EP1753847A1 - Schmierfett mit hoher wasserresistenz - Google Patents
Schmierfett mit hoher wasserresistenzInfo
- Publication number
- EP1753847A1 EP1753847A1 EP05701058A EP05701058A EP1753847A1 EP 1753847 A1 EP1753847 A1 EP 1753847A1 EP 05701058 A EP05701058 A EP 05701058A EP 05701058 A EP05701058 A EP 05701058A EP 1753847 A1 EP1753847 A1 EP 1753847A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- grease
- monomer compositions
- polymeric
- improvers
- 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.)
- Granted
Links
Classifications
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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
- 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
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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
- 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
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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
- 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
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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
- 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
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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
- 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
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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
- 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
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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
- 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—Semi-solids; greasy
Definitions
- the present invention relates to grease with high water resistance.
- Greases are known per se and are widely used. Lubricating greases, hereinafter also referred to as “greases", are solid to semi-liquid substances which are created by dispersing a thickener in a liquid lubricant. Other additives (additives) that confer special properties may be included.
- the basic consistency of a fat is determined by the combination of base liquid and thickener.
- the base liquid is usually a base oil common in the lubricant industry, e.g. Mineral oil, synthetic oil or vegetable oil.
- Simple metal soaps are very often, but not exclusively, used as thickeners. Furthermore, but rarely, complex metal soaps, organically modified clay (bentonite) or polyurea are used. From a physical point of view, the thickeners form the solid phase of the dispersion and, in addition to the base oil, decisively determine the physical / mechanical properties of the fat, e.g. Low temperature behavior, water resistance, dropping point, or oil separation behavior.
- U.S. 3,476,532, Hartman, Nov. 4, 1969 describes metal containing complexes of oxidized polyethylene containing functional oxygen groups e.g. Carbonyl, carboxyl, or hydroxy groups.
- 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.
- US 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 with a number average molecular weight between 300 and 12000 g / mol.
- US 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 made from isobutylene or a copolymer made from ethylene, butylene or isobutylene with a C3 to C30 olefin. Copolymers consisting of 60-90% ethylene and 40-10% vinyl acetate, alkyl acrylates or alkyl methacrylates are used as viscosity index improvers. The composition has very good high-temperature adhesiveness and low-temperature softening.
- EP 806,469 and US 5,858,934, Wiggins et al, May 8, 1996 describe an improved biodegradable grease composition from a base oil on a natural basis or based on a synthetic triglyceride, a performance additive consisting of an alkylphenol, a benzotriazole or an aromatic amine, and a thickener which is the reaction product of a metal-based material and a carboxylic acid or its ester.
- the grease may also contain viscosity modifiers, pour point improvers, or a combination of both.
- OCPs reactively modified copolymers based on olefin copolymers
- the addition of polymers to lubricating greases improves certain physical parameters, for example rheological properties or the water resistance of the greases.
- certain physical parameters for example rheological properties or the water resistance of the greases.
- the improvement of a property, such as water resistance should not be associated with an excessive deterioration of other properties, such as manageability or homogeneity.
- the greases should have a particularly high water resistance, an excellent consistency and a high degree of homogeneity.
- Another task can be seen in providing greases with improved temperature properties.
- the properties at low temperatures should be improved.
- the greases should be able to be used over a particularly wide temperature range.
- the greases should be able to be produced inexpensively. Production should be able to be carried out on an industrial scale without the need for new or structurally complex systems.
- a grease which comprises at least one thickener and at least one lubricating oil, contains at least one polymeric structural improver, which can be obtained by polymerizing monomer compositions, which from a) 0 to 40 wt .-%, based on the weight of the monomer compositions Preparation of the polymeric structure improvers, at least one (meth) acrylate of the formula (I) wherein R represents hydrogen or methyl, R 1 represents a linear or branched alkyl radical having 1 to 5 carbon atoms, b) 40 to 99.99% by weight, based on the weight of the monomer compositions for the preparation of the polymeric structural improvers, at least one (meth) acrylate of formula (II)
- R represents hydrogen or methyl
- R 2 represents a linear or branched alkyl radical having 6 to 30 carbon atoms
- d) 0 to 59.99% by weight based on the weight of the monomer compositions for the preparation of the polymeric structural improver, comonomer, it is possible to provide greases which have improved properties in a manner which is not readily predictable.
- the lubricating greases according to the invention can achieve a number of further advantages. These include:
- the greases according to the invention have a very high water resistance. > The greases according to the invention show good homogeneity. The consistency of the grease can be adjusted over a wide range.
- the greases according to the invention have very good temperature properties.
- the lubricating greases according to the invention can thus be used over a particularly wide temperature range.
- the properties are excellent at low temperatures.
- the lubricating greases according to the invention can be subsequently produced by modification of known lubricating greases, a polymeric structural improver being added to a known fat. In this way, in particular high storage costs can be avoided. Furthermore, customer requests can be reacted to quickly. Here, the consistency of the grease changes only slightly, whereas the water resistance increases significantly.
- the lubricating greases according to the invention comprise polymeric structure improvers. These polymers generally lead to an improvement in water resistance. It is assumed here that these polymers enter into physical-chemical interaction with the thickeners, for example the soap molecules, without this being intended to impose a restriction.
- Mixtures from which the polymeric structure improvers can be obtained can contain 0 to 40% by weight, in particular 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
- R 1 represents a linear or branched alkyl radical having 1 to 5 carbon atoms.
- (meth) acrylates encompasses methacrylates and acrylates and mixtures of the two. These monomers are well known.
- the alkyl radical can 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, isopropyl (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.
- compositions to be polymerized for the production of preferred polymeric structural improvers contain 40 to 99.99% by weight, in particular 55 to 95% by weight, based on the weight of the monomer compositions for producing the polymeric structural improvers, 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.
- Nonadecyl (meth) acrylate eicosyl (meth) acrylic, cetyleicosyl (meth) acrylate,
- Cycloalkyl (meth) acrylates such as 2,4,5-tri-t-butyl-3-vinylcyclohexyl (meth) acrylate,
- Cycloalkyl (meth) acrylates such as 3-vinylcyclohexyl (meth) acrylate,
- the (meth) acrylates with long-chain alcohol radical in particular the compounds according to component (b), can be, for example, by Reacting (meth) acrylates and / or the corresponding acids with long-chain fatty alcohols, a mixture of esters such as (meth) acrylates with different long-chain alcohol residues generally being formed.
- These fatty alcohols include, among others, Oxo Alcohol® 7911 and Oxo Alcohol® 7900, Oxo Alcohol® 1100 from Monsanto; Alphanoi® 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® types from Cognis.
- the mixture for producing preferred polymeric structure improvers has at least 60% by weight, preferably at least 70% by weight, based on the weight of the monomer compositions for producing the polymeric structure improvers, monomers of the formula (II).
- the methacrylates are preferred over the acrylates.
- the proportion of (meth) acrylates having 6 to 15 carbon atoms in the alcohol radical is preferably in the range from 20 to 95% by weight, based on the weight of the monomer composition for the preparation of the polymeric structural improvers.
- the proportion of (meth) acrylates with 16 to 30 carbon atoms in the alcohol radical is preferably in the range from 0.5 to 60% by weight, based on the weight of the monomer composition for the preparation of the polymeric structural improvers.
- Component c) of the composition to be used for the production of preferred polymeric structure improvers comprises in particular monomers comprising salts or their salts.
- Preferred salts are in particular the alkali metal salts, such as the lithium, sodium and / or potassium salts; the alkaline earth metal salts, such as, for example, the calcium and / or barium salts, and also the aluminum salts and the ammonium salts.
- alkali metal salts such as the lithium, sodium and / or potassium salts
- alkaline earth metal salts such as, for example, the calcium and / or barium salts, and also the aluminum salts and the ammonium salts.
- the proportion of components c) is generally 0.01 to 20% by weight, preferably 0.1 to 10% by weight and particularly preferably 0.5 to 5% by weight, based on the weight of the monomer compositions for the preparation the polymeric structure improver.
- These compounds can generally be copolymerized with the monomers according to component a), b) and d).
- ethylenically unsaturated compounds such as, for example, vinylsulfonic acid, vinylphosphonic acid, acrylic acid, methacrylic acid, fumaric acid, monoesters of fumaric acid, where the alcohol radical can generally comprise 1 to 30 carbon atoms, maleic acid, monoesters of maleic acid, the alcohol residue generally may include 1 to 30 carbon atoms, vinyl benzoic acid and sulfonated styrenes such as styrene sulfonic acid.
- the salts derived from these acids in particular the alkali metal, alkaline earth metal and / or aluminum salts, can be used.
- Component d) of the composition to be used to prepare preferred polymeric structure improvers comprises, in particular, ethylenically unsaturated monomers which can be copolymerized with the monomers according to components a) to c).
- comonomers are particularly suitable for the polymerization according to the present invention, which correspond to the formula:
- halogen preferably fluorine or chlorine
- Aryl (meth) acrylates such as benzyl methacrylate or
- Phenyl methacrylate where the aryl radicals can be unsubstituted or substituted up to four times;
- Halogenated alcohol methacrylates such as
- Vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride;
- Vinyl esters such as vinyl acetate
- Styrene substituted styrenes with an alkyl substituent in the side chain, such as. B. ⁇ -methylstyrene and ⁇ -ethylstyrene, substituted styrenes with a
- Halogenated alkyl substituents such as vinyltuluol and p-methylstyrene
- Styrenes such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and
- Heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl
- N-vinylpyrrolidine 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam,
- Maleic acid derivatives such as, for example, the diesters of maleic acid, the
- Alcohol radical can generally comprise 1 to 30 carbon atoms
- Fumaric acid derivatives such as, for example, the diesters of fumaric acid, the
- Alcohol radical can generally comprise 1 to 30 carbon atoms
- compositions for the production of preferred structural improvers particularly preferably comprise comonomers according to component d) which can be represented by the formula (IV),
- R is independently hydrogen or methyl
- R 9 is independently a group comprising 2 to 1000 carbon atoms with at least one hetero atom
- X is independently a sulfur or oxygen atom or a group of the formula NR 10 , wherein R 10 is independently hydrogen or a group with 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 expression "2 to 1000 carbon-containing group” denotes residues of organic compounds with 2 to 1000 carbon atoms. It includes aromatic and heteroaromatic groups as well as alkyl, cycloalkyl, alkoxy, cycloalkoxy, alkenyl, alkanoyl, alkoxycarbonyl groups and heteroalipatic groups.
- the groups mentioned can be branched or not branched. Furthermore, these groups can have customary substituents.
- Substituents are, for example, linear and branched alkyl groups with 1 to 6 carbon atoms, such as 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 denote residues of mono- or polynuclear aromatic compounds with preferably 6 to 20, in particular 6 to 12, carbon atoms.
- Heteroaromatic groups characterize 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 3 to 19 carbon atoms.
- Aromatic or heteroaromatic groups preferred according to the invention are derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane, diphenyldimethylmethane, bisphenone, diphenylsulfone, thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole, isoxazole, 3,4-oxazole, pyrazole , 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] thiophen
- the preferred alkyl groups include the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl, tert-butyl radical, 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.
- the preferred cycloalkyl groups include the cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and the cyclooctyl group, which are optionally substituted with branched or unbranched alkyl groups.
- the preferred alkenyl groups include the vinyl, allyl, 2-methyl-2-propene, 2-butenyl, 2-pentenyl, 2-decenyl and the 2-eicosenyl groups.
- the preferred alkynyl groups include the ethynyl, propargyl, 2-methyl-2-propyne, 2-butynyl, 2-pentynyl and the 2-decynyl group.
- the 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 group, hexyloxycarbonyl, 2-methylhexyloxycarbonyl, decyloxycarbonyl or dodecyloxycarbonyl group.
- Preferred alkoxy groups include alkoxy groups whose hydrocarbon residue is one of the preferred alkyl groups mentioned above.
- the preferred cycloalkoxy groups include cycloalkoxy groups whose hydrocarbon radical is one of the preferred cycloalkyl groups mentioned above.
- the preferred heteroatoms contained in the radical R 10 include 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 , where R 10 independently comprises hydrogen or a group having 1 to 20 carbon atoms.
- the group X in formula (IV) can preferably 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 in wide ranges. 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 radical R 9 of the formula (IV) comprises 2 to 1000 carbon atoms. In a particular aspect, the R 9 radical has at most 10 carbon atoms.
- the particularly preferred comonomers include, among others
- Glycol dimethacrylates such as 1,4-butanediol methacrylate, 2-butoxyethyl methacrylate,
- Methacrylates of ether alcohols such as
- Ethoxymethyl methacrylate and ethoxylated (meth) acrylates preferably 1 to
- Aminoalkyl (meth) acrylates and aminoalkyl (meth) acrylatamides such as
- Nitriles of (meth) acrylic acid and other nitrogen-containing methacrylates such as
- heterocyclic (meth) acrylates such as 2- (1-imidazolyl) ethyl (meth) acrylate,
- Oxiranyl methacrylates such as
- Phosphorus, boron and / or silicon-containing methacrylates such as
- These monomers can be used individually or as a mixture.
- the ethoxylated (meth) acrylates can, for example, by transesterification of
- Alkyl (meth) acrylates with ethoxylated alcohols which are particularly preferably obtained having 1 to 20, in particular 2 to 8, ethoxy groups.
- the hydrophobic radical of the ethoxylated alcohols can 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
- Lutensol ® A- brands especially Lutensol ® A 3 N, Lutensol ® A 4 N, N Lutensol ® A 7 and A 8 Lutensol ® 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 ® 89
- Marlipal ® 24/40 Marlipal ® 013/20, Marlipal ® 013/30, Marlipal ® 013/40, Marlipal ® O25 / 30, Marlipal ® O25 / 70, Marlipal ® O45 / 30, Marlipal ® O45 / 40, Marlipal ® O45 / 50, Marlipal ® O45 / 70 and Marlipal ® O45 / 80.
- 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 producing the polymeric structure improvers have methyl methacrylate, butyl methacrylate, lauryl methacrylate, stearyl methacrylate and / or styrene.
- the preferred polymeric structure improvers generally have a molecular weight in the range from 10,000 to 1,000,000 g / mol, preferably in the range from 15 * 10 3 to 500 * 10 3 g / mol and particularly preferably in the range from 20 * 10 3 to 300 * 10 3 g / mol, without any limitation. These values relate to the weight average molecular weight of the polydisperse polymers in the composition. This size can be determined in a known manner by gel permeation chromatography.
- polymeric structural improvers from the compositions described above is known per se.
- ATRP atom transfer radical polymerization
- RAFT reversible addition fragmentation chain transfer
- free radical polymerization is set out in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, among others.
- a polymerization initiator is generally used for this.
- azo initiators well known in the art, such as AIBN and 1, 1-azobiscyclohexane carbonitrile, and also peroxy compounds, such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert.-butyl per-2-ethylhexanoate, ketone peroxide, tert-butyl peroctoate, methyl peronutoxate, methyl peroxide, Dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, 2,5-bis (2-ethylhexanoyl-peroxy) -2,5-dimethylhexane, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3,5,5 trimethyl hexanoate, dicumyl peroxide,
- the ATRP method is known per se. It is believed that this is a "living" radical polymerization, without any limitation by the description of the mechanism.
- a transition metal compound is reacted with a compound that has a transferable atomic group.
- the transferable atom 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 transferred back to the growing polymer chain, thereby forming a controlled polymerization system. Accordingly, the structure of the polymer, the molecular weight and the molecular weight distribution can be controlled.
- This reaction is carried out, for example, by JS. Wang, et al.
- polymers according to the invention can also be obtained, for example, using RAFT methods. This method is described in detail in WO 98/01478, for example, to which express reference is made for the purposes of the disclosure.
- the polymerization can be carried out under normal pressure, negative pressure or positive pressure.
- the polymerization temperature is also not critical. In general, however, it is in the range from -20 ° to 200 ° C, preferably 0 ° to 130 ° C and particularly preferably 60 ° to 120 ° C.
- the polymerization can be carried out with or without a solvent.
- solvent is to be understood broadly here.
- the polymerization is preferably carried out in a non-polar solvent.
- a non-polar solvent include hydrocarbon solvents, such as, for example, aromatic solvents, such as toluene, benzene and xylene, saturated hydrocarbons, such as, for example, cyclohexane, heptane, octane, nonane, decane, dodecane, which can also be branched.
- hydrocarbon solvents such as, for example, aromatic solvents, such as toluene, benzene and xylene
- saturated hydrocarbons such as, for example, cyclohexane, heptane, octane, nonane, decane, dodecane, which can also be branched.
- solvents can be used individually or as a mixture.
- Particularly preferred solvents are mineral oils, natural oils and synthetic oils as well as mixtures thereof. Of these, mineral oils are particularly preferred.
- the polymeric structure improvers
- the polymeric structure improver is obtainable by graft polymerization, a composition comprising components a) to d) being polymerized onto a graft base which is an olefin copolymer (OCP) which is composed predominantly of ethylene and propylene, and / or comprises a hydrogenated copolymer (HSD) of diene and styrene.
- OCP olefin copolymer
- HSD hydrogenated copolymer
- the polyolefin copolymers (OCP) that can be used for this purpose are known per se. These are primarily polymers composed of ethylene, propylene, isoprene, butylene and / or other olefins having 5 to 20 carbon atoms. Systems which are grafted with small amounts of oxygen- or nitrogen-containing monomers (e.g. 0.05 to 5% by weight of maleic anhydride) can also be used.
- the copolymers containing diene components are generally hydrogenated to reduce the sensitivity to oxidation and the tendency to crosslink the polymers.
- the molecular weight Mw is generally from 10,000 to 300,000, preferably from 50,000 to 150,000.
- Such olefin copolymers are described, for example, in German Offenlegungsschriften DE-A 16 44 941, DE-A 17 69 834, DE-A 19 39 037, DE-A 19 63 039 and DE-A 20 59 981.
- Ethylene-propylene copolymers are particularly useful; terpolymers with the known ter components, such as ethylidene-norbornene (cf. Macromolecular Reviews, Vol. 10 (1975)) are also possible, but their tendency to crosslink during the aging process must be taken into account.
- the distribution can be largely statistical, but it can also be with Advantage sequence polymers with ethylene blocks can be applied.
- the ratio of the monomers ethylene-propylene is variable within certain limits, which can be set as the upper limit at about 75% for ethylene and about 80% for propylene.
- polypropylene is already less suitable than ethylene-propylene copolymers.
- those with more pronounced iso- or syndiotactic propylene incorporation can also be used.
- Such products are commercially available for example under the trade names Dutral CO 034 ®, ® Dutral CO 038, Dutral CO 043 ®, ® Dutral CO 058, Buna ® EPG 2050 or Buna ® EPG 5050th
- the hydrogenated styrene-diene copolymers are also known, these polymers being described for example in DE 21 56 122. They are generally hydrogenated isoprene or butadiene-styrene copolymers.
- the ratio of diene to styrene is preferably in the range from 2: 1 to 1: 2, particularly preferably around 55:45.
- the molecular weight Mw is generally from 10,000 to 300,000, preferably between 50,000 and 150,000.
- the proportion of double bonds after the hydrogenation is at most 15%, particularly preferably at most 5%, based on the number of double bonds before hydrogenation.
- Hydrogenated styrene-diene copolymers can be obtained commercially under the trade name ®SHELLVIS 50, 150, 200, 250 or 260.
- the preparation of the graft copolymers described above, which have at least one HSD and / or OCP block and at least one block comprising the components a), b) c) and / or d) described above, is known in the art.
- the production can be carried out via a Polymerization take place in solution.
- Such processes are described, inter alia, in DE-A 12 35491, BE-A 592 880, US-A 4281 081, US-A 4 338 418 and US-A-4,290,025.
- the polymeric structural improver is preferably present in the grease in an amount in the range from 0.1 to 10% by weight, particularly preferably 0.5 to 5% by weight, based on the total weight.
- the lubricating oils contained in the lubricating greases according to the invention include in particular mineral oils, synthetic oils and natural oils.
- Mineral oils are known per se and are commercially available. They are generally obtained from petroleum or crude oil by distillation and / or refining and, if appropriate, further purification and upgrading processes, the term mineral oil in particular referring to the higher-boiling proportions of the crude or petroleum. In general, the boiling point of mineral oil is higher than 200 ° C, preferably higher than 300 ° C, at 5000 Pa. It is also possible to produce by smoldering shale oil, coking hard coal, distilling with the exclusion of air from brown coal and hydrogenating hard coal or brown coal. To a small extent, mineral oils are also made from raw materials of vegetable (e.g. jojoba, rapeseed) or animal (e.g. claw oil) origin. Accordingly, mineral oils have different proportions of aromatic, cyclic, branched and linear hydrocarbons depending on their origin.
- vegetable e.g. jojoba, rapeseed
- animal e.g. claw oil
- paraffin-based, naphthenic and aromatic fractions in crude oils or mineral oils, the terms paraffin-based fraction for longer-chain or strongly branched isoalkanes and naphthenic fraction for cycloalkanes.
- mineral oils depending on their origin and refinement, have different proportions of n-alkanes, iso-alkanes with a low degree of branching, so-called monomethyl-branched paraffins, and compounds with heteroatoms, in particular O, N and / or S, which are believed to have limited polar properties. The assignment is difficult, however, since individual alkane molecules can have long-chain branched groups as well as cycloalkane residues and aromatic components.
- mineral oil mainly comprises naphthenic and paraffin-based alkanes, which generally have more than 13, preferably more than 18 and very particularly preferably more than 20 carbon atoms.
- the proportion of these compounds is generally> 60% by weight, preferably> 80% by weight, without any intention that this should impose a restriction.
- a preferred mineral oil contains 0.5 to 30% by weight of aromatic components, 15 to 40% by weight of naphthenic components, 35 to 80% by weight of paraffin-based components, up to 3% by weight of n-alkanes and 0.05 up to 5% by weight of polar compounds, in each case based on the total weight of the mineral oil.
- Liquid chromatography on silica gel shows the following components, the percentages relating to the total weight of the mineral oil used in each case: n-alkanes with about 18 to 31 carbon atoms:
- Synthetic oils include, inter alia, organic esters, for example diesters and polyesters, polyalkylene glycols, polyethers, synthetic hydrocarbons, in particular polyolefins, of which polyalphaolefins (PAO) are preferred, silicone oils and perfluoroalkyl ethers. They are usually somewhat more expensive than 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 commercially available in many cases.
- the lubricating grease preferably comprises 69.9 to 98.9% by weight, in particular 75 to 95% by weight, of lubricating oil, based on the total weight.
- the thickeners contained in the greases according to the invention are known per se in the art and can be obtained commercially. These are, among others, in Ullmanns's Encyclopedia of Industrial Chemistry, Sixth Edition, Vol. 20,2003, 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, which often have 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 can comprise anions which are 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 as well as benzoic acid.
- the soap thickeners can be used as such in the process to produce a fat-rich dispersion. Furthermore, these can also be generated in situ from the corresponding acids or their derivatives, for example, their esters and basic metal compounds are produced.
- esters with a short-chain alcohol radical having 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 aforementioned metals.
- the preferred soap thickeners include lithium 12-hydroxystearate, lithium complex soaps, aluminum complex soaps and calcium complex soaps.
- the basic compounds for the production of the soaps can be added in an excess or deficit, with under- or overbased compounds being formed.
- Inorganic thickeners can also be used. These include in particular organophilic clays, which can be derived from bentonite, and silica gel.
- Polymeric thickeners can also be used. These include polyureas and thermoplastic powders such as polytetrafluoroethylene and fluoroethylene propylene.
- the lubricating grease preferably comprises 0.01 to 30% by weight, particularly preferably 0.2 to 15% by weight and very particularly preferably 0.5 to 10% by weight, based on the total weight.
- the weight ratio of lubricating oil to thickener in the grease is generally in the range from 100: 1 to 100: 30, preferably 100: 2 to 100: 25, in particular 100: 5 to 100: 15.
- the lubricating grease according to the invention can contain further additives.
- additives include, among others, viscosity index improvers, antioxidants, anti-aging agents, anti-wear agents, corrosion inhibitors, detergents, dispersants, EP additives, friction reducers, dyes, odorants, metal deactivators and / or demulsifiers.
- a grease according to the invention preferably 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 from 175 to 385 dmm, particularly preferably in the range from 220 dmm to 340 dmm.
- 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 preferably be used below a temperature of 0 ° C., particularly preferably of -10 ° C.
- preferred lubricating greases can also be used at high temperatures of at least 50 ° C., particularly preferably at least 90 ° C.
- the lubricating greases according to the invention can be produced on the basis of the customary processes, which can be found in the aforementioned prior art.
- the grease structure or grease matrix is generated by physico-chemical processes.
- a metal soap is produced from preliminary products in a first stage.
- metal soap molecules are generated by reacting the corresponding starting materials in the base oil.
- the metal soap molecules are present as fine crystals. This level is optional because it is not necessary by choosing the appropriate pre-connections.
- the polymeric structure improvers can be added before, during or after the structure formation phase.
- the polymeric structural improver can first be produced in a mineral oil.
- a thickener, or pre-compounds for producing the thickener, can then be added to the mixture obtained.
- the polymeric structure improver can be added after the structure formation phase, for example a grease.
- the polymeric structure improver is preferably added in a composition which is liquid at 25 ° C. to a dispersion which has a fat structure.
- fat structure is known in the art, and this structure can be described as spongy.
- This structure of the dispersion can be demonstrated, for example, by microscopic images, the lubricating oil being held in a thickener.
- the composition can be both a dispersion and a solution. Accordingly, these compositions have at least one liquid medium.
- the particularly preferred media include, in particular, lubricating oils, which can also be used to produce the dispersion which comprises at least one thickener and at least one lubricating oil.
- Liquid media for dispersing or dissolving the polymeric structure improvers described above are known per se, these media should be compatible with the dispersion which comprises at least one thickener and at least one lubricating oil.
- Compatibility is understood here as the miscibility of the medium with the dispersion, which comprises at least one thickener and at least one lubricating oil.
- the composition which is liquid at 25 ° C. and has at least one polymeric structural improver has a viscosity at 25 ° C. in the range from 0.01 mm 2 / s to 100000 mm 2 / s, preferably 0.1 mm 2 / s to 20,000 mm 2 / s and particularly preferably from 1 mm 2 / s to 10,000 mm 2 / s according to DIN 51562.
- the concentration of the polymeric structural improver in the composition which is liquid at 25 ° C. is preferably in the range from 1 to 99% by weight, particularly preferably in the range from 5 to 89% by weight and very particularly preferably in the range from 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 composition which is liquid at 25 ° C. and comprises at least one polymeric structural improver is preferably in the range from 100: 1 to 1: 1, particularly preferably in the range from 50: 1 to 5: 1 and very particularly preferably in the range from 25: 1 to 10: 1.
- the liquid composition at 25 ° C. can be added, inter alia, during a mechanical phase following the structure formation phase.
- liquid composition at 25 ° C can be added to a finished grease after the mechanical phase.
- This particular aspect of the present invention makes it possible, for example, to produce a large amount of a simple lubricating grease which can then be adapted in a further step to the special needs of the end customer by adding the composition which is liquid at 25 ° C. and which may contain further additives , This enables a particularly economical production of small amounts of special greases.
- the water resistance can be improved by at least 30%, particularly preferably by at least 50% and very particularly 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 fat structure and the composition which is liquid at 25 ° C. are essentially biodegradable. This is preferably measured in accordance with RAL-ZU 64.
- the dispersion comprising the liquid structure at 25 ° C. can be added to the fat structure by generally known methods. These include stirring, mixing, kneading, rolling and / or homogenizing.
- the temperature at which the dispersion comprising the liquid structure comprising the fat structure is added at 25 ° C. is not critical per se. At a high temperature, the liquid composition at 25 ° C is often easier to incorporate into the dispersion. However, the fat structure must be stable at the addition temperature.
- the liquid composition at 25 ° C. is added to the fat structure at a temperature below the dropping point of the dispersion before the liquid composition is added.
- the dropping point can be determined in accordance with ASTM D 2265.
- the composition which is liquid at 25 ° C. is particularly preferably added to the fat structure at a temperature which is at least 40 ° C., very particularly preferably at least 60 ° C., below the dropping point of the dispersion before the liquid composition is added.
- 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 typically measured in a 150 N measuring oil; the information in () shows the polymer concentration used.
- [ ⁇ ] denotes the intrinsic viscosity, measured according to DIN ISO 16281, part 6.
- IP 50 Taper penetration unprocessed: 285 dmm, after 60 movements 288 dmm (NLGI grade 2), after 100060 movements: 317 dmm.
- Example 1 was essentially repeated, but no solution was incorporated. The data obtained are set out in Table 1. Comparative Example 2
- Example 1 was essentially repeated, but with the incorporation of a solution comprising 50% by weight of polymers without acid groups, which were obtained according to Preparation Example 2, and a lubricating oil.
- the data obtained are set out in Table 1.
- Example 2 was essentially repeated, but no solution was incorporated.
- the data obtained are set out in Table 2.
- Example 2 was essentially repeated, with 40 g of the dispersion, which comprises 50% by weight of polymers with acid groups, which were obtained according to Preparation Example 1, and a lubricating oil, being incorporated into 960 g of lubricating grease from F&S Mannheim.
- the data obtained are set out in Table 2.
- Example 2 was essentially repeated, except that 10 g of a solution comprising 50% by weight of polymers without acid groups, which were obtained according to Preparation Example 2, and a lubricating oil were incorporated.
- the data obtained are set out in Table 2.
- Example 3 was essentially repeated, but 20 g of a solution comprising 50% by weight of polymers without acid groups, which were obtained according to Preparation Example 2, and a lubricating oil, were incorporated into 980 g of fat from F&S.
- the data obtained are set out in Table 2.
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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)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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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)
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EP1753847A1 true EP1753847A1 (de) | 2007-02-21 |
EP1753847B1 EP1753847B1 (de) | 2018-05-23 |
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US (1) | US7429555B2 (de) |
EP (1) | EP1753847B1 (de) |
JP (1) | JP5150250B2 (de) |
KR (1) | KR20070015555A (de) |
CN (1) | CN100552008C (de) |
BR (1) | BRPI0510330B8 (de) |
CA (1) | CA2558546C (de) |
ES (1) | ES2680483T3 (de) |
MX (1) | MXPA06011986A (de) |
WO (1) | WO2005108532A1 (de) |
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EP1740681A1 (de) * | 2004-04-30 | 2007-01-10 | Rohmax Additives GmbH | Verfahren zur herstellung von schmierfett |
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DE102004034618A1 (de) * | 2004-07-16 | 2006-02-16 | Rohmax Additives Gmbh | Verwendung von Pfropfcopolymeren |
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-
2004
- 2004-04-30 US US10/834,861 patent/US7429555B2/en active Active
-
2005
- 2005-01-20 KR KR1020067022428A patent/KR20070015555A/ko not_active Application Discontinuation
- 2005-01-20 CN CNB2005800024109A patent/CN100552008C/zh active Active
- 2005-01-20 BR BRPI0510330A patent/BRPI0510330B8/pt not_active IP Right Cessation
- 2005-01-20 CA CA2558546A patent/CA2558546C/en not_active Expired - Fee Related
- 2005-01-20 JP JP2007509889A patent/JP5150250B2/ja active Active
- 2005-01-20 MX MXPA06011986A patent/MXPA06011986A/es active IP Right Grant
- 2005-01-20 ES ES05701058.9T patent/ES2680483T3/es active Active
- 2005-01-20 EP EP05701058.9A patent/EP1753847B1/de active Active
- 2005-01-20 WO PCT/EP2005/000509 patent/WO2005108532A1/de not_active Application Discontinuation
Non-Patent Citations (1)
Title |
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See references of WO2005108532A1 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1740681A1 (de) * | 2004-04-30 | 2007-01-10 | Rohmax Additives GmbH | Verfahren zur herstellung von schmierfett |
Also Published As
Publication number | Publication date |
---|---|
CA2558546C (en) | 2014-05-20 |
WO2005108532A1 (de) | 2005-11-17 |
KR20070015555A (ko) | 2007-02-05 |
BRPI0510330B8 (pt) | 2018-04-10 |
CN1910268A (zh) | 2007-02-07 |
CN100552008C (zh) | 2009-10-21 |
MXPA06011986A (es) | 2007-01-25 |
CA2558546A1 (en) | 2005-11-17 |
JP5150250B2 (ja) | 2013-02-20 |
BRPI0510330A (pt) | 2007-10-23 |
BRPI0510330B1 (pt) | 2014-10-29 |
US20050245406A1 (en) | 2005-11-03 |
US7429555B2 (en) | 2008-09-30 |
EP1753847B1 (de) | 2018-05-23 |
ES2680483T3 (es) | 2018-09-07 |
JP2007535595A (ja) | 2007-12-06 |
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