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  • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
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  • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
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  • C10M157/04—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential at least one of them being a nitrogen-containing compound
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  • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
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  • 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
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  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
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  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
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  • 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
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  • 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
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  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
  • C10M2209/086—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
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  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
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  • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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  • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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  • 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
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  • 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
  • C10M2217/024—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 amido or imido group
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  • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2217/028—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
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  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/04—Molecular weight; Molecular weight distribution
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  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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Definitions

• the present application relates to lubricating oil formulations which contain copolymers or graft copolymers which are composed of free-radically polymerizable monomers and which, in addition to long-chain alkyl-substituted ethylenically unsaturated compounds, in particular acrylates or methacrylates, additionally also contain monomers with hydrogen-bond donor functions.
• the monomer with hydrogen-bond donor property is either in the polymer backbone or in the grafted side branches.
• polymers which contain monomers with a hydrogen bond donor function those are also disclosed which contain monomers which simultaneously carry hydrogen bond donor and hydrogen bond acceptor functions.
• the polymers are suitable as additives for lubricating oil formulations, for example for engine oils or for hydraulic fluids with improved wear behavior. It was found that the hydrogen-bond donor functions in the polymer, but in particular the simultaneous presence of hydrogen-bond donor and acceptor functions, have positive effects on wear protection, detergent and disperse effects.
• Polyalkyl acrylates are common polymeric additives for lubricating oil formulations.
• Long alkyl chains typically chain length: C8-C18
• ester functionalities of the acrylate monomers give polyalkyl acrylates good solubility in apolar solvents, such as mineral oil.
• Common fields of application for additives are hydraulic, gear or motor oils.
• the polymers have a viscosity index (VI) - optimizing effect, where the name VI improver comes from.
• a high viscosity index means that an oil at high temperatures (e.g. in a typical range of 70-140 ° C) has a relatively high and at low temperatures (eg in a typical range of -60 - 20 ° C) a relatively low viscosity.
• the improved lubricity of an oil at high temperatures compared to an oil that does not contain polyacrylate, which has an otherwise identical kinematic viscosity at, for example, 40 ° C., is due to a higher viscosity in the elevated temperature range.
• a VI improver is used at a lower temperature, such as during the cold start phase of an engine, there is a lower viscosity compared to an oil which otherwise has the same kinematic viscosity at 100 ° C. Due to the lower viscosity of the oil during the starting phase of an engine, a cold start is much easier.
• polyacrylate systems have become established in the lubricant industry, which in addition to Vl optimization provide additional properties such as dispersing properties.
• Such polymers inter alia, either alone or together with dispersant inhibitor (DI) additives used specifically for dispersing purposes, have the effect that the oxidation products resulting from stress on the oil contribute less to a disadvantageous increase in viscosity.
• DI dispersant inhibitor
• the service life of a lubricating oil can be extended by means of improved dispersibility.
• Such detergents also have a detergent effect which has a positive effect on engine cleanliness, for example expressed by piston cleanliness or ring sticking. Oxidation products are, for example, soot or sludge.
• nitrogen-containing functionalities can be incorporated into the side chains of the polymers.
• Common systems are polymers that carry partially amine-functionalized ester sides.
• Dialkylamine-substituted methacrylates, their methacrylamide analogs or N-heterocyclic vinyl compounds are often used as comonomers to improve the dispersibility.
• Another class of monomer types, which should be mentioned in lubricants due to their dispersing action, are acrylates with ethoxylate or propoxylate-containing functions in the ester substituents.
• the dispersible monomers can either be present statistically in the polymer, ie in the sense a classic co-polymerization built into the polymer, or grafted onto a polyacrylate, which does not result in statistical systems.
• EP 164 807 (Agip Petroli S.p.A) describes a multifunctional VI improver with dispersing, detergent and low-temperature effects.
• the composition of the VI improvers corresponds to NVP-grafted polyacrylates, which additionally contain acrylates with amine-containing ethoxylate residues which are difficult to produce.
• DE-OS 1 594 612 (Shell Int. Research Maatschappij N.V.) discloses lubricating oil mixtures which contain oil-soluble polymers with carboxyl groups, hydroxyl groups and / or nitrogen-containing groups and a dispersed salt or hydroxide of an alkaline earth metal. A wear-reducing effect is observed through the synergistic mode of action of these components.
• US-P 3153640 (Shell Oil Comp.) Encompasses copolymers consisting of long-chain esters of (meth) acrylic acid and N-vinyl-lactams, which have a beneficial influence on wear in lubrication applications.
• the polymers described are statistical copolymers. Monomers with an H-bond donor function and graft copolymers are not mentioned.
• H-bond acceptors hydrogen-bond acceptors
• H-bridge donor hydrogen bridge donor
• Polymers containing dimethylaminopropyl methacrylamide are statistical copolymers and not graft copolymers.
• the lubricating oil formulations according to the invention can relate to both engine and transmission oils, but improved hydraulic oils can also result from this.
• the influence on tribological wear is one of the most important quality requirements for a hydraulic fluid.
• so-called anti-wear components are added to common hydraulic oils, which mostly contain sulfur and phosphorus, and due to their surface activity on metals reduce wear , Increasing wear tendencies in hydraulic pumps can be observed especially during the overheating of hydraulic fluids under difficult operating conditions. Friction of individual components of the hydraulic system, volume flows with a high pressure drop and the flow resistances in the line system lead to an increase in the temperature of the liquid and to increased wear behavior.
• the rheological properties of a modern hydraulic formulation are usually optimized by adding a polymeric viscosity index improver (VI improver).
• VI improver polymeric viscosity index improver
• polyalkyl methacrylates are used for this. They are mostly polymethacrylates, some of which have long-chain (C8-C18) alkyl substituents in their methacrylic ester groups.
• the thickening effect of the polymer dissolved in the oil enables the highest possible kinematic viscosity of the liquid at high temperatures (usually measured at 100 ° C). This reduces wear tendencies and a decrease in the volumetric efficiency of a hydraulic pump.
• the viscosity-increasing effect of the polymer is not as pronounced at lower temperatures (measured at 40 ° C) as, for example, at 100 ° C.
• a lower viscosity at lower temperatures has the advantage of operating a hydraulic system with lower hydromechanical losses.
• the optimized viscosity behavior, expressed by the highest possible Kinematic viscosity at 100 ° C and the lowest possible viscosity at 40 ° C is expressed by the viscosity index (VI index).
• Vl improvers which, in addition to their Vl action, are notable for their dispersing action and / or detergent action in lubricating oil formulations
• a hydraulic fluid of ISO grade 46 which according to DIN 51524 has a kinematic viscosity of 46 mm 2 / s +/- 10% measured at 40 ° C, should also be compared to a more viscous fluid, for example in comparison with a hydraulic oil of ISO grade 68 (kinematic viscosity measured at 40 ° C: 68 mm 2 / s +/- 10%), lead to less wear.
• the ISO 68 fluid should not only at 40 ° C, but also at elevated temperatures, e.g. at 100 ° C, have a higher kinematic viscosity than the ISO-46 liquid.
• R is hydrogen or methyl
• R is a linear, cyclic or branched alkyl radical having 6 to 40 carbon atoms
• R 6 and R 7 are independently hydrogen or a group of the formula -COOR 8 , where R 8 is hydrogen or a linear, cyclic or branched alkyl radical 6 to 40 carbon atoms, and
• R 1 , R 2 and R 3 can independently be hydrogen or an alkyl group having 1 to 5 carbon atoms and R 4 can be a group which has one or more structural units capable of forming H bridges and is an H donor, and
• the compound e) of the formula (IV) is likewise either only in the main chain or only in the grafted-on side chains of the polymer formed,
• the lubricating oil composition contains other components:
• the polymers according to the invention with hydrogen bond donor functions in the polymer have positive effects on wear protection, detergent and dispersing action of the lubricating oil formulations produced with them.
• the polymers therefore represent a wear-reducing alternative or supplement to the phosphorus and sulfur-containing additives which are customary in industry and help to avoid their known disadvantages.
• the copolymers can be used as Vl improvers and, regardless of the kinematic viscosity of the hydraulic oil, contribute to reducing wear in hydraulic systems.
• Wear protection is achieved either by the copolymer alone or together with common wear-reducing additives such as friction modifiers.
• the copolymers also have a pour point lowering effect.
• the formulations produced using the graft copolymers according to the invention are notable for good corrosion behavior and good oxidation resistance.
• kinematic viscosity of polymer solutions which contain, according to the invention, grafted methacrylic acid is significantly lower than that of the comparable polymer which contains only methacrylic acid in the polymer backbone.
• the method according to the invention can achieve a number of further advantages. These include:
• the polymers with VI and dispersing action previously used in motor oils preferably contain, as previously discussed, monomer types with H-bridge acceptor functionalities, which are in particular N-heterocycles. It was therefore not readily predictable that the use of monomers with H-bridge donor properties would lead to polymers which have the described improved properties.
• the lubricating oils contain 0.2 to 30% by weight, preferably 0.5 to 20% by weight, and particularly preferably 1 to 10% by weight, based on the total mixture, of a copolymer formed from units polymerized by free radicals
• R is hydrogen or methyl and R 1 is a linear or branched alkyl radical having 1 to 5 carbon atoms
• components of the formula I include (meth) acrylates which are derived from saturated alcohols, such as
• Pentyl (meth) acrylate Cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate; (Meth) acrylates derived from unsaturated alcohols, such as 2-propynyl (meth) acrylate and allyl (meth) acrylate, vinyl (meth) acrylate.
• the content of the (meth) acrylates of the formula (I) is 0 to 40% by weight
• the polymers contain 35 to 99.99% by weight of one or more ethylenically unsaturated ester compounds of the formula (II)
• R is hydrogen or methyl
• R 4 is a linear, cyclic or branched alkyl radical having 6 to 40 carbon atoms
• R 2 and R 3 are independently hydrogen or a group of the formula -COOR 5 , where R 5 is hydrogen or a linear, cyclic or branched alkyl radical having 6 to 40 carbon atoms.
• These compounds of the formula (II) include (meth) acrylates, maleates and fumarates, each of which has at least one alcohol radical having 6 to 40 carbon atoms.
• R is hydrogen or methyl and R 1 is a linear or branched alkyl radical having 6 to
• (Meth) acrylates derived from saturated alcohols such as hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, 2-tert-butylheptyl (meth) acrylate, octyl (meth) acrylate, 3-iso-propylheptyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, 5-methylundecyl (meth) acrylate, dodecyl (meth) acrylate, 2-methyldodecyl (meth) acrylate, Tridecyl (meth) acrylate, 5-methyltridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecy
• Cycloalkyl (meth) acrylates such as 3-vinylcyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, BornyI (meth) acrylate.
• the ester compounds with a long-chain alcohol residue can be obtained, for example, by reacting (meth) acrylates, fumarates, maleates and / or the corresponding acids with long-chain fatty alcohols, a mixture of esters, such as (meth) acrylates, with different long-chain alcohol residues generally being formed.
• These fatty alcohols include, among others, Oxo Alcohol® 7911 and Oxo Alcohol® 7900, Oxo Alcohol® 1100 from Monsanto; Aiphanoi® 79 from ICI; Nafol® 1620, Alfol® 610 and Alfol® 810 from Sasol; Epal® 610 and Epal® 810 from Ethyl Corporation; Linevol® 79, Linevol® 911 and Dobanol® 25L from Shell AG; Lial 125® from Sasol; Dehydad® and Lorol® from Henkel KGaA as well as Linopol® 7-11 and Acropol® 91.
• the long-chain alkyl radical of the (meth) acrylates of the formula II generally has 6 to 40 carbon atoms, preferably 6 to 24 carbon atoms, particularly preferably 8 to 18 carbon atoms and can be linear, branched, mixed linear / branched or with cyclic proportions.
• the preferred embodiment is that a mixture of methyl methacrylate and C8-C18 alkyl methacrylates is used as the methacrylate.
• the alcohols with long-chain alkyl radicals which are used to prepare the (meth) acrylic esters are commercially available and generally consist of more or less broad mixtures of different chain lengths. In these cases, the number of carbon atoms usually refers to the average carbon number. If, in the context of the present application, an alcohol or a long-chain (meth) acrylic acid ester prepared using this alcohol is referred to as, C-12'-alcohol or as, C 12'-ester, the alkyl radical of these compounds is usually next to Alkyl radicals with 12 carbon atoms also optionally contain those with 8, 10, 14 or 16 carbon atoms in smaller proportions, the average carbon number being 12.
• a compound referred to as a C12-C18 alkyl acrylate this means a mixture of esters of acrylic acid, which is characterized in that linear and / or branched alkyl substituents are present and that the alkyl substituents contain between 12 and 18 carbon atoms.
• the content of the (meth) acrylates of the formula (II) or (IIIa) is 35 to 99.99% by weight, 40 to 99% by weight or 50 to 80% by weight, based on the total weight of the ethylenically unsaturated monomers the main chain of the graft copolymer.
• Nitriles of (meth) acrylic acid and other nitrogen-containing methacrylates such as methacryloylamidoacetonitrile, 2-methacryloyloxyethylmethylcyanamide, cyanomethyl methacrylate;
• Aryl (meth) acrylates such as benzyl methacrylate or phenyl methacrylate, it being possible for the aryl radicals to be unsubstituted or substituted up to four times; carbonyl-containing methacrylates, such as oxazolidinylethyl methacrylate, N- (methacryloyloxy) formamide, acetonyl methacrylate, N-methacryloylmorpholine, N-methacryloyl-2-pyrrolidinone; Glycol dimethacrylates, such as 1,4-butanediol methacrylate, 2-butoxyethyl methacrylate, 2-ethoxyethoxymethyl methacrylate,
• 2-ethoxyethyl methacrylate methacrylates of ether alcohols, such as tetrahydrofurfuryl methacrylate, vinyloxyethoxyethyl methacrylate, methoxyethoxyethyl methacrylate, 1-butoxypropyl methacrylate, 1-methyl- (2-vinyloxy) ethyl methacrylate, cyclohexyloxymethyl methacrylate, methoxymethoxyethyl methacrylate methacrylate, methoxy methoxy methyl methacrylate, Allyloxymethyl methacrylate, 1-ethoxybutyl methacrylate, methoxymethyl methacrylate, 1-ethoxyethyl methacrylate, ethoxymethyl methacrylate; Halogenated alcohol methacrylates, such as
• Oxiranyl methacrylates such as 2,3-epoxybutyl methacrylate, 3,4-epoxybutyl methacrylate,
• glycidyl methacrylate Phosphorus, boron and / or silicon-containing methacrylates, such as
• Methacrylates such as ethylsulfinylethyl methacrylate, 4-thiocyanatobutyl methacrylate,
• Tri methacrylates such as
• Vinyl esters such as vinyl acetate
• Styrene substituted styrenes with an alkyl substituent in the side chain, such as.
• B ⁇ -methyl styrene and ⁇ -ethyl styrene, substituted styrenes with an alkyl substituent on the ring, such as vinyl toluene and p-methyl styrene, halogenated styrenes, such as
• Heterocyclic vinyl compounds such as 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,
• Maleic acid derivatives such as diesters of maleic acid, the
• Alcohol residues have 1 to 9 carbon atoms, maleic anhydride,
• Methyl maleic anhydride maleimide, methyl maleimide
• Fumaric acid derivatives such as diesters of fumaric acid, where the alcohol residues have 1 to 9 carbon atoms
• Dienes such as divinylbenzene.
• Radically polymerizable ⁇ -olefins with 4 - 40 carbon atoms examples include:
• Butene-1 Penten-1, Hexen-1, Hepten-1, Octen-1, Nonen-1, Decen-1, Undecen-1, Dodecen-1, Tridecen-1, Tetradecen-1, Pentadecen-1, Hexadecen- 1, Heptadecen-1, Octadecen-1, Nonadecen-1, Eicosen-1, Heneicosen-1, Docosen-1, Trocosen-1, Tetracosen-1, Pentacosen-1, Hexacosen-1, Heptacosen-1, Octacosen-1, Nonacosen-1, Triaconten-1, Hentriaconten-1, Dotriaconten-1, or the like.
• branched-chain alkenes such as vinylcyclohexane, 3,3-dimethylbutene-1, 3-methylbutene-1, diisobutylene-4-methylpentene-1 or the like.
• alkenes-1 having 10 to 32 carbon atoms which are obtained in the polymerization of ethylene, propylene or mixtures thereof, these materials in turn being obtained from hydrocracked materials.
• An essential component of the polymers according to the invention are 0.01 to 20% by weight of a compound of the formula (IM)
• D R7 and R are independently hydrogen or one May be an alkyl group having 1 to 5 carbon atoms and R 9 represents a group which has one or more structural units capable of forming H bonds and is an H donor.
• a grafting process with monomer d of the formula (III) or a grafting process with both monomer d of the formula (III) and with monomer e of the formula (IV) on a polymer consisting almost exclusively or exclusively of carbon and hydrogen is conceivable.
• Methods for grafting heteroatom-containing monomers onto such purely hydrocarbon-containing polymers are known to the person skilled in the art.
• suitable hydrocarbon-based polymers are copolymers of ethylene and propylene or hydrogenated styrene / diene copolymers.
• the grafted products of these polymers like the polyacrylates on which the present invention is based, can be used as additives in lubricating oil formulations to improve wear behavior and to increase the viscosity index.
• a hydrogen bond (H bond, hydrogen bond, hydrogen bridge) is an important form of secondary valence bond, which is between a hydrogen covalently bonded to an atom of an electronegative element (hydrogen bond donor, proton donor, X). Atom and the lone pair of electrons of another electronegative atom (proton acceptor, Y).
• hydrogen bond donor proton donor
• Y electronegative atom
• RX-H hydrogen bond donor
• YR ' the dotted line symbolizing the hydrogen bond.
• the main X and Y are O, N, S and halogens.
• HCN can also act as a proton donor C.
• the polarity of the covalent bond of the donor causes one positive partial charge, ⁇ + , of the hydrogen (proton), while the acceptor atom carries a corresponding negative partial charge, ⁇ " .
• Characteristic, structural and spectroscopic properties of a complex bound via a hydrogen bond are: a) the distance ⁇ HY is significantly smaller than the sum of the Van der Waals radii of the atoms H u. Y. b) The XH equilibrium core distance is increased compared to the free mol. RX-H. c) the XH stretching vibration (donor stretching vibration) undergoes a shift to longer wavelengths ("red shift"). In addition, its intensity increases significantly (by stronger H-bridges by more than an order of magnitude). d) due to mutual polarization is the dipole moment of the H-bonded complex is larger than the vector sum of the dipole moments of the components. e) The electron density at the bridge hydrogen atom is reduced when a hydrogen bond is formed. This effect manifests itself experimentally in the form of reduced NMR shifts (reduced shielding of the proton).
• dimers more than one hydrogen bond is formed, e.g. B. in dimers of carboxylic acids, which form cyclic structures. Cyclic structures are often energetically favored even in higher oligomers, e.g. B. in oligomers of methanol from the trimers.
• the dissociation energy of the trimers in 3 monomers, at 52 kJ • mol "1, is almost four times that of the dimers. Non-additivity in the dissociation energies per monomer is a typical property of complexes bound via hydrogen bonds.
• the present invention relates in particular to groups containing heteroatoms, the heteroatom preferably representing O, N, P, or S.
• the heteroatom preferably representing O, N, P, or S.
• Monomers with H-bond donor functions are, for example, the ethylenically unsaturated carboxylic acids and all of their derivatives which still have at least one free carboxyl group. Examples for this are:
• HEMA Hydroxyethyl methacrylate
• maleic acid maleic acid
• HBMA Hydroxybutyl methacrylate
• maleic acid maleic acid
• acetoacetate-functionalized ethylenically unsaturated compounds such as, for example, 2-acetoacetoxyethyl methacrylate or 2-acetoacetoxyethyl acrylate. These compounds can be at least partially in the tautomeric enol form.
• ethylenically unsaturated monomers with at least one sulfonic acid group and / or at least one phosphonic acid group are all organic compounds which have both at least one ethylenic double bond and at least one sulfonic acid group and / or at least one phosphonic acid group. They include, for example:
• 2-hydroxy-4-pentenoic acid 2-methyl-4-pentenoic acid, 2-n-propyl-4-pentenoic acid, 2-isopropyl-4-pentenoic acid, 2-ethyl-4-pentenoic acid, 2,2-dimethyl-4- Pentenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid, 10-undecenoic acid, 11-dodecenoic acid, 12-tridecenoic acid, 13-tetradecenoic acid, 14-pentadecenoic acid, 15-hexadecenoic acid, 16-heptadecenoic acid, 17-octadecenoic acid, 22-tricosenoic acid, 3-butene-1, 1-dicarboxylic acid.
• acid amides which are known to act both as H-bond donors and as H-bond acceptors at the same time as the carboxylic acids.
• the unsaturated carboxamides can either have an unsubstituted amide group or an optionally monosubstituted carboxamide group. Suitable compounds are for example:
• Amides of (meth) acrylic acid and N-alkyl-substituted (meth) acrylamides such as N- (3-dimethylaminopropyl) methacrylamide, N- (diethylphosphono) methacrylamide, 1-methacryloylamido-2-methyl-2-propanol, N- (3-dibutylaminopropyl) methacrylamide,
• Aminoalkyl methacrylates such as tris (2-methacryloxyethyl) amine
• N- (2-methacryloyloxyethyl) ethylene urea heterocyclic (meth) acrylates such as 2- (1-imidazolyl) ethyl (meth) acrylate
• Carboxylic acid esters which are also suitable as H-bond donors are:
• heterocyclic (meth) acrylates such as 2- (1-imidazolyl) ethyl (meth) acrylate, 1- (2-methacryloyloxyethyl) -2-pyrrolidone.
• Polyoxyethylene and polyoxypropylene derivatives of (meth) acrylic acid such as
• Tetrapropylengylcolmono (meth) acrylate Tetrapropylengylcolmono (meth) acrylate.
• the content of the compounds which have one or more structural units capable of forming H bridges, which is an H donor, is 0.01 to 20% by weight, preferably 0.1 to 15% by weight and particularly preferably 0.5 to 10 wt .-% based on the total weight of the ethylenically unsaturated monomers used.
• the polymers can optionally additionally contain from 0 to 20% by weight or from 0 to 10% by weight, based on the total weight of the copolymer, of one or more compounds of the formula (IV)
• R 10 , R 11 and R 12 and R 13 have the meaning already mentioned.
• Aminoalkyl methacrylates such as tris (2-methacryloxyethyl) amine
• heterocyclic (meth) acrylates such as 2- (1-imidazolyl) ethyl (meth) acrylate
• Vinylpiperidine 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxolane, vinylfuran, vinylthiophene, vinylthiolane, vinylthiazoles and hydrogenated vinylazole hydrogenated vinylazole, vinyloxoleoleole.
• the compound d) of the formula (III) can be located either only in the main chain or only in the grafted-on side chains of the polymer formed.
• the compound e) of the formula (IV) is likewise either only in the main chain or only in the grafted-on side chains of the polymer formed.
• the percentages by weight of the various components generally relate to the total weight of the monomers used.
• the lubricating oil composition also contains, as a further component, 25 to 90% by weight of mineral and / or synthetic base oil and, taken together, 0.2 to 20% by weight, preferably 0.5 to 10% by weight, of other customary additives, such as, for. B. pour point low, Vl improvers, anti-aging agents, detergents, dispergi aids or wear-reducing components.
• other customary additives such as, for. B. pour point low, Vl improvers, anti-aging agents, detergents, dispergi aids or wear-reducing components.
• DI packages which are commercially available.
• multipurpose additives which in most cases contain P- and S-containing components as anti-wear additives, are, for example
• Products from Ethyl such as Hitec 521, Hitec 522, Hitec 525, Hitec 522, Hitec 381, Hitec 343, Hitec 8610, Hitec 8611, Hitec 8680, Hitec 8689, Hitec 9230, Hitec 9240, Hitec 9360
• OLOA products of the company Oronite, which are offered under the name "OLOA” and a product-specific number, for example OLOA 4994, OLOA 4994C, OLOA 4900D, OLOA 4945, OLOA 4960, OLOA 4992, OLOA 4616, OLOA 9250, OLOA 4595 and other.
• Infineum products such as Infineum N8130
• Lubrizol 7653 Products from Lubrizol, such as Lubrizol 7653, Lubrizol 7685, Lubrizol 7888, Lubrizol 4970, Lubrizol 6950D, Lubrizol 8880, Lubrizol 8888, Lubrizol 9440, Lubrizol 5187J, Anglamol 2000, Anglamol 99, Anglamol 6043, Anglamol 6044B, Anglamol 6044B, Anglamol
• the aforementioned ethylenically unsaturated monomers can be used individually or as mixtures. It is also possible to vary the monomer composition during the polymerization.
• ATRP atom transfer radical polymerization
• RAFT reversible addition fragmentation chain transfer
• azo initiators well known in the art, such as AIBN and 1, 1-azobiscyclohexane carbonitrile, and also peroxy compounds, such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert-butyl per-2-ethylhexanoate, ketone peroxide, tert-butyl peroctoate, methyl peroxide butyl peroxide, methyl peroxide butyl, Dibenzoyl peroxide, tert.-butyl peroxybenzoate, tert.- Butylperoxyisopropyl carbonate, 2,5-bis (2-ethylhexanoyl-peroxy) -2,5-dimethylhexane, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy-3,5,5-trimethylhexanoate, di
• the ATRP method is known per se. It is believed that this is a "living" radical polymerization, without any limitation by the description of the mechanism.
• a transition metal compound is reacted with a compound that has a transferable atomic group.
• the transferable atom group is transferred to the transition metal compound, whereby the metal is oxidized.
• This reaction forms a radical that adds to ethylenic groups.
• the transfer of the atomic group to the transition metal compound is reversible, so that the atomic group is transferred back to the growing polymer chain, thereby forming a controlled polymerization system. Accordingly, the structure of the polymer, the molecular weight and the molecular weight distribution can be controlled.
• the polymers according to the invention can also be obtained, for example, using RAFT methods. This method is described in detail in WO 98/01478, for example, to which express reference is made for the purposes of the disclosure.
• the polymerization can be carried out under normal pressure, negative pressure or positive pressure.
• the polymerization temperature is also not critical. In general, however, it is in the range from -20 ° to 200 ° C, preferably 0 ° to 130 ° C and particularly preferably 60 ° to 120 ° C.
• the polymerization can be carried out with or without a solvent.
• solvent is to be understood broadly here.
• the polymerization is preferably carried out in a non-polar solvent.
• a non-polar solvent include hydrocarbon solvents, such as aromatic solvents such as toluene, benzene and xylene, saturated hydrocarbons, such as cyclohexane, heptane, octane, nonane, decane, dodecane, which can also be present in a branch.
• hydrocarbon solvents such as aromatic solvents such as toluene, benzene and xylene
• saturated hydrocarbons such as cyclohexane, heptane, octane, nonane, decane, dodecane, which can also be present in a branch.
• solvents can be used individually or as a mixture.
• Particularly preferred solvents are mineral oils, natural oils and synthetic oils as well as mixtures thereof. Of these, mineral oils are particularly preferred.
• Mineral oils are known per se and are commercially available. They are generally obtained from petroleum or crude oil by distillation and / or refining and, if appropriate, further purification and upgrading processes, the term mineral oil in particular referring to the higher-boiling proportions of the crude or petroleum. In general, the boiling point of mineral oil is higher than 200 ° C, preferably higher than 300 ° C, at 5000 Pa. It is also possible to produce by smoldering shale oil, coking hard coal, distilling with the exclusion of air from brown coal and hydrogenating hard coal or brown coal. To a small extent, mineral oils are also made from raw materials of vegetable (e.g. jojoba, rapeseed) or animal (e.g. claw oil) origin. Accordingly, mineral oils have different proportions of aromatic, cyclic, branched and linear hydrocarbons depending on their origin. A general distinction is made between paraffin-based, naphthenic and aromatic
• paraffin-based fraction for longer-chain or strongly branched is ⁇ -alkanes is ⁇ -alkanes and naphthenic fraction for
• the proportion of aromatics and monomethyl-branched paraffins is generally in the range from 0 to
• mineral oil mainly comprises naphthenic and paraffin-based alkanes, which generally have more than 13, preferably more than 18 and most preferably more than 20 carbon atoms.
• the proportion of these compounds is generally> 60% by weight, preferably> 80% by weight, without any intention that this should impose a restriction.
• Processes such as urea separation and liquid chromatography on silica gel show, for example, the following components, the percentages relating to the total weight of the mineral oil used in each case: n-alkanes with approx. 18 to 31 C atoms:
• Aromatics with 14 to 32 carbon atoms :
• Synthetic oils include organic esters, organic ethers such as silicone oils, and synthetic hydrocarbons, especially polyolefins. They are usually somewhat more expensive than mineral oils, but have advantages in terms of their performance.
• Natural oils are animal or vegetable oils, such as claw oils or jojoba oils.
• oils can also be used as mixtures and are commercially available in many cases.
• solvents are preferably used in an amount of 1 to 99% by weight, particularly preferably 5 to 95% by weight and very particularly preferably 10 to 60% by weight, based on the total weight of the mixture.
• the composition can also contain polar solvents, the amount of which is however limited by the fact that these solvents must not have an unacceptably disadvantageous effect on the solubility of the polymers.
• the molecular weights Mw of the polymers are 1,500 to 4,000,000 g / mol, in particular 5,000-2,000,000 g / mol and particularly preferably 20,000-500,000 g / mol.
• the polydispersities (Mw / Mn) are preferably in a range from 1.2 to 7.0.
• the molecular weights can be determined by known methods. For example, gel permeation chromatography, also known as “Size Exciusion Chromatography "(SEC) can also be used.
• SEC Size Exciusion Chromatography
• An osmometric method such as, for example, the" Vapor Phase Osmometry "can also be used to determine the molecular weights.
• the residual monomer contents (e.g. C8-C18 alkyl acrylate, MMA, methacrylic acid, NVP) were determined by HPLC analysis using conventional methods. Their indication is given either in ppm or% by weight in relation to the total weight of the polymer solutions produced.
• C8-C18-alkyl acrylate includes all acrylate monomers used which carry alkyl substituents in the ester side chains, which are characterized in that they contain between 8 and 18 carbon atoms.
• the syntheses described in the present invention are the production of polymer solutions without restricting the fact that the syntheses described cannot be carried out without solvents. Accordingly, the kinematic viscosities given relate to the polymer solutions and not to the pure, isolated polymers.
• the term "thickening effect" refers to the kinematic viscosity of a polymer solution, which is measured by diluting a certain amount of the polymer solution with another solvent at a certain temperature. Usually 10-15% by weight of the polymer solution produced in each case is in a 150N Oil diluted and the kinematic viscosities of the resulting solution determined at 40 ° C. or 100 ° C.
• the determination of the kinematic Viscosities are carried out using customary methods, for example in the Ubbelohde viscometer or in automatic measuring devices from Herzog. The kinematic viscosities are always given in mm 2 / s.
• the process for the preparation of the graft copolymers of the present invention is characterized in that the polymers are either prepared by copolymerization of all individual components or in another embodiment in a first step the main chain is prepared by radical polymerization of the monomers a), b) and c) and that one or more of the monomers d) and optionally e) are then grafted onto the main chain in the second step.
• a further grafting process is carried out with one or more monomers of the formula (IV) which has no structural units capable of forming H bridges.
• graft copolymers after the polymerization of the main chain, a grafting process is first carried out with one or more monomers of the formula (IV), followed by a further grafting process with one or more monomers of the formula (III).
• the present process for producing the graft copolymers can also be advantageously carried out by using a grafting process Mixture of one or more monomers of the formulas (III) and (IV) is carried out.
• a further advantageous embodiment of the present method for producing graft copolymers is characterized in that the grafting process is carried out up to 5 times in succession.
• Several grafts each with a small amount of monomer, e.g. in each case 1% by weight of a monomer which can act as an H-bridge donor. If, for example, a total of 2% by weight of such a monomer is used for the grafting, two successive grafting steps are preferably carried out, each with, for example, 1% by weight of the monomer in question.
• the N-functionalized monomer e) can be an N-vinyl-substituted monomer, such as, for example, N-vinyl-pyrrolidone, N-vinyl-caprolactam, N-vinyl-triazole, N-vinyl-benzotriazole or N-vinyl-imidazole.
• it can also be a vinyl pyridine, such as 2-vinyl pyridine.
• It can also be a methacrylate or acrylate which contains an N-heterocycle in its ester function.
• the N-containing monomer can be an N, N-dialkylaminoacrylate or its methacrylate analogs, the aminoalkyl groups containing 1-8 carbon atoms.
• Oxidation resistance is also of particular interest to the influence of a lubricating oil on the wear behavior of a machine element.
• Lubricating oils are usually added with specially designed wear-reducing additives.
• Such additives mostly contain phosphorus and / or sulfur.
• the search for phosphorus and sulfur-free lubricant additives has generated an intensive research activity of many additive manufacturers, especially in the recent past.
• wear behavior can have a positive impact on energy consumption, e.g. of a diesel or petrol engine.
• the polymers of the present invention have not previously been associated with a positive effect on wear behavior.
• the polymers of the present invention are superior to the commercially available polymers with N functionalities known in terms of wear protection.
• the crank mechanism, piston group, cylinder liner and valve control of an internal combustion engine are lubricated with an engine oil.
• the engine oil which collects in the oil pan of the engine, is conveyed to the individual lubrication points by means of a feed pump via an oil filter (pressure circulation lubrication in connection with spray and oil mist lubrication).
• the engine oil has the functions: transmission of forces, reduction of friction, reduction of wear, cooling of the components and gas sealing of the piston.
• the oil is fed to the bearing points under pressure (crankshaft, connecting rod, and camshaft bearings).
• the sliding points of the valve train, the piston group, gears and chains are supplied with spray oil, centrifugal oil or oil mist.
• Category B Light diesel engines: In 5 engine test procedures, 7 times oil deposits, 3 times wear and 2 times viscosity are determined. When determining the deposit behavior, 4 times piston cleanliness, 2 times piston ring sticking and once the sludge formation are assessed.
• the influence of the lubricant used on wear was measured using the test method CEC-L-51-A-98.
• This test procedure is suitable for the investigation of wear behavior in a car diesel engine (ACEA category B) as well as in a truck diesel engine (ACEA category E).
• the circumferential profile of each cam is determined and compared in 1 ° steps on a 2- or 3-D measuring machine before and after the test.
• the profile deviation in the test corresponds to the cam wear.
• the Wear results of the individual cams are averaged and compared with the limit value of the corresponding ACEA categories.
• Oil A (see Tables 1 and 2) of the present invention served as the first comparative example for the wear tests. It was a heavy-duty diesel engine oil formulation of the SAE 5W-30 category. As usual in practice, this oil was mixed from a commercially available base oil, in the present case Nexbase 3043 from Fortum, as well as other typical additives. On the one hand, these additives were Oloa 4549 from Oronite. The latter component is a typical DI additive for motor oils. In addition to ash-free dispersants, the product also contains components to improve wear behavior. The latter components in Oloa 4549 are zinc and phosphorus-containing compounds. Zinc and phosphorus-containing compounds can be regarded as the most common additives at present to improve wear behavior.
• ethylene-propylene copolymer (Paratone 8002 from Oronite) was used as a further additive for the purpose of thickener or VI improver effect.
• Paratone 8002 was used as a solution in a mineral oil, as is common in practice. Although limited in their VI effect, ethylene-propylene copolymers are currently the most common VI improvers in car and truck engine oils due to their good thickening effect. A striking wear-improving effect has not previously been described for such systems.
• a polyacrylate was not used as an additional component for oil A.
• oil A was composed of 75.3% by weight of Nexbase 3043, 13.2% by weight of Oloa 4594 and 11.5% by weight of a solution from Paratone 8002. Table 1. Wear results according to CEC-L-51-A-98 obtained with ⁇ len AG
• Example 1 65.55 11.44 171 n.a. n.d. 3.33 8.5
• Example 3 66.44 11, 50 169 n.a. n.d. n.d.
• Oil B (see Tables 1 and 2) served as a second comparative example for the wear tests.
• Oil B differed from oil A in that part of the Paratone 8002 was replaced by a polyacrylate, in the special case the polycrylate from comparative example 1.
• the polymer from Comparative Example 1 is an NVP-containing polyacrylate, which has already been described as advantageous in terms of wear protection.
• the polyacrylate used for oil C comes from comparative example 2 and, in contrast to the polymer from comparative example 1, is a polyacrylate with dispersing functionalities consisting of oxygen instead of nitrogen.
• the polymer solution from comparative example 2 contains a as a further solvent component small amount of an alkyl alkoxylate, which is thought to have a detergent effect in the engine.
• oils A and B and all other formulations used for the wear tests did not differ essentially with regard to their kinematic viscosity data. This can be seen from the kinematic viscosities measured at 40 and 100 ° C (referred to as KV40 ° C and KV100 ° C in Table 2).
• Table 2 also shows that the formulations used refer to Viscosity index (VI), total base number (TBN), cold start behavior expressed by crankcase simulator data (CCS) and temporary shear losses at high temperatures expressed by high temperature high shear data (HTHS) were not significantly differentiated.
• the KV40 ° C, KV100 ° C, VI, TBN, CCS and HTHS data were determined according to the ASTM methods known to the person skilled in the art.
• the oxidation behavior was determined using the PDSC method known to the person skilled in the art (CEC L-85-T-99).
• oils B, C, D and E were that 3% by weight of the Paratone 8002 solution was replaced by 3% by weight of the respective polyacrylate solution.
• Oils D and E represent formulations according to the invention with regard to wear behavior.
• the polymer from Example 1 was found to be particularly advantageous (average cam wear: 5.7 ⁇ m).
• the easy-to-prepare copolymer from Example 3 was found to be improved over the prior art, indicated by a comparison in cam wear of oil E versus oil A.
• any compound is suitable as the base oil for the production of a lubricating oil formulation according to the invention which provides an adequate lubricating film which does not tear even at elevated temperatures.
• the viscosities can be used, for example, as specified in the SAE specifications.
• Particularly suitable are, inter alia, compounds which have a viscosity which is in the range from 15 Saybolt seconds (SUS, Saybolt Universal Seconds) to 250 SUS, preferably in the range from 15 to 100 SUS, in each case at 100 ° C.
• Suitable compounds include natural oils, mineral oils and synthetic oils, as well as mixtures thereof.
• Natural oils are animal or vegetable oils, such as claw oils or jojoba oils. Mineral oils are mainly obtained from crude oil by distillation. They are particularly advantageous in terms of their low price. Synthetic oils include organic esters, synthetic hydrocarbons, especially polyolefins, which meet the above requirements. They are usually somewhat more expensive than mineral oils, but have advantages in terms of their performance.
• lubricating oils usually contain other additives. This is particularly the case with engine oils, gear oils and hydraulic oils.
• the additives suspend solids (detergent-dispersant behavior), neutralize acidic reaction products and the like. form a protective film on the cylinder surface (EP additive, for "extreme pressure").
• friction-reducing additives such as friction modifiers, anti-aging agents, pour point depressants, anti-corrosion agents, dyes, demulsifiers and odorants are used.
• the polymers of the present invention can also provide adequate wear protection in the absence of a friction modifier or an EP additive to care.
• the wear-improving effect is then contributed by the polymer according to the invention, to which one could therefore attribute the friction modifier effect.
• the amounts in which the additives mentioned above are used depend on the field of application of the lubricant. Generally the proportion is of the base oil between 25 to 90 wt .-%, preferably 50 to 75 wt .-%.
• the additives can also be used as so-called DI packets (detergent inhibitor), which are widely known and can be obtained commercially.
• particularly preferred engine oils contain, for example
• anti-corrosion agent 0.1-1% by weight of anti-corrosion agent.
• the lubricating oil according to the invention can additionally, preferably in a concentration of 0.05-10.0 percent by weight, contain an alkyl alkoxylate of the formula (V).
• the alkyl alkoxylate can be added to the lubricating oil composition directly, as part of the VI improver, as part of the DI package, as part of a lubricant concentrate or subsequently to the oil. Refurbished used oils can also be used as oil.
• R 1 , R 2 and R 3 are independently hydrogen or a hydrocarbon residue with up to 40
• R 4 is hydrogen, a methyl or ethyl radical
• L is a linking group
• n is an integer in the range from 4 to 40
• A is an alkoxy group having 2 to 25 repeating units, which of
• Ethylene oxide, propylene oxide and / or butylene oxide are derived, where A
• Homopolymers and statistical copolymers comprising at least two of the abovementioned compounds, and z is 1 or 2, the nonpolar part of the compound (VI) of the formula (V) contains at least 9 carbon atoms.
• these compounds are referred to as alkyl alkoxylates. These compounds can be used both individually and as a mixture.
• Hydrocarbon radicals with up to 40 carbon atoms are to be understood as meaning, for example, saturated and unsaturated alkyl radicals, which can be linear, branched or cyclic, and aryl radicals, which can also contain heteroatoms and alkyl substituents, which can optionally be provided with substituents, for example halogens.
• (C 1 -C 2 ) -alkyl in particular (-C-C 8 ) -alkyl and very particularly (-C-C 4 ) -alkyl residues are preferred.
• (-CC) alkyl is an unbranched or branched hydrocarbon radical having 1 to 4 carbon atoms, such as to understand the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl or tert-butyl radical;
• (Ci-C ⁇ VAlkyl) the aforementioned alkyl radicals, and for example the pentyl, 2-methylbutyl, hexyl, heptyl, octyl or the 1, 1, 3,3-tetramethylbutyl radical;
• (-CC 2 o) alkyl the aforementioned alkyl radicals, and for example the nonyl, 1-decyl, 2-decyl, undecyl, dodecyl, pentadecyl or eicosyl radical.
• (C 3 -C 8 ) cycloalkyl radicals are preferred as the hydrocarbon radical. These include the cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl group.
• (C 2 -C) alkynyl for example the ethynyl, propargyl, 2-methyl-2-propynyl or 2-butynyl group;
• (C 2 -C 2 o) alkenyl is to be understood to mean the radicals mentioned above and, for example, the 2-pentynyl or the 2-decynyl group.
• Aromatic radicals such as “aryl” or “heteroaromatic ring systems” are also preferred.
• aryl is understood to mean an isocyclic aromatic radical having preferably 6 to 14, in particular 6 to 12, carbon atoms, such as, for example, phenyl, naphthyl or biphenylyl, preferably phenyl;
• heteromatic ring system means an aryl radical 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, e.g. a residue of thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole, isoxazole, pyrazole, 1,3,4-oxadiazole, 1,3,4-thiadiazole, 1,3,4-triazole, 1,2,4 -Oxadiazole, 1, 2,4-thiadiazole, 1, 2,4-triazole, 1, 2,3-triazole, 1, 2,3,4-tetrazole, benzo [b] thiophene, benzo [b] furan, indole , Benzo [c] thiophene, benzo [c] furan, isoindole, benzoxazole, benzothiazole, benzimidazole, benz
• the radicals R 2 or R 3 which may occur repeatedly in the hydrophobic part of the molecule can in each case be the same or different.
• the linking group L serves to connect the polar alkoxide part to the non-polar alkyl radical.
• Particularly stable groups, such as the ether, keto and aromatic groups, are preferred.
• n is an integer in the range from 4 to 40, in particular in the range from 10 to 30. If n is greater than 40, the viscosity which is produced by the additive according to the invention generally becomes too large. If n is less than 4, the lipophilicity of the part of the molecule is generally not sufficient to keep the compound of the formula (V) in solution. Accordingly, the nonpolar part of the compound (V) of the formula (VI) preferably contains a total of 10 to 100 carbon atoms and very particularly preferably a total of 10 to 35 carbon atoms.
• the radical R 5 is hydrogen, a methyl radical and / or ethyl radical and m is an integer in the range from 2 to 40, preferably 2 to 25, in particular 2 and 15 and very particularly preferably 2 to 5.
• the abovementioned numerical values are to be understood as mean values in the context of the present invention, since this part of the alkyl alkoxylate is generally obtained by polymerization. If m is greater than 40, the solubility of the compound in the hydrophobic environment becomes too low, so that it can become cloudy in the oil, possibly precipitating. If the number is less than 2, the desired effect cannot be guaranteed.
• the polar portion may have units derived from ethylene oxide, propylene oxide and / or butylene oxide, with ethylene oxide being preferred. Here, the polar part can have only one of these units. However, these units can also statistically occur together in the polar remainder.
• the number z results from the choice of the connecting group or from the starting compounds used. It is 1 or 2.
• the number of carbon atoms of the nonpolar part of the alkyl alkoxylate according to formula (VI) is preferably greater than the number of carbon atoms of the polar part A, probably according to formula (VII), of this molecule.
• the non-polar part preferably contains at least twice as many carbon atoms as the polar part, particularly preferably three times or more.
• Alkyl alkoxylates are commercially available. These include, for example, the ® Marlipal and ® Marlophen varieties from Sasol and the ® Lutensol types from BASF.
• ® Mariophen NP 3 nonylphenol polyethylene glycol ether (3EO)
• ® Marlophen NP 4 nonylphenol polyethylene glycol ether (4EO)
• ® Marlophen NP 5 nonylphenol polyethylene glycol ether (5EO)
• ® Marlophen NP 6 nonylphenol polyethylene glycol (6EO);
• ® Lutensol TO 3 (iC 13 fatty alcohol with 3 EO units), ® Lutensol TO 5 (iC 13 - fatty alcohol with 5 EO units), ® Lutensol TO 7 (i-C ⁇ 3 fatty alcohol with 7 EO units), ® Lutensol TO 8 (i-C ⁇ 3 fatty alcohol with 8 EO units) and ® Lutensol TO 12 (i-Ci 3 fatty alcohol with 12 EO units).
• the starting materials used for the polymer syntheses described here were all commercially available products, such as are available, for example, from Aldrich or Akzo Nobel.
• Monomers such as, for example, MMA (Degussa), NVP (BASF), DMAPMAM (Degussa), 10-undecenic acid (Atofina) or methacrylic acid (Degussa) were also taken from commercially available sources.
• Plex 6844-0 was a methacrylate from Degussa that contained urea in the ester residue.
• an acrylate or, for example, an acrylate polymer or polyacrylate this includes not only acrylates, that is, derivatives of acrylic acid, but also methacrylates, that is, derivatives of methacrylic acid, or mixtures of acrylate or methacrylate-based systems.
• a polymer is referred to as a randomly built-up polymer, it means a copolymer in which the types of monomers used are randomly distributed in the polymer chain. Graft copolymers, block copolymers or systems with a concentration gradient of the types of monomers used along the polymer chain are used in this Context referred to as non-statistical polymers or non-statistical polymers.
• the wear protection capacity was determined according to the Vickers pump test (DIN 51389 part 2).
• a V 105-C vane pump was used for this as prescribed. This was operated at a speed of 1440 min-1.
• the size of the full flow filter used was 10 ⁇ m, the difference between the liquid level and the pump inlet was 500 mm. Under these conditions, flow rates of 38.7 l / min at 0 bar and 35.6 l / min at 70 bar were set.
• the fluid temperature to be set was adapted to the kinematic viscosity of the respective hydraulic fluid, i.e.
• a liquid with a higher kinematic viscosity at 40 ° C was heated to a higher temperature than a lower viscosity liquid for the wear test.
• the liquids used for the wear tests including information on the composition, viscosity and viscosity index, can be found in Table 4.
• the pump operating conditions during the wear tests and the respective results for wear on the ring and vane can be found in Table 5.
• the formulations were prepared in accordance with DIN 51524.
• the kinematic viscosities of oils of ISO grade 46 (F, G and H in Tab. 4) were accordingly in a viscosity range of 46 mm 2 / s +/- 10%, as well as the viscosity of the oil with ISO grade 68 (oil I) in a range of 68 mm 2 / s +/- 10%.
• Oils F and G were liquids containing polyalkyl methacrylate. G contained a polymer that is used as standard as a Vl improver for hydraulic oils. In contrast, the polymer from Example 6 contained in oil F had a composition which is typically not used for hydraulic applications. Oils H and I did not contain any polyalkymethacrylates.
• the lubricating oil compositions preferably contain a copolymer in which the monomers a) and b) are preferably selected from the monomers methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, isononyl methacrylate, isodecyl methacrylate, dodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, pentadecyl methacrylate, and pentadecyl methacrylate ,
• the lubricating oil composition according to the invention are characterized in that the copolymer is used as a VI improver and, regardless of the kinematic viscosity of the hydraulic oil, contributes to reducing wear in hydraulic systems.
• the lubricating oil compositions according to the invention are further characterized in that the wear protection is provided either solely by the copolymer or together with common wear-reducing additives such as friction modifiers.
• the copolymer predominates in the solution in 1-30% by weight, in particular 2-20% by weight and particularly advantageously in 3-15% by weight.
• the hydraulic formulations according to the invention are characterized in that, in addition to the Vl effect and wear protection, the copolymer also provides a pour point-reducing effect.
• the hydraulic formulations according to the invention can be used in a vane pump, a gear pump, radial piston pump or an axial piston pump.
• tert-butyl peroctoate 0.71 g of tert-butyl peroctoate are added and at the same time a monomer feed consisting of 522.2 g of a mixture of C12-C18-alkyl methacrylates and methyl methacrylate in a weight ratio of 99/1 and 3.92 g of tert-butyl peroctoate are started.
• the inflow time is 3.5 hours and the inflow speed is even. 2 hours after the end of the feed, a further 14.1 g of tert-butyl peroctoate are added.
• the total reaction time is 8 hours.
• the batch is then heated to 130 ° C.
• tert-butyl peroctoate After reaching 90 ° C, 1.75 g of tert-butyl peroctoate are added and at the same time an inlet of 555.6 g of a mixture consisting of C12-C18-alkyl methacrylates, methyl methacrylate and a methacrylate ester of an iso-C13 alcohol with 20 ethoxylate units in Weight ratio 87.0 / 0.5 / 12.5 and 2.78 g of tert-butyl peroctoate started.
• the run-in time is 3.5 hours.
• the feed rate is even. 2 hours after the end of the feed, a further 1.20 g of tert-butyl peroctoate are added.
• the total reaction time is 8 hours.
• the polymer solution of a pour point improver is added, which is then 5 percent by weight.
• the solution is then diluted with an ethoxylated iso-C13 alcohol which contains 3 ethoxylate units in a ratio of
• 430 g of a 150 N oil and 47.8 g of a monomer mixture consisting of C12-C18-alkyl methacrylates, methyl methacrylate and methacrylic acid in a weight ratio of 82 are in a 2 liter four-necked flask equipped with saber stirrer (operated at 150 revolutions per minute), thermometer and reflux condenser , 0 / 15.0 / 3.0 submitted. The temperature is set to 100 ° C.
• tert-butyl peroctoate After reaching 100 ° C, 0.38 g of tert-butyl peroctoate are added and at the same time an inlet of 522.2 g of a mixture of C12-C18 alkyl methacrylate, methyl methacrylate and methacrylic acid in a weight ratio of 82.0 / 15.0 / 3.0 started together with 2.09 g of tert-butyl peroctoate (dissolved in the monomer mixture).
• the inflow time is 3.5 hours and the inflow speed is even. 2 hours after the end of the feed, a further 14.1 g of tert-butyl peroctoate are added.
• the total reaction time is 8 hours.
• the mixture is then diluted with 150N oil to a total polymer content of 45% by weight. A clear, homogeneous-looking reaction product is obtained.
• tert-butyl peroctoate After reaching 100 ° C., 0.66 g of tert-butyl peroctoate is added and at the same time an inflow of 522.2 g of a monomer mixture of C12-C18-alkyl methacrylate and methacrylic acid in a weight ratio of 87/3 is started together with 3.66 g of tert-butyl peroctoate.
• the inflow time is 3.5 hours and the inflow speed is even. 2 hours after the end of the feed, a further 14.1 g of tert-butyl peroctoate are added.
• the total reaction time is 8 hours.
• the mixture is then heated to 130 ° C., after which 13.16 g of 150N oil, 17.45 g of n-vinylpyrolidone (NVP) and 1.46 g of tert-butyl perbenzoate are added. 1 hour and 2 hours thereafter, 0.73 g each of tert-butyl perbenzoate are added again. The total reaction time is 8 hours. A homogeneous-looking reaction product is obtained.
• tert-butyl peroctoate After reaching 100 ° C., 0.56 g of tert-butyl peroctoate is added and at the same time an inlet of 522.2 g of a mixture of C12-C18-alkyl methacrylate, methyl methacrylate and Plex 6844-0 in a weight ratio of 82.0 / 15.0 / 3 , 0 started together with 3.13 g of tert-butyl peroctoate.
• the inflow time is 3.5 hours and the inflow speed is even. 2 hours after the end of the feed, a further 14.1 g of tert-butyl peroctoate are added.
• the total reaction time is 8 hours. A slightly cloudy, but nevertheless homogeneous-looking reaction product is obtained.
• 300 g of 150N oil and 33.3 g of a monomer mixture of C12-C15-alkyl methacrylate and methacrylic acid in a weight ratio of 90.0 / 10 are in a 2 liter four-necked flask equipped with saber stirrer (operated at 150 revolutions per minute), thermometer and reflux condenser , 0 submitted.
• the temperature is set to 100 ° C.
• the batch is diluted with 150N oil in relation to a total polymer content of 50% by weight.
• a further 1.40 g of tert-butyl peroctoate are added. A clear, homogeneous-looking reaction product is obtained.
• Example 6 The synthesis of the polymers as described below in Example 6 and Comparative Example 3 was carried out by means of solution polymerization in a mineral oil. The resulting polymer solutions in oil were used to prepare hydraulic oils F and G as shown in Table 4.

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