EP0214542B1 - Thickener systems for functional fluids containing a large amount of water, and such functional fluids containing these thickener systems - Google Patents

Thickener systems for functional fluids containing a large amount of water, and such functional fluids containing these thickener systems Download PDF

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Publication number
EP0214542B1
EP0214542B1 EP86111729A EP86111729A EP0214542B1 EP 0214542 B1 EP0214542 B1 EP 0214542B1 EP 86111729 A EP86111729 A EP 86111729A EP 86111729 A EP86111729 A EP 86111729A EP 0214542 B1 EP0214542 B1 EP 0214542B1
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Prior art keywords
water
weight
combinations
mol
functional fluids
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EP86111729A
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German (de)
French (fr)
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EP0214542A3 (en
EP0214542A2 (en
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Karl-Heinz Dr. Hentschel
Christian Dr. Rasp
Siegfried Kussi
Udo-Winfried Dr. Hendricks
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/12—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M149/14—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds a condensation reaction being involved
    • C10M149/18—Polyamides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/02—Water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/042—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds between the nitrogen-containing monomer and an aldehyde or ketone
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/043—Mannich bases
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/044—Polyamides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/045—Polyureas; Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/042—Metal salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/043—Ammonium or amine salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01—Emulsions, colloids, or micelles

Definitions

  • the invention relates to the use of combinations of special polymeric thickeners and surfactants as thickener systems for highly water-containing functional liquids.
  • functional fluids are understood to mean hydraulic fluids, metalworking fluids (cooling lubricants) and metal hardening media.
  • functional liquids are referred to as "highly water-containing", the water content of which is either more than 90% by weight, if no low-molecular glycols are used, or more than 70% by weight, preferably more than 80% by weight. -%, for the case that in addition to the water as a diluent, larger proportions of low molecular weight glycols, such as ethylene glycol, diethylene glycol, propylene glycol or dipropylene glycol, are used.
  • the invention therefore relates to the use of combinations of water-soluble polymeric polyether polyols in which at least 50% of the hydroxyl end groups are blocked by reaction with a monoisocyanate having a C 12 -C 30 -alkyl or C 12 -C 30 -alkylene radical, and anionic and / or nonionic surfactants as thickener systems for highly water-containing functional liquids.
  • the invention further relates to highly water-containing functional liquids containing, in addition to water, combinations of water-soluble polymeric polyether polyols in which at least 50% of the hydroxyl end groups by reaction with a monoisocyanate having a C 12 -C 31 alkyl or C 12 -C 30 alkylene radical are capped, and anionic and / or nonionic surfactants and optionally lubricity improvers, metal deactivators, corrosion inhibitors, defoamers, substances for adjusting or buffering certain pH values, anti-aging agents, biocides, colorants and / or glycols.
  • the surfactants are contained in an amount such that 0.1 to 3 parts by weight, preferably 0.25, of polyether polyol capped to 1 part by weight up to 2.5 parts by weight of surfactant are eliminated.
  • Nonionic and anionic surfactants are used as surfactants.
  • Nonionic or anionic surfactants with a low tendency to foam are preferred. Both individual surfactants and mixtures of different surfactants can be used.
  • anionic and nonionic surfactants which can be used in the combinations to be used according to the invention are e.g. in the review "Tenside”, by K. Kosswig in Ullmann's encyclopedia of techn. Chemistry, 4th ed., Volume 22, pages 468-494 and 498.
  • the anionic surfactants are carboxylates, for example carboxymethylated oxethylates and derivatives of amino acids; Sulfonates, for example alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkanesulfonates, ⁇ -olefinsulfonates, ⁇ -sulfofatty acid esters, sulfosuccinic acid esters, alkoxy, acyloxy and acylaminoalkanesulfonates; as sulfates, for example alkyl sulfates and ether sulfates, phosphonates and phosphates.
  • carboxylates for example carboxymethylated oxethylates and derivatives of amino acids
  • Sulfonates for example alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkanesulfonates, ⁇ -olefinsulfonates, ⁇
  • Alkanesulfonates be preferably having 8 to 30 carbon atoms, phenols, alkyl sulfosuccinic acid esters of ethoxylated with 8 to 30 moles of ethylene oxide C, 2-C, e fatty alcohols, of reacted with 8 to 70 moles of ethylene oxide C s -C 2o, from 8 to 30 moles of ethylene oxide ethoxylated C 12 -C 18 fatty acids or C 12 -C 18 fatty alcohols; C 12 -C 18 n-alkyl sulfates; Sulphates of C 12 ⁇ C 18 fatty alcohols, C 12 ⁇ C 18 fatty acids and Cg-C20 alkylphenols ethoxylated with 8 to 30 moles of ethylene oxide.
  • Suitable nonionic surfactants are oxethylates, terminally blocked oxyethylates and fatty acid esters of polyhydroxy compounds, and also block polymers of propylene oxide and ethylene oxide.
  • Reacted as nonionic surfactants with 8 to 50 moles of ethylene oxide are preferably C 12 -C 18 fatty acids, with 8 to 40 moles of ethylene oxide, ethoxylated C 12 -C 18 fatty acid amides with 8 to 30 moles of ethylene oxide, ethoxylated C 12 -C 18 fatty alcohols, Cg-C 20 alkylphenols ethoxylated with 8 to 50 moles of ethylene oxide and styrene or benzylated phenols ethoxylated with 8 to 60 moles of ethylene oxide.
  • Nonionic surfactants with an HLB value ⁇ 18 are preferably used.
  • the monoisocyanate-capped water-soluble polymeric polyether polyols to be used in the combinations to be used according to the invention are reaction products of known polymeric water-soluble polyether polyols which have an average molecular weight of 5,000 to 70,000 (determined by determining the OH end groups; the number of OH end groups becomes average molecular weight calculated using the following formula: have, with a C 12 -C 30 alkyl or C 12 -C 30 alkylene having monoisocyanate.
  • the C 12 -C 30 alkyl radicals are, in particular, the dodecyl, hexadecyl, octadecyl and the behenyl radical, and the C 12 -C 30 alkylene radical in particular the oleyl radical.
  • These aliphatic hydrocarbon radicals do not necessarily have to be bonded directly to the isocyanate group, but can also be bonded to the isocyanate group via other groups, for example aromatic rings and / or urethane groups.
  • Such monoisocyanates in which the long-chain aliphatic hydrocarbon radicals are not directly bound to the isocyanate group are, for example, the addition products from 1 mol of a C 12 -C 30 -n-alkanol, for example lauryl, myristyl, cetyl, stearyl or behenyl alcohol or of oleyl alcohol to 1 mole of an aliphatic, cycloaliphatic, aromatic or heterocyclic diisocyanate.
  • the amount of monoisocyanate is such that at least 50%, preferably 70 to 100%, particularly preferably 85 to 100% of the hydroxyl end groups present in the water-soluble polymeric polyether polyols are capped.
  • the capping of the OH end groups of the polymeric water-soluble polyether polyols with the monoisocyanates having a C 12 -C 30 alkyl or C 12 ⁇ C 30 alkylene radical is a reaction which is known in principle (see, for example, Ullmann's Enzyklopadie der techn. Chemie, 4th ed ., Volume 19, pages 309-310).
  • the end of the reaction can be determined by IR spectroscopy on the basis of the disappearance of the absorption band typical of isocyanates at about 2,270 cm -1 . determine.
  • This addition reaction can be accelerated in a known manner by using known catalysts.
  • the water-soluble polymeric, optionally urethane or ester group-containing polyether polyols of average molecular weight 5,000 to 70,000 on which the blocked water-soluble polyether polyols are based are known or can be obtained by processes known per se, for example by polymerizing ethylene oxide or copolymerizing ethylene oxide with other alkylene oxides in the presence of compounds, which have at least two active hydrogen atoms, and optionally modifying the water-soluble polymeric polyether polyols thus obtained by reaction with diisocyanates or dicarboxylic acids to give water-soluble urethane or ester groups polymeric polyether polyols or by polymerizing ethylene oxide or copolymerizing ethylene oxide and other alkylene oxides in the presence of compounds which have two active hydrogen atoms and reacting the water-soluble polyether diols obtained with polyisocyanates, while maintaining a ratio of isocyanate groups / OH groups of at most 0.5 : 1, to water-soluble polymeric polyether polyol
  • the combinations of special monoisocyanate-capped water-soluble polymeric polyether polyols and anionic and / or nonionic surfactants to be used according to the invention are produced by mixing both components together in a liquid state to form a homogeneous liquid. Since they are often solid at room temperature, the components are generally heated to the melting temperature, ie temperatures from 60 to 100 ° C., and stirred at this temperature until a homogeneous liquid has formed. When using surfactant mixtures, it may be advantageous to first mix only one surfactant with the masked polyether polyol in the liquid state and then to stir the second or the remaining surfactants into the homogeneous melt.
  • the combinations of special capped water-soluble polymeric polyether polyols and anionic and / or nonionic surfactants obtained in this way are diluted by adding water to liquid concentrates, the water content of which is about 30 to 70% by weight, preferably 40 to, for better manageability in the preparation of the functional liquids 60% by weight, based on the weight of the concentrate.
  • the ready-to-use hydraulic fluids, metalworking fluids (cooling lubricants) and metal hardening media are produced from these concentrates by further dilution with water.
  • the concentrates, or the functional liquids prepared from them by dilution can also contain additives which are usually used in these functional liquids. These are lubricity improvers, metal deactivators, corrosion inhibitors, defoamers, substances for adjusting or buffering certain pH values, anti-aging agents, biocides, identification dyes in the usual amounts for these additives, as well as monomeric and / or oligomeric glycols.
  • the highly water-containing functional liquids which are thickened according to the invention preferably contain 3 to 7% by weight of the combination to be used according to the invention as a thickener system and optionally additionally 0.5 to 3, preferably 1 to 3% by weight % of the above-mentioned additives commonly used in functional liquids, and optionally up to 25% by weight, for example 0.5 to 20% by weight of monomeric and / or oligomeric glycols.
  • a mixture of 1346.4 g of polyether polyol A (0.06 mol), 0.15 g of 1,4-diazabicycio-2,2,2-octane (DABCO) and 500 g of dry dioxane is heated to the reflux temperature with stirring.
  • 50.6 g of dodecyl isocyanate (0.24 mol) are added dropwise within one hour.
  • the reaction mixture is then stirred at the reflux temperature until no isocyanate band can be detected in the infrared spectrum of a reaction mixture sample.
  • the dioxane has been distilled off at about 130 ° C./15 hPa, a reaction product which is viscous at elevated temperatures and solidifies at low temperatures remains.
  • Masked polyether polyol 12 (not according to the invention, comparative compound):
  • the polyether chain contains 25% by weight propylene oxide and 75% by weight ethylene oxide units in a statistical distribution. Average molecular weight: 22,400.
  • Reaction product of pentaerythritol, ethylene oxide and propylene oxide The polyether chains contain 25% by weight of propylene oxide and 75% by weight of ethylene oxide units in a statistical distribution. Average molecular weight: 15,500.
  • Polyethylene glycol with an average molecular weight of 5555 is Polyethylene glycol with an average molecular weight of 5555.
  • capped polyether polyol and surfactant given in the table below are liquefied by heating to about 90 ° C. and stirred into a homogeneous liquid. This is then diluted by adding water to a concentrate containing 50% by weight of water.
  • the amount of capped polyether polyol given in the table is first liquefied with only one of the surfactants to be used in the amount given for this surfactant in the table by heating to about 90 ° C. and stirred into a homogeneous liquid.
  • the other or the other surfactants in the amount specified for this or these surfactants in the table are then also stirred into this at an elevated temperature until a homogeneous liquid has also formed again. This is again diluted by adding water to a concentrate containing 50% by weight of water.
  • the concentrates obtained according to a) or b) are diluted to 100 parts by weight of solution with stirring by adding further water.
  • a mixture of 80% by weight of water, 10% by weight of diethylene glycol and 10% by weight of dipropylene glycol is diluted to 100 parts by weight of solution.
  • the water content of which, depending on the amount of thickener system used, is from 91 to 95.5% by weight the viscosities at 40 and 50 ° C. and the change in viscosity are reduced Influence of shear forces (according to DIN 51 382; modification: 300 cycles instead of 30 cycles) determined.

Description

Die Erfindung betrifft die Verwendung von Kombinationen aus speziellen polymeren Verdickungsmitteln und Tensiden als Verdickersysteme für hoch wasserhaltige funktionelle Flüssigkeiten.The invention relates to the use of combinations of special polymeric thickeners and surfactants as thickener systems for highly water-containing functional liquids.

Unter funktionellen Flüssigkeiten werden im Rahmen der vorliegenden Erfindung Hydraulikflüssigkeiten, Metallbearbeitungsflüssigkeiten (Kühlschmiermittel) und Metallhärtungsmedien verstanden. Als "hoch wasserhaltig" werden im Rahmen der vorliegenden Erfindung solche funktionellen Flüssigkeiten bezeichnet, deren Wassergehalt entweder mehr als 90 Gew.-% beträgt, falls keine niedermolekularen Glykole mitverwendet werden, oder mehr als 70 Gew.-%, bevorzugt mehr als 80 Gew.-%, beträgt für den Fall, daß neben dem Wasser als Verdünnungsmittel größere Anteile an niedermolekularen Glykolen, wie Ethylenglykol, Diethylenglykol, Propylenglykol oder Dipropylenglykol eingesetzt werden.In the context of the present invention, functional fluids are understood to mean hydraulic fluids, metalworking fluids (cooling lubricants) and metal hardening media. In the context of the present invention, functional liquids are referred to as "highly water-containing", the water content of which is either more than 90% by weight, if no low-molecular glycols are used, or more than 70% by weight, preferably more than 80% by weight. -%, for the case that in addition to the water as a diluent, larger proportions of low molecular weight glycols, such as ethylene glycol, diethylene glycol, propylene glycol or dipropylene glycol, are used.

Seit etwa 25 Jahren ist man bemüht, die bislang als funktionelle Flüssigkeiten verwendeten brennbaren Mineralöle bzw. Mineralölprodukte durch nicht brennbare wäßrige Flüssigkeiten zu ersetzen. Diese Entwicklung hat inzwischen zu wäßrigen funktionellen Flüssigkeiten geführt, deren Wassergehalt bereits über 90 Gew.-% beträgt (sog. viscous high water-based fluids). Für die Herstellung dieser hoch wasserhaltigen funktionellen Flüssigkeiten wurden als Verdickungsmittel vor allem wasserlösliche polymere Polyether(poly)ole bzw. Kombinationen dieser polymeren Polyether(poly)ole mit weiteren Hilfsmitteln vorgeschlagen. So sind z.B. in der US-A-4 481 367, in der EP-A-0 031 777 und der JA-A-41 300/81 polymere wasserlösliche Urethangruppen aufweisende Polyetherpolyole und in der DE-A-3 302 465 und der US-A-4 288 639 mit langkettigen 1,2-Epoxyalkanen modifizierte Polyethermonoalkohole für den genannten Zweck beschrieben. Aus den US―A―4 310 436 und 4 395 351 sind Kombinationen dieser modifizierten Polyethermonoalkohole mit sauren Phosphorsäureestern nichtionischer Polyethermonoalkohol-Emulgatoren bekannt und in der CA-A-1 163 041 werden Kombinationen dieser modifizierten Polyethermonoalkohole mit speziellen Polyetherestern, sauren Phosphorsäureestern nichtionischer Polyethermonoalkohol-Emulgatoren und speziellen geschwefelten Metallverbindungen beschrieben.For about 25 years, efforts have been made to replace the flammable mineral oils or mineral oil products previously used as functional liquids with non-flammable aqueous liquids. This development has meanwhile led to aqueous functional liquids, the water content of which is already over 90% by weight (so-called viscous high water-based fluids). In particular, water-soluble polymeric polyether (poly) oles or combinations of these polymeric polyether (poly) ole with other auxiliaries have been proposed as thickeners for the production of these highly water-containing functional liquids. For example, in US-A-4 481 367, in EP-A-0 031 777 and JA-A-41 300/81 polymeric water-soluble urethane groups containing polyether polyols and in DE-A-3 302 465 and US-A- 4,288,639 with long-chain 1,2-epoxyalkanes modified polyether monoalcohols for the stated purpose. Combinations of these modified polyether monoalcohols with acidic phosphoric acid esters of nonionic polyethermonoalcohol emulsifiers are known from US Pat. Nos. 4,310,436 and 4,395,351 and combinations of these modified polyethermonoalcohols with special polyetheresters, acidic phosphoric acid esters of nonionic polyethermonoalcohol are Emulsifiers and special sulfurized metal compounds are described.

Mit langkettigen 1,2-Epoxyalkanen modifizierte polymere wasserlösliche Polyetherpolyole und deren Verwendung als Verdickungsmittel für hoch wasserhaltige funktionelle Flüssigkeiten sind in der EP-A-61 822, der WO-A1-84/00361 und in den US―A―4 354 956 und 4 411 819 beschrieben. Kombinationen dieser modifizierten wasserlöslichen polymeren Polyetherpolyole mit weiteren Hilfsmitteln sind aus zahlreichen Patentschriften bekannt. So sind z.B. Kombinationen dieser modifizierten Polyetherpolyole mit sauren Phosphorsäureestern nichtionischer Polyethermonoalkohol-Emulgatoren in der EP―B―63 854, mit ethoxylierten Sorbit-monostearaten in der EP-B-61 823, mit Neocarbonsäuren in der US-A-4 390 439 oder längerkettigen Fettsäuren in der US-A-4 390 440, mit nichtionischen Tensiden bestimmter Strukturklassen in der EP-A-122 528, mit speziellen Aminen und sauren Phosphorsäureestern nichtionischer Polyethermonoalkohol-Emulgatoren in der US―A―4 312 775, mit speziellen Polyetherestern, definierten geschwefelten Metallverbindungen und Korrosionsinhibitoren in der US―A―4312 768 und mit Schmierfähigkeitsmodifikatoren, Dispergiermitteln und bestimmten Hochdruckadditiven in der US―A―4481 125 beschrieben.Polymeric water-soluble polyether polyols modified with long-chain 1,2-epoxyalkanes and their use as thickeners for highly water-containing functional liquids are described in EP-A-61 822, WO-A1-84 / 00361 and in US Pat. No. 4,354,956 and 4,411,819. Combinations of these modified water-soluble polymeric polyether polyols with other auxiliaries are known from numerous patents. For example, Combinations of these modified polyether polyols with acidic phosphoric acid esters of nonionic polyether monoalcohol emulsifiers in EP ― B ― 63 854, with ethoxylated sorbitol monostearates in EP-B-61 823, with neocarboxylic acids in US Pat. No. 4,390,439 or longer-chain fatty acids in US-A-4 390 440, with nonionic surfactants of certain structural classes in EP-A-122 528, with special amines and acidic phosphoric acid esters of nonionic polyether monoalcohol emulsifiers in US Pat. No. 4,312,775, with special polyether esters, defined sulfurized metal compounds and Corrosion inhibitors in US ― A ― 4312 768 and described with lubricity modifiers, dispersants and certain high pressure additives in US ― A ― 4481 125.

Diese bekannten, als Verdickungsmittel bzw. Verdickersysteme für hoch wasserhaltige funktionelle Flüssigkeiten verwendeten polymeren wasserlöslichen Polyetherpolyole und deren Kombinationen mit weiteren Hilfsstoffen haben jedoch den Nachteil, daß die mit ihnen verdickten funktionellen Flussigkeiten nicht scherstabil sind, sondern daß sich deren Viskosität bei der Einwirkung von Scherkräften (z.B. Druck) verändert. Scherstabilität ist jedoch eine der wichtigsten Eigenschaften der funktionellen Flüssigkeiten. Insbesondere bei Hydraulikflüssigkeiten ist eine von Scherkräften unabhängige Viskosität unbedingt erforderlich.These known polymeric water-soluble polyether polyols used as thickeners or thickener systems for highly water-containing functional liquids and their combinations with other auxiliaries have the disadvantage, however, that the functional liquids thickened with them are not shear-stable, but that their viscosity changes when exposed to shear forces ( e.g. pressure) changed. However, shear stability is one of the most important properties of functional liquids. With hydraulic fluids in particular, a viscosity that is independent of shear forces is absolutely necessary.

Überraschenderweise wurde nun gefunden, daß man hervorragend scherstabile, hoch wasserhaltige funktionelle Flüssigkeiten erhält, wenn man als Verdickersystem Kombinationen aus wasserlöslichen polymeren Polyetherpolyolen, in denen mindestens 50% der Hydroxyl-Endgruppen durch Umsetzung mit einem einen C12―C30-Alkyl- oder C12―C30-Alkylenrest aufweisenden Monoisocyanat verkappt sind, und anionische und/oder nichtionische Tenside verwendet.Surprisingly, it has now been found that excellent shear-stable, highly water-containing functional liquids are obtained if, as a thickener system, combinations of water-soluble polymeric polyether polyols in which at least 50% of the hydroxyl end groups are reacted with a C 12 -C 30 -alkyl or C Monoisocyanate having 12 ―C 30 alkylene radical are blocked, and anionic and / or nonionic surfactants are used.

Die Erfindung betrifft daher die Verwendung von Kombinationen aus wasserlöslichen polymeren Polyetherpolyolen, in denen mindestens 50% der Hydroxyl-Endgruppen durch Umsetzung mit einem einen C12-C30-Alkyl- oder C12―C30-Alkylenrest aufweisenden Monoisocyanat verkappt sind, und anionischen und/oder nichtionischen Tensiden als Verdicker-Systeme für hoch wasserhaltige funktionelle Flussigkeiten.The invention therefore relates to the use of combinations of water-soluble polymeric polyether polyols in which at least 50% of the hydroxyl end groups are blocked by reaction with a monoisocyanate having a C 12 -C 30 -alkyl or C 12 -C 30 -alkylene radical, and anionic and / or nonionic surfactants as thickener systems for highly water-containing functional liquids.

Die Erfindung betrifft ferner hoch wasserhaltige funktionelle Flüssigkeiten, enthaltend außer Wasser Kombinationen aus wasserlöslichen polymeren Polyetherpolyolen, in denen mindestens 50% der Hydroxyl-Endgruppen durch Umsetzung mit einem einen C12-C31-Alkyl- oder C12―C30-Alkylenrest aufweisenden Monoisocyanat verkappt sind, und anionischen und/oder nichtionischen Tensiden und gegebenenfalls Schmierfähigkeitsverbesserer, Metalldesaktivatoren, Korrosionsinhibitoren, Entschäumer, Stoffe zum Einstellen oder Abpuffern von bestimmten pH-Werten, Alterungsschutzmittel, Biozide, Kennfarbstoffe und/oder Glykole.The invention further relates to highly water-containing functional liquids containing, in addition to water, combinations of water-soluble polymeric polyether polyols in which at least 50% of the hydroxyl end groups by reaction with a monoisocyanate having a C 12 -C 31 alkyl or C 12 -C 30 alkylene radical are capped, and anionic and / or nonionic surfactants and optionally lubricity improvers, metal deactivators, corrosion inhibitors, defoamers, substances for adjusting or buffering certain pH values, anti-aging agents, biocides, colorants and / or glycols.

Mit Hilfe der erfindungsgemäß zu verwendenden Kombinationen werden hoch wasserhaltige funktionelle Flüssigkeiten erhalten, die sich nicht nur insgesamt durch eine ausgezeichnete Beständigkeit, sondern auch durch eine hervorragende Scherstabilität auszeichnen. Außerdem haben die in den erfindungsgemäßen Verdickersystemen verwendeten verkappten wasserlöslichen polymeren Polyetherpolyole den Vorteil, daß sie wesentlich einfacher herstellbar sind, als die durch langkettige 1,2-Epoxyalkane modifizierten wasserlöslichen polymeren Polyetherpolyole.With the aid of the combinations to be used according to the invention, highly water-containing functional liquids are obtained which are not only distinguished overall by excellent resistance but also by excellent shear stability. In addition, in the Capped water-soluble polymeric polyether polyols according to the invention used the advantage that they are much easier to produce than the water-soluble polymeric polyether polyols modified by long-chain 1,2-epoxyalkanes.

In den erfindungsgemäß als Verdickersysteme zu verwendenden Kombinationen aus Monoisocyanat-verkappten wasserlöslichen polymeren Polyetherpolyolen und bestimmten Tensiden sind die Tenside in einer solchen Menge enthalten, daß auf 1 Gew.-TI verkapptes Polyetherpolyol 0,1 bis 3 Gew.-Tie, vorzugsweise 0,25 bis 2,5 Gew.-Tie Tensid entfallen.In the combinations of monoisocyanate-capped water-soluble polymeric polyether polyols and certain surfactants to be used according to the invention as thickener systems, the surfactants are contained in an amount such that 0.1 to 3 parts by weight, preferably 0.25, of polyether polyol capped to 1 part by weight up to 2.5 parts by weight of surfactant are eliminated.

Als Tenside werden nichtionische und anionische Tenside verwendet. Bevorzugt sind nichtionische oder anionische Tenside mit geringer Schaumneigung. Es können sowohl einzelne Tenside als auch Gemische verschiedener Tenside eingesetzt werden.Nonionic and anionic surfactants are used as surfactants. Nonionic or anionic surfactants with a low tendency to foam are preferred. Both individual surfactants and mixtures of different surfactants can be used.

Die in den erfindungsgemäß zu verwendenden Kombinationen anwendbaren anionischen und nichtionischen Tenside sind z.B. in der Übersichtsarbeit "Tenside", von K. Kosswig in Ullmann's Enzyklopädie der techn. Chemie, 4. Aufl., Band 22, Seite 468-494 und 498 beschrieben.The anionic and nonionic surfactants which can be used in the combinations to be used according to the invention are e.g. in the review "Tenside", by K. Kosswig in Ullmann's encyclopedia of techn. Chemistry, 4th ed., Volume 22, pages 468-494 and 498.

Als anionische Tenside kommen Carboxylate, z.B. carboxymethylierte Oxethylate und Derivate von Aminosäuren; Sulfonate, z.B. Alkylbenzolsulfonate, Alkylnaphthalin sulfonate, Alkansulfonate, a-Olefinsulfonate, a-Sulfofettsäureester, Sulfobernsteinsäureester, Alkoxy-, Acyloxy- und Acylaminoalkansulfonate; als Sulfate, z.B. Alkylsulfate und Ethersulfate, Phosphonate und Phosphate in Betracht. Bevorzugt werden Alkansulfonate mit 8 bis 30 Kohlenstoffatomen, Sulfobernsteinsäureester von mit 8 bis 30 Mol Ethylenoxid ethoxylierten C,2-C,e-Fettalkoholen, von mit 8 bis 70 Mol Ethylenoxid umgesetzten Cs-C2o-Alkyl-phenolen, von mit 8 bis 30 Mol Ethylenoxid ethoxylierten C12-C18-Fettsäuren oder C12-C18-Fettalkoholen; C12-C18-n-Alkylsulfate; Sulfate von mit 8 bis 30 Mol Ethylenoxid ethoxylierten C12―C18-Fettalkoholen, C12―C18-Fettsäuren und Cg-C20-Alkylphenolen.The anionic surfactants are carboxylates, for example carboxymethylated oxethylates and derivatives of amino acids; Sulfonates, for example alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkanesulfonates, α-olefinsulfonates, α-sulfofatty acid esters, sulfosuccinic acid esters, alkoxy, acyloxy and acylaminoalkanesulfonates; as sulfates, for example alkyl sulfates and ether sulfates, phosphonates and phosphates. Alkanesulfonates be preferably having 8 to 30 carbon atoms, phenols, alkyl sulfosuccinic acid esters of ethoxylated with 8 to 30 moles of ethylene oxide C, 2-C, e fatty alcohols, of reacted with 8 to 70 moles of ethylene oxide C s -C 2o, from 8 to 30 moles of ethylene oxide ethoxylated C 12 -C 18 fatty acids or C 12 -C 18 fatty alcohols; C 12 -C 18 n-alkyl sulfates; Sulphates of C 12 ―C 18 fatty alcohols, C 12 ―C 18 fatty acids and Cg-C20 alkylphenols ethoxylated with 8 to 30 moles of ethylene oxide.

Als nichtionische Tenside kommen Oxethylate, endständig blockierte Oxethylate und Fettsäureester von Polyhydroxyverbindungen, ferner Blockpolymere des Propylenoxids und Ethylenoxids in Betracht. Bevorzugt werden als nichtionische Tenside mit 8 bis 50 Mol Ethylenoxid umgesetzte C12-C18-Fettsäuren, mit 8 bis 40 Mol Ethylenoxid ethoxylierte C12―C18-Fettsäureamide, mit 8 bis 30 Mol Ethylenoxid ethoxylierte C12-C18-Fettalkohole, mit 8 bis 50 Mol Ethylenoxid ethoxylierte Cg-C20-Alkylphenole und mit 8 bis 60 Mol Ethylenoxid ethoxylierte, styrolisierte oder benzylierte Phenole verwendet. Bevorzugt werden nichtionische Tenside mit einem HLB-Wert <18 verwendet.Suitable nonionic surfactants are oxethylates, terminally blocked oxyethylates and fatty acid esters of polyhydroxy compounds, and also block polymers of propylene oxide and ethylene oxide. Reacted as nonionic surfactants with 8 to 50 moles of ethylene oxide are preferably C 12 -C 18 fatty acids, with 8 to 40 moles of ethylene oxide, ethoxylated C 12 -C 18 fatty acid amides with 8 to 30 moles of ethylene oxide, ethoxylated C 12 -C 18 fatty alcohols, Cg-C 20 alkylphenols ethoxylated with 8 to 50 moles of ethylene oxide and styrene or benzylated phenols ethoxylated with 8 to 60 moles of ethylene oxide. Nonionic surfactants with an HLB value <18 are preferably used.

Die in den erfindungsgemäß zu verwendenden Kombinationen einzusetzenden Monoisocyanat-verkappten wasserlöslichen polymeren Polyetherpolyole sind Umsetzungsprodukte von an sich bekannten polymeren wasserlöslichen Polyetherpolyolen, die eine mittlere Molmasse von 5.000 bis 70.000 (ermittelt durch Bestimmung der OH-Endgruppen; aus der Zahl der OH-Endgruppen wird die mittlere Molmasse nach folgender Formel berechnet:

Figure imgb0001
aufweisen, mit einem einen C12-C30-Alkyl- oder C12-C30-Alkylenrest aufweisenden Monoisocyanat.The monoisocyanate-capped water-soluble polymeric polyether polyols to be used in the combinations to be used according to the invention are reaction products of known polymeric water-soluble polyether polyols which have an average molecular weight of 5,000 to 70,000 (determined by determining the OH end groups; the number of OH end groups becomes average molecular weight calculated using the following formula:
Figure imgb0001
 have, with a C 12 -C 30 alkyl or C 12 -C 30 alkylene having monoisocyanate.

Als C12-C30-Alkylreste kommen vor allem der Dodecyl-, Hexadecyl-, Octadecyl- und der Behenyl-Rest, als C12―C30-Alkylenrest vor allem der Oleylrest in Betracht. Diese aliphatischen Kohlenwasserstoffreste müssen nicht unbedingt unmittelbar an die Isocyanatgruppe gebunden sein, sondern können auch über andere Gruppen, z.B. aromatische Ringe und/oder Urethangruppen an die Isocyanatgruppe gebunden sein. Solche Monoisocyanate, in denen die langkettigen aliphatischen Kohlenwasserstoffreste nicht unmittelbar an die Isocyanatgruppe gebunden sind, sind beispielsweise die Additionsprodukte aus 1 Mol eines C12―C30-n-Alkanols, z.B. Lauryl-, Myristyl-, Cetyl-, Stearyl- oder Behenylalkohols oder des Oleylalkohols an 1 Mol eines aliphatischen, cycloaliphatischen, aromatischen oder heterocyclischen Diisocyanates.The C 12 -C 30 alkyl radicals are, in particular, the dodecyl, hexadecyl, octadecyl and the behenyl radical, and the C 12 -C 30 alkylene radical in particular the oleyl radical. These aliphatic hydrocarbon radicals do not necessarily have to be bonded directly to the isocyanate group, but can also be bonded to the isocyanate group via other groups, for example aromatic rings and / or urethane groups. Such monoisocyanates in which the long-chain aliphatic hydrocarbon radicals are not directly bound to the isocyanate group are, for example, the addition products from 1 mol of a C 12 -C 30 -n-alkanol, for example lauryl, myristyl, cetyl, stearyl or behenyl alcohol or of oleyl alcohol to 1 mole of an aliphatic, cycloaliphatic, aromatic or heterocyclic diisocyanate.

Für die Herstellung der mit den Monoisocyanaten verkappten wasserlöslichen polymeren Polyetherpolyole wird die Menge an Monoisocyanat so bemessen, daß mindestens 50%, vorzugsweise 70 bis 100%, besonders bevorzugt 85 bis 100% der im Wasser löslichen polymeren Polyetherpolyole vorliegenden Hydroxyl-Endgruppen verkappt sind.For the preparation of the water-soluble polymeric polyether polyols capped with the monoisocyanates, the amount of monoisocyanate is such that at least 50%, preferably 70 to 100%, particularly preferably 85 to 100% of the hydroxyl end groups present in the water-soluble polymeric polyether polyols are capped.

Die Verkappung der OH-Endgruppen der polymeren wasserlöslichen Polyetherpolyole mit den einen C12-C30-Alkyl- oder C12―C30-Alkylenrest aufweisenden Monoisocyanaten ist eine im Prinzip bekannte Reaktion (siehe z.B. Ullmann's Enzyklopädie der techn. Chemie, 4. Aufl., Band 19, Seiten 309-310). Das Ende der Umsetzung läßt sich IR-spektroskopisch an Hand des Verschwindens der für Isocyanate typischen Absorptionsbande bei etwa 2.270 cm-1. bestimmen. Diese Additionsreaktion läßt sich in bekannter Weise durch die Mitverwendung bekannter Katalysatoren beschleunigen.The capping of the OH end groups of the polymeric water-soluble polyether polyols with the monoisocyanates having a C 12 -C 30 alkyl or C 12 ―C 30 alkylene radical is a reaction which is known in principle (see, for example, Ullmann's Enzyklopadie der techn. Chemie, 4th ed ., Volume 19, pages 309-310). The end of the reaction can be determined by IR spectroscopy on the basis of the disappearance of the absorption band typical of isocyanates at about 2,270 cm -1 . determine. This addition reaction can be accelerated in a known manner by using known catalysts.

Die den verkappten wasserlöslichen Polyetherpolyolen zugrunde liegenden wasserlöslichen polymeren, gegebenenfalls Urethan- oder Estergruppen aufweisenden Polyetherpolyole der mittleren Molmasse 5.000 bis 70.000 sind bekannt oder nach an sich bekannten Verfahren erhältlich, z.B. durch Polymerisation von Ethylenoxid oder Copolymerisation von Ethylenoxid mit anderen Alkylenoxiden in Gegenwart von Verbindungen, die mindestens zwei aktive Wasserstoffatome aufweisen, und gegebenenfalls Modifizierung der so erhaltenen wasserlöslichen polymeren Polyetherpolyole durch Umsetzung mit Diisocyanaten oder Dicarbonsäuren zu wasserlöslichen, Urethan- bzw. Estergruppen aufweisenden polymeren Polyetherpolyolen oder durch Polymerisation von Ethylenoxid oder Copolymerisation von Ethylenoxid und anderen Alkylenoxiden in Gegenwart von Verbindungen, die zwei aktive Wasserstoffatome aufweisen und Umsetzung der erhaltenen wasserlöslichen Polyetherdiole mit Polyisocyanaten, unter Einhaltung eines Verhältnisses von Isocyanat-Gruppen/OH-Gruppen von höchstens 0,5:1, zu wasserlöslichen polymeren Urethangruppen aufweisenden Polyetherpolyolen.The water-soluble polymeric, optionally urethane or ester group-containing polyether polyols of average molecular weight 5,000 to 70,000 on which the blocked water-soluble polyether polyols are based are known or can be obtained by processes known per se, for example by polymerizing ethylene oxide or copolymerizing ethylene oxide with other alkylene oxides in the presence of compounds, which have at least two active hydrogen atoms, and optionally modifying the water-soluble polymeric polyether polyols thus obtained by reaction with diisocyanates or dicarboxylic acids to give water-soluble urethane or ester groups polymeric polyether polyols or by polymerizing ethylene oxide or copolymerizing ethylene oxide and other alkylene oxides in the presence of compounds which have two active hydrogen atoms and reacting the water-soluble polyether diols obtained with polyisocyanates, while maintaining a ratio of isocyanate groups / OH groups of at most 0.5 : 1, to water-soluble polymeric polyether polyols containing urethane groups.

Die erfindungsgemäß zu verwendenden Kombinationen aus speziellen Monoisocyanat-verkappten wasserlöslichen polymeren Polyetherpolyolen und anionischen und/oder nichtionischen Tensiden werden hergestellt, indem man beide Komponenten in flüssigem Zustand miteinander zu einer homogenen Flüssigkeit vermischt. Da sie bei Raumtemperatur vielfach fest sind, werden die Komponenten im allgemeinen auf Schmelztemperatur, das sind Temperaturen von 60 bis 100°C, erwärmt und bei dieser Temperatur so lange verrührt, bis eine homogene Flüssigkeit entstanden ist. Bei der Verwendung von Tensid-Gemischen kann es vorteilhaft sein, zunächst nur ein Tensid mit dem verkappten Polyetherpolyol in flüssigem Zustand zu vermischen und anschließend in die homogene Schmelze das zweite bzw. die restlichen Tenside einzurühren.The combinations of special monoisocyanate-capped water-soluble polymeric polyether polyols and anionic and / or nonionic surfactants to be used according to the invention are produced by mixing both components together in a liquid state to form a homogeneous liquid. Since they are often solid at room temperature, the components are generally heated to the melting temperature, ie temperatures from 60 to 100 ° C., and stirred at this temperature until a homogeneous liquid has formed. When using surfactant mixtures, it may be advantageous to first mix only one surfactant with the masked polyether polyol in the liquid state and then to stir the second or the remaining surfactants into the homogeneous melt.

Die so erhaltenen Kombinationen aus speziellen verkappten wasserlöslichen polymeren Polyetherpolyolen und anionischen und/oder nichtionischen Tensiden werden zur besseren Handhabbarkeit bei der Herstellung der funktionellen Flüssigkeiten durch Zugabe von Wasser zu flüssigen Konzentraten verdünnt, deren Wassergehalt etwa 30 bis 70 Gew.-%, vorzugsweise 40 bis 60 Gew.-% beträgt, bezogen auf das Gewicht des Konzentrates.The combinations of special capped water-soluble polymeric polyether polyols and anionic and / or nonionic surfactants obtained in this way are diluted by adding water to liquid concentrates, the water content of which is about 30 to 70% by weight, preferably 40 to, for better manageability in the preparation of the functional liquids 60% by weight, based on the weight of the concentrate.

Aus diesen Konzentraten werden durch weiteres Verdünnen mit Wasser die gebrauchsfertigen Hydraulikfluide, Metallbearbeitungsflüssigkeiten (Kühlschmiermittel) und Metallhärtungsmedien hergestellt.The ready-to-use hydraulic fluids, metalworking fluids (cooling lubricants) and metal hardening media are produced from these concentrates by further dilution with water.

Die Konzentrate, bzw. die aus ihnen durch Verdünnen hergestellten funktionellen Flüssigkeiten können zusätzlich zum Wasser und dem Verdicker-System noch in diesen funktionellen Flüssigkeiten üblicherweise verwendete Zusätze enthalten. Das sind Schmierfähigkeitsverbesserer, Metalldesaktivatoren, Korrosionsinhibitoren, Entschäumer, Stoffe zum Einstellen oder Abpuffern bestimmter pH-Werte, Alterungsschutzmittel, Biozide, Kennfarbstoffe in den für diese Zusätze üblichen Mengen, sowie monomere und/oder oligomere Glykole enthalten.In addition to the water and the thickener system, the concentrates, or the functional liquids prepared from them by dilution, can also contain additives which are usually used in these functional liquids. These are lubricity improvers, metal deactivators, corrosion inhibitors, defoamers, substances for adjusting or buffering certain pH values, anti-aging agents, biocides, identification dyes in the usual amounts for these additives, as well as monomeric and / or oligomeric glycols.

Die erfindungsgemäß verdickten, hoch wasserhaltigen funktionellen Flüssigkeiten enthalten vorzugsweise außer Wasser und gegebenenfalls monomeren und/oder oligomeren Glykolen 3 bis 7 Gew.-% der erfindungsgemäß als Verdickersystem zu verwendende Kombination und gegebenenfalls zusätzlich 0,5 bis 3, vorzugsweise 1 bis 3 Gew.-%, der vorstehend genannten in funktionellen Flüssigkeiten üblicherweise verwendeten Zusätze, sowie gegebenenfalls bis zu 25 Gew.-%, z.B. 0,5 bis 20 Gew.-% monomere und/oder oligomere Glykole.In addition to water and optionally monomeric and / or oligomeric glycols, the highly water-containing functional liquids which are thickened according to the invention preferably contain 3 to 7% by weight of the combination to be used according to the invention as a thickener system and optionally additionally 0.5 to 3, preferably 1 to 3% by weight % of the above-mentioned additives commonly used in functional liquids, and optionally up to 25% by weight, for example 0.5 to 20% by weight of monomeric and / or oligomeric glycols.

Beschreibung der in den Beispielen verwendeten Tenside (1), mit Monoisocyanaten verkappten wasserlöslichen polymeren Polyetherpolyole (11) und der zur Herstellung dieser verkappten Polyetherpolyole verwendeten wasserlöslichen Polyetherpolyole (lll).Description of the surfactants (1) used in the examples, monoisocyanate-capped water-soluble polymeric polyether polyols (11) and the water-soluble polyether polyols (III) used to prepare these capped polyether polyols.

1. Tenside:1. Tensides:

  • Tensid A: Mit 19 Mol Ethylenoxid ethoxylierter OleylalkoholSurfactant A: Oleyl alcohol ethoxylated with 19 moles of ethylene oxide
  • Tensid B: Mit 50 Mol Ethylenoxid ethoxyliertes Bis-(1-phenylethyl)-phenolSurfactant B: bis (1-phenylethyl) phenol ethoxylated with 50 moles of ethylene oxide
  • Tensid C: Mit 14 Mol Ethylenoxid ethoxyliertes 3-Benzyl-4-hydroxybiphenylSurfactant C: 3-benzyl-4-hydroxybiphenyl ethoxylated with 14 moles of ethylene oxide
  • Tensid D: Mit 12 Mol Ethylenoxid ethoxylierter OleylalkoholSurfactant D: Oleyl alcohol ethoxylated with 12 moles of ethylene oxide
  • Tensid E: N,N-Bis-(2-hydroxyethyl)-oleylaminSurfactant E: N, N-bis (2-hydroxyethyl) oleylamine
  • Tensid F: Trinatriumsalz des Phosphonosuccinatesters des mit 30 Mol Ethylenoxid ethoxylierten p-NonylphenolsSurfactant F: trisodium salt of the phosphonosuccinate ester of p-nonylphenol ethoxylated with 30 mol of ethylene oxide
  • Tensid G: Dinatriumsalz des Sulfosuccinatesters des mit 30 Mol Ethylenoxid ethoxylierten p-NonylphenolsSurfactant G: disodium salt of the sulfosuccinate ester of p-nonylphenol ethoxylated with 30 moles of ethylene oxide
  • Tensid H: Natriumsalz des C14-C18-n-AlkylsulfonatsSurfactant H: sodium salt of C 14 -C 18 n-alkyl sulfonate
  • Tensid I: Natriumsalz eines Arylalkylsulfonats mit 50% Mono- und 50% DisulfonatanteilSurfactant I: sodium salt of an arylalkyl sulfonate with 50% mono- and 50% disulfonate
  • Tensid J: Kokosfettsäure-diethanolamidSurfactant J: coconut fatty acid diethanolamide
  • Tensid K: saures Phosphat, erhalten durch Umsetzung von 1 Mol Phosphorpentoxid mit 4 Mol Octadecanol-1 und 2 Mol Octadecyl-1-decaethoxylat, nachträglich neutralisiert mit DiethanolaminSurfactant K: acidic phosphate, obtained by reacting 1 mol of phosphorus pentoxide with 4 mol of octadecanol-1 and 2 mol of octadecyl-1-decaethoxylate, subsequently neutralized with diethanolamine
  • Tensid L: Mit 50 Mol Ethylenoxid ethoxylierter Oleylalkohol.Surfactant L: oleyl alcohol ethoxylated with 50 moles of ethylene oxide.
11. Monoisocyanat-verkappte wasserlösliche polymere Polyetherpolyole11. Monoisocyanate-capped water-soluble polymeric polyether polyols Verkapptes Polyetherpolyol 1:Masked polyether polyol 1:

Eine Mischung aus 1346,4 g Polyetherpolyol A (0,06 Mol), 0,15 g 1,4-Diazabicycio-2,2,2-octan (DABCO) und 500 g trockenem Dioxan wird unter Rühren auf Rückflußtemperatur erhitzt. Innerhalb einer Stunde wird 50,6 g Dodecylisocyanat (0,24 Mol) zugetropft. Anschließend wird das Reaktionsgemisch solange bei Rückflußtemperatur gerührt, bis im Infrarotspektrum einer Reaktionsgemischprobe keine Isocyanatbande mehr nachweisbar ist. Nach dem Abdestillieren des Dioxans bei etwa 130°C/15 hPa bleibt ein bei erhöhten Temperaturen viskoses, bei tiefen Temperaturen erstarrendes Reaktionsprodukt zurück.A mixture of 1346.4 g of polyether polyol A (0.06 mol), 0.15 g of 1,4-diazabicycio-2,2,2-octane (DABCO) and 500 g of dry dioxane is heated to the reflux temperature with stirring. 50.6 g of dodecyl isocyanate (0.24 mol) are added dropwise within one hour. The reaction mixture is then stirred at the reflux temperature until no isocyanate band can be detected in the infrared spectrum of a reaction mixture sample. After the dioxane has been distilled off at about 130 ° C./15 hPa, a reaction product which is viscous at elevated temperatures and solidifies at low temperatures remains.

Verkappungsgrad der Hydroxylendgruppen im Reaktionsprodukt: 100%.Degree of capping of the hydroxyl end groups in the reaction product: 100%.

Verkapptes Polyetherpolyol 2:Masked polyether polyol 2:

1346,4 g Polyetherpolyol A (0,06 Mol) werden mit 64,1 g Hexadecylisocyanat (0,24 Mol) in der in Beispiel 1 beschriebenen Weise umgesetzt.

  • Verkappungsgrad der Hydroxylendgruppen im Reaktionsprodukt: 100%.
1346.4 g of polyether polyol A (0.06 mol) are reacted with 64.1 g of hexadecyl isocyanate (0.24 mol) in the manner described in Example 1.
  • Degree of capping of the hydroxyl end groups in the reaction product: 100%.

Verkapptes Polyetherpolyol 3:

  • 897,6 g Polyetherpolyol A (0,04 Mol) werden in 500 g trockenem Dioxan mit 87,7 g (0,16 Mol) eines Behenylalkohol-Isophorondiisocyanat (IPDI) (1:1)-Adduktes solange bei Rückflüßtemperatur umgesetzt, bis die Isocyanatbande im IR-Spektrum verschwunden ist. Die Aufarbeitung des Reaktionsgemisches erfolgt, wie im Beispiel 1 beschreiben. Verkappungsgrad der Hydroxylendgruppen im Reaktionsprodukt: 100%.
Masked polyether polyol 3:
  • 897.6 g of polyether polyol A (0.04 mol) are reacted in 500 g of dry dioxane with 87.7 g (0.16 mol) of a behenyl alcohol isophorone diisocyanate (IPDI) (1: 1) adduct at the reflux temperature until the Isocyanate band in the IR spectrum has disappeared. The reaction mixture is worked up as described in Example 1. Degree of capping of the hydroxyl end groups in the reaction product: 100%.

Verkapptes Polyetherpolyol 4:

  • 897,6 g Polyetherpolyol A (0,04 Mol) werden, wie in Beispiel 3 beschrieben, mit 45,8 g (0,155 Mol) Stearylisycyanat umgesetzt.
  • Verkappungsgrad der Hydroxylendgruppen im Reaktionsprodukt: 97%.
Masked polyether polyol 4:
  • 897.6 g of polyether polyol A (0.04 mol) are, as described in Example 3, reacted with 45.8 g (0.155 mol) of stearyl cyanate.
  • Degree of capping of the hydroxyl end groups in the reaction product: 97%.

Verkapptes Polyetherpolyol 5:

  • 1240 g Polyetherpolyol B (0,08 Mol), werden wie in Beispiel 3 beschrieben (unter Verwendung von 500 g getrocknetem Dioxan), mit 94,4 g (0,32 Mol) Stearylisocyanat umgesetzt.
  • Verkappungsgrad der Hydroxylendgruppen im Reaktionsprodukt: 100%.
Masked polyether polyol 5:
  • 1240 g of polyether polyol B (0.08 mol) are reacted as described in Example 3 (using 500 g of dried dioxane) with 94.4 g (0.32 mol) of stearyl isocyanate.
  • Degree of capping of the hydroxyl end groups in the reaction product: 100%.

Verkapptes Polyetherpolyol 6:

  • 775 g Polyetherpolyol B (0,05 Mol) werden, wie in Beispiel 3 beschrieben (unter Verwendung von 500 g absolutem Dioxan), mit 29,5 g Stearylisocyanat (0,1 Mol) umgesetzt.
  • Verkappungsgrad der Hydroxylendgruppen im Reaktionsprodukt: 50%.
Masked polyether polyol 6:
  • 775 g of polyether polyol B (0.05 mol) are, as described in Example 3 (using 500 g of absolute dioxane), reacted with 29.5 g of stearyl isocyanate (0.1 mol).
  • Degree of capping of the hydroxyl end groups in the reaction product: 50%.

Verkapptes Polyetherpolyol 7:

  • 775 g Polyetherpolyol B (0,05 Mol) werden unter den in Beispiel 3 beschriebenen Bedingungen mit 44,3 g Stearylisocyanat (0,15 Mol) umgesetzt.
  • Verkappungsgrad der Hydroxylendgruppen im Reaktionsprodukt: 75%.
Masked polyether polyol 7:
  • 775 g of polyether polyol B (0.05 mol) are reacted with 44.3 g of stearyl isocyanate (0.15 mol) under the conditions described in Example 3.
  • Degree of capping of the hydroxyl end groups in the reaction product: 75%.

Verkapptes Polyetherpolyol 8:

  • 1346,4 g Polyetherpolyol A (0,06 Mol) werden zunächst in 500 g wasserfreiem Dioxan in Gegenwart von 0,12 g DABCO mit 5,2 g 2,4-Toluylendiisocyanat (TDI) (0,03 Mol) durch einstündiges Rühren bei Rückflüßtemperatur umgesetzt (mittlere Molmasse des so erhaltenen Urethangruppenhaltigen Polyetherpolyols: 45.000). Anschließend wird das Reaktionsgemisch ebenfalls bei Rückflußtemperatur innerhalb von 1 h mit 53,1 g Stearylisocyanat (0,18 Mol) versetzt und anschließend unter Rühren weiter erhitzt, bis die Isocyanatbande im IR- Spektrum verschwunden ist. Das Reaktionsgemisch wird, wie in Beispiel 3 beschrieben aufgearbeitet.
  • Verkappungsgrad der Hydroxylendgruppen im Reaktionsprodukt: 100%.
Masked polyether polyol 8:
  • 1346.4 g of polyether polyol A (0.06 mol) are first added to 500 g of anhydrous dioxane in the presence of 0.12 g of DABCO with 5.2 g of 2,4-tolylene diisocyanate (TDI) (0.03 mol) by stirring for one hour Reflux temperature implemented (average molecular weight of the polyether polyol thus obtained containing urethane groups: 45,000). 53.1 g of stearyl isocyanate (0.18 mol) are then added to the reaction mixture, also at the reflux temperature, and the mixture is then heated further with stirring until the isocyanate band has disappeared in the IR spectrum. The reaction mixture is worked up as described in Example 3.
  • Degree of capping of the hydroxyl end groups in the reaction product: 100%.

Verkapptes Polyetherpolyol 9:

  • 897,6 g Polyol A (0,04 Mol) werden unter den in Beispiel 3 beschriebenen Reaktionsbedingungen (unter Verwendung von 500 g wasserfreiem Dioxan) mit 4,5 g IPDI (0,02 Mol) und 33,6 g Stearylisocyanat (0,114 Mol) umgesetzt. (Mittlere Molmasse des dem verkappten Polyetherpolyol zugrunde liegenden Urethangruppen-haltigen Polyetherpolyols: 45.000).
  • Verkappungsgrad der Hydroxylendgruppen im Reaktionsprodukt: 95%.
Masked polyether polyol 9:
  • 897.6 g of polyol A (0.04 mol) are mixed under the reaction conditions described in Example 3 (using 500 g of anhydrous dioxane) with 4.5 g of IPDI (0.02 mol) and 33.6 g of stearyl isocyanate (0.114 mol ) implemented. (Average molar mass of the polyether polyol containing urethane groups on which the blocked polyether polyol is based: 45,000).
  • Degree of capping of the hydroxyl end groups in the reaction product: 95%.

Verkapptes Polyetherpolyol 10:

  • 1240 g Polyol B (0,08 Mol) werden unter den in Beispiel 3 beschriebenen Bedingungen (unter Verwendung von 500 g wasserfreiem Dioxan) mit 8,9 g IPDI (0,04 Mol) und 70,8 g Stearylisocyanat (0,24 Mol) umgesetzt. (Mittlere Molmasse des dem verkappten Polyetherpolyol zugrunde liegenden Urethangruppen-haltigen Polyetherpolyols: 31.200).
  • Verkappungsgrad der Hydroxylendgruppen im Reaktionsprodukt: 100%.
Masked polyether polyol 10:
  • 1240 g of polyol B (0.08 mol) are mixed under the conditions described in Example 3 (using 500 g of anhydrous dioxane) with 8.9 g of IPDI (0.04 mol) and 70.8 g of stearyl isocyanate (0.24 mol ) implemented. (Average molar mass of the urethane group-containing polyether polyol on which the blocked polyether polyol is based: 31,200).
  • Degree of capping of the hydroxyl end groups in the reaction product: 100%.

Verkapptes Polyetherpolyol 11:

  • 1300 g Polyetherpolyol C (0,234 Mol) werden bei 90 bis 100°C aufgeschmolzen und mit 73 mg Eisenacetylacetonat, gelöst in 2 ml Toluol, versetzt. Die Mischung wird bei 125 bis 130°C gleichzeitig mit 54,5 g Stearylisocyanat (0,185 Mol) und 24,4 g eines Gemisches aus 65 Gew.-% 2,4- und 35 Gew.-% 2,6-Toluylendiisocyanat (0,14 Mol) tropfenweise versetzt. (Mittlere Molmasse des dem verkappten Polyetherpolyol zugrunde liegenden Urethangruppen-haltigen Polyetherpolyols: 14.000). Nach einer Reaktionszeit von 2 h ist die Umsetzung beendet.
  • Verkappungsgrad der Hydroxylendgruppen im Reaktionsprodukt: 100%.
Masked polyether polyol 11:
  • 1300 g of polyether polyol C (0.234 mol) are melted at 90 to 100 ° C. and 73 mg of iron acetylacetonate, dissolved in 2 ml of toluene, are added. The mixture is simultaneously at 125 to 130 ° C with 54.5 g of stearyl isocyanate (0.185 mol) and 24.4 g of a mixture of 65 wt .-% 2.4 and 35 wt .-% 2,6-tolylene diisocyanate (0 , 14 mol) added dropwise. (Average molecular weight of the urethane group-containing polyether polyol on which the blocked polyether polyol is based: 14,000). The reaction is complete after a reaction time of 2 h.
  • Degree of capping of the hydroxyl end groups in the reaction product: 100%.

Verkapptes Polyetherpolyol 12 (nicht erfindungsgemäß, Vergleichsverbindung):Masked polyether polyol 12 (not according to the invention, comparative compound):

Eine Mischung aus 1346,4 g Polyetherpolyol A (0,06 Mol) und 500 g wasserfreies Dioxan werden unter Rühren auf Rückflußtemperatur (etwa 110°C) in Gegenwart von 0,15 g DABCO erhitzt. Dann tropft man innerhalb 1 h 30,0 g Cyclohexylisocyanat (0,24 Mol) zu und rührt die Reaktionsmischung solange bei Rückflußtemperatur bis im Infrarotspektrum einer Probe keine Isocyanatbande mehr nachweisbar ist. Die Reaktionsmischung wird, wie in Beispiel 1 beschrieben, aufgearbeitet.

  • Verkappungsgrad der Hydroxylendgruppen im Reaktionsprodukt: 100%.
A mixture of 1346.4 g of polyether polyol A (0.06 mol) and 500 g of anhydrous dioxane are heated with stirring to the reflux temperature (about 110 ° C.) in the presence of 0.15 g of DABCO. 30.0 g of cyclohexyl isocyanate (0.24 mol) are then added dropwise in the course of 1 h, and the reaction mixture is stirred at the reflux temperature until no isocyanate band can be detected in the infrared spectrum of a sample. The reaction mixture is worked up as described in Example 1.
  • Degree of capping of the hydroxyl end groups in the reaction product: 100%.

Verkapptes Polyetherpolyol 13 (nicht erfindungsgemäß, Vergleichspolyetherpolyol):

  • 1346,4 g Polyetherpolyol A (0,06 Mol) werden mit 36,2 g Norborn-2-yl-methylisocyanat (0,24 Mol) unter den Polyetherpolyol 12 beschriebenen Reaktionsbedingungen umgesetzt.
  • Verkappungsgrad der Hydroxylendgruppen im Reaktionsprodukt: 100%.
Masked polyether polyol 13 (not according to the invention, comparative polyether polyol):
  • 1346.4 g of polyether polyol A (0.06 mol) are reacted with 36.2 g of norborn-2-yl-methyl isocyanate (0.24 mol) under the reaction conditions described in polyether polyol 12.
  • Degree of capping of the hydroxyl end groups in the reaction product: 100%.

111. Zur Herstellung der verkappten Polyetherpolyole 1 bis 13 verwendete wasserlösliche polymere Polyetherpolyole:111. Water-soluble polymeric polyether polyols used to prepare the capped polyether polyols 1 to 13: Polyetherpolyol A:Polyether polyol A:

Umsetzungsprodukt von Pentaerythrit, Ethylenoxid und Propylenoxid. Die Polyetherkette enthält 25 Gew.-% Propylenoxid- und 75 Gew.-% Ethylenoxid-Einheiten in statistischer Verteilung. Mittlere Molmasse: 22.400.Reaction product of pentaerythritol, ethylene oxide and propylene oxide. The polyether chain contains 25% by weight propylene oxide and 75% by weight ethylene oxide units in a statistical distribution. Average molecular weight: 22,400.

Polyetherpolyol B:Polyether polyol B:

Umsetzungsprodukt von Pentaerythrit, Ethylenoxid und Propylenoxid. Die Polyetherketten enthalten 25 Gew.-% Propylenoxid- und 75 Gew.-% Ethylenoxid-Einheiten in statistischer Verteilung. Mittlere Molmasse: 15.500.Reaction product of pentaerythritol, ethylene oxide and propylene oxide. The polyether chains contain 25% by weight of propylene oxide and 75% by weight of ethylene oxide units in a statistical distribution. Average molecular weight: 15,500.

Polyetherpolyol C:Polyether polyol C:

Polyethylenglykol mit einer mittleren Molmasse von 5555.Polyethylene glycol with an average molecular weight of 5555.

Allgemeine Beschreibung der in der nachstehenden Tabelle zusammengestellten BeispieleGeneral description of the examples in the table below

Herstellung der erfindungsgemäß als Verdickersystem zu verwendenden Kombinationen aus Monoisocyanat verkapptem wasserlöslichem polymerem Polyetherpolyol und Tensid:Preparation of the combinations of monoisocyanate-capped water-soluble polymeric polyether polyol and surfactant to be used according to the invention as a thickener system:

a) Bei Verwendung eines Tensides:a) When using a surfactant:

Die in der nachstehenden Tabelle angegebenen Gew.-Teile an verkapptem Polyetherpolyol und Tensid werden durch Erwärmen auf etwa 90°C verflüssigt und zu einer homogenen Flüssigkeit verrührt. Diese wird anschließend durch Zugabe von Wasser auf ein 50 Gew.-% Wasser enthaltendes Konzentrat verdünnt.The parts by weight of capped polyether polyol and surfactant given in the table below are liquefied by heating to about 90 ° C. and stirred into a homogeneous liquid. This is then diluted by adding water to a concentrate containing 50% by weight of water.

b. Bei Verwendung von zwei oder mehr Tensiden:b. When using two or more surfactants:

In diesem Fall wird die in der Tabelle angegebenen Menge an verkapptem Polyetherpolyol zunächst nur mit einem der zu verwendenden Tenside in der für dieses Tensid in der Tabelle angegebenen Menge durch Erwärmen auf etwa 90°C verflüssigt und zu einer homogenen Flüssigkeit verrührt. In diese wird anschießend ebenfalls noch bei erhöhter Temperatur das andere bzw. die anderen Tenside in der für dieses bzw. diese Tenside in der Tabelle angegebenen Menge eingerührt, bis ebenfalls wieder eine homogene Flüssigkeit entstanden ist. Auch diese wird wieder durch Zugabe von Wasser auf ein 50 Gew.-% Wasser enthaltendes Konzentrat verdünnt.In this case, the amount of capped polyether polyol given in the table is first liquefied with only one of the surfactants to be used in the amount given for this surfactant in the table by heating to about 90 ° C. and stirred into a homogeneous liquid. The other or the other surfactants in the amount specified for this or these surfactants in the table are then also stirred into this at an elevated temperature until a homogeneous liquid has also formed again. This is again diluted by adding water to a concentrate containing 50% by weight of water.

Die nach a) oder b) erhaltenen Konzentrate werden unter Rühren durch Zugabe von weiterem Wasser auf 100 Gewichtsteile Lösung verdünnt. In einem besonders gekennzeichneten Fall wird mit einem Gemisch aus 80 Gew.-% Wasser, 10 Gew.-% Diethylenglykol und 10 Gew.-% Dipropylenglykol auf 100 Gewichtsteile Lösung verdünnt. Von den so erhaltenen verdickten wäßrigen Lösungen (funktionellen Flüssigkeiten), deren Wassergehalt in Abhängigkeit von der verwendeten Menge an Verdicker-System 91 bis 95,5 Gew.-% beträgt, werden die Viskositäten bei 40 und 50°C und die Änderung der Viskosität bei Einwirkung von Scherkräften (gemäß DIN 51 382; Abänderung: 300 Cyclen anstelle von 30 Cyclen) bestimmt. Die erhaltenen Werte und das aus den Viskositäten bei 40 und 50°C errechnete Viskositätsverhältnis sind in der nachfolgenden Tabelle zusammengestellt. Außerdem ist in der Tabelle in der Spalte "Verdickungsfaktor durch Tensid-Zusatz" der Faktor angegeben, um den die Viskosität des erfindungsgemäß verdickten Wassers höher ist als die Viskosität des nur mit dem verkappten Polyetherpolyol verdickten Wassers (aus diesem Verdickungsfaktor geht die synergistische Wirkung des Tensids in den erfindungsgemäßen Kombinationen hervor).

Figure imgb0002
Figure imgb0003
Figure imgb0004
 The concentrates obtained according to a) or b) are diluted to 100 parts by weight of solution with stirring by adding further water. In a particularly marked case, a mixture of 80% by weight of water, 10% by weight of diethylene glycol and 10% by weight of dipropylene glycol is diluted to 100 parts by weight of solution. Of the thickened aqueous solutions (functional liquids) thus obtained, the water content of which, depending on the amount of thickener system used, is from 91 to 95.5% by weight, the viscosities at 40 and 50 ° C. and the change in viscosity are reduced Influence of shear forces (according to DIN 51 382; modification: 300 cycles instead of 30 cycles) determined. The values obtained and the viscosity ratio calculated from the viscosities at 40 and 50 ° C. are summarized in the table below. In addition, in the table in the column "thickening factor due to the addition of surfactant", the factor by which the viscosity of the water thickened according to the invention is higher than the viscosity of the water thickened only with the capped polyether polyol (this synergistic effect of the surfactant results from this thickening factor in the combinations according to the invention).
Figure imgb0002
Figure imgb0003
Figure imgb0004

Claims (7)

1. Use of combinations of water-soluble polymeric polyether polyols, in which at least 50% of the terminal hydroxyl groups are blocked by reaction with a monoisocyanate incorporating a Cll-C30-alkyl or C12―C30-alkylene radical, and anionic and/or non-ionic surfactants as thickener systems for high water content functional fluids.
2. Use according to Claim 1, characterized in that 0.1 to 3 parts by weight of surfactant are present in the combinations per part by weight of blocked polyether polyol.
3. Use according to Claims 1 and 2, characterized in that such water-soluble polymeric polyether polyols which, is appropriate, contain urethane groups or ester groups, have an average molecular weight of 5,000 to 70,000 and in which 70 to 100% of the terminal hydroxyl groups are blocked by reaction with a monoisocyanate incorporating an C'2-C30-alkyl or C12―C30-alkylene radical are employed in the combinations.
4. Use according to Claims 1 to 3, characterized in that the combinations are used in the form of concentrates whose water content is 30 to 70% by weight, relative to the weight of the concentrate.
5. Use according to Claim 4, characterized in that the concentrates also contain, in addition to water and thickener system, lubricity improvers, metal deactivators, corrosion inhibitors, anti-foam agents, substances to adjust or buffer certain pH values, anti-ageing agents, biocides, identification dyestuffs and/ or glycols.
6. High water content functional fluids containing, apart from water, combinations of water-soluble polymeric polyether polyols, in which at least 50% of the terminal hydroxyl groups are blocked by reaction with a monoisocyanate incorporating a Clg-C30-alkyl or C12-C30-alkylene radical, and anionic and/or non-ionic surfactants and, if appropriate, lubricity improvers, metal deactivators, corrosion inhibitors, anti-foam agents, substances to adjust or buffer certain pH values, anti-ageing agents, biocides, identification dyestuffs and/or glycols.
7. High water content functional fluids according to Claim 6, characterized in that they contain, in addition to water, 3 to 7% by weight of the specified combinations and 0.5 to 3% by weight of lubricity improvers, metal deactivators, corrosion inhibitors, anti-foam agents, substances to adjust or buffer certain pH values, anti-ageing agents, biocides and/or identification dyestuffs, and, if appropriate, up to 25% by weight of monomeric and/or oligomeric glycols.
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JPS6259696A (en) 1987-03-16
US4770804A (en) 1988-09-13
DE3675302D1 (en) 1990-12-06
BR8604275A (en) 1987-05-05
EP0214542A3 (en) 1989-05-10
DE3531915A1 (en) 1987-03-19
CA1288413C (en) 1991-09-03
EP0214542A2 (en) 1987-03-18

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