Classifications

• • 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
  • 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
• • 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
  • C10M2209/02—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
• • 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
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/20—Metal working
• • 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 & Material Sciences (AREA)
• 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)

Applications Claiming Priority (2)

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Citations (6)

• 1989
  • 1989-05-18 DE DE3916128A patent/DE3916128A1/de not_active Withdrawn
• 1990
  • 1990-05-10 EP EP90108785A patent/EP0398153A1/fr not_active Withdrawn
  • 1990-05-16 JP JP2124310A patent/JPH039996A/ja active Pending

Patent Citations (6)

Non-Patent Citations (1)

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