Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
  • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
  • C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
  • C10M145/14—Acrylate; Methacrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
  • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• • 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
  • C10M149/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2438/00—Living radical polymerisation
  • C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/02—Hydroxy compounds
  • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/028—Overbased salts thereof
• • 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
  • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2217/022—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
  • C10M2217/023—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group the amino group containing an ester bond
• • 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
  • 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

Definitions

• ester group-comprising polymers as antifatigue agents
• the present invention relates to the use of polymers comprising ester groups as antifatigue additives.
• Lubricants are beneficial in terms of wear resistance if they contain antiwear AW additives and are of high viscosity. Fretting on tooth flanks usually occurs at medium to high speeds. The touching surfaces weld for a short time and tear apart again immediately. A typical appearance of such damage is shown, for example, in Fig. 10.11 in T. Mang, W. Dresel (eds.): “Lubricants and Lubrication", Wiley-VCH, Weinheim 2001. The damage occurs at intersecting flank areas, where very high sliding speeds are present (often at the tooth tip). These are sudden damages which can already be caused by a one-time overload. Bearings also experience scuffing damage; These are observed especially in large bearings, eg in gearboxes of cement mills.
• Eating damage can be reduced by more than a factor of 5 in the lubricant due to extreme pressure additives (extreme pressure EP additive).
• polyalkyl (meth) acrylates have long been used in lubricating oils, for example gear oils or motor oils, some of which may be functionalized with comonomers, in particular nitrogen or oxygen-containing monomers.
• VI improvers include, in particular, polymers which have been reacted with dimethylaminoethyl methacrylate (US Pat. No. 2,737,496 to EI Dupont de Nemours and Co.), dimethylaminoethyl methacrylamide (US Pat. No. 4,021,357 to Texaco Inc.) or hydroxyethyl methacrylate (US Pat. No. 3,249,545 to Shell OiI Co) were functionalized.
• PAMA-based VI improvers for lubricating oil applications are constantly being improved.
• polymers having block-like sequences for use in lubricating oils have also been frequently used in recent times.
• WO 2004/087850 describes block copolymer-containing lubricating oil formulations having excellent frictional properties.
• the block copolymers act as friction modifiers.
• WO 2006/105926 describes inter alia block copolymers which are derived from specifically selected N / O-functional monomers and their use as coefficients of friction and dispersants (dispersant).
• WO 2006/007934 of RohMax Additive GmbH describes the use of graft polymers as anti-wear additives in lubricating oil formulations, in particular in motor oils.
• WO 2005/097956 of RohMax Additives describes lubricating oil formulations containing H-bridge-containing graft polymers as wear protection additive.
• a further object of the invention was to provide additives which can be prepared simply and inexpensively, in particular commercially available components should be used. Here, the production should be possible on an industrial scale without the need for new or structurally complex systems.
• the present invention accordingly relates to the use of polymers comprising ester groups comprising at least one nonpolar segment P and at least one polar segment D, where the polar segment D has at least 8 repeat units and the proportion by weight of dispersing repeat units in the polar segment D is at least 30% , based on the weight of the polar segment D, as an antifatigue additive in lubricants.
• additives can be prepared simply 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 polymers to be used according to the invention show a particularly favorable property profile. So the polymers can be surprising shear stable, so that the lubricants have a very long shelf life. Furthermore, the additive to be used according to the invention can bring about a multiplicity of desirable properties in the lubricant. For example, lubricants having superior low temperature properties or viscosity properties can be prepared which comprise the present ester group-comprising polymers. As a result, the number of different additives can be minimized. In addition, the present ester group-containing polymers are compatible with many additives. This allows the lubricants to be adapted to a wide variety of requirements.
• the additives to be used show no adverse effects on the fuel consumption or the environmental compatibility of the lubricant.
• polymers comprising ester groups are understood as meaning polymers obtainable by polymerization of monomer compositions which comprise ethylenically unsaturated compounds having at least one ester group, which are referred to below as ester monomers. Accordingly, these polymers contain ester groups as part of the side chain.
• These polymers include, in particular, polyalkyl (meth) acrylates (PAMA), polyalkyl fumarates and / or polyalkylene maleates.
• Estermonomers are known per se. These include in particular (meth) acrylates, maleates and fumarates, which may have different alcohol residues.
• the term (meth) acrylates includes methacrylates and acrylates as well as mixtures of both. These monomers are well known.
• the ester group-comprising polymer preferably comprises at least 40%, more preferably at least 60%, more preferably at least 80%, and most preferably at least 90%, of repeating units derived from ester monomers.
• Polymers which can be used according to the invention comprise at least one nonpolar segment P and at least one polar segment D, where the polar segment D has at least 8 repeat units and the proportion by weight of dispersing repeat units in the polar segment D is at least 30%, based on the weight of the polar segment D.
• repeating unit is well known in the art.
• the present polymers can preferably be obtained via free-radical polymerization of monomers. In this case, double bonds are opened with the formation of covalent bonds. Accordingly, the repeat unit results from the monomers used.
• the polymers of the invention have polar and non-polar segments.
• the segments may have a substantially constant composition of one or more monomer units
• the segments may have a gradient, wherein the concentration of different monomer units (repeat units) varies over the segment length.
• the polar segments D differ from the nonpolar segments P in terms of the proportion of dispersing monomers, and the nonpolar segments can have at most a small proportion of dispersing repeat units (monomer units), whereas the polar groups D Segments include a high proportion of dispersing repeat units (monomer units).
• Dispersing monomers are understood as meaning, in particular, monomers having functional groups, it being possible to assume that polymers having these functional groups can keep particles, in particular soot particles, in solution (compare RM Mortier, ST Orszulik (eds.): “Chemistry and Technology of Lubricants ", Blackie Academic & Professional, London, 2 nd ed. 1997). These include, in particular, monomers which have boron, phosphorus, silicon, sulfur, oxygen and nitrogen-containing groups, preference being given to oxygen- and nitrogen-functionalized monomers.
• the polar segments D comprise at least 8, preferably at least 12 and very particularly preferably at least 15 repeating units.
• the polar segments D comprise at least 30 wt .-%, preferably at least 40 wt .-% of dispersing repeating units, based on the weight of the polar segment D.
• the polar segment can also have repeating units that have no dispersing effect .
• the polar segment can be constructed statistically so that the different repeat units have a statistical distribution over the segment length.
• the polar segment may be block-like or gradient-shaped such that the non-dispersive repeating units and the repeating repeating units have an uneven distribution within the polar segment.
• the non-polar, hydrophobic segment P may comprise a small proportion of dispersing repeating units, preferably below 20 wt .-%, more preferably below 10 wt .-% and most preferably below 5 wt .-%, based on the weight of the nonpolar segment P.
• the non-polar segment P comprises substantially no dispersing repeat units.
• the non-polar segment P of the ester-group-comprising polymer may have from 5 to 100% by weight, in particular from 20 to 98% by weight, preferably from 30 to 95 and very particularly preferably from 70 to 92% by weight, of repeat units derived from ester monomers with 7 to 15 carbon atoms are derived in the alcohol radical.
• the nonpolar segment P of the ester group-comprising polymer may be 0 to 80% by weight, preferably 0.5 to 60% by weight, more preferably 2 to 50% by weight and most preferably 5 to 20% by weight.
• non-polar segment P of the ester-group-comprising polymer can have 0 to 40% by weight, preferably 0.1 to 30% by weight and particularly preferably 0.5 to 20% by weight, of repeat units derived from ester monomers 1 to 6 carbon atoms are derived in the alcohol radical.
• the non-polar segment P of the ester group-comprising polymer preferably comprises at least 40% by weight, more preferably at least 60% by weight, particularly preferably at least 80% by weight, and most particularly at least 90% by weight of repeating units derived from ester monomers.
• Mixtures from which the nonpolar segments of the polymer comprising ester groups according to the invention can be obtained may contain from 0 to 40% by weight, in particular from 0.1 to 30% by weight and more preferably from 0.5 to 20% by weight, of one or more ethylenically unsaturated Contain ester compounds of the formula (I)
• R is hydrogen or methyl
• R 1 is a linear or branched alkyl radical having 1 to 6 carbon atoms
• R 2 and R 3 are independently hydrogen or a group of the formula -COOR ', wherein R' is hydrogen or an alkyl group having 1 to 6 carbon atoms means.
• component (I) examples include (meth) acrylates, fumarates and maleates, which are derived from saturated alcohols, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i- Propyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate and pentyl (meth) acrylate, hexyl (meth) acrylate; Cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate;
• (Meth) acrylates derived from unsaturated alcohols, such as 2-propynyl (meth) acrylate, allyl (meth) acrylate and vinyl (meth) acrylate.
• compositions to be polymerized for the preparation of the nonpolar segments P preferably contain from 5 to 100% by weight, preferably from 10 to 98 % By weight, particularly preferably from 20 to 95% by weight, of one or more ethylenically unsaturated ester compounds of the formula (II)
• R is hydrogen or methyl
• R 4 is a linear or branched alkyl radical having 7 to 15 carbon atoms
• R 5 and R 6 are independently hydrogen or a group of the formula -COOR ", where R" is hydrogen or an alkyl group having 7 to 15 carbon atoms means.
• component (II) examples include:
• (Meth) acrylates derived from unsaturated alcohols, such as.
• unsaturated alcohols such as.
• Cycloalkyl (meth) acrylates such as 3-vinylcyclohexyl (meth) acrylate, boronyl (meth) acrylate; as well as the corresponding fumarates and maleates.
• preferred monomer compositions for the preparation of the non-polar segments P 0 to 80 wt.% Preferably 0.5 to 60 wt.%, Particularly preferably 2 to 50 wt .-% and most preferably 5 to 20 wt .-% of one or more ethylenically unsaturated ester compounds of the formula (III)
• R is hydrogen or methyl
• R 7 is a linear or branched alkyl radical having 16 to 40, preferably 16 to 30 carbon atoms
• R 8 and R 9 independently represent hydrogen or a group of the formula -COOR '", wherein R'" is hydrogen or an alkyl group having 16 to 40, preferably 16 to 30 carbon atoms.
• component (III) examples include (meth) acrylates derived from saturated alcohols, such as hexadecyl (meth) acrylate, 2-methylhexadecyl (meth) acrylate, heptadecyl (meth) acrylate, 5-iso-propylheptadecyl (meth) acrylate, 4-tert-butyloctadecyl (meth) acrylate, 5-ethyloctadecyl (meth) acrylate, 3-iso-propyloctadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate , Cetylecosyl (meth) acrylate, Stearyleicosyl (meth) acrylate, docosyl (meth) acrylate and / or Eicosyltetratriacontyl (meth
• Cycloalkyl (meth) acrylates such as 2,4,5-tri-t-butyl-3-vinylcyclohexyl (meth) acrylate, 2,3,4,5-tetra-t-butylcyclohexyl (meth) acrylate. as well as the corresponding fumarates and maleates.
• ester compounds with a long-chain alcohol radical in particular the components (II) and (III), can be obtained, for example, by reacting (meth) acrylates, fumarates, maleates and / or the corresponding acids with long-chain fatty alcohols, in which case a mixture of esters, such as (meth) acrylates with different long chain Alcohol residues arise.
• These fatty alcohols include Oxo Alcohol® 7911, Oxo Alcohol® 7900, Oxo Alcohol® 1100; Alibi® 610, Alibi® 810, Lial® 125 and Nafol® grades (Sasol); Aiphanoi® 79 (ICI); Epal® 610 and Epal® 810 (Afton); Linevol® 79, Linevol® 911 and Neodol® 25E (Shell); Dehydad®, Hydrenol® and Lorol® types (Cognis); Acropol® 35 and Exxal® 10 (Exxon Chemicals); Kalcol® 2465 (Kao Chemicals).
• the (meth) acrylates are particularly preferred over the maleates and fumarates, i.
• R 2, R 3, R 5, R 6, R 8 and R 9 of the formulas (I), (II) and (III) represent hydrogen in particularly preferred embodiments.
• the weight ratio of ester monomers of the formula (II) to the ester monomers of the formula (III) can be in a wide range.
• the ratio of ester compounds of formula (II) having 7 to 15 carbon atoms in the alcohol radical to the ester compounds of formula (III) having 16 to 40 carbon atoms in the alcohol radical is in the range of 50: 1 to 1: 30, more preferably in the range of 10: 1 to 1: 3, particularly preferably 5: 1 to 1: 1.
• the monomer mixture for producing the non-polar segments may comprise ethylenically unsaturated monomers which can be copolymerized with the ethylenically unsaturated ester compounds of the formulas (I), (II) and / or (III).
• Comonomers for polymerization according to the present invention are particularly suitable which correspond to the formula:
• Preferred comonomers include, but are not limited to, vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene chloride, and vinylidene fluoride;
• Styrene substituted styrenes having an alkyl substituent in the side chain, such as.
• Alpha-methylstyrene and alpha-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; Vinyl and isoprenyl ethers;
• monomer mixtures for preparing the non-polar segments may comprise dispersing monomers.
• the proportion of comonomers is preferably 0 to 50 wt .-%, more preferably 0.1 to 40 wt .-% and most preferably 0.5 to 20 wt .-%, based on the weight of the monomer composition for the preparation of the non-polar segment P.
• a polymer which can be used according to the invention comprises at least one polar segment D which comprises repeating units derived from dispersing monomers.
• Dispersing monomers have long been used for the functionalization of polymeric additives in lubricating oils and are therefore known to the person skilled in the art (see RM Mortier, ST Orszulik (eds.): “Chemistry and Technology of Lubricants", Blackie Academic & Professional, London, 2 nd ed. 1997).
• R is hydrogen or methyl
• X is oxygen, sulfur or an amino group of the formula -NH- or -NR a -
• R a is an alkyl radical having 1 to 40, preferably 1 to 4 carbon atoms
• R 10 is 2 to 1000, in particular from 2 to 100, preferably from 2 to 20, carbon atoms containing at least one, preferably at least two heteroatoms
• R 11 and R 12 independently represent hydrogen or a group of the formula -COX'R 10 , where X 'is oxygen or an amino group of the formula NH- or -NR a -, wherein R a is an alkyl radical having 1 to 40, preferably 1 to 4 carbon atoms, and R 10 is 1 to 100, preferably 1 to 30 and particularly preferably 1 to 15 Carbon atoms, are used as dispersing monomers.
• 2 to 1000 carbon radical denotes radicals of organic compounds having 2 to 1000 carbon atoms. Similar definitions apply to corresponding terms. It includes aromatic and heteroaromatic groups as well as alkyl, cycloalkyl, alkoxy, cycloalkoxy, alkenyl, alkanoyl, alkoxycarbonyl and heteroaliphatic groups. The groups mentioned can be branched or unbranched. Furthermore, these groups can have customary substituents.
• Substituents are, for example, linear and branched alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, 2-methylbutyl or hexyl; Cycloalkyl groups such as cyclopentyl and cyclohexyl; aromatic groups, such as phenyl or naphthyl; Amino groups, hydroxy groups, ether groups, ester groups and halides.
• aromatic groups are radicals of mononuclear or polynuclear aromatic compounds having preferably 6 to 20, in particular 6 to 12, carbon atoms.
• Heteroaromatic groups denote aryl radicals in which at least one CH group has been replaced by N and / or at least two adjacent CH groups have been replaced by S, NH or O, heteroaromatic groups having from 3 to 19 carbon atoms.
• Preferred aromatic or heteroaromatic groups according to the invention are derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane, diphenyldimethylmethane, bisphenone, diphenylsulfone, thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole, isoxazole, pyrazole, 1,3,4-oxadiazole , 2,5-diphenyl-1, 3,4-oxadiazole, 1, 3,4-thiadiazole, 1, 3,4-triazole, 2,5-diphenyl-1, 3,4- triazole, 1, 2,5-triphenyl-1, 3,4-triazole, 1, 2,4-oxadiazole, 1, 2,4-thiadiazole, 1, 2,4-triazole, 1, 2,3-triazole, 1, 2,3,4-tetrazole, benzo [b] thiophen
• the preferred alkyl groups include the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl, tert-butyl, pentyl, 2-methylbutyl, 1, 1-dimethylpropyl, hexyl, heptyl, octyl, 1,1,3,3-tetramethylbutyl, nonyl, 1-decyl, 2-decyl, undecyl, dodecyl, pentadecyl and the eicosyl group ,
• Preferred cycloalkyl groups include the cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups, optionally substituted with branched or unbranched alkyl groups.
• Preferred alkanoyl groups include the formyl, acetyl, propionyl, 2-methylpropionyl, butyryl, valeroyl, pivaloyl, hexanoyl, decanoyl and dodecanoyl groups.
• the preferred alkoxycarbonyl groups include the methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, tert-butoxycarbonyl, hexyloxycarbonyl, 2-methylhexyloxycarbonyl, decyloxycarbonyl or dodecyloxycarbonyl group.
• the preferred alkoxy groups include alkoxy groups whose hydrocarbon radical is one of the aforementioned preferred alkyl groups.
• the preferred cycloalkoxy groups include cycloalkoxy groups whose hydrocarbon radical is one of the aforementioned preferred cycloalkyl groups.
• R 10 includes, among others, oxygen, nitrogen, sulfur, boron, silicon, and phosphorus, with oxygen and nitrogen being preferred.
• the radical R 10 comprises at least one, preferably at least two, preferably at least three heteroatoms.
• the radical R 10 in ester compounds of the formula (IV) preferably has at least 2 different heteroatoms.
• the radical R 10 in at least one of the ester compounds of the formula (IV) may comprise at least one nitrogen atom and at least one oxygen atom.
• Examples of ethylenically unsaturated, polar ester compounds 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
• heterocyclic (meth) acrylates include, among others
• Aminoalkyl (meth) acrylate amides such as
• heterocyclic vinyl compounds include 2-vinylpyridine, 3-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, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxolane, Vinyl- furan, vinylthiophene, vinylthiolane, vinylthiazoles and hydrogenated vinylthiazoles, vinyl oxazoles and hydrogenated vinyl oxazoles, with N-vinylimidazole and N-vinylpyrrolidone being particularly preferably used for functionalization.
• the monomers set forth above may be used singly or as a mixture.
• ester group-comprising polymers which are prepared by using 2-hydroxypropyl methacrylate, 2
• a composition for preparing the polar segments may also include non-dispersing monomers as set forth above. These include in particular ethylenically unsaturated ester compounds of the formulas (I), (II) and / or (III).
• polymeric additives having a polar segment D comprising at least 3, preferably at least 5, units derived from monomers of formula (IV) and / or heterocyclic vinyl compounds, which are bonded directly to one another.
• the weight ratio of the hydrophobic segments to the polar segments in the range of 100: 1 to 1: 1, particularly preferably in the rich 30: 1 to 2: 1, and most preferably in the range of 10: 1 to 4: 1.
• the length of the hydrophobic and polar segments can vary widely.
• the non-polar segments P have a weight-average degree of polymerization of at least 10, in particular at least 40.
• the degree of polymerization of the hydrophobic segments averaged over the weight is in the range from 20 to 5000, in particular from 50 to 2000.
• the proportion of dispersing repeat units, based on the weight of the polymer comprising ester groups, is preferably in the range from 0.5% by weight to 20% by weight, particularly preferably in the range from 1.5% by weight to 15% by weight .-% and most preferably in the range of 2.5 wt .-% to 10 wt .-%.
• these repeating units preferably form a segment-like structure within the polymer comprising the ester group, so that preferably at least 70% by weight, particularly preferably at least 80% by weight, based on the total weight of the dispersing repeating units, forms part of a polar segment D. are.
• the present invention describes polymers which preferably have a high oil solubility.
• oil-soluble means that a mixture of a base oil and an ester group-comprising polymer can be prepared without macroscopic phase formation, which comprises at least 0.1 wt .-%, preferably at least 0.5 wt .-% of the polymers. In this mixture, the polymer may be dispersed and / or dissolved.
• the oil solubility depends in particular on the proportion of lipophilic side chains and of Base oil. This property is known to the person skilled in the art and can easily be adjusted for the respective base oil via the proportion of lipophilic monomers.
• ester group-comprising polymers which preferably have a weight average molecular weight M w in the range of from 7 500 to 1 000 000 g / mol, more preferably from 10 000 to 600 000 g / mol, and most preferably from 15 000 to 80 000 g / mol.
• the number average molecular weight M n may preferably be in the range of 5,000 to 800,000 g / mol, more preferably 7,500 to 500,000 g / mol, and most preferably 10,000 to 80,000 g / mol.
• ester group-comprising polymers whose polydispersity index M w / M n is in the range from 1 to 5, particularly preferably in the range from 1, 05 to 4.
• the number average and weight average molecular weights can be determined by known methods, for example, permeation chromatography (GPC).
• the ester group-comprising polymer may have a variety of construction.
• the polymer may be present as a diblock, triblock, multiblock, comb and / or star copolymer comprising corresponding polar and non-polar segments.
• the polymer may be present in particular as a graft copolymer.
• ester group-comprising polymers to be used according to the invention can be obtained in various ways. It is essential that at least one non-polar segment P and at least one polar segment D are produced. be presented.
• a preferred process consists in the radical graft copolymerization known per se, wherein in a first step, for example, a nonpolar grafting base is produced, onto which dispersing monomers are grafted in a second step.
• ATRP Atom Transfer Radical Polymerization
• RAFT Reversible Addition Fragmentation Chain Transfer
• NMP Nitroxide Mediated Polymerization
• diblock, triblock, multiblock, comb or star copolymers can be obtained by the methods of controlled radical polymerization set out above.
• azo initiators include the well-known in the art azo initiators such as AIBN and 1, 1-azobiscyclohexancarbonitrile, and peroxy compounds such as methylethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert-butyl per-2-ethylhexanoate, ketone peroxide, tert-butyl peroctoate, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, 2,5-bis (2-ethylhexanoyl-peroxy) -2 , 5-dimethylhexane, tert-butyl peroxy-2-ethylhexanoate, tert-butylperoxy-3,5,5-trimethylhexanoate, dicum
• Suitable chain transfer agents are in particular oil-soluble mercaptans such as n-dodecyl mercaptan or 2-mercaptoethanol or chain transfer agents from the class of terpenes, such as terpinolene.
• the ATRP method is known per se. It is believed that this is a "living" radical polymerization without any limitation to the description of the mechanism.
• a transition metal compound is reacted with a compound having a transferable atomic group.
• the transferable atomic group is transferred to the transition metal compound, whereby the metal is oxidized.
• This reaction forms a radical that adds to ethylenic groups.
• the transfer of the atomic group to the transition metal compound is reversible so that the atomic group is re-transferred to the growing polymer chain, forming a controlled polymerization system. Accordingly, the structure of the polymer, the molecular weight and the molecular weight distribution can be controlled.
• This reaction procedure is described for example by JS.
• polymers according to the invention can also be obtained, for example, by RAFT methods. This process is described in detail, for example, in WO 98/01478 and WO 2004/083169, to which reference is expressly made for purposes of the disclosure.
• polymers according to the invention are obtainable by NMP processes, which are described, inter alia, in US Pat. No. 4,581,429.
• the polymerization can be carried out at atmospheric pressure, lower or higher pressure.
• the polymerization temperature is not critical. In general, however, it is in the range of -20 ° - 200 0 C, preferably 50 ° - 150 0 C and particularly preferably 80 ° - 130 0 C.
• the polymerization can be carried out with or without solvent.
• the term of the solvent is to be understood here broadly.
• the selection of the solvent is carried out according to the polarity of the monomers used, wherein preferably 100N oil, lighter gas oil and / or aromatic hydrocarbons, for example toluene or xylene can be used.
• 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.
• 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 refinement, have different proportions of n-alkanes, isoalkanes with a low degree of branching, so-called monomethyl-branched paraffins, and compounds containing heteroatoms, in particular O, N and / or S, which have polar properties be awarded. The assignment is difficult, however, since individual alkane molecules can have both long-chain branched groups and cycloalkane radicals and aromatic moieties.
• mineral oil comprises primarily naphthenic and paraffinic alkanes, which generally have greater than 13, preferably greater than 18, and most preferably greater than 20, carbon atoms.
• the proportion of these compounds is generally greater than or equal to 60% by weight, preferably greater than or equal to 80% by weight, without this being intended to be 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 (reduced sulfur content, reduced nitrogen content, higher viscosity index, lower pour point) is given by hydrotreating the mineral oils (hydro isomerization, hydro cracking, 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 originating 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 III 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 ester group-comprising polymer 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 - 10 wt .-%, based on the total weight of the composition.
• the lubricating oil compositions set forth herein may also contain further additives and additives.
• additives include, among others, VI improvers, pour point improvers and DI additives (dispersants, detergents, defoamers, corrosion inhibitors, antioxidants, wear protection and extreme pressure additives, friction modifiers).
• the additionally usable VI improvers include, in particular, polyalkyl (meth) acrylates having 1 to 30 carbon atoms in the alcohol group (PAMA; partially N / O-functional with advantageous additive properties as dispersant, wear protection additive and / or Reibwertver baseer), which differ from the set forth in claim 1 copolymers, and poly (iso) butenes (PIB), fumarate-olefin copolymers, styrene Maleate copolymers, hydrogenated styrene-diene copolymers (HSD) and olefin copolymers (OCP).
• PAMA polyalkyl (meth) acrylates having 1 to 30 carbon atoms in the alcohol group
• PIB poly (iso) butenes
• PIB poly (iso) butenes
• HSD hydrogenated styrene-diene copolymers
• OCP olefin copolymers
• the pour point improvers include, in particular, polyalkyl (meth) acrylates (PAMA) having 1 to 30 carbon atoms in the alcohol group.
• PAMA polyalkyl (meth) acrylates
• Suitable dispersants include, but are not limited to, poly (isobutylene) derivatives, e.g. Poly (isobutylene) succinimide (PIBSI); Ethylene-propylene oligomers with N / O functionalities.
• poly (isobutylene) derivatives e.g. Poly (isobutylene) succinimide (PIBSI); Ethylene-propylene oligomers with N / O functionalities.
• the preferred detergents include, but are not limited to, metal-containing compounds such as phenates; salicylates; Thiophosphonates, in particular thiopyrophosphonates, thiophosphonates and phosphonates; Sulfonates and carbonates.
• metal these compounds may in particular contain calcium, magnesium and barium. These compounds can preferably be used neutral or overbased.
• Defoamers defoamer
• the silicone-containing antifoams include, but are not limited to, linear poly (dimethylsiloxane) and cyclic poly (dimethylsiloxane).
• silicone-free defoamers it is often possible to use polyethers, for example poly (ethylene glycol) or tributyl phosphate.
• the lubricating oil compositions according to the invention may comprise corrosion inhibitors. These are divided into antirust additives and metal passivators / deactivators.
• Sulphonates such as, for example, petroleum sulphonates or (often overbased) synthetic alkylbenzenesulphonates, for example dinonylnaphthene sulphonate; Carboxylic acid derivatives such as, for example, lanolin (wool fat), oxidized paraffins, zinc naphthenates, acylated succinic acids, 4-nonylphenoxyacetic acid, amides and imides (N-acylsarcosine, imidazoline derivatives); Amine-neutralized mono- and dialkylphosphoric acid esters; morpholine; Dicy cylohexylamine or diethanolamine be used.
• the metal passivators / deactivators include, but are not limited to, benzotriazole, tolyltriazole, 2-mercaptobenzothiazole, dialkyl-2,5-dimercapto-1, 3,4-thiadiazole; N 1 N'-disalicylidenethylenediamine, N, N'-disalicylidenepropylenediamine; Zinc dialkyldithiophosphates and dialkyldithiocarbamates.
• antioxidant antioxidant
• friction modifiers are friction modifiers.
• mechanically active compounds such as, for example, molybdenum disulfide, graphite (also fluorinated), poly (trifluoroethylene), polyamide, polyimide;
• Adsorption layer-forming compounds such as long-chain carboxylic acids, fatty acid esters, ethers, alcohols, amines, amides, imides;
• Compounds which form layers by tribochemical reactions such as, for example, saturated fatty acids, phosphoric acid and thiophosphoric acid esters, xanthates, sulfurized fatty acids;
• Compounds which form polymer-like layers such as, for example, ethoxylated dicarboxylic acid partial esters, dialkyl phthalic acid esters, methacrylates, unsaturated fatty acids, sulfurized olefins or organometallic compounds, for example molybdenum compounds (molybdenum dithiophosphates
• ZnDTP e.g. is primarily a wear protection additive and extreme pressure additive, but also has the character of an antioxidant and corrosion inhibitor (here: metal passivator / deactivator).
• Lubricating oil compositions have a viscosity measured in accordance with ASTM D 445 at 40 ° C.
• the measured at 100 0 C ki- nematic viscosity KV-ioo is preferably at least 5.0 mm 2 / s, more preferably at least 5.2 mnn 2 / s and most preferably at least 5.4 mm 2 / s.
• preferred lubricating oil compositions have an ASTM D 2270 viscosity index in the range of 100 to 400, more preferably in the range 125 to 325 and most preferably in the range of 150 to 250.
• Suitable lubricants are those which have a PSSI according to DIN 51350-6 (20h KRL, tapered roller bearings) of less than or equal to 100. More preferably, the PSSI is less than or equal to 65, more preferably less than or equal to 25.
• the present lubricants can be used in particular as gear oil, engine oil or hydraulic oil. Surprising advantages can be achieved, in particular, when using the present lubricants in manual (manual) (automated), automated manual (automated manual), double clutch (double clutch) or direct shift transmissions (DSG), automatic (automatic) and continuously variable transmissions achieve (continuous variable transmission CVC). Furthermore, the present lubricants can be used in particular in transfer cases and axle or differential gears.
• the present ester group-comprising polymers serve in particular as an antifatigue additive in lubricants. Surprisingly, it has been found that these additives counteract material fatigue, so that the service life of gears, motors or hydraulic systems can be increased. This finding can be determined by various methods. The determination of the fatigue life (pitting capacity) of the lubricating oil formulations can be carried out according to methods for toothing as well as for roller bearings. The following methods cover a wide range of Hertzian pressures.
• the fatigue life (number of revolutions) can be determined, for example, on a four-ball apparatus (VKA, four-ball apparatus) standardized in accordance with DIN 51350-1, in which a rotating ball is pressed under load onto three similar likewise rotating balls. It uses test specification VW-PV-1444 of Volkswagen AG ("Pitting resistance of components with rolling friction - pitting test", VW-PV-1444, Volkswagen AG).
• the fatigue can be determined by a FAG FE8 test.
• the rolling bearing lubricant tester FE8 according to DIN 51819-1 FAG (Schaeffler KG, Schweinfurt).
• VW-PV-1483 Test specification
• VW-PV-1483 Test specification
• the rolling bearing lubricant tester FE8 can also be operated according to the more stringent method ZF-702-232 / 2003 of ZF Friedrichshafen AG (see “ZF Bearing Pitting Test", ZF-702-232, ZF Friedrichshafen AG, 2004).
• the base polymer was prepared. 29.4 g of monomer mixture (75% 12/14 -alkyl methacrylate and 25% methyl methacrylate) and 0.0883 g of n-dodecylmercaptan were together with 265 g of 100N-oil in the 2L reaction flask of an apparatus with saber stirrer, condenser, thermometer, feed pump and N 2 - Supply line filled. The apparatus was rendered inert and heated to 100 0 C using an oil bath. After the mixture in the Christskol- ben a temperature of 100 0 C reached, 2.26 g te / t-butyl peroctoate were added.
• the graft yield was about 20% measured over the signal height.
• the graft yield was determined according to the method set out in WO 2006/007934.
• an 8-arm initiator was prepared.
• the synthesis of the 8-arm initiator octa ( ⁇ -bromoisobutyryl) sucrose was carried out according to a synthesis described in MH Stenzel-Rosenbaum, TP Davis, V. Chen, A. Fane, Macromolecules 34 (2001), 5433, wherein a Yield 72% was achieved.
• the structure is detected by 1 H-NMR.
• the weight-average molecular weights M w and polydispersity indices PDI of the polymers were determined by GPC, the results obtained being shown in Table.
• the measurements are carried out in tetrahydrofuran at 35 ° C against a polymethyl methacrylate calibration curve from a set of> 25 stan- standards (Polymer Standards Service or Polymer Laboratories) whose M p ⁇ a k is evenly distributed over the range of 5-10 6 to 2-10 2 g / mol.
• a combination of six columns (Polymer Standards Service SDV 100 ⁇ / 2x SDV LXL / 2x SDV 100 ⁇ / Shodex KF-800D) is used.
• a RI detector Align 1100 Series
• Additin RC 3760 ® available antiwear and extreme pressure additive wherein the here- are demonstrated by the data obtained in Table 2 as Comparison Example 3.
• the given additive is a tri (dodecyl) amine-neutralized hexylphosphoric acid ester of degree of esterification 1.5.
• the product is highly viscous and free of solvent.
• a fatigue duration can be used as an arithmetic mean or, in the case of a sufficient number of experiments, using the Weibull statistic (W. Weibull: Fatigue Testing and Analysis of Results, Pergamon Press 1961) as the fatigue probability of the probability of failure.
• P f represented 50%. that is, 50% of all samples have up to the indicated value shown fatigue.
• the failure probability P f with the confidence level P c (confidence level) of the study, c 90% in P ,
• Table 3 summarizes the results obtained for determining fatigue lives. The results clearly show that the inventive examples (with the same KV100) significantly increase the fatigue life in comparison to the prior art. Table 3. Fatigue of the compositions studied
• composition obtained with the polymer according to Example 1 was evaluated according to the FZG PT-C 10/120 study and the FZG PTX-C 10/90 investigation set out above.
• the composition with the polymers according to Example 1 reached a value of 36.0 hours (FZG PT-C 10/120) or 242 hours (FZG PTX-C 10/90).

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