HK1051661A - Double-metal cyanide catalysts for preparing polyether polyols - Google Patents

Description

Double metal cyanide catalysts for preparing polyether polyols

Technical Field

The present invention relates to double metal cyanide ("DMC") catalysts for the preparation of polyether polyols by polyaddition of alkylene oxides to starter compounds containing active hydrogen atoms.

Background

DMC catalysts for the polyaddition of alkylene oxides to starter compounds containing active hydrogen atoms are known. See, for example, U.S. patents U.S.3,404,109, U.S.3,829,505, U.S.3,941,849, and U.S.5,158,922. The use of DMC catalysts for preparing polyether polyols reduces the content of monofunctional polyethers with terminal double bonds, the so-called "monools", compared with the preparation of polyether polyols with base catalysts, such as alkali metal hydroxides.

Polyether polyols produced by DMC catalysts can be used to process high quality polyurethanes (e.g., elastomers, foams, and coatings). DMC catalysts are generally obtained by reacting aqueous solutions of metal salts with aqueous solutions of metal cyanide salts in the presence of organic ligands, such as ethers. In the typical preparation of DMC catalysts, an aqueous solution of zinc chloride (in excess) and potassium hexacyanocobaltate are mixed to form a dispersion. Dimethoxyethane (glyme) was then added to the dispersion. After filtration and washing of the dispersion with an aqueous glyme solution, Zn of the formula₃[Co(CN)₆]₂·xZnCl₂·yH₂An active catalyst for O.z glyme. See, for example, EP 700949.

The following references disclose DMC catalysts which use tert-butanol as an organic ligand (either alone or in combination with a polyether) in the preparation of polyether polyols to further reduce the content of monofunctional polyethers having terminal double bonds: JP 4145123, U.S. Pat. No. 5,470,813, EP 700949, EP 743093 and WO 97/40086. In addition, the use of these DMC catalysts shortens the induction time of the polyaddition reaction of alkylene oxides with the corresponding starter compounds. The activity of the catalyst is also increased. By shortening the alkoxylation time, the process for preparing polyether polyols becomes more cost-effective. In addition, due to their increased activity, DMC catalysts can be used at low concentrations (25ppm or less), thereby eliminating the need for expensive methods of removing the catalyst from polyether polyols.

Disclosure of Invention

It is an object of the present invention to provide DMC catalysts for the production of polyether polyols by polyaddition of alkylene oxides onto starter compounds. The DMC catalysts of the invention have an improved catalyst activity compared to known DMC catalysts. The object of the invention is achieved by providing a DMC catalyst which contains: a) at least one DMC compound; b) at least one organic ligand which is not a polyether, polyester, polycarbonate, polyalkylene glycol sorbitan ester, polyalkylene glycol glycidyl ether, glycoside, polyol carboxylate, cyclodextrin, phosphorus compound, α, β -unsaturated carboxylate, or ionic surfactant compound; c) at least one polyether; and d) at least one polyester, polycarbonate, polyalkylene glycol sorbitan ester, polyalkylene glycol glycidyl ether, glycoside, polyol carboxylate, cyclodextrin, phosphorus compound, α, β -unsaturated carboxylate, or ionic surfactant compound.

Hereinafter, the polyether c) and the polyester, polycarbonate, polyalkylene glycol sorbitan ester, polyalkylene glycol glycidyl ether, glycoside, polyol carboxylate, cyclodextrin, phosphorus compound, α, β -unsaturated carboxylate, or ionic surfactant compound d) may be collectively referred to as "formulation component" or individually referred to as "formulation component".

The DMC catalyst of the present invention may optionally contain water, preferably in an amount of 1 to 10 wt%. The DMC catalysts of the present invention may also optionally contain one or more water-soluble metal salts, preferably in an amount of from 5 to 25% by weight.

The DMC compound a) is the reaction product of a water-soluble metal salt and a water-soluble metal cyanide salt. Water-soluble metal salts suitable for preparing DMC compounds a) are represented by the formula (I)

M(X)_n(I) Wherein

M is selected from 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), (preferably Zn (II)),

Fe (II), Co (II), and Ni (II));

each X is the same or different, preferably the same, and X is an anion selected from the group consisting of halide, acetate,

Hydroxyl, sulfate radical, carbonate radical, cyanate radical, thiocyanate radical, isocyanic acid radical, isothio

Cyanate, carboxylate, oxalate and nitrate; and

n is 1, 2 or 3.

Examples of suitable water-soluble metal salts useful in the present invention are zinc chloride, zinc bromide, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc nitrate, iron (II) sulfate, iron (II) bromide, iron (II) chloride, cobalt (II) thiocyanate, nickel (II) chloride, nickel (II) nitrate, and mixtures thereof.

Water-soluble metal cyanide salts suitable for preparing DMC compounds a) are represented by the formula (II)

(Y)_aM’(CN)_b(A)_c(II) wherein

M' is selected from 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) (preferably Co (II), Co (III), Fe (II), Fe (III), Cr (III)),

Ir (III) and Ni (II)), and the water-soluble metal cyanide salt may comprise one

One or more of these metals;

each Y is the same or different, preferably the same, and is selected from the group consisting of alkali metal ions and alkaline earth metals

Ions;

a is identical or different, preferably identical, and is selected from the group consisting of halide, hydroxide, sulfate, carbon

Acid radical, cyanate radical, thiocyanate radical, isocyanic acid radical, isothiocyanato radical, carboxylate radical, and grass

Acid radicals and nitrate radicals; and

a. b and c are integers, the values of a, b and c being selected so as to render the metal cyanide salt electrically neutral

And (a is preferably 1, 2, 3 or 4; b is preferably 4, 5 or 6; and c is preferably 0).

Examples of water-soluble metal cyanide salts useful in the present invention are potassium hexacyanocobaltate (III), potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), calcium hexacyanocobaltate (III) and lithium hexacyanocobaltate (III).

Preferred DMC compounds a) according to the invention are those represented by the formula (III)

M_x[M’_x’(CN)_y]_z(III) wherein

M is as defined for formula (I);

m' is as defined in formula (II); and is

x, x', y and z are integers and are selected so that the DMC compound is present

Is electrically neutral. It is preferable that the first and second liquid crystal layers are formed of,

x is 3, x' is 1, y is 6 and z is 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 DMC compounds a) useful in the present invention are zinc hexacyanocobaltate (III), zinc hexacyanocoridium (III), zinc hexacyanoferrate (III) and cobalt (II) hexacyanocobaltate (III). Further examples of suitable DMC compounds a) are found in U.S. Pat. No. 5,158,922. A preferred DMC compound useful in the present invention is zinc hexacyanocobaltate (III).

Organic ligands b) useful in the present invention are known and described in the following references: U.S. Pat. No. 5,158,922, U.S. Pat. No. 3,404,109, U.S. Pat. No. 3,829,505, U.S. Pat. No. 3,941,849, EP 700949, EP 761708, JP 4145123, U.S. Pat. No. 5,470,813, EP 743093 and WO 97/40086. Organic ligands useful in the present invention are water-soluble organic compounds which carry heteroatoms, such as oxygen, nitrogen, phosphorus or sulfur, and which can form complexes with the DMC compound a).

Soluble organic ligands useful in the present invention are alcohols, aldehydes, ketones, ethers, esters, amides, ureas, nitriles, thioethers and mixtures thereof. Preferred organic ligands are water-soluble aliphatic alcohols, such as ethanol, isopropanol, n-butanol, isobutanol, sec-butanol or tert-butanol. Tert-butanol is particularly preferred.

The organic ligands b) are added either during the preparation of the DMC catalyst or immediately after the precipitation of the DMC compound a). Usually an excess of organic ligand b) is used.

The DMC compound a) is present in an amount of from about 20 to about 90% by weight, preferably from 25 to 80% by weight, based on the total weight of the DMC catalyst. The organic ligands b) are present in an amount of from about 0.5 to about 30% by weight, preferably from 1 to 25% by weight, based on the total weight of the DMC catalyst. The DMC catalysts according to the invention preferably contain from about 1 to about 80% by weight, preferably from 1 to 40% by weight, of the mixture of the complexing components c) and d), based on the total weight of the DMC catalyst.

Polyethers c) suitable for use in the present invention are known and described in the following references: EP 700949, EP 761708 and WO 97/40086. It is preferred that the polyether polyols used in the present invention have 1 to 8, preferably 1 to 3 hydroxyl functional groups and a number average molecular weight of 150 and 10⁷Preferably between 200 and 5.10⁴In the meantime. The polyether polyols can be obtained by ring-opening polymerization of epoxides in the presence of bases, acids or coordination catalysts, such as DMC catalysts, and starter compounds containing active hydrogen atoms.

Examples of suitable polyether polyols useful in the present invention are poly (oxypropylene) polyols, poly (oxyethylene) polyols, EO-capped poly (oxypropylene) polyols, EO/PO-polyols, butylene oxide (butylene oxide) polymers, copolymers of butylene oxide and ethylene oxide and/or propylene oxide (propylene oxide), and poly (oxy-1, 4-butylene) glycol.

Polyesters suitable for use in the present invention are linear and partially branched polyesters having hydroxyl end groups and an average molecular weight of less than 10,000. Such polyesters are described in German patent application No. 19745120.9. Preferably, the polyesters used according to the invention are suitable for the preparation of polyurethanes with an average molecular weight of 400 to 6000 and an OH number of 28 to 300mg KOH/g. Examples of preferred polyesters are poly (ethylene glycol adipate), poly (diethylene glycol adipate), poly (dipropylene glycol adipate) branched with trimethylolpropane, poly (diethylene glycol adipate), poly (1, 4-butanediol adipate) and poly (2-methyl-1, 3-propylene glutarate).

Polycarbonates useful in the present invention are aliphatic polycarbonates having hydroxyl end groups and an average molecular weight of less than 12,000. Such polycarbonates are described in German patent application No. 19757574.9. Preferably, polycarbonate diols having an average molecular weight of 400 to 6000 are used in the present invention. Preferred polycarbonate diols are poly (1, 6-hexanediol) carbonate, poly (diethylene glycol) carbonate, poly (dipropylene glycol) carbonate, poly (triethylene glycol) carbonate, poly (1, 4-dimethylolcyclohexane) carbonate, poly (1, 4-butanediol) carbonate and poly (tripropylene glycol) carbonate.

The polyalkylene glycol sorbitan esters useful in the present invention are those described in german patent application No. 19842382.9 (polysorbate). Preferred for use herein are the polyalkylene glycol sorbitan mono-, di-and tri-esters of fatty acids having from 6 to 18 carbon atoms and from 2 to 40 moles of ethylene oxide.

The polyalkylene glycol glycidyl ethers useful in the present invention are the monoglycidyl and diglycidyl ethers of polypropylene glycol and polyethylene glycol described in German patent application No. 19834573.9.

Glycidyl ethers of monomeric or polymeric (having at least two monomer units) aliphatic, aromatic or araliphatic monofunctional alcohols, difunctional alcohols, trifunctional alcohols, tetrafunctional alcohols or polyfunctional alcohols are suitable for use in the present invention.

Preferred for use herein are the glycidyl ethers of monofunctional, difunctional, trifunctional, tetrafunctional or multifunctional aliphatic alcohols such as butanol, hexanol, octanol, decanol, dodecanol, tetradecanol, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 2-dimethyl-1, 3-propanediol, 1, 2, 3-propanetriol, 1, 6-hexanediol, 1, 1, 1-tris (hydroxymethyl) ethane, 1, 1, 1-tris (hydroxymethyl) propane, tetrakis (hydroxymethyl) methane, sorbitol, polyethylene glycol and polypropylene glycol. Monoethers, diethers, triethers, tetraethers and polyethers are suitable for use in the present invention.

Preferred for use in the present invention are butanol, hexanol, octanol, decanol, dodecanol, tetradecanol, ethylene glycol, 1, 4-butanediol, and the monoglycidyl or diglycidyl ethers of polypropylene or polyethylene glycols, especially polypropylene or polyethylene glycols having a degree of polymerization of 2 to 1000 monomer units.

Glycidyl ethers are typically obtained by reacting a monofunctional, difunctional, trifunctional, tetrafunctional or polyfunctional alcohol with epichlorohydrin in the presence of a lewis acid such as tin tetrachloride or boron tetrafluoride to form the corresponding chlorohydrin, followed by dehydrohalogenation with a base (e.g. sodium hydroxide).

The preparation of glycidyl ethers is well known and described in Kirk-Othmer Encyclopedia of Chemical Technology, volume 9 (fourth edition 1994), page 739 down and Ullmann, Encyclopedia of Industrial chemistry, volume A9 (5 th edition 1987, Weinheim/New York), page 552.

The glycidyl ethers useful for preparing the DMC catalysts of the present invention may be present in the finished catalyst both in the form as originally used and in chemically modified (hydrolyzed) form.

Glycosides d) suitable for use in the present invention are compounds consisting of carbohydrates (sugars) and non-sugars (ligands), wherein the ligands are bonded to the perhalogen aldehyde via an oxygen atom in a glycosidic bond with the hemiacetal C-atom of the carbohydrate.

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

A suitable non-sugar component is C₁-C₃₀The hydrocarbon group such as aryl, aralkyl and alkyl groups, preferably aralkyl and alkyl groups, more preferably alkyl groups having 1 to 30 carbon atoms.

Preferred glycosides useful in the present invention are polyglycosides, which are generally obtained by reacting carbohydrates with alcohols such as methanol, ethanol, propanol and butanol, or by transacetalization with short chain alkyl glycosides of fatty alcohols having 8 to 20 carbon atoms in the presence of an acid. More preferred are alkylpolyglycosides having glucose as the repeating unit in the chain, wherein the alkyl chain length is C₈-C₁₆And an average polymerization degree of 1 to 2.

The preparation of glycosides is well known and described in the following: Kirk-Othmer Encyclopedia of Chemical Technology, Vol.4 (fourth edition 1992), page 916 or less; volume 2 of R * mpp Lexikon Chemie (10 th edition 1996, Stuttgart/New York) at page 1581 or less; angewandte Chemie 1998 Vol 110 pages 1394 to 1412.

The polyol carboxylic acid ester suitable for use in the present invention is C₂-C₃₀Esters of carboxylic acids with aliphatic or cycloaliphatic alcohols having 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-trimethylolEthyl acetate, 1, 1, 1-trimethylolpropane, pentaerythritol, carbohydrates (sugars) and sugar alcohols, such as sorbitol and sorbitan. Sugars suitable for use in the present invention include monosaccharides such as glucose, galactose, mannose, fructose, arabinose, xylose and ribose, disaccharides such as sucrose and maltose, oligosaccharides and polysaccharides such as starch.

The carboxylic acid suitable for use in the present invention is C₂-C₃₀Carboxylic acids such as aryl, aralkyl and alkyl carboxylic acids, preferred are aralkyl and alkyl carboxylic acids, and more preferred are alkyl carboxylic acids such as oxalic acid, butyric acid, isovaleric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid and linolenic acid.

Preferred polyol carboxylic acid esters for use in the present invention are 1, 2, 3-propanetriol (glycerol), 1, 1, 1-trimethylolpropane, pentaerythritol, maltose and sorbitan and C₂-C₁₈Esters of alkyl carboxylic acids.

More preferred polyol carboxylic acid esters for use in the present invention are 1, 2, 3-propanetriol (glycerol), pentaerythritol and sorbitan with C₂-C₁₈Monoesters, diesters, triesters or tetraesters of alkyl carboxylic acids.

The preparation of polyol carboxylic acid esters or the separation of polyol carboxylic acid esters from fats is well known and is described in the following: Kirk-Othmer Encyclopedia of chemical technology, volume 9 (3 rd edition 1980), page 795 or less; r * mpp, Lexikon Chemie, 8 th edition 1981 (Stuttgart/New York); ullmann's encyclopedia of Industrial Chemistry, volume A10 (5 th edition 1987), pages 173 to 218.

The cyclodextrins useful in the present invention are unsubstituted cyclodextrins and esters, alkyl ethers, hydroxyalkyl ethers, alkoxycarbonyl alkyl ethers and carboxyalkyl ether derivatives of cyclodextrins and salts thereof.

Cyclodextrins useful in the present invention are cyclohexane amylose, cycloheptane amylose and cyclooctane amylose with 6, 7 or 8 glucose units bonded in a1, 4 manner, which arise in starch degradation with Bacillus macerans and Bacillus circulans under the action of cyclodextrin glycosyltransferases, for example alpha, beta, gamma or delta-cyclodextrins.

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

Suitable alkyl components for the cyclodextrin alkyl ethers, hydroxyalkyl ethers, alkoxycarbonyl alkyl ethers and carboxyalkyl ethers are straight-chain alkyl groups having from 1 to 30 carbon atoms, preferably from 1 to 24 carbon atoms, more preferably from 1 to 20 carbon atoms.

Preferred cyclodextrins are alpha, beta and gamma-cyclodextrins and mono-, di-and tri-ethers, mono-, di-and tri-esters and mono/diethers of alpha, beta and gamma-cyclodextrins, which are generally obtained by etherification of alpha, beta and gamma-cyclodextrins with alkylating agents, such as dimethyl sulfate and alkyl halides with 1 to 30 carbon atoms, such as methyl chloride, ethyl chloride, propyl chloride, butyl chloride, pentyl chloride, hexyl chloride, heptyl chloride, octyl chloride, methyl bromide, ethyl bromide, propyl bromide, butyl bromide, pentyl bromide, hexyl bromide, heptyl bromide, octyl bromide, methyl iodide, ethyl iodide, propyl iodide, butyl iodide, pentyl iodide, hexyl iodide, heptyl iodide and octyl iodide, and/or esterification with acetic acid and succinic acid in the presence of an acid.

More preferred cyclodextrins useful in the present invention are methyl- α -cyclodextrin, methyl- β -cyclodextrin, methyl- γ -cyclodextrin, ethyl- β -cyclodextrin, butyl- α -cyclodextrin, butyl- β -cyclodextrin, butyl- γ -cyclodextrin, 2, 6-dimethyl- 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, methyl- β -cyclodextrin, methyl- γ -cyclodextrin, methyl- β -cyclodextrin, butyl- γ -cyclodextrin, 2, 2, 3, 6-trioctyl-alpha-cyclodextrin, 2, 3, 6-trioctyl-beta-cyclodextrin, 2, 3, 6-triacetyl-alpha-cyclodextrin, 2, 3, 6-triacetyl-beta-cyclodextrin, 2, 3, 6-triacetyl-gamma-cyclodextrin, (2-hydroxy) propyl-alpha-cyclodextrin, (2-hydroxy) propyl-beta-cyclodextrin, (2-hydroxy) propyl-gamma-cyclodextrin, partially or fully acetylated or succinylated alpha, beta or gamma-cyclodextrin, 2, 6-dimethyl-3-acetyl-beta-cyclodextrin and 2, 6-dibutyl-3-acetyl-beta-cyclodextrin.

The preparation of cyclodextrins is well known and described in R * mpp Lexikon Chemie, 10 th edition 1997 (Stuttgart/New York) page 845 and Chemical Review 98(1998) 1743.

Phosphorus compounds suitable for use in the present invention are organic phosphates, organic phosphites, organic phosphonates, organic phosphonites, organic phosphinates and organic phosphinites.

The organic phosphoric acid esters suitable for use in the present invention are monoesters, diesters or triesters of phosphoric acid with alcohols having 1 to 30 carbon atoms; monoesters, diesters, triesters or tetraesters of pyrophosphoric acid with alcohols having 1 to 30 carbon atoms; and mono-, di-, tri-, tetra-, and polyesters of polyphosphoric acid and alcohols having 1 to 30 carbon atoms.

The organophosphites useful in the present invention are monoesters, diesters or triesters of phosphorous acid with alcohols having 1 to 30 carbon atoms.

The organic phosphonate esters suitable for use in the present invention are the mono-or diesters of phosphonic, alkylphosphonic, arylphosphonic, alkoxycarbonylalkylphosphonic, alkoxycarbonylphosphonic, cyanoalkylphosphonic and cyanophosphonic acids with alcohols having from 1 to 30 carbon atoms or the mono-, di-, tri-or tetraesters of alkylphosphonic acids with alcohols having from 1 to 30 carbon atoms.

Phosphonites suitable for use in the present invention are diesters of phosphonous and arylphosphonous acids with alcohols having from 1 to 30 carbon atoms.

Other phosphinic acid esters suitable for use according to the invention are esters of phosphinic, alkylphosphinic, dialkylphosphinic and arylphosphinic acids with alcohols having from 1 to 30 carbon atoms.

Still other phosphinic acid esters suitable for use in the present invention are the esters of alkyl, dialkyl and aryl phosphinic acids and alcohols having from 1 to 30 carbon atoms.

The alcohols useful in the present invention are monohydric or polyhydric alcohols of aryl alcohols, arylalkyl alcohols, alkoxyalkyl alcohols and alkyl alcohols having from 1 to 30 carbon atoms, preferably from 1 to 24 carbon atoms, and more preferably from 1 to 20 carbon atoms. Preferably, aralkyl alcohols, alkoxyalkyl alcohols and alkyl alcohols are used in the present invention. More preferred for use herein are alkoxyalkyl alcohols and alkyl alcohols.

The organic phosphates, organic phosphites, organic phosphonates, organic phosphonites, organic phosphinites and organic phosphinites useful in the present invention are generally obtained by reacting phosphoric acid, pyrophosphoric acid, polyphosphoric acid, phosphonic acid, alkylphosphonic acid, arylphosphonic acid, alkoxycarbonylalkylphosphonic acid, alkoxycarbonylahosphonic acid, cyanoalkylphosphonic acid, cyanophosphonic acid, alkylphosphonic acid, phosphonous acid, phosphorous acid, phosphinic acid or their halogen derivatives or phosphorus oxide with hydroxyl compounds having from 1 to 30 carbon atoms, such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, methoxymethanol, ethoxymethanol, propoxymethanol, Butoxymethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, phenol, ethyl hydroxyacetate, propyl hydroxyacetate, ethyl hydroxypropionate, propyl hydroxypropionate, 1, 2-ethanediol, 1, 2-propanediol, 1, 2, 3-trihydroxypropane, 1, 1, 1-trimethylolpropane and pentaerythritol.

Preferred for use herein are triethyl phosphate, tributyl phosphate, trioctyl phosphate, tris (2-ethylhexyl) phosphate, tris (2-butoxyethyl) phosphate, dibutyl butyl phosphonate, dioctyl phenyl phosphonate, triethyl phosphonoformate, trimethyl phosphonoacetate, triethyl phosphonoacetate, trimethyl 2-phosphonopropionate, triethyl 2-phosphonopropionate, tripropyl 2-phosphonopropionate, tributyl 2-phosphonopropionate, triethyl 3-phosphonopropionate, tributyl phosphite, trilauryl phosphite, tris (3-ethylxethany 1-3-methyl) phosphite and hepta (dipropylene glycol) phosphite.

Processes for the preparation of phosphates, phosphites, phosphonates, phosphonites, phosphinites and phosphinites are well known and described in the following: Kirk-Othmer Encyclopedia of Chemical Technology, volume 8 (1996, 4 th edition) page 737 or less; r * mpp Lexikon Chemie, volume 4, 1998, 10 th edition (Stuttgart/New York), p 3280 or less; ullmann's encyclopedia of Industrial Chemistry, volume A19 (5 th edition 1991), p.545 and below; Houben-Weyl "Methoden der organischen Chemie", volumes XII/1 and XII/2 (Stuttgart 1963/1964).

The α -, β -unsaturated carboxylic acid esters suitable for use in the present invention are aryl acids and the monoesters, diesters, triesters and polyesters of alkylaryl, alkoxyaryl, alkoxycarbonylalkyl aryl and alkoxycarbonylalkyl aryl acids with alcohols having 1 to 30 carbon atoms and polyether polyols.

Suitable alcohol moieties are monohydroxy, dihydroxy, trihydroxy and polyhydroxy aryl, arylalkyl, alkoxyalkyl and alkyl alcohols having from 1 to 30 carbon atoms, preferably from 1 to 24 carbon atoms, more preferably from 1 to 20 carbon atoms, preferably arylalkyl, alkoxyalkyl and alkyl alcohols, more particularly preferably alkoxyalkyl and alkyl alcohols.

Suitable alcohol moieties also include polyglycols and polyalkylene glycol ethers, preferably polypropylene glycols and polyethylene glycols and polypropylene glycol ethers and polyethylene glycol ethers, having molecular weights of from 200 to 10,000, preferably from 300 to 9000, more preferably from 400 to 8000.

Suitable alpha-, beta-unsaturated carboxylic acids are acrylic acid and acrylic acids with 1 to 20 carbon atoms and also alkylacrylic acids, alkoxyacrylic acids and alkoxycarbonylalkylacrylic acids, such as 2-methacrylic acid (methacrylic acid), 3-methacrylic acid (crotonic acid), trans-2, 3-dimethylacrylic acid (maleic acid), 3-dimethylacrylic acid (isopentenoic acid) and 3-methoxyacrylic acid. Preferred are acrylic acid, 2-methacrylic acid, 3-methacrylic acid and 3-methoxyacrylic acid. More preferred are acrylic acid and 2-methacrylic acid.

The α -, β -unsaturated carboxylic acid esters useful in the present invention are generally obtained by esterifying monohydroxy, dihydroxy, trihydroxy, tetrahydroxy and polyhydroxy compounds having 1 to 30 carbon atoms, such as methanol, ethanol, ethylene glycol (glycol), 1-propanol, 2-propanol, 1, 2-propanediol, 1, 3-propanediol, 1, 2, 3-glycerol (glycerol), butanol, 2-butanol, isobutanol, 1, 2-butanediol, 1, 3-butanediol, 2, 3-butanediol, 1, 4-butanediol, 1, 2, 3-butanetriol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-hexadecanol, 1-heptadecanol, 9-octadecanol, 1, 1, 1-tris (hydroxymethyl) propane, pentaerythritol, methoxymethanol, ethoxymethanol, propoxymethanol, butoxymethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, methyl glycolate, ethyl glycolate, propyl glycolate, methyl hydroxypropionate, ethyl hydroxypropionate, propyl hydroxypropionate, and polyether polyols such as polyethylene glycol and polypropylene glycol.

Preferred are the mono-, di-and triesters of acrylic and methacrylic acid with ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butylene glycol, 1, 6-hexanediol, 1, 2, 3-glycerol (glycerol), 1, 1, 1-tris (hydroxymethyl) propane ethoxylate, 1, 1, 1-tris (hydroxymethyl) propane propoxylate, polyethylene glycol and polypropylene glycol.

More preferred are α -, β -unsaturated carboxylic acid esters such as polyethylene glycol acrylate, polyethylene glycol diacrylate, polyethylene glycol methacrylate, polyethylene glycol dimethacrylate, polypropylene glycol acrylate, polypropylene glycol diacrylate, polypropylene glycol methacrylate, polypropylene glycol dimethacrylate, 1, 2, 3-propanetriol diacrylate, 1, 2, 3-propanetriol dimethacrylate, 1, 2, 3-propanetriol triacrylate, 1, 2, 3-propanetriol-1, 3-di (2-hydroxypropoxylate) diacrylate, 1, 2, 3-propanetriol propoxylate triacrylate, 1, 4-butanediolacrylate, 1, 4-butanedioldimethacrylate, 1, 6-hexanedioldiacrylate, 1, 4-butanedioldimethacrylate, 1, 2-propanetriol propoxylate triacrylate, 1, 3-butanedioldimethacrylate, 1, 2, 3-propanetriol, 2-hydroxypropyl methacrylate, 1, 1, 1-tris (hydroxymethyl) propane triacrylate, 1, 1, 1-tris (hydroxymethyl) propane ethoxylate trimethacrylate, 1, 1, 1-tris (hydroxymethyl) propane propoxylate triacrylate and 1, 1, 1-tris (hydroxymethyl) propane propoxylate trimethacrylate.

Methods for preparing α -, β -unsaturated carboxylic acid esters are known and described in the following: Kirk-Othmer Encyclopedia of Chemical Technology, volume 8 (1996, 4 th edition) page 737 or less; volume 4 of R * mpp Lexikon Chemie (10 th edition 1998, Stuttgart/New York) at page 3286 or less; ullmann's encyclopedia of Industrial Chemistry, volume A19 (5 th edition), page 991 or less; Houben-Weyl "Methoden der organischen Chemie", volumes XII/1 and XII/2 (Stuttgart 1963/1964).

The structural characteristics of the ionic surfactant compounds useful in the present invention are their amphiphilic molecular structure, i.e., they contain at least one hydrophilic ionic group (or one hydrophilic ionic molecular moiety) and at least one hydrophobic ionic group (or one hydrophobic ionic molecular moiety). Examples of ionic surfactant compounds useful in the present invention are surfactants, soaps, emulsifiers, detergents and dispersants.

The hydrophilic ionic group may have anionic, cationic or zwitterionic (amphoteric) properties. Examples of anionic groups are carboxylate, sulfonate, sulfate, thiosulfate, phosphonate, phosphinate, phosphate and dithiophosphate. Examples of cationic groups are ammonium groups, phosphonium groups and sulfonium groups. Examples of zwitterionic groups are glycine betaine, sulfoglycine betaine and amine oxide groups.

The hydrophobic group is preferably C₂-C₅₀Hydrocarbyl groups such as aryl, aralkyl and alkyl groups. However, fluoroalkyl, silalkyl (silaalkyl), thioalkyl, and oxaalkyl (oxaalkyl) groups are also suitable for use in the present invention.

Examples of suitable compounds with hydrophilic anionic groups are carboxylates, such as alkylcarboxylates (soaps); ether carboxylates (carboxymethylated ethoxylates); polycarboxylates, such as malonates and succinates; bile acid salts, such as salt-type bile acid amides with thioalkyl and carboxyalkyl groups; amino acid derivatives, such as sarcosinates (alkanoyl sarcosinates); a thioamido carboxylate; sulfates, such as alkyl phosphates; ether sulfates such as fatty alcohol ether sulfates, aryl ether sulfates, and amido ether sulfates; a sulfated carboxylate; sulfated glycerol carboxylate esters; sulfated carboxylic acid esters; a sulfated carboxylic acid amide; sulfonates such as alkylsulfonates, arylsulfonates, and alkylarylsulfonates; a sulfonated carboxylate; a sulfonated carboxylic acid ester; a sulfonated carboxylic acid amide; carboxylate sulfonates such as alpha-sulfofatty acid esters; a carboxyamide sulfonate; a sulfosuccinate ester; an ethersulfonate; a thiosulfate salt; phosphates such as alkyl phosphates and glycerophosphates; a phosphonate; phosphonites and dithiophosphates.

Examples of the class of compounds having a hydrophilic cationic group suitable for use in the present invention are primary, secondary, tertiary and quaternary ammonium salts having alkyl, aryl and aralkyl groups; an alkoxylated ammonium salt; a quaternary ammonium ester; a benzylammonium salt; an alkanolammonium salt; a pyridine salt; imidazolinium salts; oxazolinium salts (oxolinium salts); thiazolinium salts; amine oxide salts; a sulfonium salt; quinolinium salts; isoquinolinium salts and  onium salts.

Examples of compounds with hydrophilic zwitterionic groups suitable for use in the present invention are amine oxides; imidazolinium derivatives such as imidazolinium carboxylates; betaines, such as alkyl and amidopropyl betaines; sulfobetaine; aminocarboxylic acids and phospholipids, such as phosphatidylcholine (lecithin).

The ionic surfactant compounds may also contain some hydrophilic (anionic and/or cationic and/or zwitterionic) groups or molecular moieties.

The ionic surfactant compounds may be used alone or in combination.

Ionic surfactant compounds suitable for use in the present invention are known and described in the following: ullmann's Encyclopedia of Industrial Chemistry, volume A25 (5 th edition 1994, VCH, Weinheim), pages 747-817; Kirk-Othmer Encyclopedia of Chemical Technology, Vol.23 (4 th edition 1997, John Wiley & Sons, New York) pp.477-541; Tensid-Taschenbuch, 2 nd edition 1982 (H.Stache, Carl Hanser Verlag, Munich); surfactant Science Series, Vol.1-74 (M.J. Schick, Marcel Decker, New York, 1967-1998); methods in Enzymology, Vol.182, pages 239-253 (M.P. Deutscher, Academic Press, SanDiego, 1990).

The catalyst of the present invention may be crystalline, partially crystalline or amorphous. Crystallinity analysis is usually performed by powder X-ray diffraction.

Catalyst composition analysis is usually carried out by elemental analysis, thermogravimetric analysis or extraction to remove complex-forming components followed by gravimetric determination.

Preferred DMC catalysts of the invention comprise a) zinc hexacyanocobaltate (III); b) tert-butyl alcohol; c) at least one polyether; and d) at least one polyester, polycarbonate, polyalkylene glycol sorbitan ester, polyalkylene glycol glycidyl ether, glycoside, polyol carboxylate, cyclodextrin, phosphorus compound, alpha-, beta-unsaturated carboxylate, or ionic surfactant compound.

DMC catalysts are usually prepared by reacting in aqueous solution a metal salt, preferably a metal salt of formula (I), with a metal cyanide salt, preferably a metal cyanide salt of formula (II), in the presence of an organic ligand b), and the organic ligand b) is neither a polyether nor a polyester, a polycarbonate, a polyalkylene glycol sorbitan ester, a polyalkylene glycol glycidyl ether, a glycoside, a carboxylic ester of a polyol, a cyclodextrin, a phosphorus compound, an α -, β -unsaturated carboxylic ester or an ionic surfactant compound. In this preparation, the metal salt (e.g. zinc chloride, used in stoichiometric excess, i.e. at least 50 mol% based on the molar amount of metal cyanide salt) is reacted with the metal cyanide salt (e.g. potassium hexacyanocobaltate) in aqueous solution in the presence of an organic ligand b) (e.g. tert-butanol). A suspension is formed containing the DMC compound a) (e.g., zinc hexacyanocobaltate), water, excess metal salt, and organic ligand b).

The organic ligands b) are either present in the aqueous solution of the metal salt and/or metal cyanide salt or are added directly to the suspension after precipitation of the DMC compound a). Preferably, the mixture of aqueous solution and organic ligand b) is stirred vigorously. The formed suspension is then treated with a mixture of the coordination components c) and d). The mixture of the coordination partners c) and d) is preferably used in a mixture of water and organic ligands b).

Subsequently, the DMC catalyst is separated from the suspension by known techniques, such as centrifugation or filtration. In a preferred embodiment of the invention, the separated DMC catalyst is washed with an aqueous solution of the organic ligand b) (for example by resuspension and then re-separation by filtration or centrifugation). Water-soluble by-products, such as potassium chloride, are removed from the DMC catalyst by washing the DMC catalyst with an aqueous solution of an organic ligand b).

In the aqueous washing liquids, the amount of organic ligands b) is preferably between 40 and 80% by weight, based on the total weight of the aqueous washing liquid. Preferably, to this aqueous washing solution small amounts of complexing components c) and d), preferably 0.5 to 5% by weight, based on the total weight of the aqueous washing solution, are added.

Preferably the DMC catalyst is washed one or more times. This can be achieved by repeating the water wash procedure described above. However, it is preferred to carry out further washing operations using a non-aqueous washing liquid. The non-aqueous washing liquid comprises a mixture of a coordinating ligand b) and coordinating components c) and d).

The washed DMC catalyst (optionally after pulverization) is then dried at a temperature of from 20 to 100 ℃ and a pressure of from 0.1mbar to 1,013 mbar.

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

Alkylene oxides preferred for use in the present invention are ethylene oxide, propylene oxide, butylene oxide and mixtures thereof. The formation of polyether chains by alkoxylation can be achieved by using only one monomeric epoxide or with 2 or 3 different monomeric epoxides, either randomly or in blocks. Further details regarding this can be found below page 670 of Ullmann's encyclopedia der industrillen Chemie, volume A21 (1992).

Preferred active hydrogen atom-containing starting compounds for use in the present invention are those having 1 to 8 hydroxyl groups and a number average molecular weight of 18 to 2,000. Examples of such starting compounds are ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propanediol, 1, 4-butanediol, 1, 6-hexanediol, bisphenol A, trimethylolpropane, glycerol, pentaerythritol, sorbitol, sucrose, degraded starch and water.

The active hydrogen atom-containing starting compounds preferably used in the present invention are prepared from the above-mentioned low molecular weight starting compounds by conventional base catalysis and are oligomeric alkoxylation products having a number average molecular weight of 200 to 2,000.

The polyaddition reactions catalyzed by the DMC catalysts of the present invention for the polyaddition of alkylene oxides onto starter compounds containing active hydrogen atoms are carried out at temperatures of from 20 to 200 deg.C, preferably from 40 to 180 deg.C, more preferably from 50 to 150 deg.C. The reaction can be carried out at a total pressure of from 0.0001 to 20 bar. The polyaddition reaction can be carried out in bulk or in an inert organic solvent such as toluene and/or tetrahydrofuran ("THF"). The amount of the solvent is usually 10 to 30% by weight based on the total weight of the polyether polyol to be produced.

The DMC catalyst concentration is chosen so that adequate control of the polyaddition reaction is possible under the given reaction conditions. The concentration of the catalyst is usually in the range of 0.0005% to 1% by weight, preferably 0.001% to 0.1% by weight, more preferably 0.001% to 0.0025% by weight, based on the total weight of the polyether polyol to be produced.

The number average molecular weight of the polyether polyols prepared by the process of the present invention is in the range of from 500 to 100,000g/mol, preferably from 1,000 to 50,000g/mol, more preferably from 2,000 to 20,000 g/mol.

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

In view of its significantly improved activity, the DMC catalyst of the present invention can be used at low concentrations (25ppm or less, based on the amount of polyether polyol to be prepared). In the preparation of polyurethanes, if the polyether polyol is prepared in the presence of the DMC catalyst of the present invention, the step of removing the DMC catalyst from the polyether polyol can be omitted without adversely affecting the product quality of the resulting polyurethane. See Kunststoffhandbuch (3 rd edition 1993) volume 7, "polyurethane", pages 25-32 and pages 57-67.

Preparation of embodiment catalyst

Example 1 preparation of a DMC catalyst with a ligand component of polyether and cyclodextrin (catalyst a):

a solution of 12.5g (91.5 mmol) of zinc chloride in 20ml of distilled water was added to a solution of 4g (12 mmol) of potassium hexacyanocobaltate in 70ml of distilled water and stirred vigorously (24,000 revolutions per minute) until a suspension was formed. Subsequently, a mixture of 50g of tert-butanol and 50g of distilled water was immediately added to the suspension formed, followed by vigorous stirring for 10 minutes (24,000 revolutions per minute). A mixture of 0.5g of polypropylene glycol ("polypropylene glycol 2000", number average molecular weight 2000) and 0.5g of 2, 6-dimethyl- β -cyclodextrin Beta W7M 1, 8(Wacker-Chemie GmbH, D-81737 Munich), 1g of tert-butanol and 100g of distilled water was then added and stirred for 3 minutes (1000 revolutions/minute). The solid was separated by filtration and then stirred with a mixture of 70g of tert-butanol, 30g of distilled water, 0.5g of polypropylene glycol 2000 and 0.5g of 2, 6-dimethyl-Beta-cyclodextrin Beta W7M 1,8 for 10 minutes (10,000 revolutions per minute) and filtered again. Finally, the solid was again stirred with a mixture of 100g of tert-butanol, 0.25g of polypropylene glycol 2000 and 0.25g of 2, 6-dimethyl- β -cyclodextrin Beta W7M 1,8 for 10 minutes (10,000 revolutions per minute). After filtration, the catalyst was dried to constant weight at 50 ℃ and conventional pressure.

Example 2 preparation of a DMC catalyst with the complexing components polyether and phosphorus compound (catalyst B):

the procedure was as described in example 1, but 2, 6-dimethyl- β -cyclodextrin Beta W7M 1,8 was replaced with triethyl 2-phosphonopropionate.

Example 3 preparation of a DMC catalyst with a ligand set consisting of polyether and polyester (catalyst C):

the procedure is as described in example 1, but 2, 6-dimethyl- β -cyclodextrin Beta W7M 1,8 is replaced by poly (2-methyl-1, 3-propyleneglycolate) having a number average molecular weight of 1020 g/mol.

Example 4 preparation of a DMC catalyst with a ligand set of polyether and polycarbonate (catalyst D):

the procedure is as described in example 1, but 2, 6-dimethyl- β -cyclodextrin Beta W7M 1,8 is replaced by dipropylene glycol polycarbonate diol having a number-average molecular weight of 1968g/mol (determined by measuring the OH number).

Example 5 preparation of a DMC catalyst with the complexing components polyether and glycidyl ether (catalyst E):

the procedure is as described in example 1, but the 2, 6-dimethyl- β -cyclodextrin Beta W7M 1,8 is replaced by polypropylene glycol diglycidyl ether having a number-average molecular weight of 640 g/mol.

Example 6 preparation of a DMC catalyst with complexing components polyether and polyol carboxylate (catalyst F):

the procedure is as described in example 1, but replacing 2, 6-dimethyl- β -cyclodextrin Beta W7M 1,8 with tri-n-hexanoglyceride (RILANIT  GTC, from Henkel KG a.A., D-40589D usseldorf).

Example 7 preparation of a DMC catalyst with the complexing components polyether and glycoside (catalyst G):

the procedure is as described in example 1, but the 2, 6-dimethyl- β -cyclodextrin Beta W7M 1,8 is replaced by an alkylpolyglycoside (GIUCOPON  650 EC, from Henkel KG a.A., D-40589D usseldorf).

Example 8 preparation of a DMC catalyst (catalyst H) with a ligand set consisting of a polyether and an α -, β -unsaturated carboxylic acid ester:

the procedure was as described in example 1, but 1, 1, 1-tris (hydroxymethyl) propane triacrylate was used instead of 2, 6-dimethyl- β -cyclodextrin Beta W7M 1, 8.

Example 9 preparation of a DMC catalyst with complexing components polyether and sorbitan ester (catalyst I):

the procedure is as described in example 1, but 2, 6-dimethyl- β -cyclodextrin Beta W7M 1,8 is replaced by polyethylene glycol (20) sorbitan monolaurate (TWEEN  20, from Sigma-Aldrich Chemie GmbH, D-82041 Deisenhofen).

Example 10 preparation of DMC catalyst with coordination components polyether and ionic surfactant compound (catalyst J):

the procedure was as described in example 1, but replacing 2, 6-dimethyl- β -cyclodextrin Beta W7M 1,8 with L- α -lecithin.

Example 11 (comparative) a DMC catalyst with a polyether as complexing component (catalyst K) was prepared:

a solution of 12.5g (91.5 mmol) of zinc chloride in 20ml of distilled water was added to a solution of 4g (12 mmol) of potassium hexacyanocobaltate in 70ml of distilled water and stirred vigorously (24,000 revolutions per minute) until a suspension was formed. Subsequently, a mixture of 50g of tert-butanol and 50g of distilled water was immediately added to the suspension formed, followed by vigorous stirring for 10 minutes (24,000 revolutions per minute). A mixture of 1g of polypropylene glycol 2000, 1g of tert-butanol and 100g of distilled water was then added and stirred for 3 minutes (1000 revolutions per minute). The solid was separated by filtration, and then stirred with a mixture of 70g of t-butanol, 30g of distilled water, 1g of polypropylene glycol 2000 for 10 minutes (10,000 rpm), and filtered again. Finally, the solid was again stirred with a mixture of 100g of tert-butanol and 0.5g of polypropylene glycol 2000 for 10 minutes (10,000 revolutions per minute). After filtration, the catalyst was dried to constant weight at 50 ℃ and conventional pressure. Yield of powdery dry catalyst: 6.2g elemental analysis, thermogravimetric analysis and extraction: 11.6% by weight of cobalt, 24.6% by weight of zinc, 3.0% by weight of tert-butanol and 25.8% by weight of polypropylene glycol 2000.

Example 12 (comparative) a DMC catalyst with cyclodextrin as complexing component (catalyst L) was prepared:

the procedure was as described in example 11, but the polypropylene glycol 2000 was replaced by 2, 6-dimethyl- β -cyclodextrin Beta W7M 1, 8. Yield of powdery dry catalyst: 5.4g elemental analysis, thermogravimetric analysis and extraction: cobalt 10.5 wt%, zinc 24.4 wt%, tert-butanol 10.0 wt%, 2, 6-dimethyl- β -cyclodextrin 13.8 wt%.

Example 13 (comparative) a DMC catalyst with a phosphorus compound as complexing component (catalyst M) was prepared:

the procedure was as described in example 11, but polypropylene glycol 2000 was replaced by triethyl 2-phosphonopropionate. Yield of powdery dry catalyst: 5.9g elemental analysis, thermogravimetric analysis and extraction: 10.2% by weight of cobalt, 23.5% by weight of zinc, 2.3% by weight of tert-butanol and 26.1% by weight of triethyl 2-phosphonopropionate.

Example 14 (comparative) a DMC catalyst with polyester as complexing component (catalyst N) was prepared:

the procedure is as described in example 11, but the polypropylene glycol 2000 is replaced by poly (2-methyl-1, 3-propyleneglycolate) having a number average molecular weight of 1020 g/mol. Yield of powdery dry catalyst: 5.4g elemental analysis: cobalt was 12.1 wt%, and zinc was 27.0 wt%.

Example 15 (comparative) a DMC catalyst with polycarbonate as complexing component (catalyst O) was prepared:

the procedure is as described in example 11, but the polypropylene glycol 2000 is replaced by dipropylene glycol polycarbonate having a number-average molecular weight of 1968g/mol (determined by measuring the OH number). Yield of powdery dry catalyst: 5.33g elemental analysis, thermogravimetric analysis and extraction: 10.8% by weight of cobalt, 24.4% by weight of zinc, 20.2% by weight of tert-butanol and 15.0% by weight of polycarbonate.

Example 16 (comparative) a DMC catalyst with glycidyl ether as complexing component (catalyst P) was prepared:

the procedure is as described in example 11, but polypropylene glycol 2000 is replaced by polypropylene glycol diglycidyl ether having a number-average molecular weight of 380 g/mol. Yield of powdery dry catalyst: 8.70g elemental analysis, thermogravimetric analysis and extraction: cobalt 8.7 wt%, zinc 20.2 wt%, tert-butanol 4.2 wt%, and polypropylene glycol diglycidyl ether 30.5 wt%. Example 17 (comparative) a DMC catalyst (catalyst Q) with a polyol carboxylic ester as complexing component was prepared:

the procedure is as described in example 11, but polypropylene glycol 2000 is replaced by tri-n-hexanoglyceride (RILANIT  GTC from Henkel KG a.A., D-40589D ü sseldorf). Yield of powdery dry catalyst: 5.0g elemental analysis, thermogravimetric analysis and extraction: 12.4% by weight of cobalt, 26.9% by weight of zinc, 8.6% by weight of tert-butanol and 8.4% by weight of tri-n-hexanoin.

Example 18 (comparative) a DMC catalyst with a glycoside as complexing component (catalyst R) was prepared:

the procedure is as described in example 11, but the polypropylene glycol 2000 is replaced by an alkylpolyglycoside (GIUCOPON  650 EC, from Henkel KG a.A., D-40589D ü sseldorf). Yield of powdery dry catalyst: 8.70g elemental analysis, thermogravimetric analysis and extraction: cobalt 8.7 wt.%, zinc 20.2 wt.%, tert-butanol 4.2 wt.%, and alkylpolyglycoside 30.5 wt.%.

Example 19 (comparative) a DMC catalyst (catalyst S) with an α -, β -unsaturated carboxylic acid ester as complexing component was prepared:

the procedure was as described in example 11, but 1, 1, 1-tris (hydroxymethyl) propane triacrylate was used instead of polypropylene glycol 2000. Yield of powdery dry catalyst: 5.0g elemental analysis, thermogravimetric analysis and extraction: 11.8% by weight of cobalt, 27.7% by weight of zinc, 11.8% by weight of tert-butanol and 2.4% by weight of 1, 1, 1-tris (hydroxymethyl) propane triacrylate.

Example 20 (comparative) a DMC catalyst with sorbitan ester as coordinating component (catalyst T) was prepared:

the procedure is as described in example 11, but the polypropylene glycol 2000 is replaced by polyethylene glycol (20) sorbitan monolaurate (TWEEN  20, from Sigma-Aldrich Chemie GmbH, D-82041 Deisenhofen). Yield of powdery dry catalyst: 5.6g elemental analysis, thermogravimetric analysis and extraction: 11.9% by weight of cobalt, 24.9% by weight of zinc, 3.6% by weight of tert-butanol and 14.6% by weight of polyethylene glycol (20) sorbitan monolaurate.

Example 21 (comparative) a DMC catalyst (catalyst U) with an ionic surfactant compound as complexing component was prepared:

the procedure was as described in example 11, but replacing the polypropylene glycol 2000 with L-alpha-lecithin. Yield of powdery dry catalyst: 2.0g elemental analysis, thermogravimetric analysis and extraction: 13.7% by weight of cobalt, 25.6% by weight of zinc, 7.5% by weight of tert-butanol and 12.0% by weight of L- α -lecithin. General procedure for preparation of polyether polyols

50g of polypropylene glycol starter (number average molecular weight 1,000g/mol) and 3 to 5mg of catalyst (15 to 25ppm, based on the amount of polyether polyol to be prepared) were charged under inert gas (argon) into a 500ml pressure reactor and heated to 105 ℃ with stirring. Propylene oxide (ca. 5g) was then added in one portion until the total pressure had risen to 2.5 bar. Only when an accelerated pressure drop in the reactor was observed was further propylene oxide added. The accelerated pressure drop indicates that the catalyst has been activated. The remainder of the propylene oxide (145g) was then added continuously at a constant total pressure of 2.5 bar. After all the propylene oxide had been added and a post-reaction time of 2 hours at 105 ℃, the volatiles were distilled at 90 ℃ (1mbar) and the mixture was cooled to room temperature.

The obtained polyether polyol was examined by measuring the OH value, double bond content and viscosity.

The progress of the reaction was monitored on the basis of a time conversion curve (propylene oxide consumption [ g ] vs. reaction time [ min ]). The induction time is determined by the intersection of the tangent at the sharpest point of the time-transfer curve with the extension of the curve base. The propoxylation time, which is decisive for the catalyst activity, corresponds to the time between the activation of the catalyst (at the end of the induction period) and the end of the propylene oxide feed. The total reaction time is the sum of the induction time and the propoxylation time. Example 22 preparation of polyether polyol with catalyst B (25 ppm): induction time: propoxylation time of 99 min: 110 min total reaction time: 209 polyether polyol: OH number (mg KOH/g): 29.9

Double bond content (mmol/kg): 10

Viscosity at 25 ℃ (mPas): 931

Example 23 (comparative) a polyether polyol was prepared with catalyst K (25 ppm): induction time: propoxylation time of 100 min: 110 min total reaction time: polyether polyol type 210 min: OH number (mg KOH/g): 28.1

Double bond content (mmol/kg): 7

Viscosity at 25 ℃ (mPas): 849

Example 24 (comparative) a polyether polyol was prepared with catalyst L (25 ppm): induction time: 160 min propoxylation time: 160 min total reaction time: 320 part polyether polyol: OH number (mg KOH/g): 30.2

Double bond content (mmol/kg): 9

Viscosity at 25 ℃ (mPas): 855

Example 25 (comparative) a polyether polyol was prepared with catalyst M (25 ppm): induction time: propoxylation time of 99 min: 110 min total reaction time: 209 polyether polyol: OH number (mg KOH/g): 29.9

Double bond content (mmol/kg): 10

Viscosity at 25 ℃ (mPas): 931

Example 26 (comparative) preparation of a polyether polyol with catalyst N (25 ppm): induction time: propoxylation time of 90 min: 93 min total reaction time: 183 min polyether polyol: OH number (mg KOH/g): 29.9

Double bond content (mmol/kg): 6

Viscosity at 25 ℃ (mPas): 845

Example 27 (comparative) preparation of a polyether polyol with catalyst O (15 ppm): induction time: time to propoxylation at 120 min: 190 min total reaction time: polyether polyol type 310 part: OH number (mg KOH/g): 29.6

Double bond content (mmol/kg): 6

Viscosity at 25 ℃ (mPas): 901

Example 28 (comparative) a polyether polyol was prepared with catalyst P (25 ppm): induction time: propoxylation time of 130 min: 31 min total reaction time: 161 part polyether polyol: OH number (mg KOH/g): 29.5

Double bond content (mmol/kg): 7

Viscosity at 25 ℃ (mPas): 849 example 29 (comparative) a polyether polyol was prepared with catalyst Q (25 ppm): induction time: 180 min propoxylation time: 115 minutes total reaction time: 295 polyol type polyether: OH number (mg KOH/g): 29.6

Double bond content (mmol/kg): 9

Viscosity at 25 ℃ (mPas): 914

Example 30 (comparative) a polyether polyol was prepared with catalyst R (20 ppm): induction time: propoxylation time of 350 min: 355 min total reaction time: 705 polyether polyol: OH number (mg KOH/g): 29.6

Double bond content (mmol/kg): 6

Viscosity at 25 ℃ (mPas): 1013

Example 31 (comparative) a polyether polyol was prepared with catalyst S (25 ppm): induction time: time to propoxylation at 120 min: 87 min total reaction time: 207 polyether polyol: OH number (mg KOH/g): 29.8

Double bond content (mmol/kg): 7

Viscosity at 25 ℃ (mPas): 922

Example 32 (comparative) a polyether polyol was prepared with catalyst T (25 ppm): induction time: propoxylation time of 265 min: 175 min total reaction time: 440 part polyether polyol: OH number (mg KOH/g): 30.2

Double bond content (mmol/kg): 8

Viscosity at 25 ℃ (mPas): 926

Example 33 (comparative) a polyether polyol was prepared with catalyst U (25 ppm): induction time: propoxylation time at 125 min: 140 min total reaction time: 265-part polyether polyol: OH number (mg KOH/g): 29.5

Double bond content (mmol/kg): 6

Viscosity at 25 ℃ (mPas): 921

Claims (10)

1. A double metal cyanide catalyst comprising:

a) at least one double metal cyanide compound;

b) at least one organic ligand which is not a polyether, polyester, polycarbonate, polyalkylene glycol sorbitan ester, polyalkylene glycol glycidyl ether, glycoside, polyol carboxylate, cyclodextrin, phosphorus compound, α, β -unsaturated carboxylate, or ionic surfactant compound;

c) at least one polyether; and

d) at least one polyester, polycarbonate, polyalkylene glycol sorbitan ester, polyalkylene glycol glycidyl ether, glycoside, polyol carboxylate, cyclodextrin, phosphorus compound, α, β -unsaturated carboxylate, or ionic surfactant compound.

2. The double metal cyanide catalyst according to claim 1, further comprising water and/or a water-soluble metal salt.

3. The double metal cyanide catalyst of claim 1, wherein the double metal cyanide compound is zinc hexacyanocobaltate (III).

4. The double metal cyanide catalyst according to claim 1, wherein the organic ligand is an alcohol, aldehyde, ketone, ether, ester, amide, urea, nitrile, thioether and/or mixtures thereof.

5. The double metal cyanide catalyst of claim 1 wherein the organic ligand is t-butanol.

6. The double metal cyanide catalyst of claim 1, wherein the double metal cyanide catalyst contains up to about 80 wt.% of the mixture of c) and d), based on the total weight of the double metal cyanide catalyst.

7. A process for preparing the double metal cyanide catalyst of claim 1, comprising the steps of: (a) reacting, in an aqueous solution, (i) at least one metal salt, (ii) with at least one metal cyanide salt, in the presence of (iii) an organic ligand to form a suspension, wherein the organic ligand is not a polyether, polyester, polycarbonate, polyalkylene glycol sorbitan ester, polyalkylene glycol glycidyl ether, glycoside, polyol carboxylate, cyclodextrin, phosphorus compound, α, β -unsaturated carboxylate, or ionic surfactant compound; and (b) treating the suspension with at least one polyether and at least one polyester, polycarbonate, polyalkylene glycol sorbitan ester, polyalkylene glycol glycidyl ether, glycoside, polyol carboxylate, cyclodextrin, phosphorus compound, α, β -unsaturated carboxylate, or ionic surfactant compound.

8. The method of claim 7, further comprising the steps of: (c) separating the catalyst from the suspension after (b); (d) washing the separated catalyst; and (e) drying the separated catalyst.

9. A process for producing a polyether polyol by addition polymerization of an alkylene oxide to an active hydrogen atom-containing starting compound, wherein the addition polymerization of the alkylene oxide is carried out in the presence of the double metal cyanide catalyst of claim 1.

10. A polyether polyol made by the process of claim 9.