EP0398153A1 - Aqueous functional liquids containing a poly(meth)acrylat thickening agent - Google Patents
Aqueous functional liquids containing a poly(meth)acrylat thickening agent Download PDFInfo
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- EP0398153A1 EP0398153A1 EP90108785A EP90108785A EP0398153A1 EP 0398153 A1 EP0398153 A1 EP 0398153A1 EP 90108785 A EP90108785 A EP 90108785A EP 90108785 A EP90108785 A EP 90108785A EP 0398153 A1 EP0398153 A1 EP 0398153A1
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- aqueous functional
- weight
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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
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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
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
- C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
- C10M145/14—Acrylate; Methacrylate
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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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/02—Water
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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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
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- 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
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- 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
- C10N2040/20—Metal working
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- 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 water-soluble thickeners based on poly (meth) acrylate, which are used as additives in aqueous functional fluids, such as hydraulic fluids.
- Any liquid substance can be used as a hydraulic fluid for energy transmission in hydrostatic or hydrokinetic systems.
- Common hydraulic fluids are, in particular, those based on mineral oil or based on synthetic products, such as glycols, glycerols, esters or silicone oils.
- Emulsions of water and oils or solutions of organic substances, low molecular weight compounds such as glycols and polymeric compounds in water can be used for special areas of application in which flame retardant hydraulic fluids must be used.
- HWBHF High Water Based Hydraulic Fluids
- thickeners which (1) consist of a water-soluble polymer which contains hydrophobic groups, e.g. an acrylamide / dodecyl acrylate copolymer, and (2) a water-dispersible surface active agent which has hydrophobic groups which associate with the hydrophobic groups of the polymer, the ratio of the water-soluble polymer and the dispersing agent being adjusted so that at Normal conditions Water with a content of 0.5% by weight of the thickener has at least twice the viscosity as untreated water.
- hydrophobic groups e.g. an acrylamide / dodecyl acrylate copolymer
- a water-dispersible surface active agent which has hydrophobic groups which associate with the hydrophobic groups of the polymer
- DE-A 34 04 537 describes copolymers which are composed of unsaturated, optionally subsequently neutralized carboxylic acids, such as acrylic acid or methacrylic acid, a surface-active unsaturated ester, primarily a crotonic acid ester, the alkyl or alkylaryl groups of which are bonded to the unsaturated carboxylic acid in the ester residue via polyglycol ether residues , and one or several acrylic acid or methacrylic acid esters of aliphatic C1 to C18 alcohols are constructed, and which are used in aqueous functional fluids, especially in hydraulic and metal working fluids.
- the concentration of the active polymer substance with sufficient thickening action in the aqueous liquid is 1 to 20% by weight.
- the copolymers proposed there are all based on ethyl acrylate as the main monomer component of the polymeric thickeners.
- Copolymers also based on ethyl acrylate with unsaturated carboxylic acids and (meth) acrylic esters with polyglycol ether residues, which are saturated in the ester residue with alkyl or alkyl aryl esters and which have a thickening effect in aqueous medium when alkali is added, are also described in EP 0 011 806.
- Polymeric thickeners for aqueous hydraulic fluids the polymers from 95 to 100% by weight of water-soluble derivatives of acrylic acid or methacrylic acid, such as especially dialkylaminoalkylamides these are unsaturated acids, and which can also be constructed with 0 to 5% by weight of C6-C18 alkyl esters of acrylic or methacrylic acid, are described in DE-A 34 47 421.
- the prior art thickeners as polymer additives for aqueous functional fluids can only incompletely meet the requirements placed on them for these fields of application, for which both technological properties and economic aspects are responsible.
- the problem of separately adding emulsifiers or dispersants tailored to thickeners was solved by the copolymerization of surface-active unsaturated esters with further monomers to form water-soluble thickeners, but the proportion of these polymerizable emulsifiers in the aqueous functional liquids is as described in the examples from DE-A 34 04 537 and EP 0 11 806 are very high with 5 to 30% by weight.
- alkyl- or alkylaryl polyglycol ether esters of unsaturated carboxylic acids are expensive monomers which hinder the broader use of thickeners thus produced, for example for hydraulic fluids. This price argument also applies to the water-soluble polymers described in DE-A 34 47 421.
- alkali-soluble thickeners are obtained which, with their property profile, can be used as polymer additives for aqueous functional fluids and which, from a qualitative and quantitative point of view, are inexpensive (Meth) acrylic monomers are made.
- the invention relates to aqueous functional fluids, characterized by a content of copolymers based on (meth) acrylate, which consist of the monomers a) 10 to 90% by weight of C1 to C4 alkyl esters of acrylic acid and / or methacrylic acid, b) 5 to 80 wt .-% acrylic acid and / or methacrylic acid and c) 0.1 to 10 wt .-% C8 to C20 alkyl esters of acrylic acid and / or methacrylic acid are built up, and the acid groups before or optionally after the polymerization are partially or completely neutralized by adding bases, the copolymers having average molecular weights M w between 30,000 and 300,000 and in their preparation still other polymerizable compounds having no more than one polymerizable double bond can be used in amounts of 0 to 20 wt .-%.
- the copolymers are produced by free radical polymerization, in particular by solution or, above all, emulsion polymerization. In partial or fully neutralized form, they are called Thickener of aqueous systems with a viscosity-increasing effect, used in particular in aqueous hydraulic and metalworking fluids.
- copolymer in amounts of 5 to 10% by weight, in particular in amounts of 7 to 10% by weight, to the water has the effect that the viscosity of the system at least 10 mm2 / s, measured at 40 degrees C, especially between 50 and 10 mm2 / s at 40 degrees C, advantageously between 25 and 12 mm2 / s at 40 degrees C.
- copolymers according to the invention in their partially or completely neutralized form, surprisingly develop an at least comparable thickening effect in the aqueous systems to be used according to the invention as the polymers known for this from the prior art. Furthermore, the systems according to the invention prove themselves under practical conditions, e.g. when used in pumps or as brake fluids, as shear stable.
- the amounts of the monomer components a), b) and c) can be varied within the claimed ranges. They can preferably be a) 20 to 80% by weight, b) 10 to 70% by weight and c) 0.5 to 5% by weight, with a) 30 to 70% by weight being very particularly preferred. %, b) 20 to 60% by weight and c) 0.5 to 3% by weight.
- copolymer In minor amounts, ie in amounts of 0 to 20% by weight, especially 0 to approx. 10% by weight, of the copolymer, instead of the acrylic and / or methacrylic esters given under a), other monofunctional ⁇ , ⁇ unsaturated, polymerizable compounds, such as styrene, acrylonitrile, (meth) acrylamides or vinyl esters, and the acrylic and / or methacrylic acid specified under b) also other carboxylic acid groups-containing or Polymerizable compounds which form carboxylic acid groups, such as itaconic acid, maleic acid, maleic anhydride or crotonic acid, are used in the preparation of the copolymer.
- other monofunctional ⁇ , ⁇ unsaturated, polymerizable compounds such as styrene, acrylonitrile, (meth) acrylamides or vinyl esters, and the acrylic and / or methacrylic acid specified under b) also other carboxylic acid groups-containing or
- Preferred for use as thickeners for the aqueous functional fluids according to the invention are copolymers of methyl methacrylate, methacrylic acid and C8- to C14-alkyl methacrylates, which are required as additives in relatively small amounts, ie in amounts of about 0.5 to about 10% by weight to give the aqueous systems the rheological and physico-chemical properties necessary for their intended use.
- the (meth) acrylate-based copolymers can be prepared by the usual methods by radical polymerization of the monomers in bulk, in solution or in emulsion. (See H. Rauch-Puntigam, Th. Völker, Acryl- und Methacryl für n-octyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-N-phenyl-N-N-phenyl-N-N-phenyl-N-N-N-phenyl-N-N-(trimethyl)-propylene glycol dimethacryl-propylene glycol dimethacryl-propylene glycol dimethacryl-propyl-N-propyl-propyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-pheny
- water-soluble polymerization initiators which include, for example, alkali or ammonium persulfate or redox systems, and which are used in amounts of from 0.02 to about 2% by weight, based on the comonomers, the emulsion polymerization is carried out at temperatures in the range from about 30 to 100 degrees C. carried out.
- molecular weight regulators during the copolymerization, for which purpose the compounds with radical-transferring properties, preferably those with one or more functional mercaptans, such as e.g. 2-ethylhexylthioglycolate, n-butyl mercaptan, n- or t-dodecyl mercaptan, pentaerythritol tetrathioglycolate, molecular weights can be set in a targeted manner, which allow better handling with such copolymers than with the corresponding unregulated polymers.
- one or more functional mercaptans such as e.g. 2-ethylhexylthioglycolate, n-butyl mercaptan, n- or t-dodecyl mercaptan, pentaerythritol tetrathioglycolate
- a molecular weight setting M w according to the invention of 30,000 to 300,000 g / mol, in particular 50,000 to 300,000 g / mol, especially 50,000 to 200,000 g / mol of the copolymers, is likewise advantageous for improving the shear stability of the thickeners with the highest possible Shear viscosity when used in the aqueous functional fluids.
- the copolymers can be prepared in their free acid form or even in the form of partially or completely neutralized products. They are used according to the invention as salts with bases, in particular as alkali, ammonium or amine salts.
- the aqueous functional liquids according to the invention the copolymers prepared from the monomers a), b) and c) in amounts of 0.2 to 25% by weight, especially in amounts of 0.5 up to 20% by weight, for example in aqueous hydraulic fluids and in particular in amounts of 0.3 to 10% by weight, for example in aqueous metalworking fluids.
- the functional additives according to the invention can also be admixed with the known additives that are usually used, such as dispersants, antiwear agents, rust inhibitors and optionally biocides, in the usual amounts.
- An emulsion consisting of: 1 160.0 g methyl methacrylate 800.0 g methacrylic acid 40.0 g alkyl methacrylate (mixture of isomeric isodecyl alcohols, average C number 10) 30.0 g of triisobutylphenol polyglycol ether sulfate Na salt 20.0 g of 2-ethylhexylthioglycolate and 1 880.0 g of demineralized water, added within 3 hours.
- the batch After the end of the feed, the batch is cooled to room temperature; 1.25 g of 1.4 diisopropylbenzene hydroperoxide and 0.99 g of sodium hydroxymethyl sulfinate are added at 70 degrees C. Then the dispersion is filtered. The pH of the approx. 40% dispersion is 2.6.
- the aqueous solution diluted to 10% by weight with NaOH after neutralization has a kinematic viscosity (measured according to DIN 51 562) at 40 degrees C of 13.1 mm2 / s, at 50 degrees C 10.5 mm2 / s, at 60 degrees C 9.0 mm2 / s and at 70 degrees C 8.0 mm2 / s.
- An aqueous solution containing 5% by weight of solid shows a kinematic viscosity of 4.5 mm2 / s at 40 ° C, an 8% by weight solution 11.0 mm2 / s.
- An emulsion consisting of: 417.6 g methyl methacrylate 288.0 g methacrylic acid 14.4 g dodecyl methacrylate 10.8 g of triisobutylphenol polyglycol ether sulfate Na salt 7.2 g of 2-ethylhexylthioglycolate and 675.0 g demineralized water, added within 3 hours.
- the batch After the end of the feed, the batch is cooled to room temperature; 0.45 g of 1.4 diisopropylbenzene hydroperoxide and 0.36 g of sodium hydroxymethyl sulfinate are added at 70 degrees C. Then the dispersion is filtered. The pH of the approx. 40% dispersion is 2.8.
- the dispersion preparation and preparation takes place as described in Example 1, with the difference that an inlet consisting of: 1 160.0 g methyl methacrylate 800.0 g methacrylic acid 40.0 g alkyl methacrylate (mixture of isomeric isodecyl alcohols, average C number 10) 30.0 g of triisobutylphenol polyglycol ether sulfate Na salt 2.0 g of 2-ethylhexyl thioglycolate and 1 850.0 g of demineralized water, is added within 3 hours.
- the pH of the approx. 40% dispersion is 2.6.
- This polymer is particularly suitable for thickening metalworking fluids.
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Die Erfindung betrifft wasserlösliche Verdickungsmittel auf Poly(meth)acrylat-Basis, die als Zusätze in wäßrigen Funktionsflüssigkeiten, wie Hydraulikflüssigkeiten verwendet werden.The invention relates to water-soluble thickeners based on poly (meth) acrylate, which are used as additives in aqueous functional fluids, such as hydraulic fluids.
Für die Energieübertragung in hydrostatischen oder hydrokinetischen Systemen kann jeder flüssige Stoff als Hydraulikflüssigkeit verwendet werden. Gebräuchliche Hydraulikflüssigkeiten sind insbesondere solche auf Basis Mineralöl oder auf Basis synthetischer Produkte, wie Glykole, Glycerine, Ester oder Siliconöle. Der Verwendung von Wasser als billigster Hydraulikflüssigkeit, das ursprünglich auch dazu eingesetzt wurde, steht seine Korrosivität und seine niedere Viskosität entgegen. Für spezielle Einsatzgebiete, bei denen schwerentflammbare Hydraulikflüssigkeiten verwendet werden müssen, können Emulsionen von Wasser und Ölen oder Lösungen von organischen Stoffen, niedermolekularen Verbindungen, wie z.B. Glykole, und polymeren Verbindungen, in Wasser eingesetzt werden.
Zeiten der Ölverknappung und weiter die Gefahren der Umweltverschmutzung und Umweltgefährdung bei Leckagen von mehr oder weniger großen auf hydraulischer Basis arbeitenden Maschinen beschleunigen die Entwicklung von Hydraulikflüssigkeiten mit hohem Wassergehalt, d.h. mit einem Wassergehalt von 80 bis 95 %, den sogenannten High Water Based Hydraulic Fluids (HWBHF). Dabei gewannen insbesondere Hydraulikflüssigkeiten auf der Basis von Wasser, die polymere Verdickungsmittel enthalten, an Bedeutung (Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 12, page 715, 3rd edition).Any liquid substance can be used as a hydraulic fluid for energy transmission in hydrostatic or hydrokinetic systems. Common hydraulic fluids are, in particular, those based on mineral oil or based on synthetic products, such as glycols, glycerols, esters or silicone oils. The use of water as the cheapest hydraulic fluid, which was originally used for this purpose, stands in the way of its corrosiveness and low viscosity. Emulsions of water and oils or solutions of organic substances, low molecular weight compounds such as glycols and polymeric compounds in water can be used for special areas of application in which flame retardant hydraulic fluids must be used.
Times of oil shortage and further the dangers of pollution and environmental risks in the event of leakages of more or less large machines working on a hydraulic basis accelerate the development of hydraulic fluids with a high water content, ie with a water content of 80 to 95%, the so-called High Water Based Hydraulic Fluids (HWBHF). Hydraulic fluids based on water, which contain polymeric thickeners, became particularly important (Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 12, page 715, 3rd edition).
Aus dem europäischen Patent 0 057 875 sind Verdickungsmittel bekannt, die (1) aus einem wasserlöslichen Polymeren, das hydrophobe Gruppen eingebaut enthält, z.B. ein Acrylamid/Dodecylacrylat-Copolymerisat, und (2) einem in Wasser dispergierbaren oberflächenaktivem Mittel, das hydrophobe Gruppen besitzt, die sich mit den hydrophoben Gruppen des Polymeren assoziieren, bestehen, wobei das Verhältnis des wasserlöslichen Polymeren und des Dispersionsmittels so eingestellt ist, daß bei Normalbedingungen Wasser mit einem Gehalt von 0,5 Gew.-% an dem Verdickungsmittel mindestens die doppelte Viskosität wie unbehandeltes Wasser aufweist.From European patent 0 057 875 thickeners are known which (1) consist of a water-soluble polymer which contains hydrophobic groups, e.g. an acrylamide / dodecyl acrylate copolymer, and (2) a water-dispersible surface active agent which has hydrophobic groups which associate with the hydrophobic groups of the polymer, the ratio of the water-soluble polymer and the dispersing agent being adjusted so that at Normal conditions Water with a content of 0.5% by weight of the thickener has at least twice the viscosity as untreated water.
Die DE-A 34 04 537 beschreibt Copolymerisate, die aus ungesättigten, gegebenenfalls nachfolgend neutralisierten Carbonsäuren, wie z.B. Acrylsäure oder Methacrylsäure, einem grenzflächenaktiven ungesättigten Ester, vornehmlich eines Crotonsäureesters, dessen Alkyl- bzw. Alkylarylgruppen im Esterrest über Polyglykoletherreste an die ungesättigte Carbonsäure gebunden sind, und einem oder mehreren Acrylsäure- oder Methacrylsäureestern aliphatischer C₁- bis C₁₈-Alkohole aufgebaut sind, und die in wäßrigen Funktionsflüssigkeiten, insbesondere in Hydraulik- und Metallbearbeitungsflüssigkeiten, Verwendung finden. Die Konzentration der Polymerwirksubstanz mit ausreichender Verdickerwirkung in der wäßrigen Flüssigkeit liegt bei 1 - 20 Gew.-%.DE-A 34 04 537 describes copolymers which are composed of unsaturated, optionally subsequently neutralized carboxylic acids, such as acrylic acid or methacrylic acid, a surface-active unsaturated ester, primarily a crotonic acid ester, the alkyl or alkylaryl groups of which are bonded to the unsaturated carboxylic acid in the ester residue via polyglycol ether residues , and one or several acrylic acid or methacrylic acid esters of aliphatic C₁ to C₁₈ alcohols are constructed, and which are used in aqueous functional fluids, especially in hydraulic and metal working fluids. The concentration of the active polymer substance with sufficient thickening action in the aqueous liquid is 1 to 20% by weight.
Die dort vorgeschlagenen Copolymerisate sind, wie die zahlreichen Beispiele ausweisen, alle auf Basis Ethylacrylat als dem Hauptmonomerbestandteil der polymeren Verdickungsmittel hergestellt.As the numerous examples show, the copolymers proposed there are all based on ethyl acrylate as the main monomer component of the polymeric thickeners.
Copolymerisate, ebenfalls auf Ethylacrylat-Basis mit ungesättigten Carbonsäuren und (Meth)acrylestern mit Polyglykoletherresten, die im Esterrest mit Alkyl- bzw. Alkylarylestern abgesättigt sind, und die in wäßrigem Medium bei Alkalizugabe verdickend wirken, sind auch in der EP 0 011 806 beschrieben.Copolymers, also based on ethyl acrylate with unsaturated carboxylic acids and (meth) acrylic esters with polyglycol ether residues, which are saturated in the ester residue with alkyl or alkyl aryl esters and which have a thickening effect in aqueous medium when alkali is added, are also described in EP 0 011 806.
Ihr Aufbau mit relativ kleinen Mengen einpolymerisierter grenzflächenaktiver Ester bewirkt eine Assoziation der in Wasser gelösten Polymermoleküle, so daß schon mit relativ niedermolekularen Polymeren (Mw ca. 100 000) erhebliche Verdickerwirkungen erzielt werden. Solche Verdickungsmittel werden auch als assoziative Verdicker bezeichnet.Their construction with relatively small amounts of polymerized surface-active esters brings about an association of the polymer molecules dissolved in water, so that considerable thickening effects are achieved even with relatively low molecular weight polymers (Mw approx. 100,000). Such thickeners are also known as associative thickeners.
Polymere Verdickungsmittel für wäßrige Hydraulikflüssigkeiten, die Polymere aus 95 bis 100 Gew.-% wasserlöslicher Derivate der Acrylsäure bzw. der Methacrylsäure, wie vor allem von Dialkylaminoalkylamiden dieser ungesättigten Säuren sind, und die noch mit 0 bis 5 Gew.-% C₆-C₁₈-Alkylestern der Acryl- bzw. Methacrylsäure aufgebaut sein können, werden in der DE-A 34 47 421 beschrieben.Polymeric thickeners for aqueous hydraulic fluids, the polymers from 95 to 100% by weight of water-soluble derivatives of acrylic acid or methacrylic acid, such as especially dialkylaminoalkylamides these are unsaturated acids, and which can also be constructed with 0 to 5% by weight of C₆-C₁₈ alkyl esters of acrylic or methacrylic acid, are described in DE-A 34 47 421.
Die Verdickungsmittel des Standes der Technik als Polymerzusätze für wäßrige Funktionsflüssigkeiten, wie z.B. Hydraulikflüssigkeiten oder Metallbearbeitungsflüssigkeiten können die an sie für diese Anwendungsbereiche gestellten Anforderungen nur unvollständig erfüllen, wofür sowohl technologische Eigenschaften als auch ökonomische Gesichtspunkte verantwortlich sind. Durch die Copolymerisation von grenzflächenaktiven ungesättigten Estern mit weiteren Monomeren zu wasserlöslichen Verdickungsmitteln wurde zwar das Problem des gesonderten Zusetzens von auf Verdickungsmittel zugeschnittenen Emulgier- oder Dispergiermitteln gelöst, jedoch ist der Anteil dieser polymerisierbaren Emulgiermittel in den wäßrigen Funktionsflüssigkeiten, wie aus den Beispielen von DE-A 34 04 537 und EP 0 11 806 hervorgeht mit 5 bis 30 Gew.-% sehr hoch. Die Alkyl- bzw. Alkylarylpolyglykoletherester ungesättigter Carbonsäuren sind teure Monomere, die eine wünschenswert breitere Anwendung damit hergestellter Verdickungsmittel für z.B. Hydraulikflüssigkeiten behindern. Dieses preisliche Argument gilt auch für die in der DE-A 34 47 421 beschriebenen wasserlöslichen Polymeren.The prior art thickeners as polymer additives for aqueous functional fluids, such as hydraulic fluids or metalworking fluids, can only incompletely meet the requirements placed on them for these fields of application, for which both technological properties and economic aspects are responsible. The problem of separately adding emulsifiers or dispersants tailored to thickeners was solved by the copolymerization of surface-active unsaturated esters with further monomers to form water-soluble thickeners, but the proportion of these polymerizable emulsifiers in the aqueous functional liquids is as described in the examples from DE-A 34 04 537 and EP 0 11 806 are very high with 5 to 30% by weight. The alkyl- or alkylaryl polyglycol ether esters of unsaturated carboxylic acids are expensive monomers which hinder the broader use of thickeners thus produced, for example for hydraulic fluids. This price argument also applies to the water-soluble polymers described in DE-A 34 47 421.
Überraschenderweise wurde gefunden, daß durch Einbau von langkettigen Alkylmethacrylaten in herkömmliche, marktgängige und billige wasserlösliche Copolymerisate auf (Meth)acrylatbasis, alkalilösliche Verdicker erhalten werden, die mit ihrem Eigenschaftsprofil als Polymerzusätze für wäßrige Funktionsflüssigkeiten verwendbar sind und die aus qualitativer und quantitativer Sicht, aus preiswerten (Meth)acrylmonomeren hergestellt sind.Surprisingly, it was found that by incorporating long-chain alkyl methacrylates into conventional, commercially available and inexpensive water-soluble copolymers based on (meth) acrylate, alkali-soluble thickeners are obtained which, with their property profile, can be used as polymer additives for aqueous functional fluids and which, from a qualitative and quantitative point of view, are inexpensive (Meth) acrylic monomers are made.
Die Erfindung betrifft wäßrige Funktionsflüssigkeiten, gekennzeichnet durch einen Gehalt an Copolymerisaten auf (Meth)Acrylatbasis, die aus den Monomeren
a) 10 bis 90 Gew.-% C₁ bis C₄-Alkylestern der Acrylsäure und/oder Methacrylsäure,
b) 5 bis 80 Gew.-% Acrylsäure und/oder Methacrylsäure und
c) 0,1 bis 10 Gew.-% C₈- bis C₂₀-Alkylestern der Acrylsäure und/oder Methacrylsäure
aufgebaut sind, und deren Säuregruppen vor oder gegebenenfalls nach der Polymerisation teilweise oder vollständig durch Zusatz von Basen neutralisiert sind, wobei die Copolymerisate mittlere Molmassen Mw zwischen 30 000 und 300 000 besitzen und bei deren Herstellung noch andere polymerisierbare Verbindungen mit nicht mehr als einer polymerisierbaren Doppelbindung in Mengen von 0 bis 20 Gew.-% mitverwendet werden können.The invention relates to aqueous functional fluids, characterized by a content of copolymers based on (meth) acrylate, which consist of the monomers
a) 10 to 90% by weight of C₁ to C₄ alkyl esters of acrylic acid and / or methacrylic acid,
b) 5 to 80 wt .-% acrylic acid and / or methacrylic acid and
c) 0.1 to 10 wt .-% C₈ to C₂₀ alkyl esters of acrylic acid and / or methacrylic acid
are built up, and the acid groups before or optionally after the polymerization are partially or completely neutralized by adding bases, the copolymers having average molecular weights M w between 30,000 and 300,000 and in their preparation still other polymerizable compounds having no more than one polymerizable double bond can be used in amounts of 0 to 20 wt .-%.
Die Copolymerisate werden durch radikalisch initiierte Polymerisation, insbesondere durch Lösungs- oder vor allem durch Emulsionspolymerisation hergestellt. In teilweiser bzw. vollständiger neutralisierter Form werden sie als Verdicker wäßriger Systeme mit viskositätserhöhender Wirkung, insbesondere in wäßrigen Hydraulik- und Metallbearbeitungsflüssigkeiten eingesetzt.The copolymers are produced by free radical polymerization, in particular by solution or, above all, emulsion polymerization. In partial or fully neutralized form, they are called Thickener of aqueous systems with a viscosity-increasing effect, used in particular in aqueous hydraulic and metalworking fluids.
Der Copolymerzusatz in Mengen von 5 bis 10 Gew.-%, insbesondere in Mengen von 7 bis 10 Gew.-%, zum Wasser bewirkt, daß dadurch die Viskosität des Systems bei mindestens 10 mm²/s, gemessen bei 40 Grad C, vor allem zwischen 50 und 10 mm²/s bei 40 Grad C, vorteilhaft zwischen 25 und 12 mm²/s bei 40 Grad C, zu liegen kommt.The addition of copolymer in amounts of 5 to 10% by weight, in particular in amounts of 7 to 10% by weight, to the water has the effect that the viscosity of the system at least 10 mm² / s, measured at 40 degrees C, especially between 50 and 10 mm² / s at 40 degrees C, advantageously between 25 and 12 mm² / s at 40 degrees C.
Die erfindungsgemäßen Copolymerisate entfalten in ihrer teilweisen oder vollständig neutralisierten Form in den erfindungsgemäß zu verwendenden wäßrigen Systemen überraschenderweise eine mindestens vergleichbare Verdickerwirkung wie die aus dem Stand der Technik dafür bekannten Polymeren. Weiterhin erweisen sich die erfindungsgemäßen Systeme unter praktischen Bedingungen, z.B. beim Einsatz in Pumpen oder als Bremsflüssigkeiten, als scherstabil.The copolymers according to the invention, in their partially or completely neutralized form, surprisingly develop an at least comparable thickening effect in the aqueous systems to be used according to the invention as the polymers known for this from the prior art. Furthermore, the systems according to the invention prove themselves under practical conditions, e.g. when used in pumps or as brake fluids, as shear stable.
Für die Herstellung der Copolymerisate werden als Monomere verwendet:
- a) C₁- bis C₄-Alkylester der Acrylsäure und/oder Methacrylsäure, wie beispielsweise Methylacrylat, Isopropylmethacrylat, n-Butylacrylat, n-Butylmethacrylat, Isobutylacrylat, vor allem Ethylacrylat und Methylmethacrylat und insbesondere Methylmethacrylat,
- b) Acrylsäure und/oder Methacrylsäure, vor allem Methacrylsäure in der Säureform und/oder als Salze und
- c) C₈- bis C₂₀-, insbesondere C₁₀- bis C₁₈-Alkylester der Acrylsäure und/oder Methacrylsäure, wie beispielsweise n-Octylmethacrylat, 2-Ethylhexylacrylat bzw. -methacrylat, n-Decylmethacrylat, n-Decylacrylat, Isodecylmethacrylat, Dodecylmethacrylat, Octadecylmethacrylat, Octadecylacrylat, wobei die für die Esterherstellung verwendeten langkettigen Alkohole bevorzugt als synthetische Alkohole eingesetzt werden, und die Gemische verschiedener Alkohole im C₈-bis C₂₀-Bereich darstellen. Solche Alkohole sind im Handel beispielsweise unter den Markennamen ®Lorol, ®Alfol, ®Dobanol bekannt. Ein beispielsweise für die Herstellung von Isodecylmethacrylat brauchbarer technischer Alkohol, ist ein Gemisch aus isomeren Isodecylalkoholen mit mittleren C-Zahlen von 9,9 bis 10,3.
- a) C₁ to C₄ alkyl esters of acrylic acid and / or methacrylic acid, such as methyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, especially ethyl acrylate and methyl methacrylate and especially methyl methacrylate,
- b) acrylic acid and / or methacrylic acid, especially methacrylic acid in the acid form and / or as salts and
- c) C₈ to C₂₀, especially C₁₀ to C₁₈ alkyl esters of acrylic acid and / or methacrylic acid, such as n-octyl methacrylate, 2-ethylhexyl acrylate or methacrylate, n-decyl methacrylate, n-decyl acrylate, isodecyl methacrylate, dodecyl methacrylate, octadecyl methacrylate Octadecyl acrylate, the long-chain alcohols used for the ester production preferably used as synthetic alcohols, and the mixtures of various alcohols in the C₈ to C₂₀ range. Such alcohols are known commercially, for example, under the brand names ®Lorol, ®Alfol, ®Dobanol. A technical alcohol that can be used, for example, for the production of isodecyl methacrylate is a mixture of isomeric isodecyl alcohols with average C numbers from 9.9 to 10.3.
Zur Herstellung der erfindungsgemäß zu verwendenden Copolymeren können die Mengen der Monomerkomponenten a), b) und c) in den beanspruchten Bereichen variiert werden. Sie können vorzugsweise bei a) 20 bis 80 Gew.-%, b) 10 bis 70 Gew.-% und c) 0,5 bis 5 Gew.-% betragen, wobei ganz besonders bevorzugt sind für a) 30 bis 70 Gew.-%, b) 20 bis 60 Gew.-% und c) 0,5 bis 3 Gew.-%.To produce the copolymers to be used according to the invention, the amounts of the monomer components a), b) and c) can be varied within the claimed ranges. They can preferably be a) 20 to 80% by weight, b) 10 to 70% by weight and c) 0.5 to 5% by weight, with a) 30 to 70% by weight being very particularly preferred. %, b) 20 to 60% by weight and c) 0.5 to 3% by weight.
In untergeordneten Mengen, d.h. in Mengen von 0 bis 20 Gew.-%, vor allem von 0 bis ca. 10 Gew.-% des Copolymerisats können an Stelle der unter a) angegebenen Acryl -und/oder Methacrylester auch andere monofunkionell α,β-ungesättigte, polymerisierbare Verbindungen, wie z.B. Styrol, Acrylnitril, (Meth)acrylamide oder Vinylester, und der unter b) angegebenen Acryl- und/oder Methacrylsäure auch andere Carbonsäuregruppen-haltige bzw. Carbonsäuregruppen-bildende polymerisierbare Verbindungen, wie Itakonsäure, Maleinsäure, Maleinsäureanhydrid oder Crotonsäure, bei der Herstellung des Copolymerisates eingesetzt werden.
Bevorzugt für die Verwendung als Verdickungsmittel für die erfindungsgemäßen wäßrigen Funktionsflüssigkeiten, sind Copolymerisate aus Methylmethacrylat, Methacrylsäure und C₈- bis C₁₄-Alkylmethacrylaten, die als Zusätze in relativ geringen Mengen, d.h. in Mengen von etwa 0,5 bis etwa 10 Gew.-% benötigt werden, um den wäßrigen Systemen, die für ihren Verwendungszweck notwendigen rheologischen und physikalisch-chemischen Eigenschaften zu verleihen.In minor amounts, ie in amounts of 0 to 20% by weight, especially 0 to approx. 10% by weight, of the copolymer, instead of the acrylic and / or methacrylic esters given under a), other monofunctional α, β unsaturated, polymerizable compounds, such as styrene, acrylonitrile, (meth) acrylamides or vinyl esters, and the acrylic and / or methacrylic acid specified under b) also other carboxylic acid groups-containing or Polymerizable compounds which form carboxylic acid groups, such as itaconic acid, maleic acid, maleic anhydride or crotonic acid, are used in the preparation of the copolymer.
Preferred for use as thickeners for the aqueous functional fluids according to the invention are copolymers of methyl methacrylate, methacrylic acid and C₈- to C₁₄-alkyl methacrylates, which are required as additives in relatively small amounts, ie in amounts of about 0.5 to about 10% by weight to give the aqueous systems the rheological and physico-chemical properties necessary for their intended use.
Die Herstellung der Copolymerisate auf (Meth)Acrylat-Basis kann nach den üblichen Verfahren durch radikalische Polymerisation der Monomeren in Substanz, in Lösung oder in Emulsion vorgenommen werden. (Vgl. H. Rauch-Puntigam, Th. Völker, Acryl- und Methacrylverbindungen, Springer-Verlag, Berlin, 1967, insb. Seiten 203, 207, 230 - 233, 238, 327).
Bevorzugt ist die Herstellung durch Emulsionspolymerisation. Diese wird in Gegenwart von ionischen oder nichtionischen Emulgatoren zur Emulgierung der Monomeren und zur Stabilisierung des entstehenden Polymerlatex durchgeführt. Mit wasserlöslichen Polymerisationsinitiatoren, wozu beispielsweise Alkali- oder Ammoniumpersulfat oder Redoxsysteme gehören, und die in Mengen von 0,02 bis etwa 2 Gew.-% bezogen auf die Comonomeren angewandt werden, wird die Emulsionspolymerisation bei Temperaturen im Bereich von etwa 30 bis 100 Grad C durchgeführt.The (meth) acrylate-based copolymers can be prepared by the usual methods by radical polymerization of the monomers in bulk, in solution or in emulsion. (See H. Rauch-Puntigam, Th. Völker, Acryl- und Methacrylverbindungen, Springer-Verlag, Berlin, 1967, esp. Pages 203, 207, 230 - 233, 238, 327).
Production by emulsion polymerization is preferred. This is carried out in the presence of ionic or nonionic emulsifiers to emulsify the monomers and to stabilize the resulting polymer latex. With water-soluble polymerization initiators, which include, for example, alkali or ammonium persulfate or redox systems, and which are used in amounts of from 0.02 to about 2% by weight, based on the comonomers, the emulsion polymerization is carried out at temperatures in the range from about 30 to 100 degrees C. carried out.
Durch die Mitverwendung von Molekulargewichtsreglern während der Copolymerisation, wozu die Verbindungen mit radikalübertragenden Eigenschaften, vorzugsweise solche ein- oder mehrfunktioneller Mercaptane, wie z.B. 2-Ethylhexylthioglycolat, n-Butylmercaptan, n- bzw. t-Dodecylmercaptan, Pentaerythrittetrathioglycolat, gehören, lassen sich gezielt Molekulargewichte einstellen, die ein besseres Handling mit solchen Copolymerisaten erlauben, als mit den entsprechenden ungeregelten Polymerisaten. Eine erfindungsgemäß entsprechende Molekulargewichtseinstellung Mw von 30 000 bis 300 000 g/mol, insbesondere 50 000 bis 300 000 g/mol, vor allem 50 000 bis 200 000 g/mol der Copolymerisate, ist ebenso vorteilhaft zur Verbesserung der Scherstabilität der Verdickungsmittel bei möglichst hoher Scherviskosität bei der Verwendung in den wäßrigen Funktionsflüssigkeiten. Dies hat weiter den Vorteil, daß der assoziative Verdicker zur Erzielung der gewünschten Funktionen in den erfindungsgemäßen Funktionsflüssigkeiten in geringen Mengen benötigt wird.Through the use of molecular weight regulators during the copolymerization, for which purpose the compounds with radical-transferring properties, preferably those with one or more functional mercaptans, such as e.g. 2-ethylhexylthioglycolate, n-butyl mercaptan, n- or t-dodecyl mercaptan, pentaerythritol tetrathioglycolate, molecular weights can be set in a targeted manner, which allow better handling with such copolymers than with the corresponding unregulated polymers. A molecular weight setting M w according to the invention of 30,000 to 300,000 g / mol, in particular 50,000 to 300,000 g / mol, especially 50,000 to 200,000 g / mol of the copolymers, is likewise advantageous for improving the shear stability of the thickeners with the highest possible Shear viscosity when used in the aqueous functional fluids. This has the further advantage that the associative thickener is required in small amounts to achieve the desired functions in the functional fluids according to the invention.
Die Copolymerisate können in ihrer freien Säureform hergestellt werden oder auch schon in Form teilweiser oder vollständig neutralisierter Produkte. Zur erfindungsgemäßen Anwendung kommen sie als Salze mit Basen, insbesondere als Alkali-, Ammonium- oder Amminsalze.
Zur Erzielung eines ausreichenden bis guten viskositätserhöhenden Effekts müssen die erfindungsgemäßen wäßrigen Funktionsflüssigkeiten, die aus den Monomeren a), b), und c) hergestellten Copolymerisate in Mengen von 0,2 bis 25 Gew.-%, vor allem in Mengen von 0,5 bis 20 Gew.-%, z.B. in wäßrigen Hydraulikflüssigkeiten und in insbesondere in Mengen von 0,3 bis 10 Gew.-%, z.B. in wäßrigen Metallbearbeitungsflüssigkeiten, enthalten.The copolymers can be prepared in their free acid form or even in the form of partially or completely neutralized products. They are used according to the invention as salts with bases, in particular as alkali, ammonium or amine salts.
To achieve a sufficient to good viscosity-increasing effect, the aqueous functional liquids according to the invention, the copolymers prepared from the monomers a), b) and c) in amounts of 0.2 to 25% by weight, especially in amounts of 0.5 up to 20% by weight, for example in aqueous hydraulic fluids and in particular in amounts of 0.3 to 10% by weight, for example in aqueous metalworking fluids.
Den erfindungsgemäßen Funktionsflüssigkeiten können auch noch die sonst üblicherweise mitverwendeten bekannten Additive, wie vor allem Dispergiermittel, Antiverschleißmittel, Rostinhibitoren und gegebenenfalls Biocide, in den dafür üblichen Mengen zugesetzt werden.The functional additives according to the invention can also be admixed with the known additives that are usually used, such as dispersants, antiwear agents, rust inhibitors and optionally biocides, in the usual amounts.
Molekulargewichtsermittlungen an den erfindungsgemäß zu verwendenden Copolymerisaten sind bisher direkt nicht oder nur auf indirektem Wege möglich. Die in den Beispielen angegebenen Molekulargewichte wurden durch Analogieschluß an reinen Methylmethacrylatpolymerisaten gleicher Herstellungsweise abgeschätzt.Molecular weight determinations of the copolymers to be used according to the invention have hitherto not been possible directly or only indirectly. The molecular weights given in the examples were estimated by analogy with pure methyl methacrylate polymers of the same preparation.
In einem 5 l Reaktionsgefäß, ausgerüstet mit Rückflußkühler, Rührwerk und Zulaufgefäß, werden 0,06 g Triisobutylphenolpolyglykolethersulfat-Na-Salz (Ethoxilierungsgrad 7) und 1,2 g Ammoniumperoxodisulfat in 120 g entsalztem Wasser bei 20 Grad C gelöstIn a 5 l reaction vessel equipped with a reflux condenser, stirrer and feed vessel, 0.06 g of triisobutylphenol polyglycol ether sulfate Na salt (degree of ethoxylation 7) and 1.2 g of ammonium peroxodisulfate are dissolved in 120 g of demineralized water at 20 ° C.
In diese Lösung wird bei 80 Grad C unter Rühren eine Emulsion, bestehend aus:
1 160,0 g Methylmethacrylat
800,0 g Methacrylsäure
40,0 g Alkylmethacrylat (Gemisch isomerer Isodecylalkohole, mittlerer C-Zahl 10)
30,0 g Triisobutylphenolpolyglykolethersulfat-Na-Salz
20,0 g 2-Ethylhexylthioglykolat und 1 880,0 g entsalztes Wasser,
innerhalb von 3 Stunden zugegeben.An emulsion consisting of:
1 160.0 g methyl methacrylate
800.0 g methacrylic acid
40.0 g alkyl methacrylate (mixture of isomeric isodecyl alcohols, average C number 10)
30.0 g of triisobutylphenol polyglycol ether sulfate Na salt
20.0 g of 2-ethylhexylthioglycolate and 1 880.0 g of demineralized water,
added within 3 hours.
Nach Zulaufende wird der Ansatz auf Raumtemperatur abgekühlt; hierbei erfolgt bei 70 Grad C die Zugabe von 1,25 g 1,4 Diisopropylbenzolhydroperoxid und 0,99 g Natriumhydroxymethylsulfinat. Dann wird die Dispersion filtriert. Der pH der ca. 40 %igen Dispersion beträgt 2,6.After the end of the feed, the batch is cooled to room temperature; 1.25 g of 1.4 diisopropylbenzene hydroperoxide and 0.99 g of sodium hydroxymethyl sulfinate are added at 70 degrees C. Then the dispersion is filtered. The pH of the approx. 40% dispersion is 2.6.
Molekulargewicht des Copolymerisats: ca. 50 000 g/mol.Molecular weight of the copolymer: approx. 50,000 g / mol.
Die nach Neutralisation mit NaOH auf 10 Gew.-% Feststoff verdünne wäßrige Lösung hat eine kinematische Viskosität (gemessen nach DIN 51 562) bei 40 Grad C von 13,1 mm²/s, bei 50 Grad C 10,5 mm²/s, bei 60 Grad C 9,0 mm²/s und bei 70 Grad C noch 8,0 mm²/s. Eine 5 Gew.-% Feststoff enthaltende wäßrige Lösung zeigt bei 40 Grad C eine kinematische Viskosität von 4,5 mm²/s, eine 8 Gew.-%ige Lösung 11,0 mm²/s. Der Viskositätsverlust einer 10 %igen wäßrigen Lösung beträgt bei einem 14-stündigen Schertest bei 48 Grad C in einer Zahnradpumpe (Zahnradpumpe Tyrone Mobil Master P16-45, 14,4 cm³/w, Füllmenge: 3,5 l, Fördermenge: 15 l/min, Zyklen: 3 600, Druck: 70 bar, Temp: 48 Grad C, Zusatz von 5 Gew.-% eines handelsüblichen HWBF-Verschleißschutzadditivpakets auf Mikroemulsionsbasis) nur 10 %.The aqueous solution diluted to 10% by weight with NaOH after neutralization has a kinematic viscosity (measured according to DIN 51 562) at 40 degrees C of 13.1 mm² / s, at 50 degrees C 10.5 mm² / s, at 60 degrees C 9.0 mm² / s and at 70 degrees C 8.0 mm² / s. An aqueous solution containing 5% by weight of solid shows a kinematic viscosity of 4.5 mm² / s at 40 ° C, an 8% by weight solution 11.0 mm² / s. The viscosity loss of a 10% aqueous solution in a 14-hour shear test at 48 degrees C in a gear pump (gear pump Tyrone Mobil Master P16-45, 14.4 cm³ / w, filling quantity: 3.5 l, delivery quantity: 15 l / min, cycles: 3,600, pressure: 70 bar, temp: 48 degrees C, addition of 5% by weight of a commercially available HWBF wear protection additive package based on microemulsions) only 10%.
In einem 2 l Reaktionsgefäß, ausgerüstet mit Rückflußkühler, Rührwerk und Zulaufgefäß, werden 0,02 g Triisobutylphenolpolyglykolethersulfat-Na-Salz (Ethoxilierungsgrad 7) und 0,22 g Ammoniumperoxodisulfat in 430 g entsalztem Wasser bei 20 Grad C gelöst.0.02 g of triisobutylphenol polyglycol ether sulfate Na salt (degree of ethoxylation 7) and 0.22 g of ammonium peroxodisulfate are dissolved in 430 g of deionized water at 20 ° C. in a 2 l reaction vessel equipped with a reflux condenser, stirrer and feed vessel.
In diese Lösung wird bei 80 Grad C unter Rühren eine Emulsion, bestehend aus:
417,6 g Methylmethacrylat
288,0 g Methacrylsäure
14,4 g Dodecylmethacrylat
10,8 g Triisobutylphenolpolyglykolethersulfat-Na-Salz
7,2 g 2-Ethylhexylthioglykolat und
675,0 g entsalztes Wasser,
innerhalb von 3 Stunden zugegeben.An emulsion consisting of:
417.6 g methyl methacrylate
288.0 g methacrylic acid
14.4 g dodecyl methacrylate
10.8 g of triisobutylphenol polyglycol ether sulfate Na salt
7.2 g of 2-ethylhexylthioglycolate and
675.0 g demineralized water,
added within 3 hours.
Nach Zulaufende wird der Ansatz auf Raumtemperatur abgekühlt; hierbei erfolgt bei 70 Grad C die Zugabe von 0,45 g 1,4 Diisopropylbenzolhydroperoxid und 0,36 g Natriumhydroxymethylsulfinat. Dann wird die Dispersion filtriert. Der pH der ca. 40 %igen Dispersion beträgt 2,8.After the end of the feed, the batch is cooled to room temperature; 0.45 g of 1.4 diisopropylbenzene hydroperoxide and 0.36 g of sodium hydroxymethyl sulfinate are added at 70 degrees C. Then the dispersion is filtered. The pH of the approx. 40% dispersion is 2.8.
Molekulargewicht des Copolymerisats: ca. 30 000 bis 50 000 g/mol.Molecular weight of the copolymer: approx. 30,000 to 50,000 g / mol.
Die Prüfung des Copolymeren zur Verwendung als HWBHF-Verdicker von 10 Gew.-% neutralisiertem enthaltenden wäßrigen Lösungen bei Temperaturen von 40, 50 und Grad C ergab kinematische Viskositäten von 15 mm²/s bis 10 mm²/s.
Der Viskositätsverlust einer 10 %igen wäßrigen Lösung unter den in Beispiel 1 genannten Bedingungen beträgt 8 %.Examination of the copolymer for use as an HWBHF thickener containing 10% by weight neutralized aqueous solutions at temperatures of 40, 50 and degrees C showed kinematic viscosities of 15 mm² / s to 10 mm² / s.
The viscosity loss of a 10% aqueous solution under the conditions mentioned in Example 1 is 8%.
Die Dispersionsherstellung und Aufbereitung erfolgt, wie bei Beispiel 1 beschrieben, mit dem Unterschied, daß ein Zulauf, bestehend aus:
1 160,0 g Methylmethacrylat
800,0 g Methacrylsäure
40,0 g Alkylmethacrylat (Gemisch isomerer Isodecylalkohole, mittlerer C-Zahl 10)
30,0 g Triisobutylphenolpolyglykolethersulfat-Na-Salz
2,0 g 2-Ethylhexylthioglykolat und
1 850,0 g entsalztes Wasser,
innerhalb von 3 Stunden zugegeben wird. Der pH der ca. 40 %igen Dispersion beträgt 2,6.The dispersion preparation and preparation takes place as described in Example 1, with the difference that an inlet consisting of:
1 160.0 g methyl methacrylate
800.0 g methacrylic acid
40.0 g alkyl methacrylate (mixture of isomeric isodecyl alcohols, average C number 10)
30.0 g of triisobutylphenol polyglycol ether sulfate Na salt
2.0 g of 2-ethylhexyl thioglycolate and
1 850.0 g of demineralized water,
is added within 3 hours. The pH of the approx. 40% dispersion is 2.6.
Molekulargewicht des Copolymerisats: ca. 250 000 bis 300 000 g/mol.Molecular weight of the copolymer: approx. 250,000 to 300,000 g / mol.
Dieses Polymerisat ist besonders zum Verdicken von Metallbearbeitungsflüssigkeiten geeignet.This polymer is particularly suitable for thickening metalworking fluids.
Claims (6)
gekennzeichnet durch
einen Gehalt an Copolymerisaten auf (Meth)Acrylat-Basis, die aus den Monomeren
a) 10 bis 90 Gew.-% C₁- bis C₄-Alkylester der Acrylsäure und/oder Methacrylsäure,
b) 5 bis 80 Gew.-% Acrylsäure und/oder Methacrylsäure und
c) 0,1 bis 10 Gew.-% C₈- bis C₂₀-Alkylester der Acrylsäure und/oder Methacrylsäure
aufgebaut sind, und deren Säuregruppen vor oder gegebenenfalls nach der Polymerisation teilweise oder vollständig durch Zusatz von Basen neutralisiert sind, und die Copolymerisate mittlere Molmassen Mw zwischen 30 000 und 300 000 besitzen und bei deren Herstellung noch andere polymerisierbare Verbindungen mit nicht mehr als einer polymerisierbaren Doppelbindung in Mengen von 0 bis 20 Gew.-% mitverwendet werden können.1. aqueous functional fluids containing polymeric thickeners,
marked by
a content of copolymers based on (meth) acrylate, which consist of the monomers
a) 10 to 90% by weight of C₁ to C₄ alkyl esters of acrylic acid and / or methacrylic acid,
b) 5 to 80 wt .-% acrylic acid and / or methacrylic acid and
c) 0.1 to 10 wt .-% C₈ to C₂₀ alkyl esters of acrylic acid and / or methacrylic acid
are built up, and the acid groups before or, if appropriate, after the polymerization are partially or completely neutralized by adding bases, and the copolymers have average molecular weights M w between 30,000 and 300,000 and in their preparation still other polymerizable compounds having no more than one polymerizable double bond can be used in amounts of 0 to 20 wt .-%.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3916128A DE3916128A1 (en) | 1989-05-18 | 1989-05-18 | AQUEOUS FUNCTIONAL LIQUIDS CONTAINING THICKENING AGENTS ON A POLY (METH) ACRYLATE BASE |
| DE3916128 | 1989-05-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0398153A1 true EP0398153A1 (en) | 1990-11-22 |
Family
ID=6380849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90108785A Withdrawn EP0398153A1 (en) | 1989-05-18 | 1990-05-10 | Aqueous functional liquids containing a poly(meth)acrylat thickening agent |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0398153A1 (en) |
| JP (1) | JPH039996A (en) |
| DE (1) | DE3916128A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2748104B2 (en) * | 1994-03-08 | 1998-05-06 | 三洋化成工業株式会社 | Viscosity index improver and lubricating oil |
| JP2002275493A (en) * | 2001-01-09 | 2002-09-25 | Noritz Corp | Lubricating agent and clean water instrument |
| JP2006265345A (en) * | 2005-03-23 | 2006-10-05 | Sanyo Chem Ind Ltd | Lubricating oil for ship propulsor bearing |
| US8524649B2 (en) * | 2007-08-03 | 2013-09-03 | Basf Se | Associative thickener dispersion |
| JP5524500B2 (en) * | 2008-03-27 | 2014-06-18 | 三洋化成工業株式会社 | Viscosity index improver and lubricating oil composition |
| JP2010202789A (en) * | 2009-03-04 | 2010-09-16 | Cosmo Oil Lubricants Co Ltd | Aqueous lubricating liquid composition |
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|---|---|---|---|---|
| FR2105236A1 (en) * | 1970-06-18 | 1972-04-28 | Mollco Patentverwertung | |
| DE2529892A1 (en) * | 1974-07-08 | 1976-01-29 | Nippon Paint Co Ltd | SURFACE TREATMENT FOR METALWORKING |
| GB2053264A (en) * | 1979-07-09 | 1981-02-04 | Steetley Minerals Ltd | Polymer lubricants for metal forming |
| EP0057875A2 (en) * | 1981-02-06 | 1982-08-18 | The Dow Chemical Company | Water-dispersible hydrophobic thickening agent |
| DE3404537A1 (en) * | 1984-02-09 | 1985-08-14 | Hoechst Ag, 6230 Frankfurt | AQUEOUS FUNCTIONAL LIQUIDS BASED ON POLYMERS |
| EP0251192A2 (en) * | 1986-06-27 | 1988-01-07 | Nihon Parkerizing Co., Ltd. | Lubricant for metal formation |
-
1989
- 1989-05-18 DE DE3916128A patent/DE3916128A1/en not_active Withdrawn
-
1990
- 1990-05-10 EP EP90108785A patent/EP0398153A1/en not_active Withdrawn
- 1990-05-16 JP JP2124310A patent/JPH039996A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2105236A1 (en) * | 1970-06-18 | 1972-04-28 | Mollco Patentverwertung | |
| DE2529892A1 (en) * | 1974-07-08 | 1976-01-29 | Nippon Paint Co Ltd | SURFACE TREATMENT FOR METALWORKING |
| GB2053264A (en) * | 1979-07-09 | 1981-02-04 | Steetley Minerals Ltd | Polymer lubricants for metal forming |
| EP0057875A2 (en) * | 1981-02-06 | 1982-08-18 | The Dow Chemical Company | Water-dispersible hydrophobic thickening agent |
| DE3404537A1 (en) * | 1984-02-09 | 1985-08-14 | Hoechst Ag, 6230 Frankfurt | AQUEOUS FUNCTIONAL LIQUIDS BASED ON POLYMERS |
| EP0251192A2 (en) * | 1986-06-27 | 1988-01-07 | Nihon Parkerizing Co., Ltd. | Lubricant for metal formation |
Non-Patent Citations (1)
| Title |
|---|
| CHEMICAL ABSTRACTS, Band 98, Nr. 20, 1990, NLN-STN, Zusammenfassung Nr. 162524z, Columbus, Ohio, US; & JP-A-57 188 699 (SUMITOMO METAL INDUSTRIES) November 1982 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH039996A (en) | 1991-01-17 |
| DE3916128A1 (en) | 1990-11-22 |
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