EP2710103B1 - Polymers modifiant la friction pour surfaces revêtue avec dlc - Google Patents

Polymers modifiant la friction pour surfaces revêtue avec dlc Download PDF

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EP2710103B1
EP2710103B1 EP12722320.4A EP12722320A EP2710103B1 EP 2710103 B1 EP2710103 B1 EP 2710103B1 EP 12722320 A EP12722320 A EP 12722320A EP 2710103 B1 EP2710103 B1 EP 2710103B1
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meth
acrylate
element according
derived
acrylates
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EP2710103A1 (fr
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Boris Eisenberg
Torsten Stöhr
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Evonik Operations GmbH
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Evonik Oil Additives GmbH
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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
    • 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
    • C10M7/00—Solid or semi-solid compositions essentially based on lubricating components other than mineral lubricating oils or fatty oils and their use as lubricants; Use as lubricants of single solid or semi-solid substances
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/02—Macromolecular compounds obtained by reactions only involving 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
    • 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
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022—Ethene
    • 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
    • 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
    • C10M2209/086—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 polycarboxylic, e.g. maleic acid
    • 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
    • C10M2215/065—Phenyl-Naphthyl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
    • 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
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • 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
    • C10N2050/023—Multi-layer lubricant coatings
    • C10N2050/025—Multi-layer lubricant coatings in the form of films or sheets

Definitions

  • the present invention relates to a component comprising at least two components movable relative to one another, between the surfaces of which a film formed by a lubricating oil composition is located.
  • polymers which lead to a dispersion of soot particles in the lubricating oil, which may contain, inter alia, monomer units derived from amine derivatives of maleic acid.
  • Such polymers are used inter alia in WO 2007/070845 A2 .
  • US 2004/0254080 A1 and US 5,942,471 it is not aimed at a possible improvement of the friction properties of these polymers.
  • DLC diamond L ike C arbon coated surfaces
  • A. Morina J. Tribology, 2010, 132, 032101-1 to 032101-13 ; Surface & Coatings Tech., 2010, 204, 4001-4011 ) can be removed.
  • DLC-coated steel components such as e.g. Camshafts or other components of the valve train such. Roller rocker arm examined as an alternative to the usually used pure steel components.
  • AW components are usually organic compounds based on sulfur, phosphorus and zinc (zinc dialkyldithiophosphates).
  • the component according to the invention should make it possible to provide the advantages of a friction-reducing DLC surface compared to conventional steel surfaces with the friction-reducing properties of a lubricant composition in combination.
  • DLC-coated metal parts have a lower coefficient of friction compared to uncoated parts, further measures to reduce friction losses and the associated reduction in fuel consumption are desirable.
  • a further object of the invention was to provide components, lubricating oil compositions and friction-reducing additives which can be produced simply and cost-effectively, in which case commercially available components should be used in particular.
  • the production should be possible on an industrial scale without the need for new or structurally complex systems.
  • the additive should lead to an improvement in fuel consumption, without affecting the environmental compatibility of the lubricating oil composition.
  • the additives used are intended to improve the durability of the lubricating oil used so far that the necessary oil change intervals can be extended without this resulting in a qualitative reduction of the lubricating oil.
  • the subject of the present invention is accordingly a component comprising at least two components movable relative to one another, between the surfaces of which a film formed by a lubricating oil composition is located, characterized in that the surface of at least one of the movable components is at least partially covered by a diamond-like carbon Layer (DLC layer) is formed and the lubricating oil composition contains at least one polyalkyl (meth) acrylate comprising 0.1 to 10 wt .-% of repeating units derived from amine derivatives of at least one polar ethylenically unsaturated monomer, wherein the polar ethylenic unsaturated monomer from which the amine derivative is derived, maleic acid or a maleic acid derivative, and the amine derivative represented by the general formula (IIIa) wherein R 'is hydrogen and the radicals R "may be independently selected from the group consisting of H or an alkyl radical having 1 to 9 carbon atoms, is derived.
  • DLC layer diamond-like carbon Layer
  • the present invention succeeds in an unpredictable manner to provide a component and a lubricating oil composition having an improved property profile, in particular by the combination of the favorable properties of a DLC coating of the components with the lubricating oil compositions to be used according to the invention, the longevity engines, fuel consumption and other desirable characteristics can be improved.
  • a very low coefficient of friction and a surprisingly high abrasion resistance can be achieved.
  • Dispersant polymers comprising repeating units derived from amine derivatives of at least one polar ethylenically unsaturated monomer are known per se. Their friction-reducing effect on DLC surfaces has not yet been described.
  • the present invention provides components and lubricating oil compositions that can be produced easily and inexpensively, in particular, commercially available components can be used.
  • the production can be done on an industrial scale, without the need for new or structurally complex systems are needed.
  • the friction reducing polymers of this invention can provide a variety of desirable properties in the lubricating oil composition. As a result, the number of different additives can be minimized. For example, preferred polymers lead to an improvement in the rheological properties, in particular the viscosity index.
  • the component and the lubricating oil composition can lead to an improvement in fuel consumption, with no adverse effects on the environmental compatibility are connected.
  • the additives used achieve improved durability of the lubricating oil used, so that the necessary oil change intervals can be extended without this intolerable disadvantages arise.
  • the component according to the invention can represent a motor and / or a mechanical component of an engine.
  • the component according to the invention may be characterized in that at least one of the components which are movable relative to one another is a camshaft, a valve, a gear or a pump of an engine.
  • the surface of at least one of the movable components of the component according to the invention is at least partially formed by a diamond-like carbon layer (DLC layer).
  • DLC layer diamond-like carbon layer
  • DLC layers can be amorphous or tetragonal carbon layers, which essentially have properties of graphite and diamond. They include sp 2 and sp 3 bonds, with sp 2 bonds characteristic of the graphite structure and sp 3 bonds characteristic of the diamond structure.
  • DLC layers are characterized by high electrical resistance, extreme hardness and optical transparency.
  • the synthesis can be carried out by means of physical vapor deposition (PVD) or by means of plasma-enhanced chemical vapor deposition (PECVD).
  • PVD physical vapor deposition
  • PECVD plasma-enhanced chemical vapor deposition
  • the material is deposited as an amorphous carbon layer.
  • the layer thickness can be determined by means of a key cutting device, the hardness by means of a nanoindenter, the roughness or the surface structure by atomic force microscopy (AFM), the determination of the hydrogen concentration in the DLC layers by means of nuclear reaction analysis, and the density by X-ray reflectometry (XRR).
  • AFM atomic force microscopy
  • XRR X-ray reflectometry
  • DLC layers may preferably comprise hydrogen in the range of 5 to 75, preferably 10 to 65 atomic percent (at%) with respect to the total layer.
  • the DLC layers may be doped or undoped, wherein in the case of doping, the DLC layers atoms of at least one metal and / or Non-metal include.
  • doping by means of metallic atoms include titanium, tungsten and molybdenum or for doping by means of non-metallic atoms silicon, nitrogen and fluorine.
  • the component according to the invention can be designed such that the DLC layer comprises carbon which is present in a graphitic structure (sp 2 hybridization), the proportion of the carbon present in a graphite structure based on the total carbon being preferred in the range of 20 to 80 mol%, particularly preferably in the range of 30 to 70 mol%, measured according to X-ray structure analysis (eg DIN 50433 Part 1-4).
  • a graphitic structure sp 2 hybridization
  • the proportion of the carbon present in a graphite structure based on the total carbon being preferred in the range of 20 to 80 mol%, particularly preferably in the range of 30 to 70 mol%, measured according to X-ray structure analysis (eg DIN 50433 Part 1-4).
  • the component according to the invention is designed such that the DLC layer comprises carbon which is present in a diamond structure (sp 3 hybridization), the proportion of the carbon present in a diamond structure , based on the total carbon, preferably in the range of 20 to 80 mol%, particularly preferably in the range of 30 to 70 mol%, measured according to X-ray structure analysis (eg DIN 50433 Part 1-4).
  • the thickness of the DLC layer used is in the range of 1 to 20 ⁇ m, preferably in the range of 1.5 to 15 ⁇ m, and particularly preferably in the range of 2 to 10 ⁇ m.
  • the density of the DLC layer may preferably be in the range of 0.90 g / cm 3 to 2.20 g / cm 3, more preferably in the range of 0.92 to 2.15 g / cm 3 , measured according to J. Robertson et al, Diamond-like amorphous carbon, Materials Science and Engineering, R37 (2002) 129 , According to a preferred embodiment, the hardness of the DLC layer is preferably in the range of 10 GPa to 30 GPa, measured according to DIN EN ISO 14577.
  • Diamond-Like-Carbon layers More information about preferred Diamond-Like-Carbon layers (DLC layers) can be found in particular in a diploma thesis entitled “ Studies on the high-rate deposition of hard DLC layers "by Graupner from 2004 and in A. Grill et al. Diamond-like carbon: state of the art, Diamond and Related Materials (1998 ), both of which are incorporated herein by reference in the present application for the purposes of disclosure.
  • the movable components are constructed with a surface which is at least partially formed by a DLC layer, at least partially substantially of a metal, preferably steel.
  • the movable component having a surface which is at least partially formed by a diamond-like carbon layer, at least 80 wt .-%, preferably at least 90 wt .-% of a metal or a metal alloy, preferably one Stole.
  • the polymer of the invention is based on (meth) acrylates.
  • Polyalkyl (meth) acrylates are polymers by which polymerization of alkyl (meth) acrylates can be obtained.
  • the term (meth) acrylates include methacrylates and acrylates as well as mixtures of both. These monomers are well known.
  • Polyalkyl (meth) acrylates preferably comprise at least 40% by weight, more preferably at least 60% by weight, especially preferably at least 80% by weight and most preferably at least 90% by weight of repeating units derived from (meth) acrylates, preferably Alkyl (meth) acrylates are derived.
  • Preferred polyalkyl (meth) acrylates include
  • the polyalkyl (meth) acrylates can preferably be obtained by free-radical polymerization. Accordingly, the proportion by weight of the respective repeating units which comprise these polymers results from the proportions by weight of corresponding monomers used to prepare the polymers.
  • Examples of (meth) acrylates of the formula (I) include linear and branched (meth) acrylates which are 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; and cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate.
  • 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)
  • the (meth) acrylates of the formula (II) include, in particular, linear and branched (meth) acrylates which are 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 (
  • oleyl (meth) acrylate For example, oleyl (meth) acrylate; Cycloalkyl (meth) acrylates, such as cyclohexyl (meth) acrylate, 3-vinylcyclohexyl (meth) acrylate, bornyl (meth) acrylate, 2,4,5-tri-tert-butyl-3-vinylcyclohexyl (meth) acrylate, 2 , 3,4,5-tetra-t-butylcyclohexyl (meth) acrylate;
  • monomers of the formula (III) include linear and branched (meth) acrylates which are derived from saturated alcohols, such as cetyleicosyl (meth) acrylate, stearyl eicosyl (meth) acrylate and / or eicosyltetratriacontyl (meth) acrylate; Cycloalkyl (meth) acrylates, such as 2,3,4,5-te
  • the monomers of the formula (III) include so-called polyolefin-based macromonomers with (meth) acrylate groups which are described, inter alia, in US Pat DE 10 2007 032 120 A1 , filed on 09.07.2007 with the German Patent Office with the application number DE 102007032120.3 ; and DE 10 2007 046 223 A1 , filed on 26.09.2007 with the German Patent Office with the application number DE 102007046223.0 ; are described.
  • Alkyl (meth) acrylates with a long-chain alcohol radical in particular the components (II) and (III), can be obtained, for example, by reacting (meth) acrylates and / or the corresponding acids with long-chain fatty alcohols, in which case a mixture of esters, such as For example, (meth) acrylates with different long-chain alcohol radicals formed.
  • These fatty alcohols include Oxo Alcohol® 7911, Oxo Alcohol® 7900, Oxo Alcohol® 1100; Alfol® 610, Alfol® 810, Lial® 125 and Nafol® grades (Sasol); C13-C15 alcohol (BASF); Epal® 610 and Epal® 810 (Afton); Linevol® 79, Linevol® 911 and Neodol® 25 (Shell); Dehydad®, Hydrenol® and Lorol® types (Cognis); Acropol® 35 and Exxal® 10 (Exxon Chemicals); Kalcol® 2465 (Kao Chemicals).
  • a polyalkyl (meth) acrylate to be used according to the invention comprises repeating units derived from amine derivatives of a polar ethylenically unsaturated monomer.
  • polar ethylenically unsaturated monomer illustrates that the monomer can be radically polymerized.
  • polar expresses that the monomer is also particularly polar after reaction with an amine, for example, to form a higher order amine (primary to secondary or secondary to tertiary), an amide, or an imide adjacent to the reaction site.
  • the groups which belong to this include in particular resulting imide groups or carboxylic acid groups, for example, in the reaction of acid anhydrides with amines or hydroxy groups which are obtained in the reaction of epoxides.
  • Carboxylic acid groups may be present in the form of the free acid or as salt.
  • the amide group of the amine derivative accordingly preferably represents an imide group.
  • the term "environment of the reaction site" indicates that the polar groups which are formed for at most 6, preferably at most 5, covalent bonds are formed by the amine or amide groups obtained. Group are removed, based on the distance between the oxygen atom and nitrogen atom.
  • the polar ethylenically unsaturated monomer from which the amine derivative is derived is maleic acid or a maleic acid derivative such as maleic acid monoester, maleic diester, maleic anhydride, methylmaleic anhydride, with maleic anhydride being particularly preferred.
  • the residue of the amine derivative of a polar ethylenically unsaturated monomer formed by the amine is derived from a primary amine.
  • the amines are compounds of the following general formula (IIIa) wherein R 'and R "may be independently selected from the group consisting of H or an alkyl radical having 1 to 9 carbon atoms.
  • Particularly preferred amines from which the above-mentioned derivatives of polar ethylenically unsaturated monomers can be derived include in particular N-phenyl-1,4-phenylenediamine (DPA).
  • DPA N-phenyl-1,4-phenylenediamine
  • the repeating units derived from amine derivatives of a polar ethylenically unsaturated monomer are produced in the polyalkyl (meth) acrylate to be used according to the invention by first producing a polymer having reactive, polar repeating units which are preferably prepared from Maleic anhydride or glycidyl (meth) acrylate are derived. Subsequently, these reactive groups are reacted with the amines set forth above to the polymers to be used according to the present invention.
  • the monomer mixture may comprise monomers which can be copolymerized with the monomers described above.
  • monomers which can be copolymerized with the monomers described above include, inter alia, aryl (meth) acrylates, such as benzyl methacrylate or phenyl methacrylate, where the aryl radicals may each be unsubstituted or substituted up to four times; Styrenic monomers, such as styrene, substituted styrenes having an alkyl substituent in the side chain, such.
  • styrene and ⁇ -ethylstyrene substituted styrenes having an alkyl substituent on the ring such as vinyltoluene and p-methylstyrene, halogenated styrenes such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes; Itaconic acid and itaconic acid derivatives such as itaconic acid monoester, itaconic diester and itaconic anhydride; Fumaric acid and fumaric acid derivatives such as fumaric acid monoesters, fumaric diesters and fumaric anhydride; Vinyl and isoprenyl ethers, for example alkyl vinyl ethers, in particular methyl vinyl ether, ethyl vinyl ether and dodecyl vinyl ether; Vinyl esters, for example vinyl acetate; 1-alkenes, in particular 1-butene, 1-pentene
  • dispersing monomers can be used.
  • Dispersing monomers have long been used for the functionalization of polymeric additives in lubricating oils and are therefore known to the skilled person (see. RM Mortier, ST Orslik (eds.): “Chemistry and Technology of Lubricants", Blackie Academic & Professional, London, 2nd ed. 1997 ).
  • dispersing monomers of the formula (IV) include aminoalkyl (meth) acrylates, aminoalkyl (meth) acrylamides, hydroxylalkyl (meth) acrylates, heterocyclic (meth) acrylates and / or carbonyl-containing (meth) acrylates.
  • aminoalkyl (meth) acrylamides can be used as dispersing monomers, such as N, N-dimethylaminopropyl (meth) acrylamide.
  • heterocyclic vinyl compounds include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, N-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxolane, Vinylfuran, vinylthiophene, vinylthiolane, vinylthiazoles and hydrogenated vinylthiazoles, vinyloxazoles and hydrogenated vinyloxazoles.
  • the particularly preferred dispersing monomers include, in particular, ethylenically unsaturated compounds which comprise at least one nitrogen atom, these particularly preferably from the heterocyclic vinyl compounds and / or aminoalkyl (meth) acrylates, aminoalkyl (meth) acrylamides and / or heterocyclic (meth) acrylates set forth above are selected.
  • the aforementioned ethylenically unsaturated monomers can be used individually or as mixtures. It is also possible, the Monomer composition to vary during the polymerization of the main chain to obtain defined structures, such as graft polymers.
  • graft copolymers wherein the grafting base comprises recurring units derived from olefins and the grafting comprises repeating units derived from amine derivatives of a polar ethylenically unsaturated monomer.
  • graft copolymers wherein the grafting base comprises repeating units derived from (meth) acrylates of 6 to 22 carbon atoms in the alcohol radical, and the grafting comprises repeating units derived from amine derivatives of a polar ethylenically unsaturated monomer.
  • the weight ratio of graft to graft base in the range of 1 to 2000 to 1 to 5, more preferably 1 to 1000 to 1 to 10 and particularly preferably 1 to 100 to 1 to 20.
  • the graft can be very short-chained, this property can be determined by comparative experiments in which the graft polymerization is carried out without grafting.
  • the number-average degree of polymerization of the graft may be at most 10, more preferably at most 5, and most preferably at most 3 repeat units.
  • polyalkyl (meth) acrylates which preferably have a weight-average molecular weight M w in the range from 5000 to 10,000,000 g / mol, preferably 10,000 to 1,000,000 g / mol, more preferably 10,000 to 750,000 g / mol, and most preferably 200,000 to 500000 g / mol.
  • the number average molecular weight M n may preferably be in the range from 1000 to 500 000 g / mol, particularly preferably 2500 to 500 000 g / mol and very particularly preferably 5000 to 250 000 g / mol.
  • polyalkyl (meth) acrylates whose polydispersity index M w / M n in the range from 1.1 to 5.0 is particularly preferably in the range from 1.4 to 4.5 and very particularly preferably in the range from 1.6 to 3.0 are also useful.
  • the number average and weight average molecular weights can be determined by known methods, for example, gel permeation chromatography (GPC), preferably using a PMMA standard.
  • GPC gel permeation chromatography
  • the molecular weight of the polymer may be made prior to derivatization thereof with an amine.
  • polyalkyl (meth) acrylates from the above-described compositions is known per se.
  • the ATRP method is known per se. This reaction is, for example, of JS. Wang, et al., J. Am. Chem. Soc., Vol.117, p.5614-5615 (1995 ), from Matyjaszewski, Macromolecules, vol.28, p.7901-7910 (1995 ).
  • the patent applications disclose WO 96/30421 . WO 97/47661 . WO 97/18247 . WO 98/40415 and WO 99/10387 Variants of the previously discussed ATRP.
  • polymers according to the invention can also be obtained, for example, by RAFT methods. This method is for example in WO 98/01478 and WO 2004/083169 shown in detail.
  • polymers according to the invention are obtainable by NMP processes (nitroxide mediated polymerization), which inter alia in US 4,581,429 are described.
  • the free-radical polymerization of the ethylenically unsaturated compounds can be carried out in a manner known per se.
  • the usual free-radical polymerization is, inter alia, in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Editi on set.
  • the polymerization is started by using at least one polymerization initiator for the radical polymerization.
  • polymerization initiators include, among others, the well-known in the art azo initiators, such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and 1,1-Azobiscyclohexancarbonitril, organic peroxides, such as dicumyl peroxide, diacyl peroxides, such as Dilauroyl peroxide, peroxydicarbonates such as diisopropyl peroxydicarbonate, peresters such as tert-butyl peroxy-2-ethylhexanoate, and the like.
  • azo initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and 1,1-Azobiscyclohexancarbonitril
  • organic peroxides such as di
  • particularly suitable polymerization initiators comprise in particular the following compounds: methyl ethyl ketone peroxide, acetylacetone peroxide, dilauroyl 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-butyl peroxy-2-ethylhexanoate, tert-butylperoxy-3,5,5-trimethylhexanoate, dicumyl peroxide, 1, 1-Bis (tert-butylperoxy)
  • polymerization initiators having a half-life of 1 hour at a temperature in the range from 25 ° C. to 200 ° C., preferably in the range from 50 ° C. to 150 ° C., in particular in the range from 50 ° C. to 120 ° C., are very particularly preferred .
  • peroxidic polymerization initiators in particular tert-butyl peroctoate, are particularly suitable for the present purposes.
  • the process can be carried out either in the presence or absence of a chain transfer agent.
  • chain transfer agents also called molecular weight regulators, it is possible to use typical species described for free-radical polymerizations, as are known to the person skilled in the art.
  • the sulfur-free molecular weight regulators include, but are not limited to, dimeric ⁇ -methylstyrene (2,4-diphenyl-4-methyl-1-pentene), enol ethers of aliphatic and / or cycloaliphatic aldehydes, terpenes, ⁇ -terpinene, terpinolene, 1,4-cyclohexadiene, 1,4-dihydronaphthalene, 1,4,5,8-tetrahydronaphthalene, 2,5-dihydrofuran, 2,5-dimethylfuran and / or 3,6-dihydro-2H-pyran, preference is given to dimeric ⁇ methyl styrene.
  • Mercury compounds, dialkyl sulfides, dialkyl disulfides and / or diaryl sulfides can preferably be used as the sulfur-containing molecular weight regulator.
  • the following polymerization regulators are exemplified: din-butyl sulfide, di-n-octyl sulfide, diphenyl sulfide, thiodiglycol, ethylthioethanol, diisopropyl disulfide, di-n-butyl disulfide, di-n-hexyl disulfide, diacetyl disulfide, diethanol sulfide, di-tert-butyl trisulfide and dimethyl sulfoxide ,
  • Preferred compounds used as molecular weight regulators are mercapto compounds, dialkyl sulfides, dialkyl disulfides and / or diaryl sulfides.
  • Examples of these compounds are ethyl thioglycolate, 2-ethylhexyl thioglycolate, pentaerythritol tetrathioglycolate, cysteine, 2-mercaptoethanol, 1, 3-mercaptopropanol, 3-mercaptopropane-1,2-diol, 1,4-mercaptobutanol, mercaptoacetic acid, 3-mercaptopropionic acid, thioglycolic acid, mercaptosuccinic acid, thioglycerol, thioacetic acid, thiourea and alkylmercaptans such as n-butylmercaptan, n-hexylmercaptan, tert-dodecylmercaptan or n-dodecylmercaptan , Particularly preferably used polymerization regulators are mercapto alcohols and mercaptocarboxylic acids. In the context of the present
  • the repeating units derived from amine derivatives of a polar ethylenically unsaturated monomer are produced in the polyalkyl (meth) acrylate by a polymer analogous reaction according to the preparation of a polyalkyl (meth) acrylate set forth above. Accordingly, it is preferred to first prepare a polymer having reactive polar moieties wherein the reactive moieties are reacted with an amine of the kind set forth above.
  • the reactive polar units include in particular anhydride or epoxide units.
  • the reaction of the reactive polar units contained in the polymer, preferably the anhydride or epoxy groups with amines, can usually be between 40 ° C and 180 ° C, preferably between 80 ° C and 180 ° C and more preferably between 100 ° C and 160 ° C done.
  • the amine may preferably be added in equimolar amount to the reactive polar groups, preferably the anhydride or epoxy groups. If excess amounts of amine are added, this may subsequently be separated from the mixture. If the proportions are too low, reactive groups remain which, if appropriate, can be converted into less reactive groups by addition of small amounts of water.
  • the amine may be added in pure form or added in a suitable solvent to the reaction mixture.
  • polar solvents in particular esters, for example butyl acetate or diisononyl adipate (Plastomoll DNA).
  • water can arise.
  • water is liberated, which according to a particular aspect of the present invention can be removed as completely as possible from the reaction mixture, wherein water can be expelled, for example, by dry nitrogen.
  • drying agents can be used.
  • Volatile solvents such as butyl acetate, if used, can be distilled off preferably in vacuo after the reaction.
  • the polymers to be used according to the invention are preferably used for improving lubricating oil properties.
  • the lubricating oils include, in particular, mineral oils, synthetic oils and natural oils.
  • 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.
  • 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.
  • Natural oils are animal or vegetable oils, such as claw oils or jojoba oils.
  • Base oils for lubricating oil formulations are grouped according to API (American Petroleum Institute). Mineral oils are subdivided into Group I (not hydrogen treated) and, depending on the degree of saturation, sulfur content and viscosity index, in Groups II and III (both hydrogen-treated). PAOs correspond to Group IV. All other base oils are grouped in Group V.
  • lubricating oils can also be used as mixtures and are often commercially available.
  • the concentration of the polyalkyl (meth) acrylate according to the invention in the lubricating oil composition is preferably in the range from 0.01 to 30% by weight, more preferably in the range from 0.1 to 20% by weight and most preferably in the range from 0.5 to 15% by weight. %, based on the total weight of the composition.
  • the lubricating oil compositions set forth herein may also contain further additives and additives.
  • additives include VI improvers, pour point improvers and DI additives (dispersants, detergents, defoamers, corrosion inhibitors, antioxidants, anti-wear and extreme pressure additives, friction modifiers).
  • Preferred lubricating oil compositions have a viscosity measured in accordance with ASTM D 445 at 40 ° C in the range of 10 to 120 mm 2 / s, more preferably in the range of 15 to 100 mm 2 / s.
  • the kinematic viscosity KV 100 measured at 100 ° C. is preferably at least 2.0 mm 2 / s, more preferably at least 3.5 mm 2 / s and most preferably at least 4.0 mm 2 / s.
  • the polymer according to the invention can be characterized by a segmental structure, wherein the polar, oil-insoluble segments comprise the repeating units derived from amine derivatives of a polar ethylenically unsaturated monomer, and the nonpolar, soluble segments consist of repeating units which are good Ensure oil solubility of the entire polymer.
  • the polymer according to the invention comprises more nonpolar than polar segments.
  • Example 1 (polymer according to the invention):
  • LMA alkyl methacrylate having 12 to 14 C atoms in the alkyl radical
  • SMA alkyl methacrylate having 16 to 18 C atoms in the alkyl radical
  • DPMA alkyl methacrylate containing 12 to 15 C atoms in the alkyl group
  • MMA methyl methacrylate
  • DDM n-dodecylmercaptan
  • the mixture was then heated to 105 ° C. with stirring and introduction of nitrogen. After reaching the reaction temperature, 0.99 g of tBPO (tert-butyl perbenzoate) was fed in and the monomer feed was started.
  • the monomer feed consisted of the remaining reaction mixture to which 8.6 g of tBPO was added. The feed was even over 3.5 hours. 2 hours after the end of the feed, 0.5 g of tBPO was again fed in at 95 ° C. The batch was held at 105 ° C for a further 2 hours.
  • the mixture was then heated to 130 ° C., 7.7 g of MSA (maleic anhydride) were added and the grafting reaction started with 0.64 g of tBPB. 1 and 2 hours after the beginning of the grafting reaction, 0.32 g of tBPB was re-fed. After the last addition of initiator stirring was continued for 3 hours at 130.degree.
  • the reaction of the anhydride contained in the polymer was carried out in a polymer-analogous reaction with N-phenyl-1,4-phenylenediamine (DPA) at 140 ° C. 14.5 g DPA was dissolved in 58.1 g diisononyl adipate and the solution was added uniformly over 1.5 h. Forming water was expelled by blowing dry nitrogen. The finished polymers according to the invention were reacted after the end of the reaction to eliminate Impurities filtered through a depth filter layer (SEITZ T1000). The polymer content of the final product was 62%.
  • DPA N-phenyl-1,4-phenylenediamine
  • the coefficient of friction at 120 ° C was measured as in WO 2004/087850 but instead of the usual steel test pieces, DLC coated disks and balls were used.
  • the 2-3 ⁇ m thick DLC layer corresponded to the type aC: H, sp 2 - a type of DLC that produced larger amounts of hydrogen into the plasma, which increased the formation of a graphitic structure (sp 2 -Hybrid) of the carbon the surface leads. Further details about this type can be found eg in the following references: A. Grill et al, Diamond-like carbon: state of the art, Diamond and Related Materials (1998 ) or Report VDI2840, Association of German Engineers (2006).
  • Table 1 Quantitative evaluation of the friction reduction reference example 1 Comparison 1 Comparison 2 Comparison 3 Area in mm / s 56837 45331 51546 52165 50733 % Friction reduction for reference 0.0% 02.20% 09.03% 08.02% 07.10%
  • Table 2 shows the integration data of the friction curves in the sliding speed range of 0.01 to 0.1 m / s.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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Claims (11)

  1. Pièce de construction comprenant au moins deux composants mobiles l'un par rapport à l'autre, entre les surfaces desquels se trouve une film formé par une composition d'huile lubrifiante, caractérisée en ce que la surface d'au moins l'un des composants mobiles est au moins en partie constituée d'une couche de Diamond-Like-Carbon (couche de DLC) et la composition d'huile lubrifiante contient au moins un poly((méth)acrylate d'alkyle) qui comprend 0,1 à 10 % en poids de motifs répétitifs qui sont dérivés de dérivés aminés d'au moins un monomère polaire à insaturation éthylénique, le monomère polaire à insaturation éthylénique duquel est dérivé le dérivé aminé représentant l'acide maléique ou un dérivé d'acide maléique et le dérivé aminé étant dérivé de la formule générale (IIIa)
    Figure imgb0015
     dans laquelle R' représente un atome d'hydrogène et les radicaux R" peuvent être choisis indépendamment l'un de l'autre dans le groupe constitué par H ou un radical alkyle ayant de 1 à 9 atomes de carbone.
  2. Pièce de construction selon la revendication 1, caractérisée en ce que la couche de DLC comprend du carbone qui est présent en une structure de graphite, pour laquelle les liaisons sp2 sont caractéristiques, la proportion du carbone qui est présent en une structure de graphite, par rapport au carbone total, se situant dans la plage de 30 à 70 % en moles.
  3. Pièce de construction selon la revendication 1 ou 2, caractérisée en ce que la couche de DLC comprend du carbone qui est présent en une structure de diamant, pour laquelle les liaisons sp3 sont caractéristiques, la proportion du carbone qui est présent en une structure de diamant, par rapport au carbone total, se situant dans la plage de 30 à 70 % en moles.
  4. Pièce de construction selon au moins l'une quelconque des revendications précédentes, caractérisée en ce que l'épaisseur de la couche de DLC se situe dans la plage de 1 à 20 µm.
  5. Pièce de construction selon au moins l'une quelconque des revendications précédentes, caractérisée en ce que le polymère est un copolymère greffé, l'enveloppe de greffage comprenant des motifs répétitifs qui sont dérivés de dérivés aminés du monomère polaire à insaturation éthylénique.
  6. Pièce de construction selon au moins l'une quelconque des revendications précédentes, caractérisée en ce que le dérivé d'acide maléique est choisi dans le groupe constitué par un monoester d'acide maléique, un diester d'acide maléique, l'anhydride maléique et l'anhydride méthylmaléique.
  7. Pièce de construction selon au moins l'une quelconque des revendications précédentes, caractérisée en ce que le monomère polaire à insaturation éthylénique duquel est dérivé le dérivé aminé est l'anhydride maléique.
  8. Pièce de construction selon au moins l'une quelconque des revendications précédentes, caractérisée en ce que le poly((méth)acrylate d'alkyle) comprend
    a) 0 à 40 % en poids de motifs répétitifs qui sont dérivés de (méth)acrylates de formule (I)
    Figure imgb0016
     dans laquelle R représente un atome d'hydrogène ou un groupe méthyle et R1 représente un radical alkyle ayant de 1 à 5 atomes de carbone,
    b) 20 à 99,99 % en poids de motifs répétitifs qui sont dérivés de (méth)acrylates de formule (II)
    Figure imgb0017
     dans laquelle R représente un atome d'hydrogène ou un groupe méthyle et R2 représente un radical alkyle ayant de 6 à 22 atomes de carbone,
    c) 0 à 20 % en poids de motifs répétitifs qui sont dérivés de (méth)acrylates de formule (III)
    Figure imgb0018
     dans laquelle R représente un atome d'hydrogène ou un groupe méthyle et R3 représente un radical alkyle ayant de 23 à 4 000, de préférence 23 à 400 atomes de carbone, et
    d) 0,1 à 10 % en poids de motifs répétitifs, qui sont dérivés de dérivés aminés d'un monomère polaire à insaturation éthylénique.
  9. Pièce de construction selon au moins l'une quelconque des revendications précédentes, caractérisée en ce que le dérivé aminé est dérivé d'un monomère polaire à insaturation éthylénique de N-phényl-1,4-phénylènediamine.
  10. Pièce de construction selon au moins l'une quelconque des revendications précédentes, caractérisée en ce que la pièce de construction est un moteur.
  11. Pièce de construction selon au moins l'une quelconque des revendications précédentes, caractérisée en ce que ledit au moins un des composants mobiles l'un par rapport à l'autre est un arbre à cames ou une soupape d'un moteur.
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