HK1063642A - Double metal cyanide catalysts for the preparation of polyether polyols - Google Patents

Description

Double metal cyanide catalysts for preparing polyether polyols

Technical Field

The present invention relates to novel Double Metal Cyanide (DMC) catalysts for the preparation of polyether polyols by polyaddition reactions between alkylene oxides and starter compounds containing active hydrogen atoms.

Background

Double Metal Cyanide (DMC) catalysts for polyaddition reactions between alkylene oxides and starter compounds containing active hydrogen atoms are known (e.g.from U.S. Pat. No. 5,3404109, U.S. Pat. No. 3,3829505, U.S. Pat. No. 3,3941849 and U.S. Pat. No. 5,51922). The use of these DMC catalysts for preparing polyether polyols makes it possible in particular to reduce the proportion of monofunctional polyethers containing terminal double bonds, the so-called monools (monols), in comparison with conventional preparation processes for polyether polyols by using alkali catalysts, such as alkali metal hydroxides. The polyether polyols thus obtained can be processed to form higher polyurethanes (e.g.elastomers, foams, coatings). Generally, DMC catalysts are obtained by: the aqueous metal salt solution is reacted with an aqueous metal cyanide salt solution in the presence of an organic ligand such as an ether. In a typical catalyst preparation, for example, an aqueous solution (excess) of zinc chloride is mixed with potassium hexacyanocobaltate, and dimethoxyethane (glyme) is then added to the resulting suspension. The catalyst is then filtered and washed with an aqueous solution of glyme to give an active catalyst corresponding to the general formula (see, for example, EP-a 700949):

Zn₃[Co(CN)₆]₂ xZnCl₂ yH₂O z glyme.

the DMC catalysts disclosed in JP-A4145123, U.S. Pat. No. 5,0813, EP-A700949, EP-A743093, EP-A761708 and WO 97/40086 further reduce the proportion of monofunctional polyethers containing terminal double bonds in the preparation of polyether polyols by using tert-butanol as organic ligand, alone or in combination with polyethers (EP-A700949, EP-A761708, WO 97/40086). Moreover, the use of these DMC catalysts shortens the induction time of the polyaddition reaction of alkylene oxides with the corresponding starter compounds and increases the catalytic activity.

Disclosure of Invention

It has now been found that DMC catalysts containing one or more fluorine-containing complex-forming components can be used advantageously in the preparation of polyether polyols. In particular, they are also suitable for the polymerization of ethylene oxide or the copolymerization of ethylene oxide with higher epoxides, such as propylene oxide.

These and other advantages and benefits of the present invention will become apparent from the detailed description of the invention which follows.

Detailed Description

The present invention will now be described for purposes of illustration and not limitation. Except in the operating examples, or where otherwise indicated, all numbers expressing quantities, percentages, functionalities and so forth in the specification are to be understood as being modified in all instances by the term "about".

The present invention provides a double metal Cyanide (CMD) catalyst comprising:

a) at least one double metal cyanide compound, at least one metal cyanide compound,

b) at least one organic ligand free of fluorine atoms, and

c) at least one fluorine-containing ligand.

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

The double metal cyanide compounds a) in the catalysts of the invention can be obtained by reaction of water-soluble metal salts with water-soluble metal cyanide salts.

The water-soluble metal salts suitable for preparing the double metal cyanide compounds a) according to the invention are preferably of the formula (I)

M (X) n, (I) wherein M is selected from the group consisting of 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). More preferred are Zn (II), Fe (II), Co (II), and Ni (II). The anions X are identical or different, preferably identical, and are preferably selected from halides, hydroxides, sulfates, carbonates, cyanates, thiocyanates, isocyanates, isothiocyanates, carboxylates, oxalates or nitrates. The value of n is preferably 1, 2 or 3.

Examples of suitable water-soluble metal salts include, but are not limited to, zinc chloride, zinc bromide, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc nitrate, iron (II) sulfate, iron (II) bromide, iron (II) chloride, cobalt (II) thiocyanate, nickel (II) chloride, and nickel (II) nitrate. Mixtures of different water-soluble metal salts may also be used.

Water-soluble metal cyanide salts suitable for preparing the double metal cyanide compounds a) preferably have the following formula (II),

(Y) a M '(CN) b (A) c, (II) wherein 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 more preferably selected from the metals Co (II), Co (III), Fe (II), Fe (III), Cr (III), Ir (III) and Ni (II). The water soluble metal cyanide salt may include one or more of these metals. The cations Y are identical or different, preferably identical, and are selected from alkali metal ions and alkaline earth metal ions. The anions A are identical or different, preferably identical, and are selected from halides, hydroxides, sulfates, carbonates, cyanates, thiocyanates, isocyanates, isothiocyanates, carboxylates, oxalates or nitrates. a and also b and c are integers, wherein the values of a, b and c are selected such that the metal cyanide salt is electrically neutral; a is preferably 1, 2, 3 or 4; b is preferably 4, 5 or 6; c is preferably 0. Examples of suitable water-soluble metal cyanide salts include, but are not limited to, potassium hexacyanocobaltate (III), potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), calcium hexacyanocobaltate (III), and lithium hexacyanocobaltate (III).

Preferred double metal cyanide compounds a) in the catalysts of the invention are compounds corresponding to the following formula (III),

mx [ M 'x' (CN) y ] z (III) wherein M is as defined for formula (I), and

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

x, x', y and z are integers and are selected such that the double metal cyanide compound is electrically neutral.

Preferably, the first and second electrodes are formed of a metal,

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 double metal cyanide compounds a) include, but are not limited to, zinc hexacyanocobaltate (III), zinc hexacyanateiridate (III), zinc hexacyanateferricyanide (III) and cobalt hexacyanatecobaltate (II). Further examples of suitable double metal cyanide compounds can be found, for example, in US-A5158922. Zinc hexacyanocobaltate (III) is most preferably used.

The organic ligands b) in the DMC catalysts of the present invention are known in principle and are described in detail in the art (for example in U.S. Pat. No. 5,922,340, 4109, U.S. Pat. No. 3,3829505, U.S. Pat. No. 3,3941849, EP-A700949, EP-A761708, JP-A4145123, U.S. Pat. No. 5,0813, EP-A743093 and WO 97/40086). Preferred organic ligands include, but are not limited to, 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 ligands are, for example: alcohols, aldehydes, ketones, ethers, esters, amides, ureas, nitriles, sulfides, and mixtures thereof. Preferred organic ligands are water-soluble aliphatic alcohols such as ethanol, isopropanol, n-butanol, iso-butanol, sec-butanol and tert-butanol. Tert-butanol is more preferred.

The catalyst of the invention contains at least one fluorine-containing ligand c), which may preferably be a fluorine-containing monomeric compound or a fluorine-containing functionalized polymer, more preferably a polymer which does not carry ionic groups.

Suitable monomeric fluoro-ligands include, but are not limited to, fluorinated alcohols, ethers, aldehydes, ketones, acetals, carboxylic esters, carboxamides, carboxylic nitriles and phosphorus compounds.

Suitable fluoroalcohols for use in preparing the catalysts of the present invention include, but are not limited to, monohydric or polyhydric, acyclic or cyclic, aliphatic or aromatic alcohols containing from 1 to 30 carbon atoms. Examples are 2, 2, 2-trifluoroethanol, 1, 3-difluoro-2-propanol, 2, 2, 3, 3-tetrafluoro-1-propanol, 2, 2, 3, 3, 3-pentafluoro-1-propanol, 1, 1, 1, 3, 3, 3-hexafluoro-2-propanol, perfluoro-tert-butanol, 2, 2, 3, 4, 4-hexafluoro-1-butanol, 2, 2, 3, 3, 4, 4-heptafluoro-1-butanol, 1, 1, 1, 3, 3, 4, 4, 4-octafluoro-2-butanol, 2, 2, 3, 3, 4, 4, 5, 5-octafluoro-1-pentanol, 2-fluorocyclohexanol, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-tridecafluoro-1-octanol, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-pentadecafluoro-1-octanol, 2-fluoroethoxyethanol, 1-fluoroethylene glycol, 3-fluoro-1, 2-propanediol, 2, 3-difluoro-1, 4-butanediol, 2, 3, 3, 4, 4-hexafluoro-1, 5-pentanediol, 2, 3, 3, 4, 4, 5, 5-octafluoro-1, 6-hexanediol, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9-hexadecafluoro-1, 10-decanediol, 2-fluoro-1, 2, 3-glycerol, 2-fluoromethyl-2-hydroxymethyl-1, 3-propanediol, 2-fluoroethyl-2-hydroxymethyl-1, 3-propanediol, 2, 3, 3, 4, 4, 5, 5-octafluoro-1, 6-hexanediol, 1, 1, 1, 5, 5, 5-hexafluoropentanetriol, 4-fluorophenol and 4-trifluoromethylphenol. Preference is given to 2, 2, 3, 3, 4, 4, 5, 5-octafluoro-1, 6-hexanediol and 2-fluoroethoxyethanol.

Fluorine-containing ethers suitable for use in preparing the catalyst of the present invention include, but are not limited to, saturated or unsaturated, straight or branched, acyclic or cyclic, aliphatic or aromatic, dialkyl, alkylaryl or diaryl ethers having from 1 to 30 carbon atoms, such as bis (2, 2, 2-trifluoroethyl) ether, allyl-1, 1, 2, 2-tetrafluoroethyl ether, allyl-1, 1, 2, 3, 3, 3-hexafluoropropyl ether, epifluoroalcohol, hexafluoropropylene oxide, 2, 3-epoxypropyl-1, 1, 2, 2-tetrafluoroethyl ether, 2, 3-epoxypropyl-2, 2, 3, 3-tetrafluoropropyl ether, 2, 3-epoxypropyl-2, 2, 3, 3, 4, 4, 5, 5-octafluoropentyl ether, 2, 3-epoxypropyl-2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9-hexadecafluorononyl ether, ethylene glycol mono-4, 4, 5, 5, 5-pentafluoropentyl ether and tetraethyleneglycol pentafluoroethyl ether, 2, 2-bis (trifluoromethyl) -1, 3-dioxolane, trifluoromethoxybenzene, 1-methyl-2- (1, 1, 2, 2-tetrafluoroethoxy) benzene, 2-fluoroanisole, 3- (trifluoromethyl) anisole, 4- (trifluoromethoxy) toluene, 1-bromo-4- (trifluoromethoxy) benzene, 2, 4-difluoroanisole, 2, 3, 5, 6-tetrafluoroanisole and 2, 3, 4, 5, 6-pentafluoroanisole. Ethylene glycol mono-4, 4, 5, 5, 5-pentafluoroamyl ether and tetraethyleneglycol pentafluoroethyl ether are preferred.

Fluorine-containing aldehydes and ketones suitable for use in preparing the catalysts of the present invention include, but are not limited to, saturated or unsaturated, straight or branched chain, acyclic or cyclic, aliphatic or aromatic aldehydes and ketones containing from 1 to 30 carbon atoms, such as trifluoroacetal, fluoroacetone, 1, 1, 1-trifluoroacetone, hexafluoroacetone, perfluoro-2-butanone, perfluorocyclopentanone, 1, 1, 1-trifluoro-2, 4-pentanedione and 1, 1, 1, 5, 5, 5-hexafluoro-2, 4-pentanedione.

Fluorine-containing acetals suitable for use in preparing the catalyst of the present invention include, but are not limited to, saturated or unsaturated, linear or branched, acyclic or cyclic, aliphatic or aromatic acetals containing from 1 to 30 carbon atoms in which fluorine may be in the carbonyl component and/or in the alcohol component, such as trifluoro-acetaldehyde ethyl hemiacetal, trifluoro-acetaldehyde dimethyl acetal and hexafluoroacetone dimethyl acetal.

Fluorine-containing carboxylic acid esters suitable for use in preparing the catalyst of the present invention include, but are not limited to, saturated or unsaturated, straight or branched chain, acyclic or cyclic, aliphatic or aromatic mono-, di-, tri-or polyesters of mono-or polyvalent carboxylic acids having 1 to 30 carbon atoms with mono-or polyhydric alcohols having 1 to 30 carbon atoms, wherein fluorine may be in the carboxylic acid component and/or the alcohol component, such as methyl difluoroacetate, ethyl difluoroacetate, methyl trifluoroacetate, ethyl fluoroacetate, ethyl trifluoroacetate, isopropyl trifluoroacetate, butyl trifluoroacetate, 2, 2, 2-trifluoroethyl trifluoroacetate, methyl pentafluoropropionate, ethyl pentafluoropropionate, 2, 2, 2-trifluoroethylbutyrate, methyl heptafluorobutyrate, ethyl heptafluorobutyrate, methyl pentadecafluorooctanoate, Methyl nonafluorodecanoate, diethyl fluoromalonate, bis (2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7-dodecafluoroheptyl) camphorate, glycerol triperoxyloctanoate, glycerol perfluorododecanoate, 1- (trifluoromethyl) vinylacetate, 2, 2, 2-trifluoroethylacrylate, 2, 2, 3, 3-tetrafluoropropyl acrylate, 1, 1, 1, 3, 3, 3-hexafluoroisopropyl acrylate, 2, 2, 2-trifluoroethylmethacrylate, 2, 2, 3, 3-tetrafluoropropyl methacrylate, 1, 1, 1, 3, 3, 3-hexafluoroisopropyl methacrylate, 2, 2, 3, 4, 4-hexafluorobutyl methacrylate, ethyl-4, 4, 4-trifluorocrotonate, croton, Vinyl trifluoroacetate, allyl trifluoroacetate, ethyl-4, 4, 4-trifluoro-3-hydroxybutyrate and sorbitan trifluoroacetate. Tri-perfluorooctanoate, perfluorododecanoate and 2, 2, 3, 4, 4, 4-hexafluorobutyl methacrylate are preferred.

Poly (alkylene) glycols or polyalkylene glycol ethers optionally substituted by fluorine, preferably polypropylene glycols, polyethylene glycols, poly (oxypropylene-oxyethylene) glycols and poly (tetramethylene) glycols having a molecular weight of 200-1,0000 g/mol, preferably 300-9,000 g/mol, particularly preferably 400-8,000 g/mol, or ethers formed therefrom are also suitable as the alcohol component.

Fluorocarboxamides suitable for use in preparing the catalysts of the present invention include, but are not limited to, saturated or unsaturated, straight or branched chain, acyclic or cyclic, aliphatic or aromatic amides of mono-or polyvalent carboxylic acids and mono-or polyvalent amines in which fluorine may be in the carboxylic acid component and/or in the amine component, such as 2-fluoroacetamide, 2, 2, 2-trifluoroacetamide, 2-chloro-2, 2-difluoroacetamide, N-methyl-2, 2, 2-trifluoroacetamide, N-methyl-bis (trifluoroacetamide), N- (2-hydroxyethyl) -2, 2, 2-trifluoroacetamide, N-diethyl-2, 2, 2-trifluoroacetamide, N-cyclopentyl-2, 2, 2-trifluoroacetamide, N-methyl-bis (trifluoroacetamide), N- (2-hydroxyethyl) -2, 2-trifluoroacetamide, N-diethyl, Trifluoromethyl carbamate, 1-methyl-2, 2, 3, 3-tetrafluoropropyl carbamate, 3-trifluoromethyl-2-oxazolidinone, 1-trifluoromethyl pyrrolidone, 1-pentafluoroethyl pyrrolidone, and 1-trifluoromethyl caprolactam.

Suitable fluorine-containing carboxylic acid nitriles for use in preparing the catalysts of the present invention include, but are not limited to, saturated or unsaturated, straight or branched chain, acyclic or cyclic, aliphatic or aromatic nitriles containing from 1 to 30 carbon atoms, such as fluoroacetonitrile, pentafluoropropionitrile, heptafluorobutyronitrile, and 2, 2, 3, 3-tetrafluorocyclobutanecarboxylic acid nitrile.

Fluorine-containing phosphorus compounds suitable for use in preparing the catalysts of the present invention include, but are not limited to, fluorine-containing organophosphates, phosphites, phosphonates, phosphonites, phosphinites, and phosphinites (phosphinites).

Suitable organic phosphates include, but are not limited to, phosphoric monoesters, diesters, triesters, or tetraesters of fluorine substituted alcohols containing 1 to 30 carbon atoms and polyphosphoric monoesters, diesters, triesters, tetraesters, or polyesters, such as diisopropyl fluorophosphate and tris (1-fluorobutyl) phosphate.

Suitable organophosphites include, but are not limited to, phosphorous acid and fluorine-containing monoesters, diesters or triesters of fluorine-substituted alcohols containing 1 to 30 carbon atoms, such as tris (2, 2, 2-trifluoroethyl) phosphite, tris (1, 1, 1, 3, 3, 3-hexafluoro-2-propyl) phosphite and bis (2, 2, 2-trifluoroethyl) phosphite.

Organic phosphonates suitable for use as fluorine-containing ligands c) include, but are not limited to, monoesters or diesters of fluoroalcohols having 1 to 30 carbon atoms with phosphonic acids, alkylphosphonic acids, arylphosphonic acids, fluoroalkylphosphonic acids, fluoroarylphosphonic acids, alkoxycarbonylalkylphosphonic acids, alkoxycarbonylfluoroalkylphosphonic acids, fluoroalkoxycarbonylalkylphosphonic acids, fluoroalkoxycarbonylphosphonic acids, cyanoalkylphosphonic acids, cyanofluoroalkylphosphonic acids and cyanophosphonic acids or monoesters, diesters, triesters or tetraesters of fluoroalcohols having 1 to 30 carbon atoms with alkylphosphonic acids and fluoroalkyldiphosphonic acids, such as diethyl (difluoromethyl) phosphonate, diethyl (trifluoromethyl) phosphonate, bis (2, 2, 2-trifluoroethyl) methylphosphonate, (triethyl-2-fluoro-2-phosphoacetone, phospholidinone, phospholidine, Bis (2, 2, 2-trifluoroethyl) (methoxycarbonylmethyl) phosphonate and diethyl (2, 2, 2-trifluoro-1-hydroxyethyl) phosphonate.

Fluorinated diesters of phosphonous acids, alkylphosphonous acids, fluorinated alkylphosphonous acids, arylphosphonous acids or fluorinated arylphosphonous acids with fluoroalcohols having 1 to 30 carbon atoms are also suitable as fluorinated ligands c).

Phosphinates suitable for use as fluorine-containing ligands c) include, but are not limited to, fluorine-containing ester compounds of phosphinic acid, alkylphosphinic acid, fluoroalkylphosphinic acid, dialkylphosphinic acid, difluoroalkylphosphinic acid, arylphosphinic acid or fluoroarylphosphinic acid with fluorine-substituted alcohols having from 1 to 30 carbon atoms.

The phosphinic acid esters suitable for use as fluorine-containing ligands c) include, but are not limited to, fluorine-containing ester compounds of alkyl phosphinic acids, fluoroalkyl phosphinic acids, dialkyl phosphinic acids, difluoroalkyl phosphinic acids, aryl phosphinic acids or fluoroaryl phosphinic acids with fluorine-substituted alcohols having from 1 to 30 carbon atoms.

Suitable for use as the alcohol component are partially or perfluorinated mono-or polyhydroxyaryl, aralkyl, alkoxyalkyl and alkyl alcohols, preferably aralkyl, alkoxyalkyl and alkyl alcohols, more preferably alkoxy and alkyl alcohols, containing from 1 to 30 carbon atoms, preferably from 1 to 24 carbon atoms, more preferably from 1 to 20 carbon atoms.

The fluorine-containing organic phosphates, phosphites, phosphonates, phosphonites, phosphinites or phosphinites used for preparing the catalysts of the present invention are generally obtained by: reacting phosphoric acid, pyrophosphoric acid, polyphosphoric acid, phosphonic acid, alkylphosphonic acids, arylphosphonic acids, alkoxycarbonylalkylphosphonic acids, alkoxycarbonylahosphonic acids, cyanoalkylphosphonic acids, fluoroalkylphosphonic acids, fluoroarylphosphonic acids, fluoroalkoxycarbonylalkylphosphonic acids, fluoroalkoxycarbonylphosphonic acids, cyanofluoroalkylphosphonic acids, cyanophosphonic acids, alkylphosphonic acids, phosphonous acids, phosphorous acids, phosphinic acids, or halogen derivatives thereof or partially or perfluorinated phosphorus oxides with hydroxyl groups having 1 to 30 carbon atoms, for example fluorine derivatives of the following compounds: methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, heptanol, octanol, nonanol, decanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, methoxymethanol, ethoxymethanol, propoxymethanol, butoxymethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, phenol, ethyl glycolate, propyl glycolate, ethyl hydroxypropionate, propyl hydroxypropionate, 1, 2-ethanediol, 1, 2-propanediol, 1, 2, 3-trihydroxypropane, 1, 1, 1-trimethylolpropane or pentaerythritol.

Examples of suitable fluorine-containing functionalized polymers include, but are not limited to, fluorinated derivatives of the following polymers: polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycol glycidyl ethers, polyacrylamides, poly (acrylamide-co-acrylic acid), polyacrylic acid, poly (acrylic acid-co-maleic acid), polyacrylonitrile, polyalkylacrylates, polyalkylmethacrylates, polyvinyl methyl ethers, polyvinyl ethyl ethers, polyvinyl acetates, polyvinyl alcohols, poly-N-vinylpyrrolidone, poly (N-vinylpyrrolidone-co-acrylic acid), polyvinyl methyl ketones, poly (4-vinylphenol), poly (acrylic acid-co-styrene), oxazoline polymers, polyalkyleneimines, maleic acid copolymers or maleic anhydride copolymers, hydroxyethylcellulose or polyacetals.

Preferred fluorine-containing functionalized polymers for use include, but are not limited to, partially or fully fluorinated polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters and polyalkylene glycol glycidyl ethers. More preferably, partially or fully fluorinated polyethers are used.

Fluoropolyether derivatives suitable for use in preparing the catalyst of the present invention include, but are not limited to, those having a hydroxyl functionality of 1 to 8, particularly preferably 1 to 3, and a number average molecular weight of 150 to 10⁷G/mol, particularly preferably from 200 to 5X 10⁴Gram/mole of the fluorine-containing polyether polyol and their alkyl, aralkyl, aryl, fluoroalkyl, fluoroalkylaryl, or fluoroaryl ethers. They are usually obtained by: the epoxide is polymerized by ring opening in the presence of the corresponding starter compound containing an active hydrogen atom, with base, acid or coordination catalysis (e.g., DMC catalysis). Suitable polyether polyols include, but are not limited to, poly (oxyperfluoropropenyl) polyols, poly (oxyperfluorovinyl) polyols, ethylene oxide-capped poly (oxyperfluoropropenyl) polyols, mixed poly (oxyperfluoropropyl-oxyperfluoropropenyl) polyols, mixed perfluoropropenyl-perfluoroformaldehyde polyols, fluorobutylene oxide polymers, copolymers of fluorobutylene oxide with ethylene oxide and/or propylene oxide, and poly (oxyperfluorotetramethylene) glycols and poly (oxypropenyl) fluoroalkyl ethers, poly (oxypropylene) fluoroaryl ethers, poly (oxyethylene) fluoroalkyl ethers, poly (oxyethylene) fluoroaryl ethers, poly (oxyperfluoropropyl) alkyl ethers, poly (oxyperfluoropropyl) fluoroalkyl ethers, poly (oxyperfluoropropyl) fluoroaryl ethers, poly (oxyperfluoropropylPropenyl) fluoroalkyl ether, poly (perfluorooxyethylene) alkyl ether, poly (perfluorooxyethylene) fluoroalkyl ether, poly (perfluorooxyethylene) aryl ether, and poly (perfluoropropenyl) perfluorooxymethylene copolymer.

The DMC catalysts of the present invention contain the double metal cyanide compound a) in an amount of from 20 to 90% by weight, preferably from 25 to 80% by weight, calculated with respect to the amount of finished catalyst, and the organic ligand b) in an amount of from 0.5 to 30% by weight, preferably from 1 to 25% by weight, calculated with respect to the amount of finished catalyst. The DMC catalysts of the present invention contain from 1 to 80% by weight, preferably from 1 to 40% by weight, of at least one fluorine-containing ligand c), calculated with respect to the amount of finished catalyst. The amounts of double metal cyanide compound and organic ligand b) present in the DMC catalyst of the invention are each any combination of these values, inclusive of the stated values.

Analysis of the catalyst composition can be carried out by elemental analysis, thermogravimetric analysis or extractive removal of the ligand followed by gravimetric determination.

The catalysts of the invention may be crystalline, partially crystalline or amorphous. The analysis of the crystallinity is preferably carried out by powder X-ray diffraction analysis.

Comprises the following steps:

a) zinc hexacyanocobaltate (III),

b) tert-butanol and

c) at least one fluorine-containing ligand

The catalyst of the present invention is preferred.

The DMC catalysts of the present invention can be prepared, preferably in aqueous solution, by reacting metal salts, in particular those corresponding to the formula (I), with metal cyanide salts, in particular those corresponding to the formula (II), in the presence of organic ligands b) which are free of fluorine atoms and one or more fluorine-containing ligands c).

An aqueous solution of a metal salt, for example zinc chloride, used in stoichiometric excess (at least 50 mol% relative to the metal cyanide salt) and a metal cyanide salt, for example potassium hexacyanocobaltate, is preferably first reacted in the presence of an organic ligand b), for example tert-butanol, and a fluorine-containing ligand c), wherein a suspension is formed which comprises a double metal cyanide compound a), for example zinc hexacyanocobaltate, water d), excess metal salt e) and organic ligand b) and fluorine-containing ligand c).

The organic ligands b) and/or fluorine-containing ligands c) may preferably be present in aqueous solutions of metal salts and/or metal cyanide salts or may be added directly to the suspension obtained after precipitation of the double metal cyanide compound a). It has proven advantageous to mix the aqueous solution with the organic ligand b) and the fluorine-containing ligand c) under vigorous stirring.

The catalyst may be separated from the suspension by known techniques such as centrifugation or filtration. In a preferred embodiment, the separated catalyst can subsequently be washed with an aqueous solution of the organic ligand b) (for example by resuspension followed by re-separation by filtration or centrifugation). For example, water-soluble by-products such as potassium chloride can be removed from the catalyst of the invention in this manner.

The amount of organic ligand b) in the aqueous washing solution is preferably from 40 to 80% by weight, relative to the total solution. It is also advantageous to add to the aqueous washing solution a small amount of a mixture of one or more fluorine-containing ligands c), preferably from 0.5 to 5% by weight, relative to the total solution.

It is also advantageous to wash the catalyst more than once. For this purpose, for example, the first washing operation may be repeated. However, it is preferred to carry out the further washing operation with a non-aqueous solution, for example with a mixture of organic ligands b) and one or more fluorine-containing ligands c).

Optionally after grinding, the washed catalyst is dried at a temperature of from 20 to 100 ℃ and a pressure of from 0.1 mbar to standard pressure (1013 mbar).

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

Ethylene oxide, propylene oxide, butylene oxide and mixtures thereof are preferably used as the alkylene oxide. The polyether chains are built up by alkoxylation, which can be carried out, for example, using only one monomeric epoxide, or else using 2 or 3 different monomeric epoxides, in random or block fashion, for example using the so-called "ethylene oxide chain ends", in which case a polyether having a terminal polyethylene oxide block is produced. For further details see "Ullmanns encyclopedie der industrillen Chemie", volume A21, 1992, P.670 et seq.

Compounds having a (number average) molecular weight of 18 to 2,000 and 1 to 8 hydroxyl groups are preferably used as starter compounds containing active hydrogen atoms. The following are examples of enumeration: ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propanediol, 1, 4-butanediol, 1, 6-hexanediol, bisphenol a, trimethylolpropane, glycerol, pentaerythritol, sorbitol, sucrose, degraded starch or water.

These starter compounds containing active hydrogen atoms can be used as they are prepared, for example, by conventional basic catalysis from the low molecular weight starters mentioned above, advantageously in the form of oligomeric alkoxylation products having a (number average) molecular weight of 200-2,000.

The polyaddition reaction between alkylene oxides and starter compounds containing active hydrogen atoms is catalyzed by the catalysts of the present invention, which takes place at temperatures of from 20 to 200 ℃, preferably from 40 to 180 ℃, more preferably from 50 to 150 ℃. The reaction can be carried out at a total pressure of from 0.0001 to 20 bar. The polyaddition reaction can be carried out without solvent or in an inert solvent, such as toluene and/or tetrahydrofuran. The amount of the solvent is 10 to 30% by weight, calculated with respect to the amount of the polyether polyol to be produced.

The concentration of the catalyst is chosen such that the polyaddition reaction can be well controlled under the given reaction conditions. The catalyst concentration is from 0.0005% by weight to 1% by weight, preferably from 0.001% by weight to 0.1% by weight, more preferably from 0.001 to 0.0025% by weight, calculated with respect to the amount of polyether polyol to be produced. The concentration of catalyst may be any combination of these values, inclusive of the recited values.

The (number average) molecular weight of the polyether polyol prepared by the process of the present invention is 500-100,000 g/mol, preferably 1,000-50,000 g/mol, more preferably 2,000-20,000 g/mol.

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

Due to its significantly increased activity, the catalyst of the present invention can be used at very low concentrations (25ppm or less, calculated with respect to the amount of polyether polyol to be produced). If the polyether polyol prepared in the presence of the catalyst of the present invention is used for the production of Polyurethane (Kunststoffhandbuch, volume 7, Polyurethane, third edition 1993, pages 25-32 and 57-67), the step of removing the catalyst from the polyether polyol can be omitted without impairing the quality of the obtained Polyurethane product.

The invention is further illustrated, but is not limited, by the following examples in which all parts and percentages are by weight unless otherwise specified.

Examples

Preparation of the catalyst

Example 1

Preparation of DMC catalyst (catalyst A) with Triperfluorooctanoate Glycerin

A solution of 41 g (300 mmol) of zinc chloride in 41 ml of distilled water was added to a solution of 4 g (12 mmol) of potassium hexacyanocobaltate in 144 ml of distilled water, 21 g of tert-butanol and 0.4 g of glycerol trifluoropropionate with vigorous stirring (24,000rpm) for 10 minutes. The solid was isolated by filtration, stirred (10,000rpm) with a mixture of 54 g of tert-butanol, 27 g of distilled water and 1.6 g of glycerol perfluorooctanoate for 10 minutes, and filtered again. Finally, the mixture was stirred (10,000rpm) with a mixture of 78 g of tert-butanol and 0.7 g of glycerol perfluorooctanoate for a further 10 minutes. After filtration, the catalyst was dried under high vacuum at 60 ℃ for 2 hours.

Yield of dried powdered catalyst: 3.4 g

Example 2

Preparation of DMC catalyst (catalyst B) with ethylene glycol mono-4, 4, 5, 5, 5-pentafluoropentyl ether

The procedure of example 1 was followed except that ethylene glycol mono-4, 4, 5, 5, 5-pentafluoropentyl ether was used instead of the glycerol trifluoropropionate in example 1.

Yield of dried powdered catalyst: 2.5 g

Example 3

Preparation of DMC catalyst (catalyst C) from tetraethylene glycol pentafluoroethyl ether

The procedure of example 1 was followed, but tetraethylene glycol pentafluoroethyl ether was used instead of glycerol trifluoropropionate in example 1.

Yield of dried powdered catalyst: 2.6 g

Example 4

Preparation of DMC catalyst with 2, 2, 3, 4, 4, 4-hexafluorobutyl methacrylate (catalyst D)

The procedure of example 1 was followed except that 2, 2, 3, 4, 4, 4-hexafluorobutyl methacrylate was used in place of the perfluorooctanoate in glycerol of example 1.

Yield of dried powdered catalyst: 1.2 g

Example 5

Preparation of DMC catalyst with 2-fluoroethoxyethanol (catalyst E)

The procedure of example 1 was followed, but 2-fluoroethoxyethanol was used instead of the glycerol trifluoropropionate of example 1.

Yield of dried powdered catalyst: 2.3 g

Example 6

Preparation of DMC catalyst with 2, 2, 3, 3, 4, 4, 5, 5-octafluoro-1, 6-hexanediol (catalyst F)

The procedure of example 1 was followed except that 2, 2, 3, 3, 4, 4, 5, 5-octafluoro-1, 6-hexanediol was used in place of the perfluorooctanoate in example 1.

Yield of dried powdered catalyst: 3.4 g

Example 7 (comparative)

Preparation of DMC catalyst (catalyst G) with ethylene glycol monopentyl ether

A solution of 41 g (300 mmol) of zinc chloride in 41 ml of distilled water was added to a solution of 4 g (12 mmol) of potassium hexacyanocobaltate in 144 ml of distilled water, 21 g of tert-butanol and 0.4 g of ethylene glycol monopentyl ether with vigorous stirring (24,000rpm) and the batch was stirred vigorously for 10 minutes. The solid was isolated by filtration, stirred (10,000rpm) with a mixture of 54 g of tert-butanol, 27 g of distilled water and 1.6 g of ethylene glycol monopentyl ether for 10 minutes, and filtered again. Finally, the mixture was stirred (10,000rpm) with a mixture of 78 g of tert-butanol and 0.7 g of ethylene glycol monopentyl ether for a further 10 minutes. After filtration, the catalyst was dried under high vacuum at 60 ℃ for 2 hours.

Yield of dried powdered catalyst: 1.7 g

Example 8 (comparative)

Preparation of DMC catalyst (catalyst H) with 1, 6-hexanediol

The procedure of example 7 (comparative) was followed, but 1, 6-hexanediol was used instead of ethylene glycol monopentyl ether in example 7.

Yield of dried powdered catalyst: 2.6 g

Preparation of polyether polyols

General procedure

50 g of polypropylene glycol starter (molecular weight 1,000 g/mol) and 5 mg of catalyst (25ppm, calculated with respect to the amount of polyether polyol to be prepared) were introduced under a protective gas (argon) into a 500 ml pressure reactor and heated to 105 ℃ with stirring. Immediately, (about 5 g) propylene oxide was completely dispersed until the total pressure rose to 2.5 bar. Additional propylene oxide was dispersed into the reactor only when an accelerated pressure drop was observed in the reactor. The accelerated pressure drop indicates the activation of the catalyst. The remaining propylene oxide (145 g) was continuously dispersed at a constant total pressure of 2.5 bar. After 2 hours after the propylene oxide had been dispersed and reacted at 105 ℃, the volatile components were distilled off at 90 ℃ (1 mbar) and the reaction mixture was cooled to room temperature.

The polyether polyol obtained was characterized by determining its OH number, double bond content and viscosity.

The course of the reaction is depicted by a time-activity curve (propylene oxide consumption [ g ] vs. reaction time [ min ]). The induction time is determined by the point of intersection of the tangent of the steepest point on the time-activity curve with the extension of the curve's baseline. The propoxylation time, which determines the catalyst activity, is determined by the time period between catalyst activation (end of the induction period) and termination of the propylene oxide dispersion.

Example 9

Preparation of polyether polyol with catalyst A (25ppm)

Time of propoxylation:		41 minutes
			Polyether polyol:	OH number (mg KOH/g):	29.7
	double bond content (mmol/kg):	7
				viscosity at 25 ℃ (mpa):	915

example 10

Preparation of polyether polyol with catalyst B (25ppm)

Time of propoxylation:		17 minutes
			Polyether polyol:	OH number (mg KOH/g):	29.7
	double bond content (mmol/kg):	7
				viscosity at 25 ℃ (mpa):	980

example 11

Preparation of polyether polyol with catalyst C (25ppm)

Time of propoxylation:		14 minutes
			Polyether polyol:	OH number (mg KOH/g):	30.1
	double bond content (mmol/kg):	5
				viscosity at 25 ℃ (mpa):	834

example 12

Preparation of polyether polyol with catalyst D (25ppm)

Time of propoxylation:		30 minutes
			Polyether polyol:	OH number (mg KOH/g):	29.1
	double bond content (mmol/kg):	7
				viscosity at 25 ℃ (mpa):	1000

example 13

Preparation of polyether polyol with catalyst E (25ppm)

Time of propoxylation:		31 minutes
			Polyether polyol:	OH number (mg KOH/g):	30.3
	double bond content (mmol/kg):	7
				viscosity at 25 ℃ (mpa):	986

example 14

Preparation of polyether polyol with catalyst F (25ppm)

Time of propoxylation:		18 minutes
			Polyether polyol:	OH number (mg KOH/g):	29.5
	double bond content (mmol/kg):	7
				viscosity at 25 ℃ (mpa):	855

example 15 (comparative)

Preparation of polyether polyol with catalyst G (25ppm)

Time of propoxylation:		20 minutes
			Polyether polyol:	OH number (mg KOH/g):	29.9
	double bond content (mmol/kg):	9
				viscosity at 25 ℃ (mpa):	812

example 16 (comparative)

Preparation of polyether polyol with catalyst H (25ppm)

Time of propoxylation:		31 minutes
			Polyether polyol:	OH number (mg KOH/g):	30.0
	double bond content (mmol/kg):	5
				viscosity at 25 ℃ (mpa):	1049

although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.

Claims (8)

1. A Double Metal Cyanide (DMC) catalyst comprising:

at least one double metal cyanide compound;

at least one organic ligand free of fluorine atoms; and

at least one fluorine-containing ligand.

2. The Double Metal Cyanide (DMC) catalyst of claim 1, further comprising water and/or at least one water-soluble metal salt.

3. The Double Metal Cyanide (DMC) catalyst of claim 1, wherein the double metal cyanide compound comprises zinc hexacyanocobaltate (III).

4. The Double Metal Cyanide (DMC) catalyst of claim 1, wherein the organic ligand comprises t-butanol.

5. The Double Metal Cyanide (DMC) catalyst of claim 1, wherein the catalyst comprises from about 1 to about 80 wt% of one or more fluorine-containing ligands.

6. A method of preparing a DMC catalyst comprising the steps of:

forming a catalyst by reacting in an aqueous solution at least one metal salt with at least one metal cyanide salt, at least one organic ligand free of fluorine atoms and one or more fluorine-containing ligands;

separating the catalyst;

washing the catalyst; and are

Optionally drying the catalyst.

7. In a process for the preparation of polyether polyols by a polyaddition reaction between an alkylene oxide and a starter compound containing active hydrogen atoms, the improvement which comprises carrying out said polyaddition in the presence of one or more DMC catalysts as claimed in claim 1.

8. A polyether polyol prepared by the process of claim 7.