EP1753847B1 - Schmierfett mit hoher wasserresistenz - Google Patents

Schmierfett mit hoher wasserresistenz Download PDF

Info

Publication number
EP1753847B1
EP1753847B1 EP05701058.9A EP05701058A EP1753847B1 EP 1753847 B1 EP1753847 B1 EP 1753847B1 EP 05701058 A EP05701058 A EP 05701058A EP 1753847 B1 EP1753847 B1 EP 1753847B1
Authority
EP
European Patent Office
Prior art keywords
weight
lubricating grease
polymeric structure
meth
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP05701058.9A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1753847A1 (de
Inventor
Markus Dr. Scherer
Matthias Fischer
Michael Müller
Bernard Kinker
Alexndra Pauker
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Oil Additives GmbH
Original Assignee
Evonik Oil Additives GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Evonik Oil Additives GmbH filed Critical Evonik Oil Additives GmbH
Publication of EP1753847A1 publication Critical patent/EP1753847A1/de
Application granted granted Critical
Publication of EP1753847B1 publication Critical patent/EP1753847B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/06—Mixtures of thickeners and additives
    • 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
    • C10M151/00—Lubricating compositions characterised by the additive being a macromolecular compound containing sulfur, selenium or tellurium
    • C10M151/02—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • C10M153/00—Lubricating compositions characterised by the additive being a macromolecular compound containing phosphorus
    • C10M153/02—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/128—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
    • C10M2207/1285—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof used as thickening agents
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
    • 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
    • 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
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/26—Waterproofing or water resistance
    • 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
    • C10N2050/10—Form in which the lubricant is applied to the material being lubricated semi-solid; greasy

Definitions

  • the present invention relates to grease having high water resistance.
  • Greases are known per se and are widely used. Greases, hereinafter also referred to as “fats", are solid to semi-liquid substances which are formed by dispersion of a thickening agent in a liquid lubricant. Other additives (additives) that impart special properties may be included.
  • the basic consistency of a fat is determined by the combination of base fluid and thickening agent.
  • the base liquid is usually a base oil customary in the lubricant industry, e.g. Mineral oil, synthetic oil or vegetable oil.
  • thickening agents are very often, but not exclusively, simple metal soaps used. Furthermore, but more rarely, complex metal soaps, organically modified clay (bentonite) or polyurea are used. Physically, the thickening agents form the solid phase of the dispersion and thus determine, in addition to the base oil, decisively the physical / mechanical properties of the grease, such as low-temperature behavior, water resistance, dropping point or oil separation behavior.
  • the different combinations of base oil and thickening agent are known to the expert and determine the range of application of the grease in technical application.
  • the material can be used to make grease-like compositions.
  • the composition consists of a mixture of oxidized polyethylene and a complexing agent selected from at least divalent metal salts, fatty acids and metal complexes.
  • U.S. 3,705,853, Fau et al., Sept. 23, 1970 describes a grease consisting of a paraffinic mineral oil, a calcium complex soap thickener and an organic terpolymer consisting of 65% ethylene, 5% ester comonomer and 0.01-3% acidic comonomer with a melt index between 0.5 and 200.
  • the fats have better water resistance, measured by the water wash test according to ASTM D 1264.
  • U.S. 4,877,557, Kaneshige et al., Oct. 31, 1989 describes a lubricant composition containing a synthetic lubricating oil, a wear protection additive and a liquid, modified copolymer of ethylene and alpha-olefin having a number average molecular weight between 300 and 12,000 g / mol.
  • U.S. 5,116,522, Brown et al, Aug. 23, 1989 describes a lubricant composition consisting of ethylene copolymers, a lubricating oil, a thickener and a viscosity index improver.
  • the ethylene copolymer is a polymer of isobutylene or a copolymer of ethylene, butylene, or isobutylene with a C3 to C30 olefin.
  • the viscosity index improver copolymers consisting of 60-90% of ethylene and 40-10% of vinyl acetate, alkyl acrylates or alkyl methacrylates are used.
  • the composition has very good high temperature adhesion and low temperature softening.
  • EP 806,469 and U.S. 5,858,934, Wiggins et al, May 8, 1996 describe an improved biodegradable grease composition from a natural base or synthetic triglyceride based base oil, a performance additive consisting of an alkylphenol, a benzotriazole or an aromatic amine, and a thickening agent comprising the reaction product of a metal based material and a carboxylic acid or its ester.
  • the grease may also contain viscosity modifier, pour point improver or the combination of both. The nature of the viscosity modifier or pour point improver will not be discussed.
  • US 2,577,706 discloses a lubricant containing a major portion of a grease consisting essentially of a lubricating oil, the organic acid alkali metal salt as a thickener, and a small amount of polymeric compound sufficient to enhance the emulsification of the grease in water; Compound saponifiable repeat units selected from carboxyl and carboxylic acid ester groups, of which 10% to 60% are saponified by metals selected from alkali and alkaline earth metals.
  • the addition of polymers to lubricating greases determines certain physical parameters, e.g. improved rheological properties or the water resistance of fats.
  • certain physical parameters e.g. improved rheological properties or the water resistance of fats.
  • the improvement of a property, such as the water resistance should not be associated with an excessive deterioration of other properties, such as handleability or homogeneity.
  • the greases should have a particularly high water resistance, an excellent consistency and a high homogeneity.
  • Another object may be seen to provide greases having improved temperature characteristics.
  • the properties should be improved at low temperatures.
  • the greases should be able to be used over a particularly wide temperature range.
  • the greases should be able to be produced inexpensively.
  • the production should be possible on an industrial scale without the need for new or structurally complex systems.
  • the greases of the invention include polymeric structural improvers. These polymers generally result in an improvement in water resistance. It is believed that these polymers physico-chemical interaction with the thickening agents, for example the Soap molecules enter, without this being a limitation.
  • Mixtures from which the polymeric structure improvers are obtainable may contain 0 to 40% by weight, especially 0.5 to 20% by weight, based on the weight of the monomer compositions for the preparation of the polymeric structure improvers, of at least one (meth) acrylate of the formula (I) included wherein R represents hydrogen or methyl, R 1 represents a linear or branched alkyl radical having 1 to 5 carbon atoms.
  • (meth) acrylates include methacrylates and acrylates as well as mixtures of both. These monomers are well known.
  • the alkyl radical may be linear, cyclic or branched.
  • component a) examples include (meth) acrylates derived from saturated alcohols, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n Butyl (meth) acrylate, tert-butyl (meth) acrylate and pentyl (meth) acrylate; Cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate; (Meth) acrylates derived from unsaturated alcohols, such as 2-propynyl (meth) acrylate, allyl (meth) acrylate and vinyl (meth) acrylate.
  • saturated alcohols such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n But
  • compositions to be polymerized for the preparation of preferred polymeric structural improvers contain from 40 to 99.99% by weight, in particular 55 to 95% by weight, based on the weight of the monomer compositions for the preparation of the polymeric structure improvers, of at least one (meth) acrylate of the formula (II) wherein R represents hydrogen or methyl, R 2 represents a linear or branched alkyl radical having 6 to 30 carbon atoms.
  • acrylates derived from saturated alcohols, such as hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, 2-tert-butylheptyl (meth) acrylate, octyl (meth) acrylate, 3-iso-propylheptyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, 5-methylundecyl (meth) acrylate, dodecyl (meth) acrylate, 2-methyldodecyl (meth) acrylate, Tridecyl (meth) acrylate, 5-methyltridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexyl (meth)
  • oleyl (meth) acrylate For example, oleyl (meth) acrylate; Cycloalkyl (meth) acrylates, such as 3-vinylcyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, bornyl (meth) acrylate.
  • the (meth) acrylates with a long-chain alcohol radical in particular the compounds according to component (b), can be, for example, by Reacting of (meth) acrylates and / or the corresponding acids with long-chain fatty alcohols obtained, which generally produces a mixture of esters, such as (meth) acrylates with different long-chain alcohol residues.
  • These fatty alcohols include Oxo Alcohol® 7911 and Oxo Alcohol® 7900, Oxo Alcohol® 1100 from Monsanto; Alphanol® 79 from ICI; Nafol® 1620, Alfol® 610 and Alfol® 810 from Sasol; Epal® 610 and Epal® 810 from Ethyl Corporation; Linevol® 79, Linevol® 911 and Dobanol® 25L from Shell AG; Lial 125 from Sasol; Dehydad® and Lorol® grades from Cognis.
  • the mixture for preparing preferred polymeric structural improvers comprises at least 60% by weight, preferably at least 70% by weight, based on the weight of the monomer compositions for the preparation of the polymeric structure improvers, of monomers of formula (II).
  • the methacrylates are preferred over the acrylates.
  • the proportion of the (meth) acrylates having 6 to 15 carbon atoms in the alcohol moiety is in the range of 20 to 95 wt .-%, based on the weight of the monomer composition for the preparation of the polymeric structure improvers.
  • the proportion of (meth) acrylates having 16 to 30 carbon atoms in the alcohol residue is preferably in the range of 0.5 to 60 wt .-%, based on the weight of the monomer composition for the preparation of the polymeric structure improvers.
  • Component c) of the composition to be used for the preparation of preferred polymeric structure improvers comprises, in particular, monomers comprising acid groups or salts thereof.
  • Preferred salts are, in particular, the alkali metal salts, such as, for example, the lithium, sodium and / or potassium salts; the alkaline earth metal salts, such as the calcium and / or barium salts, as well as the aluminum salts and the ammonium salts.
  • the alkali metal salts such as, for example, the lithium, sodium and / or potassium salts
  • the alkaline earth metal salts such as the calcium and / or barium salts, as well as the aluminum salts and the ammonium salts.
  • the proportion of components c) is generally 0.01 to 5 wt .-%, preferably 0.1 to 5 wt .-% and particularly preferably 0.5 to 5 wt .-%, based on the weight of the monomer compositions for the preparation the polymeric structural improver.
  • These compounds can generally be copolymerized with the monomers according to component a), b) and d).
  • These include, inter alia, ethylenically unsaturated compounds such as vinylsulfonic acid, vinylphosphonic acid, acrylic acid, methacrylic acid, fumaric acid, monoesters of fumaric acid, wherein the alcohol radical may generally comprise 1 to 30 carbon atoms, maleic acid, monoesters of maleic acid, the alcohol radical being generally 1 to 30 Carbon atoms, vinyl benzoic acid and sulfonated styrenes such as styrenesulfonic acid.
  • the from salts derived from these acids in particular the alkali metal, alkaline earth metal and / or aluminum salts.
  • Component d) of the composition to be used for the preparation of preferred polymeric structure improvers comprises, in particular, ethylenically unsaturated monomers which can be copolymerized with the monomers according to components a) to c).
  • compositions for preparing preferred structure improvers comprise comonomers according to component d) which can be represented by the formula (IV), wherein R is independently hydrogen or methyl, R 9 is independently a 2 to 1000 carbon group comprising at least one heteroatom, X is independently a sulfur or oxygen atom or a group of formula NR 10 , wherein R 10 is independently hydrogen or a group of 1 to 20 carbon atoms and n represents an integer greater than or equal to 3.
  • the radical R 9 represents a group comprising 2 to 1000, in particular 2 to 100, preferably 2 to 20 carbon atoms.
  • the term "2 to 1000 carbon group” denotes radicals of organic compounds having 2 to 1000 carbon atoms. It includes aromatic and heteroaromatic groups as well as alkyl, cycloalkyl, alkoxy, cycloalkoxy, alkenyl, alkanoyl, alkoxycarbonyl and heteroaliphatic groups.
  • the groups mentioned can be branched or unbranched. Furthermore, these groups may have conventional substituents.
  • Substituents are, for example, linear and branched alkyl groups having 1 to 6 carbon atoms, such as, for example, methyl, ethyl, propyl, butyl, pentyl, 2-methylbutyl or hexyl; Cycloalkyl groups such as cyclopentyl and cyclohexyl; aromatic groups, such as phenyl or naphthyl; Amino groups, ether groups, ester groups and halides.
  • aromatic groups are radicals of mononuclear or polynuclear aromatic compounds having preferably 6 to 20, in particular 6 to 12, carbon atoms.
  • Heteroaromatic groups denote aryl radicals in which at least one CH group has been replaced by N and / or at least two adjacent CH groups have been replaced by S, NH or O, heteroaromatic groups having from 3 to 19 carbon atoms.
  • Preferred aromatic or heteroaromatic groups according to the invention are derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane, diphenyldimethylmethane, bisphenone, diphenylsulfone, thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole, isoxazole, pyrazole, 1,3,4-oxadiazole , 2,5-diphenyl-1,3,4-oxadiazole, 1,3,4-thiadiazole, 1,3,4-triazole, 2,5-diphenyl-1,3,4-triazole, 1,2,5 -Triphenyl-1,3,4-triazole, 1,2,4-oxadiazole, 1,2,4-thiadiazole, 1,2,4-triazole, 1,2,3-triazole, 1,2,3,4 Tetrazole, benzo [b] thiophene
  • the preferred alkyl groups include the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl, tert-butyl, pentyl, 2-methylbutyl, 1,1- Dimethylpropyl, hexyl, heptyl, octyl, 1,1,3,3-tetramethylbutyl, nonyl, 1-decyl, 2-decyl, undecyl, dodecyl, pentadecyl and the eicosyl group.
  • Preferred cycloalkyl groups include the cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups, optionally substituted with branched or unbranched alkyl groups.
  • Preferred alkenyl groups include the vinyl, allyl, 2-methyl-2-propene, 2-butenyl, 2-pentenyl, 2-decenyl and 2-eicosenyl groups.
  • the preferred alkynyl groups include the ethynyl, propargyl, 2-methyl-2-propyne, 2-butynyl, 2-pentynyl and 2-decynyl groups.
  • Preferred alkanoyl groups include the formyl, acetyl, propionyl, 2-methylpropionyl, butyryl, valeroyl, pivaloyl, hexanoyl, decanoyl and dodecanoyl groups.
  • the preferred alkoxycarbonyl groups include the methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, tert-butoxycarbonyl, hexyloxycarbonyl, 2-methylhexyloxycarbonyl, decyloxycarbonyl or dodecyloxycarbonyl group.
  • the preferred alkoxy groups include alkoxy groups whose hydrocarbon radical is one of the aforementioned preferred alkyl groups.
  • Preferred cycloalkoxy groups include cycloalkoxy groups whose hydrocarbon radical is one of the aforementioned preferred cycloalkyl groups.
  • the preferred heteroatoms contained in R 10 include, among others, oxygen, nitrogen, sulfur, boron, silicon and phosphorus.
  • the radical R 8 in formula (IV) has at least one group of the formula -OH or -NR 10 R 10 , in which R 10 independently comprises hydrogen or a group having 1 to 20 carbon atoms.
  • the group X in formula (IV) can be represented by the formula NH.
  • the number ratio of heteroatoms to carbon atoms in the radical R 9 of the formula (IV) can be within a wide range. This ratio is preferably in the range from 1: 1 to 1:10, in particular 1: 1 to 1: 5 and particularly preferably 1: 2 to 1: 4.
  • the residue R 9 of the formula (IV) comprises 2 to 1000 carbon atoms. In a particular aspect, R 9 has at most 10 carbon atoms.
  • the particularly preferred comonomers include, inter alia, hydroxyalkyl (meth) acrylates, such as 3-hydroxypropyl methacrylate, 3,4-dihydroxybutyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,5-dimethyl-1,6-hexanediol (meth) acrylate, 1,10-decanediol (meth) acrylate; carbonyl-containing methacrylates, such as 2-carboxyethyl methacrylate, Carboxymethylmethacrylat, oxazolidinylethyl, N- (methacryloyloxy) formamide, Acetonylmethacrylat, N-methacryloylmorpholine, N-methacryloyl-2-pyrrolidinone, N- (2-methacryloyloxyethyl) -2-pyrrolidinone, N- (3-methacryloyloxypropyl) -2
  • the ethoxylated (meth) acrylates can be obtained, for example, by transesterification of alkyl (meth) acrylates with ethoxylated alcohols, which more preferably have from 1 to 20, in particular from 2 to 8, ethoxy groups.
  • the hydrophobic radical of the ethoxylated alcohols may preferably comprise 1 to 40, in particular 4 to 22, carbon atoms, it being possible to use both linear and branched alcohol radicals.
  • the ethoxylated (meth) acrylates have an OH end group.
  • ethoxylates which can be used for the preparation of ethoxylated (meth) acrylates are ethers of the Lutensol® A brands, in particular Lutensol® A 3 N, Lutensol® A 4 N, Lutensol® A 7 N and Lutensol® A 8 N, ethers of the Lutensol® TO brands, in particular Lutensol® TO 2, Lutensol® TO 3, Lutensol® TO 5, Lutensol® TO 6, Lutensol® TO 65, Lutensol® TO 69, Lutensol® TO 7, Lutensol® TO 79 , Lutensol® 8 and Lutensol® 89, ethers of the Lutensol® AO brands, in particular Lutensol® AO 3, Lutensol® AO 4, Lutensol® AO 5, Lutensol® AO 6, Lutensol® AO 7, Lutensol® AO 79, Lutensol® AO 8 and Lutensol® AO 89, ethers of the Lutensol® ON brands, in particular Lutensol® ON
  • aminoalkyl (meth) acrylates and aminoalkyl (meth) acrylamides for example, N- (3-dimethylaminopropyl) methacrylamide (DMAPMAM), and hydroxyalkyl (meth) acrylates, for example, 2-hydroxyethyl methacrylate (HEMA) are particularly preferred.
  • DMAPMAM N- (3-dimethylaminopropyl) methacrylamide
  • HEMA 2-hydroxyethyl methacrylate
  • Very particularly preferred mixtures for the preparation of the polymeric structure improvers comprise methyl methacrylate, butyl methacrylate, lauryl methacrylate, stearyl methacrylate and / or styrene.
  • the preferred polymeric structural improvers generally have a molecular weight in the range of 10,000 to 1,000,000 g / mol, preferably in the range of 15 * 10 3 to 500 * 10 3 g / mol, and more preferably in the range of 20 * 10 3 to 300 * 10 3 g / mol, without this being a limitation. These values are based on the weight average molecular weight of the polydisperse polymers in the composition. This size can be determined by gel permeation chromatography in a known manner.
  • polymeric structural improvers from the compositions described above is known per se.
  • ATRP atom transfer radical polymerization
  • RAFT reversible addition fragmentation chain transfer
  • azo initiators well known in the art, such as AIBN and 1,1-azobiscyclohexanecarbonitrile, and peroxy compounds such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert-butyl per-2-ethylhexanoate, ketone peroxide, tert-butyl peroctoate, methyl isobutyl ketone peroxide, cyclohexanone peroxide, Dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy-3,5,5 trimethylhexanoate, dicum
  • the ATRP method is known per se. It is believed that this is a "living" radical polymerization without any limitation to the description of the mechanism.
  • a transition metal compound is reacted with a compound having a transferable atomic group.
  • the transferable atomic group is transferred to the transition metal compound, whereby the metal is oxidized.
  • This reaction forms a radical that adds to ethylenic groups.
  • the transfer of the atomic group to the transition metal compound is reversible so that the atomic group is re-transferred to the growing polymer chain, forming a controlled polymerization system. Accordingly, the structure of the polymer, the molecular weight and the molecular weight distribution can be controlled.
  • polymers according to the invention can also be obtained, for example, by RAFT methods. This method is for example in WO 98/01478 which is expressly referred to for purposes of the disclosure.
  • the polymerization can be carried out at atmospheric pressure, lower or higher pressure.
  • the polymerization temperature is not critical. In general, however, it is in the range of -20 ° - 200 ° C, preferably 0 ° - 130 ° C and particularly preferably 60 ° - 120 ° C.
  • the polymerization can be carried out with or without solvent.
  • the term of the solvent is to be understood here broadly.
  • the polymerization is carried out in a nonpolar solvent.
  • nonpolar solvent include hydrocarbon solvents such as aromatic solvents such as toluene, benzene and xylene, saturated hydrocarbons such as cyclohexane, heptane, octane, nonane, decane, dodecane, which may also be branched.
  • hydrocarbon solvents such as aromatic solvents such as toluene, benzene and xylene, saturated hydrocarbons such as cyclohexane, heptane, octane, nonane, decane, dodecane, which may also be branched.
  • solvents can be used individually or as a mixture.
  • Particularly preferred solvents are mineral oils, natural oils and synthetic oils and mixtures thereof. Of these, mineral oils are most preferred.
  • the polymeric structural improvers may be random copolymers.
  • the polymeric structural improver is present in the grease in an amount in the range of 0.1 to 10 wt.%, More preferably 0.5 to 5 wt.%, Based on the total weight.
  • the lubricating oils contained in the lubricating greases of the invention include, in particular, mineral oils, synthetic oils and natural oils.
  • Mineral oils are known per se and commercially available. They are generally obtained from petroleum or crude oil by distillation and / or refining and, if appropriate, further purification and refining processes, the term "mineral oil” in particular falling to the relatively high-boiling fractions of crude oil or crude oil. In general, the boiling point of mineral oil is higher than 200 ° C, preferably higher than 300 ° C, at 5000 Pa. The production by smoldering of shale oil, coking of hard coal, distillation under exclusion of lignite and hydration of coal or lignite is also possible. To a small extent, mineral oils are also produced from raw materials of plant origin (eg from jojoba, rapeseed) or animal (eg claw oil) of origin. Accordingly, mineral oils, depending on the origin of different proportions of aromatic, cyclic, branched and linear hydrocarbons.
  • mineral oils depending on the origin of different proportions of aromatic, cyclic, branched and linear hydrocarbons.
  • paraffin-based, naphthenic and aromatic fractions in crude oils or mineral oils, the terms paraffin-based fraction being longer-chain or highly branched isoalkanes and naphthenic fraction being cycloalkanes.
  • mineral oils depending on their origin and refinement, have different proportions of n-alkanes, isoalkanes with a low degree of branching, so-called monomethyl-branched paraffins, and compounds with heteroatoms, in particular O, N and / or S, which are attributed to polar properties ,
  • the assignment is difficult because individual alkane molecules have both long-chain branched groups and cycloalkane groups and may have aromatic moieties.
  • the assignment can be made, for example, according to DIN 51 378. Polar proportions may also be determined according to ASTM D 2007.
  • the proportion of n-alkanes in preferred mineral oils is less than 3 wt .-%, the proportion of O, N and / or S-containing compounds less than 6 wt .-%.
  • the proportion of aromatics and monomethyl branched paraffins is generally in the range of 0 to 40 wt .-%.
  • mineral oil mainly comprises naphthenic and paraffinic alkanes, which generally have more than 13, preferably more than 18 and most preferably more than 20 carbon atoms.
  • the proportion of these compounds is generally ⁇ 60 wt .-%, preferably ⁇ 80 wt .-%, without this being a restriction.
  • a preferred mineral oil contains from 0.5 to 30% by weight of aromatic fractions, from 15 to 40% by weight of naphthenic fractions, from 35 to 80% by weight of paraffinic fractions, up to 3% by weight of n-alkanes and 0.05% to 5 wt .-% polar compounds, each based on the total weight of the mineral oil.
  • Synthetic oils include, but are not limited to, organic esters such as diesters and polyesters, polyalkylene glycols, polyethers, synthetic hydrocarbons, especially polyolefins, of which polyalphaolefins (PAO) are preferred, silicone oils and perfluoroalkyl ethers. They are usually slightly more expensive than the mineral oils, but have advantages in terms of their performance.
  • Natural oils are animal or vegetable oils, such as claw oils or jojoba oils.
  • lubricating oils can also be used as mixtures and are often commercially available.
  • the grease comprises 69.9 to 98.9 wt .-%, in particular 75 to 95 wt .-% lubricating oil, based on the total weight.
  • the thickening agents contained in the lubricating greases according to the invention are known per se in the art and can be obtained commercially. These are among others in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, Vol. 20, 200, Wiley, ISBN 3-527-30385-5 , in T. Mang and W. Dresel, Lubricants and Lubrication, 2001, Wiley, ISBN 3-527-29536-4 , and Wilfried J. Bartz et al, greases, expert Verl., 2000, ISBN 3-8169-1533-7 , These include in particular soap thickeners, inorganic thickeners and polymeric thickeners.
  • the soap thickeners generally comprise at least one metal component and at least one carboxylic acid anion component.
  • the usual metal components include in particular the alkali metals such as lithium, sodium and potassium, the alkaline earth metals such as calcium or barium and aluminum.
  • the carboxylic acid anion component generally comprises anions derived from long chain carboxylic acids, many of which have from 6 to 30 carbon atoms. These include, in particular, stearic acid, 12-hydroxystearic acid, octadecanoic acid, eicosanoic acid and hexadecanoic acid.
  • carboxylic acid anion component may include anions derived from short chain carboxylic acids having 1 to 6 carbon atoms or from aromatic carboxylic acids. These include in particular acetic acid, propanoic acid and butanoic acid and benzoic acid.
  • the soap thickeners can be used as such in the process to produce a dispersion comprising a fatty structure. Furthermore, these can also be prepared in situ from the corresponding acids or their derivatives, for example their esters, as well as basic metal compounds.
  • esters having a short-chain alcohol radical with 1 to 6 Carbon atoms for example the methyl, ethyl, propyl and / or butyl esters are preferred.
  • the preferred basic compounds include, in particular, the oxides, hydroxides and carbonates of the abovementioned metals.
  • Preferred soap thickeners include lithium 12-hydroxystearate, lithium complex soaps, aluminum complex soaps, and calcium complex soaps.
  • the basic compounds for the preparation of the soaps can be added in an excess or deficiency, resulting in under- or overbased compounds.
  • inorganic thickening agents can be used. These include in particular organophilic clays, which may be derived from bentonite, and silica gel.
  • polymeric thickeners can be used. These include polyureas as well as thermoplastic powders such as polytetrafluoroethylene and fluoroethylene propylene.
  • the lubricating grease preferably comprises 0.01 to 30% by weight, more preferably 0.2 to 15% by weight and most preferably 0.5 to 10% by weight of thickener, based on the total weight.
  • the weight ratio of lubricating oil to thickener in the grease is generally in the range of 100: 1 to 100: 30, preferably 100: 2 to 100: 25, especially 100: 5 to 100: 15.
  • the grease according to the invention may contain further additives and additives.
  • additives include, but are not limited to, viscosity index improvers, antioxidants, antiaging agents, anti-wear agents, corrosion inhibitors, detergents, dispersants, EP additives, friction modifiers, dyes, fragrances, metal deactivators, and / or demulsifiers.
  • a lubricating grease according to the invention has a water resistance of 1 to 50%, particularly preferably in the range of 5 to 35%.
  • the cone penetration of preferred greases is in the range of 175 to 385 dmm, more preferably in the range of 220 dmm to 340 dmm.
  • the water resistance can be determined according to ASTM D 4049.
  • the cone penetration can be measured according to ASTM D 1403.
  • special greases can be used at very low temperatures.
  • the greases can be used below a temperature of 0 ° C, more preferably of -10 ° C.
  • preferred lubricating greases can also be used at high temperatures of at least 50.degree. C., particularly preferably at least 90.degree.
  • the grease structure or grease matrix is generated by physico-chemical processes.
  • a metal soap is produced from precursors in a first stage.
  • metal soap molecules are generated by reaction of the corresponding starting materials in the base oil.
  • the metal soap molecules are present as fine crystals. This level is optional as it is not necessary by choosing appropriate precursors.
  • the addition of the polymeric structure improvers can be done before, during or after the patterning phase.
  • the polymeric structure improver may first be prepared in a mineral oil. Subsequently, a thickener, or precursors for the preparation of the thickener, are added to the resulting mixture.
  • the polymeric structural improver may be added after the patterning phase, for example, to a grease.
  • the polymeric structural enhancer is added in a liquid at 25 ° C composition of a dispersion having a fatty structure.
  • fat structure is known in the art, and this structure may be termed spongy. This structure of the dispersion can be detected for example by microscopic images, wherein the lubricating oil is kept in a thickener.
  • composition can be both a dispersion and a solution. Accordingly, these compositions have at least one liquid medium.
  • Particularly preferred media include, in particular lubricating oils, which can also be used for the preparation of the dispersion, which comprises at least one thickener and at least one lubricating oil.
  • Liquid media for dispersing or dissolving the polymeric structural improvers described above are known per se, which media should be compatible with the dispersion comprising at least one thickener and at least one lubricating oil.
  • Compatibility means the miscibility of the medium with the dispersion, which comprises at least one thickener and at least one lubricating oil.
  • the composition having at least one polymeric structural improver liquid at 25 ° C has a viscosity at 25 ° C in the range of 0.01 mm 2 / s to 100000 mm 2 / s, preferably 0.1 mm 2 / s up to 20000 mm 2 / s and more preferably from 1 mm 2 / s to 10000 mm 2 / s according to DIN 51562 on.
  • the concentration of the polymeric structure improver in the liquid composition at 25 ° C is preferably in the range of 1 to 99% by weight, more preferably in the range of 5 to 89% by weight, and most preferably in the range of 10 to 80% by weight. %, based on the total weight of the composition.
  • the ratio of the weight of the dispersion to the weight of the 25 ° C liquid composition comprising at least one polymeric structure improver is preferably in the range of 100: 1 to 1: 1, more preferably in the range of 50: 1 to 5: 1 and most preferably in the range of 25: 1 to 10: 1.
  • composition which is liquid at 25 ° C. can be added inter alia during a mechanical phase following the structure-forming phase.
  • the liquid composition at 25 ° C can be added to a finished grease after the mechanical phase.
  • a large amount of a simple grease can be prepared, which can then be adapted in a further step to the particular needs of the end customer by the addition of the liquid at 25 ° C composition, which may contain other additives , As a result, a particularly economical production of small amounts of special greases is possible.
  • the water resistance can be improved by at least 30%, more preferably by at least 50% and most preferably by at least 70%, based on the water resistance of the dispersion to which the liquid composition at 25 ° C is added become.
  • the dispersion comprising the fatty structure and the composition which is liquid at 25 ° C. are substantially biodegradable.
  • this is measured according to RAL-ZU 64.
  • composition comprising the fat structure at 25 ° C.
  • generally known methods include, but are not limited to, stirring, mixing, kneading, rolling and / or homogenizing.
  • the temperature at which the dispersion comprising the fat structure at 25 ° C. is added is not critical per se. At a high temperature, the liquid composition at 25 ° C is often easier to incorporate in the dispersion. However, the fat structure must be stable at the addition temperature.
  • the composition which is liquid at 25 ° C is added at a temperature to the dispersion comprising the fatty structure which is below the dropping point of the dispersion prior to the addition of the liquid composition.
  • the dropping point can be determined according to ASTM D 2265.
  • composition which is liquid at 25 ° C. is particularly preferably added at a temperature to the dispersion comprising fatty structure, which is at least 40 ° C., very particularly preferably at least 60 ° C., below the dropping point of the dispersion before the addition of the liquid composition.
  • the composition which is liquid at 25 ° C. can be added at a temperature in the range from 0 ° C. to 75 ° C., in particular in the range from 25 ° C. to 70 ° C.
  • KV 100, KV 40 kinematic viscosity, measured according to DIN 51562 at 100 ° C and 40 ° C
  • the polymer solutions described in the example are measured in a 150 N measuring oil, the data in () shows the polymer concentration used.
  • [ ⁇ ] denotes the intrinsic viscosity, measured according to DIN ISO 16281, Part 6.
  • the kettle is opened and the resulting fat is homogenized at least twice by a three-roll mill and filled into a bucket.
  • IP 50 Cone penetration
  • IP 50 unworked: 285 dmm, after 60 movements 288 dmm (NLGI grade 2), after 100060 movements: 317 dmm.
  • Drop point (ASTM D566): 197.7 ° C Water Wash Out (ASTM D 1264): 7.5% Water Spray Off (ASTM D 4049): 33.8%
  • Example 1 was essentially repeated, but no solution was incorporated. The data obtained are shown in Table 1.
  • Example 1 was substantially repeated except that a solution comprising 50% by weight of polymers without acid groups obtained according to Preparation Example 2 and comprising a lubricating oil was incorporated.
  • the data obtained are shown in Table 1.
  • Table 1 Cone penetration after 60 movements Dropping point water resistance Improvement related to the source fat Ex. 1 291 197 ° C 20% 41% Comp. 1 288 198 ° C 34% - Comp. 2 279 198 ° C 27% 21%
  • Example 2 was essentially repeated, but no solution was incorporated. The data obtained are shown in Table 2.
  • Example 2 was substantially repeated, incorporating 40 g of the dispersion comprising 50% by weight of polymers with acid groups obtained according to Preparation Example 1 and a lubricating oil into 960 g of Grease from F & S Mannheim. The data obtained are shown in Table 2.
  • Example 2 was substantially repeated except that 10 g of a solution comprising 50% by weight of polymers without acid groups obtained in Preparation Example 2 and a lubricating oil was incorporated. The data obtained are shown in Table 2.
  • Example 3 was substantially repeated except that 20 g of a solution comprising 50% by weight of polymers without acid groups obtained according to Preparation Example 2 and a lubricating oil were incorporated in 980 g of F & S grease.
  • the data obtained are shown in Table 2.
  • Table 2 Cone penetration after 60 movements Dropping point water resistance Improvement related to the source fat Ex. 2 291 182 ° C 20% 68% Comp. 3 251 186 ° C 62% - Ex. 3 294 185 ° C 11% 82% Comp. 4 - 188 ° C 40% 35% Comp. 5 - 183 ° C 28% 55%

Landscapes

  • 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)
EP05701058.9A 2004-04-30 2005-01-20 Schmierfett mit hoher wasserresistenz Expired - Lifetime EP1753847B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10/834,861 US7429555B2 (en) 2004-04-30 2004-04-30 Lubricating grease with high water resistance
PCT/EP2005/000509 WO2005108532A1 (de) 2004-04-30 2005-01-20 Schmierfett mit hoher wasserresistenz

Publications (2)

Publication Number Publication Date
EP1753847A1 EP1753847A1 (de) 2007-02-21
EP1753847B1 true EP1753847B1 (de) 2018-05-23

Family

ID=35187854

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05701058.9A Expired - Lifetime EP1753847B1 (de) 2004-04-30 2005-01-20 Schmierfett mit hoher wasserresistenz

Country Status (10)

Country Link
US (1) US7429555B2 (enrdf_load_stackoverflow)
EP (1) EP1753847B1 (enrdf_load_stackoverflow)
JP (1) JP5150250B2 (enrdf_load_stackoverflow)
KR (1) KR20070015555A (enrdf_load_stackoverflow)
CN (1) CN100552008C (enrdf_load_stackoverflow)
BR (1) BRPI0510330B8 (enrdf_load_stackoverflow)
CA (1) CA2558546C (enrdf_load_stackoverflow)
ES (1) ES2680483T3 (enrdf_load_stackoverflow)
MX (1) MXPA06011986A (enrdf_load_stackoverflow)
WO (1) WO2005108532A1 (enrdf_load_stackoverflow)

Families Citing this family (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PT1453872E (pt) * 2002-03-01 2016-06-02 Evonik Oil Additives Gmbh Copolímeros como aditivos de desparafinagem
DE10249295A1 (de) 2002-10-22 2004-05-13 Rohmax Additives Gmbh Polymerdispersionen mit hoher Stabilität und Verfahren zur Herstellung
DE10249292A1 (de) * 2002-10-22 2004-05-13 Rohmax Additives Gmbh Polymerdispersionen mit geringer Viskosität und Verfahren zur Herstellung
DE10249294A1 (de) * 2002-10-22 2004-05-13 Rohmax Additives Gmbh Stabile Polymerdispersionen und Verfahren zur Herstellung
DE10314776A1 (de) * 2003-03-31 2004-10-14 Rohmax Additives Gmbh Schmierölzusammensetzung mit guten Reibeigenschaften
DE102004018094A1 (de) * 2004-04-08 2005-11-03 Rohmax Additives Gmbh Polymere mit H-Brücken bildenden Funktionalitäten zur Verbesserung des Verschleißschutzes
DE102004018093A1 (de) * 2004-04-08 2005-10-27 Rohmax Additives Gmbh Polymere mit H-Brücken bildenden Funktionalitäten
DE102004021778A1 (de) * 2004-04-30 2005-12-08 Rohmax Additives Gmbh Verwendung von Polyalkyl(meth)acrylaten in Schmierölzusammensetzungen
US7429555B2 (en) 2004-04-30 2008-09-30 Rohmax Additives Gmbh Lubricating grease with high water resistance
DE102004021717A1 (de) * 2004-04-30 2005-11-24 Rohmax Additives Gmbh Verfahren zur Herstellung von Schmierfett
DE102004034618A1 (de) * 2004-07-16 2006-02-16 Rohmax Additives Gmbh Verwendung von Pfropfcopolymeren
DE102004037929A1 (de) * 2004-08-04 2006-03-16 Rohmax Additives Gmbh Verfahren zur radikalischen Polymerisation ethylenisch-ungesättigter Verbindungen
DE102005015931A1 (de) * 2005-04-06 2006-10-12 Rohmax Additives Gmbh Polyalkyl(meth) acrylat-Copolymere mit hervorragenden Eigenschaften
US7648950B2 (en) * 2005-04-22 2010-01-19 Rohmax Additives Gmbh Use of a polyalkylmethacrylate polymer
DE102005031244A1 (de) * 2005-07-01 2007-02-15 Rohmax Additives Gmbh Öllösliche Kammpolymere
DE102005041528A1 (de) * 2005-08-31 2007-03-01 Rohmax Additives Gmbh Öllösliche Polymere
US20070087804A1 (en) * 2005-09-09 2007-04-19 Knowles Brandon D Method and apparatus for wagering on event outcomes of a game
DE102006001771A1 (de) * 2006-01-12 2007-07-19 Röhm Gmbh Verfahren zur Aufreinigung von (Meth)acrylaten
DE102006016588A1 (de) * 2006-04-06 2007-10-18 Rohmax Additives Gmbh Kraftstoffzusammensetzungen umfassend nachwachsende Rohstoffe
FR2902103B1 (fr) * 2006-06-09 2011-11-18 Coatex Sas Procede pour epaissir des compositions aqueuses notamment a ph acide, au moyen de polymeres organophosphates, et compositions aqueuses obtenues
DE102006039420A1 (de) 2006-08-23 2008-02-28 Evonik Rohmax Additves Gmbh Verfahren zur Herstellung von Methacrylatestern
US20080090742A1 (en) * 2006-10-12 2008-04-17 Mathur Naresh C Compound and method of making the compound
RU2470066C2 (ru) * 2007-04-13 2012-12-20 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Композиция гидроксида лития, способ получения композиции гидроксида лития и способ использования композиции гидроксида лития
DE102007036856A1 (de) * 2007-08-06 2009-02-26 Evonik Rohmax Additives Gmbh Verwendung von Estergruppen-umfassenden Polymeren als Antifatigue-Additive
US8802606B2 (en) 2010-08-06 2014-08-12 Basf Se Lubricant composition having improved antiwear properties
CN102549124B (zh) 2009-08-07 2016-05-11 巴斯夫欧洲公司 包含烷基醚羧酸的润滑剂组合物
US8415284B2 (en) * 2009-11-05 2013-04-09 Afton Chemical Corporation Olefin copolymer VI improvers and lubricant compositions and uses thereof
WO2011066455A1 (en) * 2009-11-25 2011-06-03 Skf Usa Inc. Grease test kit and methods of testing grease
JP5826626B2 (ja) * 2011-12-22 2015-12-02 昭和シェル石油株式会社 グリース組成物
EP2695932A1 (en) 2012-08-08 2014-02-12 Ab Nanol Technologies Oy Grease composition
WO2015172846A1 (en) 2014-05-16 2015-11-19 Ab Nanol Technologies Oy Additive composition for lubricants
JP2016089108A (ja) * 2014-11-10 2016-05-23 株式会社日立製作所 エレベーターロープ及びそれを用いたエレベーター
JP6862359B2 (ja) * 2016-01-12 2021-04-21 Ｅｎｅｏｓ株式会社 潤滑油組成物
EP3404049B1 (en) 2016-01-12 2020-08-12 Kuraray Co., Ltd. (meth)acrylate polymer
WO2018033449A1 (en) * 2016-08-15 2018-02-22 Evonik Oil Additives Gmbh Functional polyalkyl (meth)acrylates with enhanced demulsibility performance
EP3722395A4 (en) * 2017-12-05 2021-08-04 Adeka Corporation Anti-friction compound and anti-friction compound with the anti-friction compound

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2577706A (en) * 1948-11-26 1951-12-04 California Research Corp High melting-high water-resistant grease
US2704276A (en) * 1954-02-12 1955-03-15 Gulf Research Development Co Lubricating compositions
FR1226563A (fr) * 1959-02-20 1960-07-13 Exxon Standard Sa Graisses améliorées
US3252949A (en) * 1960-12-30 1966-05-24 Monsanto Co Syndiotactic oil-soluble methacrylate polymers
US3705853A (en) * 1970-09-23 1972-12-12 Mobil Oil Corp Grease compositions
US4357249A (en) * 1980-09-11 1982-11-02 Arguto, Inc. Self-lubricating bearing and the like, and method of making same
US5416162A (en) * 1993-09-20 1995-05-16 Rohm And Haas Company Compatibilizer for a viscosity index improving polymer blend
PT1453872E (pt) 2002-03-01 2016-06-02 Evonik Oil Additives Gmbh Copolímeros como aditivos de desparafinagem
JP3813595B2 (ja) * 2002-03-27 2006-08-23 三洋化成工業株式会社 潤滑油用摩擦調整剤及び潤滑油組成物
DE10249295A1 (de) 2002-10-22 2004-05-13 Rohmax Additives Gmbh Polymerdispersionen mit hoher Stabilität und Verfahren zur Herstellung
DE10249294A1 (de) 2002-10-22 2004-05-13 Rohmax Additives Gmbh Stabile Polymerdispersionen und Verfahren zur Herstellung
DE10249292A1 (de) 2002-10-22 2004-05-13 Rohmax Additives Gmbh Polymerdispersionen mit geringer Viskosität und Verfahren zur Herstellung
DE10314776A1 (de) 2003-03-31 2004-10-14 Rohmax Additives Gmbh Schmierölzusammensetzung mit guten Reibeigenschaften
US7429555B2 (en) 2004-04-30 2008-09-30 Rohmax Additives Gmbh Lubricating grease with high water resistance
DE102004021717A1 (de) * 2004-04-30 2005-11-24 Rohmax Additives Gmbh Verfahren zur Herstellung von Schmierfett

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
WO2005108532A1 (de) 2005-11-17
KR20070015555A (ko) 2007-02-05
ES2680483T3 (es) 2018-09-07
CN100552008C (zh) 2009-10-21
US20050245406A1 (en) 2005-11-03
MXPA06011986A (es) 2007-01-25
JP5150250B2 (ja) 2013-02-20
CA2558546A1 (en) 2005-11-17
CA2558546C (en) 2014-05-20
US7429555B2 (en) 2008-09-30
BRPI0510330A (pt) 2007-10-23
BRPI0510330B8 (pt) 2018-04-10
JP2007535595A (ja) 2007-12-06
BRPI0510330B1 (pt) 2014-10-29
CN1910268A (zh) 2007-02-07
EP1753847A1 (de) 2007-02-21

Similar Documents

Publication Publication Date Title
EP1753847B1 (de) Schmierfett mit hoher wasserresistenz
EP1866351B1 (de) Schmierölzusammensetzung enthaltend polyalkyl(meth)acrylat-copolymere
WO2006094520A9 (de) Verfahren zur herstellung von schmierfett
WO2004087850A1 (de) Schmierölzusammensetzung mit guten reibeigenschaften
DE102004021778A1 (de) Verwendung von Polyalkyl(meth)acrylaten in Schmierölzusammensetzungen
EP1240218B1 (de) Gradientencopolymere sowie verfahren zur herstellung und verwendung
EP1740631B1 (de) Polymere mit h-brücken bildenden funktionalitäten
DE102005041528A1 (de) Öllösliche Polymere
DE102004034618A1 (de) Verwendung von Pfropfcopolymeren
DE102007036856A1 (de) Verwendung von Estergruppen-umfassenden Polymeren als Antifatigue-Additive
EP1733011A1 (de) Polymere mit h-brücken bilden funktionalitäten zur verbesserung des verschleisschutzes
WO2012123192A1 (de) Estergruppen-umfassende copolymere und deren verwendung in schmiermitteln
EP1334133B1 (de) Verfahren zur kontinuierlichen herstellung von polymerzusammensetzungen sowie verwendung
DE102009002730A1 (de) Verfahren zur Herstellung von polymeren (VI)-Verbesserern mit polaren Gruppen sowie deren Verwendung
MXPA06011985A (es) Proceso para producir grasa lubricante

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20060613

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU MC NL PL PT RO SE SI SK TR

RIN1 Information on inventor provided before grant (corrected)

Inventor name: KINKER, BERNARD

Inventor name: FISCHER, MATTHIAS

Inventor name: MUELLER, MICHAEL

Inventor name: PAUKER, ALEXNDRA

Inventor name: SCHERER, MARKUS, DR.

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: EVONIK ROHMAX ADDITIVES GMBH

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: EVONIK OIL ADDITIVES GMBH

17Q First examination report despatched

Effective date: 20160205

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20180125

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 502005015835

Country of ref document: DE

Owner name: EVONIK OPERATIONS GMBH, DE

Free format text: FORMER OWNER: ROEHM ROHMAX HOLDING GMBH, 64293 DARMSTADT, DE

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1001519

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180615

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502005015835

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2680483

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20180907

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180823

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180523

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180523

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180824

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180523

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180523

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180523

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180523

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180523

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180523

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502005015835

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20190226

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180523

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180523

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190120

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190131

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190120

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 1001519

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190120

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180523

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190120

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180924

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 502005015835

Country of ref document: DE

Owner name: EVONIK OPERATIONS GMBH, DE

Free format text: FORMER OWNER: EVONIK OIL ADDITIVES GMBH, 64293 DARMSTADT, DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: HC

Owner name: EVONIK OPERATIONS GMBH; DE

Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), CHANGE OF OWNER(S) NAME; FORMER OWNER NAME: EVONIK DEGUSSA GMBH

Effective date: 20210209

Ref country code: NL

Ref legal event code: PD

Owner name: EVONIK DEGUSSA GMBH; DE

Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), MERGE; FORMER OWNER NAME: EVONIK OIL ADDITIVES GMBH

Effective date: 20210209

REG Reference to a national code

Ref country code: ES

Ref legal event code: PC2A

Owner name: EVONIK OPERATIONS GMBH

Effective date: 20210322

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20210325 AND 20210331

REG Reference to a national code

Ref country code: BE

Ref legal event code: HC

Owner name: EVONIK OPERATIONS GMBH; DE

Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), CHANGE OF OWNER(S) NAME

Effective date: 20210223

Ref country code: BE

Ref legal event code: PD

Owner name: EVONIK DEGUSSA GMBH; DE

Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), MERGE

Effective date: 20210223

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180523

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180923

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20050120

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230124

Year of fee payment: 19

Ref country code: ES

Payment date: 20230330

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20230119

Year of fee payment: 19

Ref country code: IT

Payment date: 20230120

Year of fee payment: 19

Ref country code: GB

Payment date: 20230119

Year of fee payment: 19

Ref country code: DE

Payment date: 20230123

Year of fee payment: 19

Ref country code: BE

Payment date: 20230119

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20230119

Year of fee payment: 19

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230526

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502005015835

Country of ref document: DE

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20240201

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20240120

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240801

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240120

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240201

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240120

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240131

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240801

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240131

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20240131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240120

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20250228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240121