5</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">Viscosity 25 ° C (mPas)</entry><entry namest="col3" nameend="col3" align="right">861</entry></row></tbody></tgroup></table></tables>

<u>Example 53 (comparison)</u>

Preparation of polyether polyol with catalyst XXVII (25 ppm)

<tables id="tabl0026" num="0026"><table frame="all"><tgroup cols="3" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Induction time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">217 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Propoxylation time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">33 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Total response time</entry><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="right">250 min</entry></row><row><entry namest="col1" nameend="col1" align="left">Polyether polyol</entry><entry namest="col2" nameend="col2" align="left">OH number (mg KOH / g)</entry><entry namest="col3" nameend="col3" align="right">29,6</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">Double bond content (mmol / kg)</entry><entry namest="col3" nameend="col3" align="right">6</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">Viscosity 25 ° C (mPas)</entry><entry namest="col3" nameend="col3" align="right">855</entry></row></tbody></tgroup></table></tables>