EP2714871B1 - Lubrifiantes avec polymers phosphorises - Google Patents

Lubrifiantes avec polymers phosphorises Download PDF

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EP2714871B1
EP2714871B1 EP12716392.1A EP12716392A EP2714871B1 EP 2714871 B1 EP2714871 B1 EP 2714871B1 EP 12716392 A EP12716392 A EP 12716392A EP 2714871 B1 EP2714871 B1 EP 2714871B1
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meth
acrylate
weight
hydroxypropyl
acrylates
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EP2714871A1 (fr
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Boris Eisenberg
Ellen Suchert
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Evonik Oil Additives 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
    • 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
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms 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
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/047—Thioderivatives not containing metallic elements
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/049—Phosphite
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon 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
    • C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2225/02—Macromolecular compounds from phosphorus-containg monomers, 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
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • 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
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • 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

Definitions

  • the present invention relates to a lubricant composition with phosphate-functionalized polymers, phosphate-functionalized polyalkyl (meth) acrylates, and the use of a polyalkyl (meth) acrylate to reduce friction.
  • the publication US 3,484,504 describes reaction products of a basic, nitrogen-containing polymer and a (thio) phosphoric acid partial ester and their use as lubricating oil additive.
  • nitrogen-containing monomer are, for example, N, N-dimethylaminoethyl (meth) acrylate or morpholinoethyl (meth) acrylate.
  • Other comonomers may include C 2 -C 18 acrylates or methacrylates, styrene monomers, vinyl esters, allyl esters and vinyl ethers.
  • the pamphlets DE 69431710 A and EP 0 686 690 A describe lubricant compositions for transmissions having improved slurry dispersing properties.
  • the improved sludge dispersion is achieved by the interaction of a phosphorus-containing compound (eg, phosphate ester, phosphonate ester) and a nitrogen-containing oil-soluble copolymer.
  • the nitrogen-containing monomer here is, for example, N, N-dialkylaminoalkyl (meth) acrylate.
  • C 1 -C 24 acrylates or methacrylates are listed.
  • the pamphlets WO 2003/089554 and US 6,586,375 describe lubricant compositions containing a salt of a nitrogen-containing poly (meth) acrylate and a phosphoric acid partial ester.
  • Nitrogen-containing monomers used here were N-vinylpyrrolidone and N, N-dimethylaminopropylmethacrylamide.
  • Comonomers here include C 1 -C 30 acrylates or methacrylates.
  • the lubricant compositions should have a high wear protection, at the same time an excellent friction behavior should be provided.
  • the lubricant compositions are said to have increased hydrolytic stability to provide an extended temperature range under stable conditions for the use of lubricant compositions.
  • a further object of the invention was to provide lubricant compositions and friction-reducing polymers as additives which can be prepared simply and inexpensively, in particular using commercially available components.
  • 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 lubricant composition.
  • the lubricant composition according to the invention show, surprisingly, improved wear protection combined with excellent friction behavior.
  • the friction behavior can be increased together with the wear protection. This is particularly surprising because usually the addition of an additive to reduce wear results in a simultaneous deterioration of the coefficient of friction.
  • the lubricant compositions according to the invention in comparison to the lubricant compositions of the prior art comprising salts of phosphoric acid partial esters and a nitrogen-containing polymer.
  • a further advantage here is that the wear-reducing properties and the viscosity index-improving effect of the polyalkyl (meth) acrylate (PAMA) used according to the invention comprising repeating units having at least one covalently bonded phosphorus atom are combined in one component.
  • PAMA polyalkyl (meth) acrylate
  • polymers having a wear-reducing effect are provided for a lubricant composition which do not exhibit dispersibility, but rather are demulsifiable (water-separating), so that they can be used in larger quantities in industrial hydraulic oils.
  • the present invention provides lubricant 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 lubricant composition can lead to an improvement in fuel consumption, with no adverse effects on the environmental compatibility are connected.
  • the present invention describes a lubricant composition.
  • Lubricating compositions especially lubricating oils serve to reduce friction and wear, as well as for power transmission, cooling, vibration damping, sealing effect and corrosion protection.
  • transmission oils from other lubricating oils which can be used, for example, to lubricate engines.
  • these differences usually show up, in particular, in the added additives, with gear oils having much higher levels of wear protection and extreme pressure additives in comparison to engine oils.
  • the lubricant composition can be used as hydraulic oil.
  • the lubricant composition of the invention contains at least one polyalkyl (meth) acrylate.
  • Polyalkyl (meth) acrylates are polymers which can be obtained by polymerization of alkyl (meth) acrylates.
  • 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%, more preferably at least 60%, more preferably at least 80%, and most preferably at least 90%, of repeating units derived from alkyl (meth) acrylates are.
  • polyalkyl (meth) acrylates which are preferably at least 20% by weight, particularly preferably at least 40% by weight, particularly preferably at least 60% by weight and very particularly at least 80% by weight. Repeating units derived from alkyl (meth) acrylates having 6 to 22 carbon atoms in the alcohol residue.
  • polyalkyl (meth) acrylates which preferably have a weight-average molecular weight M w in the range from 10,000 to 600,000 g / mol and very particularly preferably from 15,000 to 80,000 g / mol.
  • the number average molecular weight M n may preferably be in the range of 1,000 to 500,000 g / mol, more preferably 7,500 to 500,000 g / mol, and most preferably 10,000 to 80,000 g / mol.
  • polyalkyl (meth) acrylates whose polydispersity index M w / M n in the range from 1.1 to 5.0, more preferably in the range from 1.4 to 4.5, and very particularly preferably in the range from 1.6 to, are also suitable 3.0 is.
  • 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 carried out prior to derivatization thereof with a phosphorus compound.
  • 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 (me
  • 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; and Cycloalkyl (meth) acrylates, such as cyclohexyl (meth) acrylate, 3-vinylcyclohexyl (meth) acrylate, bornyl (meth) acrylate, 2,4,5-tri-t-butyl-3-vinylcyclohexyl (meth) acrylate, 2, 3,4,5-tetra-t-butylcyclohexyl (meth) acrylate.
  • Cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate, 3-vinylcyclohexyl (meth) acrylate, bornyl (meth) acrylate, 2,4,5-tri-t-butyl-3-vinylcyclohexyl (meth) acrylate, 2, 3,4,5-tetra-t-butylcyclohexyl (meth)
  • Examples of 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-tetra-t-hexylcyclohexyl (meth) acrylate.
  • 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 DE102007032120.3 ; and DE 10 2007 046 223 A1 , filed on 26.09.2007 with the German Patent Office with the application number DE 102007046223.0 ; wherein the disclosures of these references, in particular the therein described (meth) acrylates having at least 23 carbon atoms in the radical for purposes of disclosure in the present application are incorporated by reference thereto.
  • Polyolefin-based macromonomers are known in the art. These repeating units comprise at least one group derived from polyolefins.
  • Polyolefins are known in the art, these being prepared by polymerization of alkenes and / or alkadienes consisting of the elements carbon and hydrogen, for example C 2 -C 10 -alkenes such as ethylene, propylene, n-butene, isobutene, norbornene and / or C 4 -C 10 alkadienes such as butadiene, isoprene, norbornadiene can be obtained.
  • the repeating units derived from polyolefin-based macromonomers preferably comprise at least 70% by weight and more preferably at least 80% by weight and most preferably at least 90% by weight of groups derived from alkenes and / or alkadienes Weight of repeating units derived from polyolefin-based macromonomers.
  • the polyolefinic groups may in particular also be hydrogenated.
  • repeat units derived from polyolefin-based macromonomers may include other groups. These include low levels of copolymerizable monomers.
  • These monomers are known per se and include, inter alia, alkyl (meth) acrylates, styrene monomers, fumarates, maleates, vinyl esters and / or vinyl ethers.
  • the proportion of these groups based on copolymerizable monomers is preferably at most 30% by weight, particularly preferably at most 15% by weight, based on the weight of repeating units derived from polyolefin-based macromonomers.
  • the repeating units derived from polyolefin-based macromonomers may include initial groups and / or end groups that function to functionalize or that are due to the production of repeating units derived from polyolefin-based macromonomers.
  • the proportion of these initial groups and / or end groups is preferably at most 30 wt .-%, particularly preferably at most 15 wt .-%, based on the weight of the polyolefin-based macromonomer derived repeating units.
  • the number average molecular weight of repeating units derived from polyolefin-based macromonomers is in the range of 500 to 50,000 g / mol, more preferably 700 to 10,000 g / mol, especially 1,500 to 4900 g / mol, and most preferably 2000 to 3000 g / mol.
  • the repeating units derived from polyolefin-based macromonomers preferably have a low melting temperature, wherein this is measured by DSC.
  • the melting temperature of the recurring units derived from the polyolefin-based macromonomers is preferably less than or equal to -10 ° C., particularly preferably less than or equal to -20 ° C., particularly preferably less than or equal to -40 ° C. Most preferably, no melting temperature can be measured according to DSC in the repeating units derived from the polyolefin-based macromonomers.
  • the monomers of the formula (III) in particular include long-chain branched (meth) acrylates, which inter alia in US 6,746,993 , filed on 07.08.2002 with the US Patent Office (USPTO) with the application number 10 / 212.784 ; and US 2004/077509 , filed on 01.08.2003 with the US Patent Office (USPTO) with the application number 10 / 632.108 ; wherein the disclosures of these references, in particular the therein described (meth) acrylates having at least 23 carbon atoms in the radical for purposes of disclosure in the present application are incorporated by reference thereto.
  • 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).
  • the polyalkyl (meth) acrylate comprises 0.2 to 0.9 wt .-%, particularly preferably 0.3 to 0.8 wt .-% of phosphorus atoms, based on the weight of the polyalkyl (meth) acrylate.
  • These polyalkyl (meth) acrylates comprising repeating units derived from (meth) acrylates having 6 to 22 carbon atoms in the alcohol radical, are novel and thus also subject of this invention.
  • the ethylenically unsaturated monomers having at least one covalently bonded phosphorus atom, from which the repeating units of the polyalkyl (meth) acrylate are derived, are known per se.
  • the polyalkyl (meth) acrylate comprises repeating units derived from phosphorus derivatives of a polar ethylenically unsaturated monomer.
  • polar ethylenically unsaturated monomer illustrates that the monomer can be radically polymerized. Furthermore, the term polar expresses that the monomer is particularly polar even after reaction with a phosphorus derivative in the vicinity of the reaction site.
  • the groups which belong to this include in particular resulting hydroxy groups which are obtained in the reaction of epoxides.
  • the polar ethylenically unsaturated monomer from which the phosphorus derivative is derived is a (meth) acrylate having an epoxy group.
  • the monomer mixture may comprise monomers which can be copolymerized with the monomers described above.
  • 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, 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, itac
  • 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.
  • the hydroxyalkyl (meth) acrylates include, inter alia 2-hydroxypropyl (meth) acrylate, 3,4-dihydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2,5-dimethyl-1,6-hexanediol (meth) acrylate and 1,10-decanediol (meth) acrylate.
  • Carbonyl-containing (meth) acrylates include, for example 2-carboxyethyl (meth) acrylate, Carboxymethyl (meth) acrylate, N- (methacryloyloxy) formamide, Acetonyl (meth) acrylate, Succinic acid mono-2- (meth) acryloyloxyethyl, N- (meth) acryloylmorpholine, N- (meth) acryloyl-2-pyrrolidinone, N- (2- (meth) acryloyloxyethyl) -2-pyrrolidinone, N- (3- (meth) acryloyloxypropyl) -2-pyrrolidinone, N- (2- (meth) acryloyloxypentadecyl) -2-pyrrolidinone, 2-acetoacetoxyethyl (meth) acrylate, N- (3- (meth) acryloyloxyheptadecyl)
  • the heterocyclic (meth) acrylates include, among others 2- (1-imidazolyl) ethyl acrylate (meth), Oxazolidinylethyl (meth) acrylate, 2- (4-morpholinyl) ethyl (meth) acrylate 1- (2-methacryloyloxyethyl) -2-pyrrolidone, N-methacryloylmorpholine, N-methacryloyl-2-pyrrolidinone, N- (2-methacryloyloxyethyl) -2-pyrrolidinone, N- (3-methacryloyloxypropyl) -2-pyrrolidinone.
  • the aminoalkyl (meth) acrylates include in particular N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopentyl (meth) acrylate, N, N-Dibutylaminohexadecyl (meth) acrylate.
  • 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 proportion of comonomers can be varied depending on the purpose and property profile of the polymer. In general, this proportion can be in the range from 0 to 30 wt .-%, preferably 0.01 to 20 wt .-% and particularly preferably 0.1 to 10 wt .-%.
  • the aforementioned ethylenically unsaturated monomers can be used individually or as mixtures. It is further possible to vary the monomer composition during the main chain polymerization to obtain defined structures such as block copolymers or graft polymers. According to a particular aspect of the present invention, the present polyalkyl (meth) acrylates are designed as random copolymers in which the distribution of the two monomers in the chain is random. As a result, surprising advantages can be achieved, which are reflected in particular in better rheology values.
  • 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 which is expressly referred to for purposes of the disclosure.
  • polymers according to the invention are obtainable by NMP processes (nitroxide mediated polymerization), which inter alia in US 4581429 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.
  • particularly suitable polymerization initiators include in particular the following compounds: Methyl ethyl ketone peroxide, acetyl acetone 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 peroxy isopropyl carbonate, 2,5-bis- (2-ethylhexanoyl-peroxy) -2,5-dimethylhexane, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy-3,5,5-trimethylhexanoate, dicumylperoxide, 1,1-bis (tert) (tert) (ter
  • 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 100 ° C., are very particularly preferred .
  • 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-t-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, t-dodecylmercaptan or n-d
  • Particularly preferably used polymerization regulators are mercapto alcohols and mercaptocarboxylic acids.
  • the use of n-dodecyl mercaptan and tert-dodecyl mercaptan as chain transfer agents is very particularly preferred.
  • the repeating units derived from phosphorus derivatives of a polar ethylenically unsaturated monomer can be produced in the polyalkyl (meth) acrylate by a polymer analogous reaction according to the preparation of a polyalkyl (meth) acrylate set forth above. Accordingly, first, a polymer having reactive polar units can be prepared wherein the reactive units are reacted with a phosphorus compound 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 epoxide groups with phosphorus compounds, can usually take place between 25 ° C and 110 ° C.
  • the phosphorus compound may preferably be added in equimolar amount to the reactive polar groups, preferably the anhydride or epoxy groups.
  • the content of polyalkyl (meth) acrylate having repeating units derived from ethylenically unsaturated monomers having at least one covalently bonded phosphorus atom is preferably in the range from 0.5 to 30 and more preferably in the range of 2 to 15 wt .-%, based on the weight of the lubricant composition.
  • the lubricant composition has a phosphorus compound having a molecular weight of preferably at most 800 g / mol, more preferably at most 600 g / mol.
  • the phosphorus compound having a molecular weight of at most 1000 g / mol is a phosphoric acid ester, a phosphoric acid thioester, a metal dithiophosphate, a phosphite, a phosphonate, a phosphine or a mixture of these compounds.
  • the preferred phosphorus compounds include, for example, trialkyl phosphates, triaryl phosphates, e.g. Tricresyl phosphate and especially amine-neutralized mono- and dialkylphosphoric acid esters. These are obtained by reacting phosphoric acid pentaoxide with alcohols, whereby the remaining acid groups in the molecule, which have not reacted despite the excess of the alcohol, are neutralized with long-chain amines.
  • the alkyl and / or aryl groups preferably comprise 1 to 40, preferably 3 to 30 and more preferably 4 to 20 carbon atoms.
  • Alkyl groups of the long-chain amines, with which remaining acid groups of the phosphoric acid derivatives can be reacted preferably comprise 4 to 40, preferably 6 to 30 and particularly preferably 8 to 20 carbon atoms.
  • a metal salt e.g. Zinc sulfate / hydroxide or molybdenum sulfate / hydroxide reacted.
  • the resulting ash-forming zinc-containing anti-wear additives are commonly referred to as zinc dialkyl dithiophosphate, ZnDDP for short.
  • additives are commercially available either as individual components or in the form of formulations (i.e., mixture with other additives such as antioxidants or detergents), e.g. NA-LUBE AW 6110 from KING-Industries (wear protection additive) or Additin RC 9200 from Rheinchemie (additive package).
  • additives e.g. NA-LUBE AW 6110 from KING-Industries (wear protection additive) or Additin RC 9200 from Rheinchemie (additive package).
  • the lubricant composition of the present invention comprises at least one lubricating oil, also called base oil.
  • the lubricating oils include, in particular, mineral oils, synthetic oils and natural oils.
  • Mineral oils are known per se and commercially available. They are generally obtained from petroleum or crude oil by distillation and / or refining and, if appropriate, further purification and refining processes, the term "mineral oil” in particular falling to the relatively high-boiling fractions of crude oil or crude oil. In general, the boiling point of mineral oil is higher than 200 ° C, preferably higher than 300 ° C, at 5000 Pa. The production by smoldering of shale oil, coking of hard coal, distillation under exclusion of air from brown coal and hydrogenation of hard coal or lignite is also possible. Accordingly, mineral oils, depending on the origin of different proportions of aromatic, cyclic, branched and linear hydrocarbons.
  • paraffin-based, naphthenic and aromatic fractions in crude oils or mineral oils, the terms paraffin-based fraction being longer-chain or highly branched isoalkanes and naphthenic fraction being cycloalkanes.
  • mineral oils depending on their origin and processing different proportions of n-alkanes, iso-alkanes with a low degree of branching, so-called monomethyl branched paraffins, and compounds with heteroatoms, especially O, N and / or S, which are attributed polar properties .
  • the assignment is difficult, however, since individual alkane molecules can have both long-chain branched groups and cycloalkane radicals and aromatic moieties.
  • the assignment can be made, for example, according to DIN 51 378.
  • Polar proportions may also be determined according to ASTM D 2007.
  • the proportion of n-alkanes in preferred mineral oils is less than 3 wt .-%, the proportion of O, N and / or S-containing compounds less than 6 wt .-%.
  • the proportion of aromatics and monomethyl branched paraffins is generally in the range of 0 to 40 wt .-%.
  • mineral oil mainly comprises naphthenic and paraffinic alkanes, which generally have more than 13, preferably more than 18 and most preferably more than 20 carbon atoms.
  • the proportion of these compounds is generally greater than or equal to 60 wt .-%, preferably greater than or equal to 80 wt .-%, without this being a restriction.
  • a preferred mineral oil contains from 0.5 to 30% by weight of aromatic fractions, from 15 to 40% by weight of naphthenic fractions, from 35 to 80% by weight of paraffinic fractions, up to 3% by weight of n-alkanes and 0.05% to 5 wt .-% polar compounds, each based on the total weight of the mineral oil.
  • An improved class of mineral oils is due to Hydrogen treatment of mineral oils ( hydro isomerization, hydrocracking, hydro treatment, hydro finishing ). In this case, essentially all aromatic components are reduced in hydrogen presence and naphthenic components are built up.
  • 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.
  • synthetic base oils with origin from gas to liquid (GTL), coal to liquid (CTL) or biomass to liquid (BTL) processes can be used. They are usually slightly more expensive than the mineral oils, but have advantages in terms of their performance.
  • Natural oils are animal or vegetable oils, such as claw oils or jojoba oils.
  • 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.
  • a preferred embodiment of the lubricant composition which can be used according to the invention provides that the lubricant composition is preferably at least 40% by weight, particularly preferably at least 50% by weight, especially preferably comprises at least 60% by weight of a base oil.
  • a base oil may be a Group I oil, Group II oil, Group III oil or a Polyalphaolefin or a mixture of these oils.
  • a lubricant composition of the invention may contain other additives and additives.
  • a polyalkyl (meth) acrylate having repeating units derived from ethylenically unsaturated monomers having at least one covalently bonded phosphorus atom be used to reduce friction.
  • the graphical evaluation of the coefficient of friction measurements is shown in diagram 2.
  • a quantifiable result, where the friction reduction in a number can be expressed, is obtained by integration of the coefficient of friction curves in the range 5 - 2500 mm / s sliding speed.
  • the area corresponds to the "total friction" in the entire speed range examined.
  • the determined surface areas are summarized in Table 2.
  • the shell four-ball apparatus is a standardized in DIN 51 350 Part 1 tester for determining the welding and Gutkraft (DIN 51 350 parts 2 and 3) and various friction and wear characteristics of lubricants (DIN 51 350 Part 3 and 5).
  • DIN 51 350 Part 1 tester for determining the welding and Gutkraft (DIN 51 350 parts 2 and 3) and various friction and wear characteristics of lubricants (DIN 51 350 Part 3 and 5).
  • a rotating ball bearing ball is pressed under load on three similar but stationary balls.
  • the test bench is widely used in the lubricant industry where it is routinely used for product development and quality control.
  • the wear is determined by optical measurement of the resulting dome. From the individual measured calotte diameters, the mean value is formed for the load stage (300N). The final result is the mean value (multiplied by the magnification correction factor of the eyepiece).
  • the polymer according to the invention shows a significant improvement in the wear behavior compared to the reference polymer.
  • both polymers were measured in the same oil mixture but with the addition of 0.9% by weight of a commercially available ashless phosphorus-containing antiwear additive (AW additive).
  • AW additive ashless phosphorus-containing antiwear additive
  • the lubricant composition of the invention is defined by the characterizing features of the appended claims.

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Claims (9)

  1. Composition d'agent lubrifiant, contenant un composé de phosphore ayant un poids moléculaire d'au plus 1 000 g/mol et 0,1 à 40 % en poids, par rapport au poids de la composition d'agent lubrifiant, d'au moins un poly(méth)acrylate d'alkyle ayant une moyenne en poids du poids moléculaire Mw dans la plage allant de 10 000 à 600 000 g/mol, comprenant :
    a) 0 à 40 % en poids d'unités de répétition qui sont dérivées de (méth)acrylates de formule (I)
    Figure imgb0021
     dans laquelle R représente hydrogène ou méthyle et R1 signifie un radical alkyle de 1 à 5 atomes de carbone,
    b) 20 à 99,9 % en poids d'unités de répétition qui sont dérivées de (méth)acrylates de formule (II)
    Figure imgb0022
     dans laquelle R représente hydrogène ou méthyle, et R2 signifie un radical alkyle de 6 à 22 atomes de carbone,
    c) 0 à 20 % en poids d'unités de répétition qui sont dérivées de (méth)acrylates de formule (III)
    Figure imgb0023
     dans laquelle R représente hydrogène ou méthyle, et R3 signifie un radical alkyle de 23 à 4 000 atomes de carbone, et
    d) 0,1 à 22 % en poids d'unités de répétition qui sont dérivées de monomères éthyléniquement insaturés contenant au moins un atome de phosphore relié par une liaison covalente, choisis dans le groupe constitué par le (méth)acrylate de 2-(diméthylphosphato)-3-hydroxypropyle, le (méth)acrylate de 2-(éthylène-phosphito)-3-hydroxypropyle, le phosphonate de 3-(méth)acryloyloxy-2-hydroxypropyldiéthyle, le phosphonate de 3-(méth)acryloyloxy-2-hydroxypropyldipropyle, le (méth)acrylate de 3-(diméthylphosphato)-2-hydroxypropyle, le (méth)acrylate de 3-(éthylène-phosphito)-2-hydroxypropyle, le phosphonate de 2-(méth)acryloyloxy-3-hydroxypropyldiéthyle, le phosphonate de 2-(méth)acryloyloxy-3-hydroxypropyldipropyle et le (méth)acrylate de 2-(dibutylphosphono)-3-hydroxypropyle, la teneur en atomes de phosphore, par rapport au poids du poly(méth)acrylate d'alkyle, se situant dans la plage allant de 0,2 à 0,9 % en poids.
  2. Composition d'agent lubrifiant selon la revendication 1, caractérisée en ce que le composé de phosphore ayant un poids moléculaire d'au plus 1 000 g/mol est un ester de l'acide phosphorique, un thioester de l'acide phosphorique, un dithiophosphate de métal, un phosphite, un phosphonate, une phosphine ou un mélange de ces composés.
  3. Composition d'agent lubrifiant selon la revendication 1 ou 2, caractérisée en ce que le rapport en poids entre le poly(méth)acrylate d'alkyle contenant des unités de répétition qui sont dérivées de monomères éthyléniquement insaturés contenant au moins un atome de phosphore relié par une liaison covalente, et le composé de phosphore ayant un poids moléculaire d'au plus 1 000 g/mol se situe dans la plage allant de 10 000:1 à 1:10 000.
  4. Composition d'agent lubrifiant selon au moins l'une quelconque des revendications 1 à 3 précédentes, caractérisée en ce que la teneur en composé de phosphore ayant un poids moléculaire d'au plus 1 000 g/mol se situe dans la plage allant de 0,01 à 10 % en poids, par rapport au poids de la composition d'agent lubrifiant.
  5. Composition d'agent lubrifiant selon au moins l'une quelconque des revendications précédentes, caractérisée en ce que le poly(méth)acrylate d'alkyle contenant des unités de répétition qui sont dérivées de monomères éthyléniquement insaturés contenant au moins un atome de phosphore relié par une liaison covalente est un copolymère statistique.
  6. Composition d'agent lubrifiant selon au moins l'une quelconque des revendications précédentes, caractérisée en ce que la composition d'agent lubrifiant comprend au moins 50 % en poids d'une huile de base.
  7. Composition d'agent lubrifiant selon la revendication 6, caractérisée en ce que l'huile de base est une huile du groupe I, une huile du groupe II, une huile du groupe III ou une polyalpha-oléfine ou un mélange de ces huiles.
  8. Poly(méth)acrylate d'alkyle approprié pour une composition d'agent lubrifiant selon au moins l'une quelconque des revendications 1 à 7, comprenant :
    a) 0 à 40 % en poids d'unités de répétition qui sont dérivées de (méth)acrylates de formule (I)
    Figure imgb0024
     dans laquelle R représente hydrogène ou méthyle, et R1 signifie un radical alkyle de 1 à 5 atomes de carbone,
    b) 20 à 99,9 % en poids d'unités de répétition qui sont dérivées de (méth)acrylates de formule (II)
    Figure imgb0025
     dans laquelle R représente hydrogène ou méthyle, et R2 signifie un radical alkyle de 6 à 22 atomes de carbone dans le radical alcool,
    c) 0 à 20 % en poids d'unités de répétition qui sont dérivées de (méth)acrylates de formule (III)
    Figure imgb0026
     dans laquelle R représente hydrogène ou méthyle, et R3 signifie un radical alkyle de 23 à 4 000 atomes de carbone, et
    d) 0,1 à 22 % en poids d'unités de répétition qui sont dérivées de monomères éthyléniquement insaturés contenant au moins un atome de phosphore relié par une liaison covalente, choisis dans le groupe constitué par le (méth)acrylate de 2-(diméthylphosphato)-3-hydroxypropyle, le (méth)acrylate de 2-(éthylène-phosphito)-3-hydroxypropyle, le phosphonate de 3-(méth)acryloyloxy-2-hydroxypropyldiéthyle, le phosphonate de 3-(méth)acryloyloxy-2-hydroxypropyldipropyle, le (méth)acrylate de 3-(diméthylphosphato)-2-hydroxypropyle, le (méth)acrylate de 3-(éthylène-phosphito)-2-hydroxypropyle, le phosphonate de 2-(méth)acryloyloxy-3-hydroxypropyldiéthyle, le phosphonate de 2-(méth)acryloyloxy-3-hydroxypropyldipropyle et le (méth)acrylate de 2-(dibutylphosphono)-3-hydroxypropyle, et la teneur en atomes de phosphore, par rapport au poids du poly(méth)acrylate d'alkyle, se situant dans la plage allant de 0,2 à 0,9 % en poids.
  9. Utilisation d'un poly(méth)acrylate d'alkyle selon la revendication 8 pour la réduction des frottements.
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DE102007046223A1 (de) 2007-09-26 2009-04-02 Evonik Rohmax Additives Gmbh Verwendung von Kammpolymeren zur Verringerung des Kraftstoffverbrauchs
DE102007032120A1 (de) 2007-07-09 2009-01-15 Evonik Rohmax Additives Gmbh Verwendung von Kammpolymeren zur Verringerung des Kraftstoffverbrauchs
DE102007036856A1 (de) * 2007-08-06 2009-02-26 Evonik Rohmax Additives Gmbh Verwendung von Estergruppen-umfassenden Polymeren als Antifatigue-Additive
JP5340707B2 (ja) 2007-11-30 2013-11-13 三洋化成工業株式会社 粘度指数向上剤及び潤滑油組成物
JP5420237B2 (ja) 2007-12-26 2014-02-19 三洋化成工業株式会社 潤滑油添加剤及び潤滑油組成物
DE102010028195A1 (de) * 2010-04-26 2011-10-27 Evonik Rohmax Additives Gmbh Schmiermittel für Getriebe

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US9914896B2 (en) 2018-03-13
CA2837001C (fr) 2019-07-16
DE102011076364A1 (de) 2012-11-29
CA2837001A1 (fr) 2012-11-29
EP2714871A1 (fr) 2014-04-09
KR20140032388A (ko) 2014-03-14
WO2012159828A1 (fr) 2012-11-29
CN103443257A (zh) 2013-12-11
US20140135242A1 (en) 2014-05-15
SG194799A1 (en) 2013-12-30
JP2014518925A (ja) 2014-08-07
BR112013029905A2 (pt) 2016-12-20

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