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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
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  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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  • C08G18/40—High-molecular-weight compounds
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  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/18—Block or graft polymers
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  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
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  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
  • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
  • C08G65/2645—Metals or compounds thereof, e.g. salts
  • C08G65/2663—Metal cyanide catalysts, i.e. DMC's
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  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
  • C08G65/2696—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the process or apparatus used
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  • C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
  • C08G71/04—Polyurethanes
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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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  • C08G2101/00—Manufacture of cellular products
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  • C08G2110/00—Foam properties
  • C08G2110/0008—Foam properties flexible
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  • C08G2110/00—Foam properties
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  • C08G2110/005—< 50kg/m3
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  • C08G2110/00—Foam properties
  • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

Definitions

• the present invention relates to a process for the preparation of polyethercarbonate polyols from one or more H-functional starter substances, one or more alkylene oxides and carbon dioxide in the presence of at least one double metal cyanide catalyst, the polyethercarbonate polyols having a mixed block of at least two alkylene oxides at the end of the chain, and to flexible polyurethane foams obtainable therefrom.
• Scheme (I) is ecologically very advantageous because it represents the conversion of a greenhouse gas like CO 2 to a polymer.
• the cyclic carbonate shown in Scheme (I) e.g. propylene carbonate for R ⁇ CH 3
• Activation in terms of the invention is a step in which a fraction of the alkylene oxide compound, optionally in the presence of CO 2 , is added to the DMC catalyst and the addition of the alkylene oxide compound is then interrupted; an evolution of heat, which can lead to a hotspot, is observed due to a subsequent exothermic chemical reaction, and a pressure drop in the reactor is observed due to the conversion of alkylene oxide and optionally CO 2 .
• the process step of activation is the period of time from the addition of the fraction of alkylene oxide compound to the DMC catalyst, optionally in the presence of CO 2 , up to the start of the evolution of heat.
• the activation step can be preceded by a step for drying of the DMC catalyst and optionally the starter at elevated temperature and/or reduced pressure, this drying step not being part of the activation step in terms of the present invention.
• WO-A 2008/058913 discloses a process for the preparation of polyethercarbonate polyols having a block of pure alkylene oxide units, especially a block of pure propylene oxide units, at the end of the chain.
• WO-A 2008/058913 does not disclose polyethercarbonate polyols having a mixed block of at least two alkylene oxides at the end of the chain.
• the object of the present invention was to provide polyethercarbonate polyols that produce flexible polyurethane foams with an increased compressive strength and an increased tensile strength.
• a flexible polyurethane foam quality improved in this way has the technical advantage that said foams have an increased mechanical load-bearing capacity.
• the present invention also provides a process for the production of flexible polyurethane foams wherein the starting material used is a polyol component (component A) comprising a polyethercarbonate polyol obtainable by a process which is characterized in that
• the flexible polyurethane foams according to the invention preferably have a gross density according to DIN EN ISO 3386-1-98 in the range from ⁇ 10 kg/m 3 to ⁇ 150 kg/m 3 , preferably from ⁇ 20 kg/m 3 to ⁇ 70 kg/m 3 , and a compressive strength according to DIN EN ISO 3386-1-98 in the range from ⁇ 0.5 kPa to ⁇ 20 kPa (at 40% deformation after 4 th cycle).
• the preparation of the polyethercarbonate polyol according to step (i) is preferably carried out by adding one or more alkylene oxides and carbon dioxide, in the presence of at least one DMC catalyst, on to one or more H-functional starter substances (“copolymerization”).
• step (i) the process for the preparation of polyethercarbonate polyol according to step (i) is characterized in that
• alkylene oxides (epoxides) having 2-24 carbon atoms can be used for the process according to the invention.
• alkylene oxides having 2-24 carbon atoms are one or more compounds selected from the group comprising ethylene oxide, propylene oxide, 1-butene oxide, 2,3-butene oxide, 2-methyl-1,2-propene oxide (isobutene oxide), 1-pentene oxide, 2,3-pentene oxide, 2-methyl-1,2-butene oxide, 3-methyl-1,2-butene oxide, 1-hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2-methyl-1,2-pentene oxide, 4-methyl-1,2-pentene oxide, 2-ethyl-1,2-butene oxide, 1-heptene oxide, 1-octene oxide, 1-nonene oxide, 1-decene oxide, 1-undecene oxide, 1-dodecene oxide, butadiene monoxide, isoprene monoxide, cyclopen
• Suitable H-functional starter substances which can be used are compounds with H atoms that are active for alkoxylation.
• groups with H atoms that are active for alkoxylation are —OH, —NH 2 (primary amines), —NH— (secondary amines), —SH and —CO 2 H; —OH and —NH 2 are preferred and —OH is particularly preferred.
• H-functional starter substances used are one or more compounds selected from the group comprising monohydric or polyhydric alcohols, polybasic amines, polyhydric thiols, amino alcohols, thio alcohols, hydroxy esters, polyether polyols, polyester polyols, polyesterether polyols, polyethercarbonate polyols, polycarbonate polyols, polycarbonates, polyethyleneimines, polyetheramines (e.g.
• Jeffamine® from Huntsman, such as D-230, D-400, D-2000, T-403, T-3000 or T-5000, or corresponding products from BASF, such as polyetheramine D230, D400, D200, T403 or T5000), polytetrahydrofurans (e.g.
• PolyTHF® from BASF such as PolyTHF® 250, 650S, 1000, 1000S, 1400, 1800 or 2000
• polytetrahydrofuranamines BASF product polytetrahydrofuranamine 1700
• poly-etherthiols polyacrylate polyols
• castor oil such as PolyTHF® 250, 650S, 1000, 1000S, 1400, 1800 or 2000
• polytetrahydrofuranamines such as PolyTHF® 250, 650S, 1000, 1000S, 1400, 1800 or 2000
• polytetrahydrofuranamines BASF product polytetrahydrofuranamine 1700
• poly-etherthiols polyacrylate polyols
• castor oil such as PolyTHF® 250, 650S, 1000, 1000S, 1400, 1800 or 2000
• fatty acid monoglycerides such as PolyTHF® 250, 650S, 1000, 1000S, 1400, 1800 or 2000
• polytetrahydrofuranamine 1700 such as Poly
• fatty acid C 1 -C 24 -alkyl esters comprising an average of at least 20H groups per molecule are commercially available products such as Lupranol Balance® (BASF AG), various types of Merginol® (Hobum Oleochemicals GmbH), various types of Sovermol® (Cognis Deutschland GmbH & Co. KG) and various types of Soyol® TM (USSC Co.).
• Monofunctional starter compounds which can be used are alcohols, amines, thiols and carboxylic acids.
• the following monofunctional alcohols can be used: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 3-buten-1-ol, 3-butyn-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, propargyl alcohol, 2-methyl-2-propanol, 1-tert-butoxy-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol, phenol, 2-hydroxybiphenyl, 3-
• the following monofunctional amines are suitable: butylamine, tert-butylamine, pentylamine, hexylamine, aniline, aziridine, pyrrolidine, piperidine, morpholine.
• the following monofunctional thiols can be used: ethanethiol, 1-propanethiol, 2-propanethiol, 1-butanethiol, 3-methyl-1-butanethiol, 2-butene-1-thiol, thiophenol.
• the following monofunctional carboxylic acids may be mentioned: formic acid, acetic acid, propionic acid, butyric acid, fatty acids such as stearic acid, palmitic acid, oleic acid, linoleic acid and linolenic acid, benzoic acid, acrylic acid.
• polyhydric alcohols suitable as H-functional starter substances are dihydric alcohols (e.g. ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-butenediol, 1,4-butynediol, neopentyl glycol, 1,5-pentanediol, methylpentanediols (e.g.
• tetrahydric alcohols e.g. pentaerythritol
• polyalcohols e.g. sorbitol, hexitol, sucrose, starch, starch hydrolysates, cellulose, cellulose hydrolysates, hydroxy-functionalized fats and oils, especially castor oil
• any modified products of the aforesaid alcohols comprising different amounts of ⁇ -caprolactone
• the H-functional starter substances can also be selected from the class of substances comprising the polyether polyols, especially those with a molecular weight M n ranging from 100 to 4000 g/mol.
• Preferred polyether polyols are those made up of repeating ethylene oxide and propylene oxide units, preferably with a proportion of 35 to 100% of propylene oxide units and particularly preferably with a proportion of 50 to 100% of propylene oxide units. They can be random copolymers, gradient copolymers or alternating or block copolymers of ethylene oxide and propylene oxide.
• suitable polyether polyols made up of repeating propylene oxide and/or ethylene oxide units are the Desmophen®, Acclaim®, Arcol®, Baycoll®, Bayfill®, Bayflex®, Baygal®, PET° and Polyether® Polyols from Bayer MaterialScience AG (e.g. Desmophen® 3600Z, Desmophen® 1900U, Acclaim®Polyol 2200, Acclaim® Polyol 40001, Arcol® Polyol 1004, Arcol® Polyol 1010, Arcol® Polyol 1030, Arcol® Polyol 1070, Baycoll® BD 1110, Bayfill® VPPU 0789, Baygal® K55, PET® 1004, Polyether® S180).
• Desmophen® 3600Z Desmophen® 1900U
• Acclaim®Polyol 2200 Acclaim® Polyol 40001
• Examples of other suitable homo-polyethylene oxides are the Pluriol® E brands from BASF SE, examples of suitable homo-polypropylene oxides are the Pluriol® P brands from BASF SE, and examples of suitable mixed copolymers of ethylene oxide and propylene oxide are the Pluronic® PE or Pluriol® RPE brands from BASF SE.
• the H-functional starter substances can also be selected from the class of substances comprising the polyester polyols, especially those with a molecular weight M n ranging from 200 to 4500 g/mol.
• the polyester polyols used are at least difunctional polyesters and preferably consist of alternating acid and alcohol units.
• acid components used are succinic acid, maleic acid, maleic anhydride, adipic acid, phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or mixtures of said acids and/or anhydrides.
• alcohol components used are ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis(hydroxymethyl)cyclohexane, diethylene glycol, dipropylene glycol, trimethylolpropane, glycerol, pentaerythritol or mixtures of said alcohols.
• dihydric or polyhydric polyether polyols are used as the alcohol component
• H-functional starter substances which can be used are polycarbonate polyols (e.g. polycarbonate diols), especially those with a molecular weight M n ranging from 150 to 4500 g/mol, preferably from 500 to 2500 g/mol, which are prepared e.g. by reacting phosgene, dimethyl carbonate, diethyl carbonate or diphenyl carbonate with di- and/or polyfunctional alcohols, polyester polyols or polyether polyols.
• polycarbonate polyols can be found e.g. in EP-A 1359177.
• polycarbonate diols which can be used are various types of Desmophen® C from Bayer MaterialScience AG, such as Desmophen® C 1100 or Desmophen® C 2200.
• polyethercarbonate polyols can be used as H-functional starter substances.
• the polyethercarbonate polyols obtainable by the process according to the invention described here, after step (i), step (ii) or step (iii), are used in particular.
• These polyethercarbonate polyols used as H-functional starter substances are previously prepared for this purpose in a separate reaction step.
• the H-functional starter substances generally have a functionality (i.e. number of H atoms per molecule that are active for polymerization) of 1 to 8, preferably of 2 or 3.
• the H-functional starter substances are used either individually or as a mixture of at least two H-functional starter substances.
• Preferred H-functional starter substances are alcohols of general formula (II):
• alcohols of formula (II) are ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol and 1,12-dodecanediol.
• Other preferred H-functional starter substances are neopentyl glycol, trimethylolpropane, glycerol, pentaerythritol, and reaction products of the alcohols of formula (II) with ⁇ -caprolactone, e.g.
• reaction products of trimethylolpropane with ⁇ -caprolactone reaction products of trimethylolpropane with ⁇ -caprolactone, reaction products of glycerol with s-caprolactone and reaction products of pentaerythritol with ⁇ -caprolactone.
• Other H-functional starter substances which are preferably used are water, diethylene glycol, dipropylene glycol, castor oil, sorbitol, and polyether polyols made up of repeating polyalkylene oxide units.
• the H-functional starter substances are one or more compounds selected from the group comprising ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methylpropane-1,3-diol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane and di- and trifunctional polyether polyols, the polyether polyol being made up of a di- or tri-H-functional starter substance and propylene oxide or a di- or tri-H-functional starter substance, propylene oxide and ethylene oxide.
• the polyether polyols preferably have a molecular weight M n ranging from 62 to 4500 g/mol and a functionality of 2 to 3, especially a molecular weight M n ranging from 62 to 3000 g/mol a functionality of 2 to 3.
• the polyethercarbonate polyols are prepared by the catalytic addition of carbon dioxide and alkylene oxides on to H-functional starter substances.
• H-functional is understood as meaning the number of H atoms per molecule of starter compound that are active for alkoxylation.
• DMC catalysts for use in the homopolymerization of epoxides are known in principle from the state of the art (cf., for example, U.S. Pat. No. 3,404,109, U.S. Pat. No. 3,829,505, U.S. Pat. No. 3,941,849 and U.S. Pat. No. 5,158,922). DMC catalysts described e.g. in U.S. Pat. No.
• EP-A 700 949 has a very high activity in the homopolymerization of epoxides and enable polyether polyols to be prepared with very low catalyst concentrations (25 ppm or less), so it is generally no longer necessary to separate the catalyst from the finished product.
• Typical examples are the highly active DMC catalysts described in EP-A 700 949, which, in addition to a double metal cyanide compound (e.g. zinc hexacyanocobaltate(III)) and an organic complexing ligand (e.g. tert-butanol), also comprise a polyether with a number-average molecular weight greater than 500 g/mol.
• a double metal cyanide compound e.g. zinc hexacyanocobaltate(III)
• organic complexing ligand e.g. tert-butanol
• the DMC catalysts are obtained by a process in which
• the double metal cyanide compounds comprised in the DMC catalysts are the reaction products of water-soluble metal salts and water-soluble metal cyanide salts.
• an aqueous solution of zinc chloride preferably in excess, based on the metal cyanide salt, e.g. potassium hexacyanocobaltate
• potassium hexacyanocobaltate preferably in excess, based on zinc hexacyanocobaltate
• dimethoxyethane (glyme) or tert-butanol preferably in excess, based on zinc hexacyanocobaltate
• Metal salts suitable for preparing the double metal cyanide compounds preferably have general formula (III):
• M is selected from the metal cations Zn 2+ , Fe 2+ , Ni 2+ , Mn 2+ , Co 2+ , Sr 2+ , Sn 2+ , Pb 2+ and Cu 2+ , M preferably being Zn 2+ , Fe 2+ , Co 2+ or Ni 2+ ;
• X are one or more (i.e. different) anions, preferably an anion selected from the group comprising halides (i.e.
• M is selected from the metal cations Fe 3+ , Al 3+ , Co 3+ and Cr 3+ ;
• X are one or more (i.e. different) anions, preferably an anion selected from the group comprising halides (i.e.
• M is selected from the metal cations Mo 4+ , V 4+ and W 4+ ;
• M is selected from the metal cations Mo 6+ and W 6+ ;
• X are one or more (i.e. different) anions, preferably an anion selected from the group comprising halides (i.e. fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, oxalate and nitrate;
• suitable metal salts are zinc chloride, zinc bromide, zinc iodide, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc nitrate, iron(II) sulfate, iron(II) bromide, iron(II) chloride, iron(III) chloride, cobalt(II) chloride, cobalt(II) thiocyanate, nickel(II) chloride and nickel(II) nitrate. It is also possible to use mixtures of different metal salts.
• Metal cyanide salts suitable for preparing the double metal cyanide compounds preferably have general formula (VII):
• M′ is selected from one or more metal cations from the group comprising Fe(II), Fe(III), Co(II), Co(III), Cr(II), Mn(II), Mn(III), Ir(III), Ni(II), Ru(II), V(IV) and V(V), M′ preferably being one or more metal cations from the group comprising Coal), Co(III), Fe(II), Fe(III), Cr(III), Ir(III) and Ni(II); Y is selected from one or more metal cations from the group comprising alkali metals (i.e. Li + , Na + , K + , Rb + ) and alkaline earth metals (i.e.
• A is selected from one or more anions from the group comprising halides (i.e. fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, azide, oxalate and nitrate; and a, b and c are integers, the values of a, b and c being chosen so that the metal cyanide salt is electronically neutral; a is preferably 1, 2, 3 or 4; b is preferably 4, 5 or 6; c preferably has the value 0.
• suitable metal cyanide salts are sodium hexacyanocobaltate(III), potassium hexacyanocobaltate(III), potassium hexacyanoferrate(II), potassium hexacyanoferrate(III), calcium hexacyanocobaltate(III) and lithium hexacyano-cobaltate(III).
• Preferred double metal cyanide compounds comprised in the DMC catalysts are compounds of general formula (VIII):
• M is as defined in formulae (III) to (VI); M′ is as defined in formula (VII); and x, x′, y and z are integers and are chosen so that the double metal cyanide compound is electronically neutral.
• M Zn(II), Fe(II), Co(II) or Ni(II);
• M′ Co(III), Fe(III), Cr(III) or
• Suitable double metal cyanide compounds a) are zinc hexacyano-cobaltate(III), zinc hexacyanoiridate(III), zinc hexacyanoferrate(III) and cobalt(II) hexacyanocobaltate(III).
• Other examples of suitable double metal cyanide compounds can be found e.g. in U.S. Pat. No. 5,158,922 (column 8, lines 29-66). It is particularly preferable to use zinc hexacyanocobaltate(HI).
• the organic complexing ligands added in the preparation of the DMC catalysts are disclosed e.g. in U.S. Pat. No. 5,158,922 (cf. especially column 6, lines 9 to 65), U.S. Pat. No. 3,404,109, U.S. Pat. No. 3,829,505, U.S. Pat. No. 3,941,849, EP-A 700 949, EP-A 761 708, JP 4 145 123, U.S. Pat. No. 5,470,813, EP-A 743 093 and WO-A 97/40086).
• organic complexing ligands water-soluble organic compounds with heteroatoms, such as oxygen, nitrogen, phosphorus or sulfur, which can form complexes with the double metal cyanide compound are used as organic complexing ligands.
• Preferred organic complexing ligands are alcohols, aldehydes, ketones, ethers, esters, amides, ureas, nitriles, sulfides and mixtures thereof.
• Particularly preferred organic complexing ligands are aliphatic ethers (such as dimethoxyethane), water-soluble aliphatic alcohols (such as ethanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, 2-methyl-3-buten-2-ol and 2-methyl-3-butyn-2-ol), and compounds comprising both aliphatic or cycloaliphatic ether groups and aliphatic hydroxyl groups (e.g. ethylene glycol mono-tert-butyl ether, diethylene glycol mono-tert-butyl ether, tripropylene glycol monomethyl ether and 3-methyl-3-oxetanemethanol).
• aliphatic ethers such as dimethoxyethane
• water-soluble aliphatic alcohols such as ethanol, isopropanol, n-butanol, isobutanol, sec-butanol,
• Very particularly preferred organic complexing ligands are selected from one or more compounds from the group comprising dimethoxyethane, tert-butanol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, ethylene glycol mono-tert-butyl ether and 3-methyl-3-oxetanemethanol.
• one or more complexing components from the following classes of compounds are used in the preparation of the DMC catalysts: polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycol glycidyl ethers, polyacrylamide, poly(acrylamide-co-acrylic acid), polyacrylic acid, poly-(acrylic acid-co-maleic acid), polyacrylonitrile, polyalkyl acrylates, polyalkyl methacrylates, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl acetate, polyvinyl alcohol, poly-N-vinylpyrrolidone, poly(N-vinylpyrrolidone-co-acrylic acid), polyvinyl methyl ketone, poly(4-vinylphenol), poly(acrylic acid-co-styrene), oxazoline polymers, polyalkyleneimines, maleic acid and maleic anhydride copolymers, hydroxye
• the aqueous solution of the metal salt e.g. zinc chloride
• the metal salt used in stoichiometric excess (at least 50 mol %, based on the metal cyanide salt, i.e. a molar ratio of metal salt to metal cyanide salt of at least 2.25 to 1.00) is reacted with the aqueous solution of the metal cyanide salt (e.g. potassium hexacyanocobaltate) in the presence of the organic complexing ligand (e.g. tert-butanol) to form a suspension comprising the double metal cyanide compound (e.g. zinc hexacyanocobaltate), water, excess metal salt and the organic complexing ligand.
• the metal cyanide salt e.g. potassium hexacyanocobaltate
• the organic complexing ligand e.g. tert-butanol
• the organic complexing ligand can be present in the aqueous solution of the metal salt and/or the aqueous solution of the metal cyanide salt, or it is added immediately to the suspension obtained after precipitation of the double metal cyanide compound. It has been found advantageous to mix the aqueous solutions of the metal salt and metal cyanide salt and the organic complexing ligand with vigorous agitation.
• the suspension formed in the first step is then treated with another complexing component, the latter preferably being used in a mixture with water and organic complexing ligand.
• a preferred procedure for carrying out the first step involves the use of a mixing nozzle, particularly preferably a jet disperser as described in WO-A 01/39883.
• the isolation of the solid (i.e. the precursor of the catalyst according to the invention) from the suspension is effected by known techniques such as centrifugation or filtration.
• the isolated solid is then washed, in a third process step, with an aqueous solution of the organic complexing ligand (e.g. by resuspension and then re-isolation by filtration or centrifugation).
• an aqueous solution of the organic complexing ligand e.g. by resuspension and then re-isolation by filtration or centrifugation.
• the amount of organic complexing ligand in the aqueous wash solution is between 40 and 80 wt %, based on the total solution.
• another complexing component preferably in the range between 0.5 and 5 wt %, based on the total solution, is added to the aqueous wash solution in the third step.
• a first washing step (c-1) is carried out with an aqueous solution of the unsaturated alcohol (e.g. by resuspension and then re-isolation by filtration or centrifugation) in order e.g. to remove water-soluble by-products, such as potassium chloride, from the catalyst according to the invention.
• the amount of unsaturated alcohol in the aqueous wash solution is between 40 and 80 wt %, based on the total solution of the first washing step.
• either the first washing step is repeated one or more times, preferably one to three times, or, preferably, a non-aqueous solution, e.g. a mixture or solution of unsaturated alcohol and another complexing component (preferably in the range between 0.5 and 5 wt %, based on the total amount of wash solution of step (c-2)), is used as the wash solution and the solid is washed therewith one or more times, preferably one to three times.
• a non-aqueous solution e.g. a mixture or solution of unsaturated alcohol and another complexing component (preferably in the range between 0.5 and 5 wt %, based on the total amount of wash solution of step (c-2)
• the isolated and optionally washed solid is then dried, optionally after pulverization, at temperatures generally of 20 to 100° C. and at pressures generally of 0.1 mbar to normal pressure (1013 mbar).
• step (ii) of a preferred embodiment of the invention a mixture of ethylene oxide (EO) and propylene oxide (PO) is used as the mixture of at least two different alkylene oxides, the molar ratio PO/EO used in step (ii) being from 15/85 to 60/40, preferably from 15/85 to 40/60.
• the polyethercarbonate polyols resulting from step (ii), comprising a terminal mixed block of EO and PO have a proportion of primary OH groups of 10 to 90 mol %, particularly preferably of 20 to 50 mol %.
• the mean length of the mixed blocks of at least two different alkylene oxides, prepared in step (ii), is preferably 2.0 to 20.0 alkylene oxide units, particularly preferably 2.5 to 10.0 alkylene oxide units, based in each case on one OH group of the polyethercarbonate polyol.
• the polyethercarbonate polyols resulting from step (ii), comprising a mixed block at least two alkylene oxides have a hydroxyl number of 20 mg KOH/g to 80 mg KOH/g, particularly preferably of 25 mg KOH/g to 60 mg KOH/g.
• the process according to the invention for the preparation of polyethercarbonate polyols can also comprise a third step, wherein
• the mean length of a pure alkylene oxide block prepared in step (iii) is preferably 2 to 30 alkylene oxide units, particularly preferably 5 to 18 alkylene oxide units, based in each case on one OH group of the polyethercarbonate polyol.
• the reaction according to step (iii) can be carried out e.g. in the presence of DMC catalysts or else in the presence of acidic catalysts (such as BF 3 ) or basic catalysts (such as KOH or CsOH).
• the reaction according to step (iii) is carried out in the presence of a DMC catalyst.
• the invention thus also provides polyethercarbonate polyols comprising a terminal mixed block of at least two alkylene oxides, preferably a terminal mixed block of ethylene oxide (EO) and propylene oxide (PO).
• EO ethylene oxide
• PO propylene oxide
• the molar ratio PO/EO is from 15/85 to 60/40, preferably from 15/85 to 40/60.
• the polyethercarbonate polyols comprising a terminal mixed block of EO and PO have a proportion of primary OH groups of 10 to 90 mol %, particularly preferably of 20 to 50 mol %.
• the invention provides polyethercarbonate polyols comprising a terminal mixed block of at least two alkylene oxides, characterized in that the mean length of the terminal mixed block of at least two different alkylene oxides is from 2.0 to 20.0 alkylene oxide units, particularly preferably from 2.5 to 10.0 alkylene oxide units (based in each case on one OH group of the polyethercarbonate polyol).
• the polyethercarbonate polyols according to the invention comprising a mixed block of at least two alkylene oxides have a hydroxyl number preferably of 20 mg KOH/g to 80 mg KOH/g, particularly preferably of 25 mg KOH/g to 60 mg KOH/g.
• these polyethercarbonate polyols according to the invention can comprise a pure alkylene oxide block at the end of the chain, said block consisting preferably of propylene oxide or ethylene oxide units, particularly preferably of propylene oxide units.
• the mean length of such a pure alkylene oxide block at the end of the chain is preferably 2 to 30 alkylene oxide units, particularly preferably 5 to 18 alkylene oxide units, based in each case on one OH group of the polyethercarbonate polyol.
• the invention provides a process for the production of flexible polyurethane foams with a gross density according to DIN EN ISO 3386-1-98 in the range from ⁇ 10 kg/m 3 to ⁇ 150 kg/m 3 , preferably from ⁇ 20 kg/m 3 to ⁇ 70 kg/m 3 , and a compressive strength according to DIN EN ISO 3386-1-98 in the range from ⁇ 0.5 kPa to ⁇ 20 kPa (at 40% deformation after 4 th cycle) by reacting component A (polyol formulation) comprising
• the polyethercarbonate polyol of component A1 is obtainable by the above-described preparative process according to the invention.
• the starting components of component A2 are conventional polyether polyols.
• conventional polyether polyols are understood as meaning compounds that are alkylene oxide addition products of starter compounds with Zerewitinoff-active hydrogen atoms, i.e. polyether polyols with a hydroxyl number according to DIN 53240 of ⁇ 15 mg KOH/g to ⁇ 80 mg KOH/g, preferably of ⁇ 20 mg KOH/g to ⁇ 60 mg KOH/g.
• Starter compounds with Zerewitinoff-active hydrogen atoms that are used for the conventional polyether polyols usually have functionalities of 2 to 6, preferably of 3, and the starter compounds are preferably hydroxy-functional.
• Examples of hydroxy-functional starter compounds are propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, hexanediol, pentanediol, 3-methyl-1,5-pentanediol, 1,12-dodecanediol, glycerol, trimethylolpropane, triethanolamine, pentaerythritol, sorbitol, sucrose, hydroquinone, pyrocatechol, resorcinol, bisphenol F, bisphenol A, 1,3,5-trihydroxybenzene, and condensation products of formaldehyde and phenol, melamine or
• alkylene oxides examples include ethylene oxide, propylene oxide, 1,2-butylene oxide or 2,3-butylene oxide, and styrene oxide.
• propylene oxide and ethylene oxide are added to the reaction mixture individually, as a mixture or successively. If the alkylene oxides are metered in successively, the products prepared comprise polyether chains with block structures. Products with ethylene oxide blocks are characterized e.g. by increased concentrations of primary end groups, imparting an advantageous isocyanate reactivity to the systems.
• Water and/or physical blowing agents are used as component A3.
• Examples of physical blowing agents used are carbon dioxide and/or highly volatile organic substances.
• Substances used as component A4 are auxiliary substances and additives such as
• auxiliary substances and additives that are optionally to be used concomitantly are described e.g. in EP-A 0 000 389, pages 18-21.
• Other examples of auxiliary substances and additives that are optionally to be used concomitantly according to the invention, and details of the mode of use and mode of action of these auxiliary substances and additives, are described in Kunststoff-Handbuch, volume VII, edited by G. Oertel, Carl-Hanser-Verlag, Kunststoff-Handbuch, volume VII, edited by G. Oertel, Carl-Hanser-Verlag, Kunststoff-Handbuch, Kunststoff-Handbuch, volume VII, edited by G. Oertel, Carl-Hanser-Verlag, Kunststoff-Handbuch, volume VII, edited by G. Oertel, Carl-Hanser-Verlag, Kunststoff-Handbuch, volume VII, edited by G. Oertel, Carl-Hanser-Verlag, Kunststoff, 3 rd edition, 1993, e.g. on pages 104-127.
• Preferred catalysts are aliphatic tertiary amines (e.g. trimethylamine, tetramethyl-butanediamine), cycloaliphatic tertiary amines (e.g. 1,4-diaza(2,2,2)bicyclooctane), aliphatic amino ethers (e.g. dimethylaminoethyl ether and N,N,N-trimethyl-N-hydroxyethylbisaminoethyl ether), cycloaliphatic amino ethers (e.g. N-ethyl-morpholine), aliphatic amidines, cycloaliphatic amidines, urea, urea derivatives (e.g.
• aminoalkylureas cf., for example, EP-A 0 176 013, especially (3-dimethylamino-propylamine)urea) and tin catalysts (e.g. dibutyltin oxide, dibutyltin dilaurate, tin octanoate).
• tin catalysts e.g. dibutyltin oxide, dibutyltin dilaurate, tin octanoate.
• catalysts (3-dimethylaminopropylamine)urea, 2-(2-dimethylaminoethoxy)ethanol, N,N-bis-(3-dimethylaminopropyl)-N-isopropanolamine, N,N,N-trimethyl-N-hydroxyethyl-bisaminoethyl ether and 3-dimethylaminopropylamine.
• compounds used as component A5 have at least two isocyanate-reactive hydrogen atoms and a molecular weight of 32 to 399. These are understood as meaning compounds having hydroxyl groups and/or amino groups and/or thiol groups and/or carboxyl groups, preferably compounds having hydroxyl groups and/or amino groups, which serve as chain extenders or crosslinking agents. These compounds normally have 2 to 8, preferably 2 to 4, isocyanate-reactive hydrogen atoms. Examples of compounds which can be used as component A5 are ethanol-amine, diethanolamine, triethanolamine, sorbitol and/or glycerol. Other examples of compounds of component A5 are described in EP-A 0 007 502, pages 16-17.
• Suitable polyisocyanates are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates such as those described e.g. by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, for example those of formula (IX):
• n 2-4, preferably 2-3, and
• polyisocyanates such as those described in EP-A 0 007 502, pages 7-8.
• Preferred polyisocyanates are normally those which are readily available in industry, e.g. 2,4- and 2,6-toluoylene diisocyanate and any desired mixtures of these isomers (“TDI”); polyphenylpolymethylene polyisocyanates such as those prepared by aniline-formaldehyde condensation followed by phosgenation (“crude MDI”); and polyisocyanates having carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups (“modified polyisocyanates”), especially modified polyisocyanates derived from 2,4- and/or 2,6-toluoylene diisocyanate or from 4,4′- and/or 2,4′-diphenylmethane diisocyanate.
• TDI 2,4- and 2,6-toluoylene diisocyanate
• the polyisocyanate used is at least one compound selected from the group comprising 2,4- and 2,6-toluoylene diisocyanate, 4,4′-, 2,4′- and 2,2′-diphenylmethane diisocyanate, and polyphenylpolymethylene polyisocyanate (“polynuclear MDI”).
• polynuclear MDI polyphenylpolymethylene polyisocyanate
• the polyisocyanate used is a mixture comprising 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate and polyphenylpolymethylene polyisocyanate.
• the reactants are reacted by the one-stage process known per se, often using mechanical devices, e.g. those described in EP-A 355 000. Details of processing devices which are also suitable for the invention are described in Kunststoff-Handbuch, volume VII, edited by Vieweg and Hochtlen, Carl-Hanser-Verlag, Kunststoff 1993, e.g. on pages 139 to 265.
• the flexible polyurethane foams can be produced as foam mouldings or foam blocks.
• the invention therefore provides processes for the production of flexible polyurethane foams, the flexible polyurethane foams produced by these processes, the flexible polyurethane foam blocks or flexible polyurethane foam mouldings produced by these processes, the use of the flexible polyurethane foams for the production of mouldings, and the mouldings themselves.
• the flexible polyurethane foams obtainable according to the invention have e.g. the following applications: furniture upholstery, textile padding, mattresses, car seats, head supports, arm rests, sponges and component parts.
• the index indicates the percentage ratio of the amount of isocyanate actually used to the stoichiometric amount, i.e. the amount of isocyanate (NCO) groups calculated for conversion of the OH equivalent.
• index [(amount of isocyanate used):(calculated amount of isocyanate)] ⁇ 100 (X)
• the gross density was determined according to DIN EN ISO 3386-1-98.
• the compressive strength was determined according to DIN EN ISO 3386-1-98 (at 40% deformation after 4 th cycle).
• the tensile strength and elongation at break were determined according to DIN EN ISO 1798.
• the proportion of CO 2 incorporated in the resulting polyethercarbonate polyol was determined by 1 H-NMR (Bruker, DPX 400, 400 MHz, pulse program zg30, wait time d1:10 sec, 64 scans). All samples were dissolved in deuterated chloroform.
• the relevant resonances in the 1 H-NMR are as follows: cyclic carbonate (formed as a by-product) with resonance at 4.5 ppm; carbonate (resulting from carbon dioxide incorporated in the polyethercarbonate polyol) with resonances at 5.1 to 4.8 ppm; unreacted PO with resonance at 2.4 ppm; polyether polyol (i.e. without incorporated carbon dioxide) with resonances at 1.2 to 1.0 ppm; 1,8-octanediol (incorporated as starter molecule (if present)) with resonance at 1.6 to 1.52 ppm.
• F(4.5) area of the resonance at 4.5 ppm for cyclic carbonate (corresponds to one H atom)
• F(5.1-4.8) area of the resonance at 5.1-4.8 ppm for polyethercarbonate polyol and one H atom for cyclic carbonate
• F(2.4) area of the resonance at 2.4 ppm for free
• F(1.2-1.0) area of the resonance at 1.2-1.0 ppm for polyether polyol
• F(1.6-1.52) area of the resonance at 1.6 to 1.52 ppm for 1,8-octanediol (starter), if present
• the factor 102 results from the sum of the molecular weights of CO 2 (molecular weight 44 g/mol) and propylene oxide (molecular weight 58 g/mol), the factor 58 results from the molecular weight of propylene oxide and the factor 146 results from the molecular weight of the 1,8-octanediol starter used (if present).
• CC ′ F ⁇ ( 4.5 ) * 102 N * 100 ⁇ % ( XIV )
• the composition based on the polymer component consisting of polyether polyol, synthesized from starter and propylene oxide during the activation steps taking place under CO 2 -free conditions, and polyethercarbonate polyol, synthesized from starter, propylene oxide and carbon dioxide during the activation steps taking place in the presence of CO 2 and during copolymerization
• the non-polymer constituents of the reaction mixture i.e. cyclic propylene carbonate and any unreacted propylene oxide present
• the data for the CO 2 content of the polyethercarbonate polyol are normalized to the proportion of the polyethercarbonate polyol molecule formed during the copolymerization and optionally the activation steps in the presence of CO 2 (i.e. the proportion of the polyethercarbonate polyol molecule resulting from the starter (1,8-octanediol, if present) and from the reaction of the starter with epoxide, added under CO 2 -free conditions, was not taken into account here).
• the polyethercarbonate samples were first peracetylated.
• the ground-glass Erlenmeyer flask was provided with a riser tube (air condenser) and the sample was boiled for 75 min under gentle reflux.
• the sample mixture was then transferred to a 500 ml round-bottom flask and volatile constituents (essentially pyridine, acetic acid and excess acetic anhydride) were distilled off over a period of 30 min at 80° C. and 10 mbar (absolute).
• volatile constituents essentially pyridine, acetic acid and excess acetic anhydride
• the distillation residue was then treated with 3 ⁇ 100 ml of cyclohexane (toluene was used as an alternative in cases where the distillation residue did not dissolve in cyclohexane) and volatile constituents were removed for 15 min at 80° C. and 400 mbar (absolute). Volatile constituents were then removed from the sample for one hour at 100° C. and 10 mbar (absolute).
• the flexible polyurethane foam blocks according to the invention (Examples 4 to 6), in which polyethercarbonate polyols with a terminal mixed block of propylene oxide (PO) and ethylene oxide (EO) in a molar ratio PO/EO of 15/85 to 60/40 were processed, exhibited a higher compressive strength and a higher tensile strength than flexible foam blocks based on a polyether polyol (A2-1; cf. Table 1, Comparative Example 1) or on a polyethercarbonate polyol with a terminal propylene oxide block (A1-2; cf. Table 1, Comparative Example 2).
• PO propylene oxide
• EO ethylene oxide

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