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
  • 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
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
  • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double 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
  • 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
• • 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
  • C10M2217/028—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
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/02—Viscosity; Viscosity index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/04—Molecular weight; Molecular weight distribution
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/02—Pour-point; Viscosity index
• • 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
  • C10N2030/04—Detergent property or dispersant property
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/40—Low content or no content compositions
  • C10N2030/43—Sulfur free or low sulfur content compositions
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines

Definitions

• the present invention relates to the use of graft copolymers.
• crank mechanism, piston group, cylinder bore and the valve control of an internal combustion engine are lubricated with an engine oil.
• the engine oil which collects in the oil sump of the engine is conveyed by means of feed pump via an oil filter to the individual lubrication points (pressure circulation lubrication, in conjunction with spray and oil mist lubrication).
• the engine oil in this system has the functions: transmission of forces, reduction of friction, reduction of wear, cooling of components and gas sealing of the piston.
• the oil is supplied 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 splash oil, centrifugal oil or oil mist.
• engine manufacturers require proof of performance of an engine oil in the form of test results of standardized test procedures and engine tests (e.g., API Classification in USA or ACEA Test Sequences in Europe).
• test procedures and engine tests e.g., API Classification in USA or ACEA Test Sequences in Europe.
• self-defined test methods are used by individual manufacturers before an engine oil is approved for use.
• the test in commercially available car and truck engines ensures that engine oil-related signs of wear and tear are recognized before the approval is granted.
• the wear protection of the engine oil is of particular importance.
• the list of requirements of the ACEA Test Sequences 2002 as an example shows that in each category (A for petrol engines, B for passenger car diesel engines and E for truck engines) with a separate engine test the proof of sufficient wear protection for the valve train is to be led.
• NL 6505344 (20.10.1966) by Shell describes a synergistic mode of action of oil-soluble polymers with typical wear-reducing additive types, such as dispersed Ca salts or hydroxides.
• Shell's US 3,153,640 (Oct. 20, 1964) comprises copolymers consisting of two portions of methacrylate monomers and one NVP fraction. These are not graft copolymers.
• the beneficial effect on wear in lubrication applications is mentioned. However, the improvement is relatively limited. This is especially true when taking into account the high anteisl on costly comonomers, such as N-vinylpyrrolidone (NVP).
• NVP N-vinylpyrrolidone
• JP 05271331 (Nippon OiI) describes VI and wear-improving polymers prepared from copolymers of ⁇ -olefins and maleic acid which are subsequently functionalized. In the abstract rubbing and wear results obtained in the Falex test (block-on-ring) are given.
• EP 164807 (18.12.1985) by Agip describes a multifunctional VI improver with dispersing, deterging and low-temperature action.
• a wear-reducing effect is mentioned, which is rather attributed to advantages in corrosion behavior, ie an indirect influence on wear.
• the composition comprises the VI improvers comprising specific sulfur-containing moieties.
• the wear-reducing effect of sulfur compounds is known.
• the use of sulfur-containing compounds is associated with disadvantages, so efforts are made to avoid the use of such compounds (see Lubricants and Lubrication, Wiley-VCH 2001, T. Mang and W. Dresel, page 191).
• additives which have a high stability against oxidation and thermal stress as well as a high shear strength. Furthermore, the additives should also be soluble in very non-polar lubricating oils, for example in fully synthetic oils in large quantities. In addition, it was an object of the present invention to provide additives which, in addition to a wear-reducing effect, additionally improve the flow properties of the lubricating oils, ie have a viscosity index-improving effect.
• graft copolymers obtainable by a two-stage polymerization, wherein in a first stage at least one graft by free radical polymerization of a monomer composition A), the 0 to 40 wt .-%, based on the weight of the monomer composition A) of one or more ethylenically unsaturated Ester compounds of the formula (I)
• R is hydrogen or methyl
• R 1 is a linear or branched alkyl radical having 1 to 5 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 5 carbon atoms means 60 to 100 wt .-%, based on the weight of the monomer composition
• R is hydrogen or methyl
• R 4 is a linear or branched alkyl group having 6 to 40 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 6 to 40 carbon atoms and 0 to 40% by weight, based on the weight of the monomer composition A), of comonomers, and in a second stage a monomer composition B) containing 20 to 100% by weight of at least one monomer wherein the graft copolymer comprises at most 200 ppm sulfur and the ratio of the weight of the monomer composition A) to the weight of the monomer composition B) ranges from 99.7: 0.3 to 80:20
• additives are provided which are particularly inexpensive to manufacture lt can be.
• the additives to be used according to the present invention show a high stability against oxidation and thermal stress as well as a high shear strength.
• the use according to the invention provides additives for reducing wear, which are soluble in very nonpolar lubricating oils, for example in fully synthetic oils in large quantities.
• the additives show a high compatibility with lubricating oils.
• additives are provided which, in addition to a wear-reducing effect, additionally improve the flow properties of the lubricating oils, ie have a viscosity index-improving effect.
• Graft copolymers which are used according to the invention for reducing wear can be obtained by a polymerization comprising at least two steps.
• At least one grafting base can be produced, to which a grafting pad is grafted in at least a second step.
• grafting base denotes at least one polymer onto which side-chain polymers can be grafted.
• the graft base is also often referred to as main chain polymer, backbone polymer or graft substrate.
• a monomer composition A) can be radically polymerized
• R is hydrogen or methyl
• R 1 is a linear or branched alkyl radical having 1 to 5 carbon atoms
• R 2 and R 3 are independently hydrogen or a group of the formula -COOR ', in which R' is hydrogen or an alkyl group having 1 to 5 carbon atoms,
• R is hydrogen or methyl
• R 4 is a linear or branched alkyl group having 6 to 40 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 6 to 40 carbon atoms and 0 to 40 wt .-%, based on the weight of the monomer composition A) comprises comonomers.
• Monomeric compounds for the preparation of the graft base comprise one or more ethylenically unsaturated ester compounds of the formula (I)
• R is hydrogen or methyl
• R 1 is a linear or branched alkyl radical having 1 to 5 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 5 carbon atoms means.
• component a) examples include
• (Meth) acrylates, fumarates and maleates derived from saturated alcohols such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth ) acrylate, tert-butyl (meth) acrylate and
• Pentyl (meth) acrylate Cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate; (Meth) acrylates derived from unsaturated alcohols, such as 2-propynyl (meth) acrylate, allyl (meth) acrylate and vinyl (meth) acrylate.
• (meth) acrylates is used in the context of the present application, this term encompasses in each case methacrylates or acrylates alone or else mixtures of both.
• compositions to be polymerized for producing preferred grafting compositions may contain from 60 to 100% by weight, in particular from 65 to 98% by weight and particularly preferably from 70 to 90% by weight, based on the weight of the monomer compositions for the preparation of the graft base, one or more ethylenically unsaturated ester compounds of the formula (II)
• R is hydrogen or methyl
• R 4 is a linear or branched alkyl group having 6 to 40 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 6 to 40 carbon atoms means included.
• Cycloalkyl (meth) acrylates such as 3-vinylcyclohexyl (meth) acrylate,
• the ester compounds having a long-chain alcohol radical in particular the compounds according to component (b), 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 radicals is formed.
• fatty alcohols include, among others, Oxo Alcohol® 7911, Oxo Alcohol® 7900, Oxo Alcohol® 1100, Alfol® 610, Alfol® 810, Lial® 125, and Nafol® grades (Sasol Olefins & Surfactants GmbH); Aiphanoi® 79 (ICI); Epal® 610 and Epal® 810 (Ethyl Corporation); Linevol® 79, Linevol® 911 and Neodol® 25E (Shell AG); Dehydad®, Hydrenol® and Lorol® types (Cognis); Acropol® 35 and Exxal® 10 (Exxon Chemicals GmbH); Kalcol 2465 (Kao Chemicals).
• the (meth) acrylates are particularly preferred over the maleates and fumarates, ie R 2 , R 3 , R 5 and R 6 of the formulas (I) and (II) represent hydrogen in particularly preferred embodiments.
• R 2 , R 3 , R 5 and R 6 of the formulas (I) and (II) represent hydrogen in particularly preferred embodiments.
• the methacrylates are preferred to the acrylates.
• the proportion of (meth) acrylates having 6 to 15 Kohlenstoffome ⁇ in the alcohol radical in the range of 20 to 95 wt .-%, based on the weight of the monomer composition for the preparation of the graft base.
• the proportion of (meth) acrylates having 16 to 40 carbon atoms in the alcohol radical is preferably in the range of 0.5 to 60 wt .-%, based on the weight of the monomer composition for the preparation of the graft base.
• the proportion of olefinically unsaturated esters having 8 to 14 carbon atoms is preferably greater than or equal to equal to the proportion of olefinically unsaturated esters having 16 to 18 carbon atoms.
• preferred mixtures for preparing preferred grafting bases may comprise, in particular, ethylenically unsaturated monomers which can be copolymerized with the ethylenically unsaturated ester compounds of the formulas (I) and / or (II).
• the proportion of comonomers is preferably in the range from 0 to 40 wt .-%, in particular 2 to 35 wt .-% and particularly preferably 5 to 30 wt .-%, based on the weight of the monomer compositions for the preparation of the graft.
• comonomers for the polymerization according to the present invention are particularly suitable, which correspond to the formula:
• R 9 * is hydrogen, an alkali metal or an alkyl group of 1 to 40 Carbon atoms
• R 3 * and R 4 * may together form a group of formula (Ch 1) n 1 which
• Preferred comonomers which may be included in the monomer compositions A) include nitrogen-bearing monomers, which correspond to the monomers contained in the monomer composition B).
• Preferred comonomers include, but are not limited to, vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene chloride, and vinylidene fluoride;
• Vinyl esters such as vinyl acetate
• Styrene substituted styrenes having an alkyl substituent in the side chain, such as. B. ⁇ -methylstyrene and ⁇ -ethyl styrene, substituted styrenes having an alkyl substituent on the ring, such as vinyltoluene and p-methylstyrene, halogenated styrenes, such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes;
• Heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpipehdine, 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, vinyloxazoles and hydrogenated vinyloxazoles;
• maleic acid and maleic acid derivatives such as maleic anhydride,
• Fumaric acid and fumaric acid derivatives Acrylic acid and methacrylic acid; Dienes such as Divi ⁇ ylbenzol;
• Aryl (meth) acrylates such as benzyl methacrylate or
• Phe ⁇ ylmethacrylat wherein the aryl radicals may each be unsubstituted or substituted up to four times;
• Methacrylates of halogenated alcohols such as
• Hydroxyalkyl (meth) acrylates such as
• Glycol dimethacrylates such as 1,4-butanediol methacrylate, 2-butoxyethyl methacrylate,
• Methacrylates of ether alcohols such as
• Ethoxymethyl methacrylate and ethoxylated (meth) acrylates which preferably have 1 to 20, in particular 2 to 8, ethoxy groups;
• Aminoalkyl (meth) acrylates and aminoalkyl (meth) acrylatamides such as
• Nitriles of (meth) acrylic acid and other nitrogen-containing methacrylates such as
• heterocyclic (meth) acrylates such as 2- (1-imidazolyl) ethyl (meth) acrylate, 2- (4-morpholinyl) ethyl (meth) acrylate and 1- (2-methacryloyloxyethyl) -2-pyrrolidone;
• the graft layer preferably has a specific viscosity ⁇ sp / c measured in chloroform at 25 ° C. in the range from 4 to 60 ml / g, particularly preferably in the range from 5 to 40 ml / g, measured according to ISO 1628-6.
• the weight average molecular weight of the graft base is generally less than or equal to 600,000 g / mol, preferably less than or equal to 400,000 g / mol.
• the weight-average molecular weight of the grafting base is in the range of 5,000 to 200,000, in particular 6,000 to 100,000 g / mol.
• the preferred grafting bases which can be obtained by polymerization of unsaturated ester compounds preferably have a polydispersity M w / M n in the range of 1, 1 to 10.0, in particular 1, 2 to 7.0 and particularly preferably 1, 3 to 5 , 0 on.
• the molecular weight and the polydispersity can be determined by known methods. For example, gel permeation chromatography (GPC) can be used. Likewise, an osmometric method, such as, for example, "vapor phase osmometry" can be used to determine the molecular weights.
• GPC gel permeation chromatography
• osmometric method such as, for example, "vapor phase osmometry” can be used to determine the molecular weights.
• Useful initiators include the azo initiators well known in the art, such as AIBN and 1, 1-azobiscyclohexanecarbonitrile, and peroxy compounds such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert-butyl per-2-ethylhexanoate, ketoperoxide, tert-butyl peroctoate, methyl isobutyl ketone peroxide , Cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3, 5,5-trimethylhexanoate, dicumyl
• Suitable chain transfer agents are, in particular, sulfur-free compounds which are known per se. These include, for example, without this being a limitation, dimeric ⁇ -methylstyrene (2,4-diphenyl-4-methyl-1-pentene), enol ethers of aliphatic and / or cycloaliphatic aldehydes, terpenes, ⁇ -terpinene, terpinolene, 1, 4 -Cyclohexadiene, 1, 4-dihydronaphthalene, 1, 4,5,8-tetrahydronaphthalene, 2,5-dihydrofuran, 2,5-dimethylfuran and / or 3, 6-dihydro-2H-pyran, preferred is dimeric ⁇ -methylstyrene.
• chain transferers are commercially available. However, they can also be produced in a manner known to the person skilled in the art. Thus, the preparation of dimeric ⁇ -methylstyrene in the patent DE 966 375 is described. Enol ethers of aliphatic and / or cycloaliphatic aldehydes are disclosed in the patent DE 3 030 373. The representation of terpenes is explained in EP 80 405. Offenlegungsschriften ⁇ JP 78/121 891 and JP 78/121 890 illustrate the preparation of ⁇ -terpinene, terpinolene, 1, 4-cyclohexadiene, 1, 4-dihydronaphthalene, 1, 4,5,8-tetrahydronaphthalene. The preparation of 2,5-dihydrofuran, 2,5-dimethylfuran and 3,6-dihydro-2H-pyran is described in the published patent application DE 2 502 283.
• the polymerization of the graft base can be carried out at atmospheric pressure, sub-od. Overpressure.
• the polymerization temperature is not critical. In general, however, it is in the range of -20 ° - 200 0 C, preferably 0 ° - 130 0 C and particularly preferably 70 ° - 120 ° C.
• the polymerization can be carried out with or without solvent.
• the term of the solvent is to be understood here broadly.
• the polymerization is carried out in a nonpolar solvent.
• nonpolar 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 may also be branched.
• hydrocarbon solvents such as aromatic solvents such as toluene, benzene and xylene, saturated hydrocarbons such as cyclohexane, heptane, octane, nonane, decane, dodecane, which may also be branched.
• solvents can be used individually or as a mixture.
• Particularly preferred solvents are mineral oils, natural oils and synthetic oils and mixtures thereof. Of these, mineral oils are most preferred.
• the preparation of the graft base can be carried out in one or more steps, wherein different monomer compositions A) can be used, which may differ, for example, in the content of comonomers.
• different monomer compositions A) can be used, which may differ, for example, in the content of comonomers.
• mixtures of graft bases can be produced, which can advantageously be used according to the invention.
• step 1 To prepare graft copolymers of the composition obtained in step 1, which generally comprises at least one backbone polymer, at least one monomer composition B) is grafted.
• Side chains are believed to be formed by the grafting on the grafting base so that at least a portion of the grafting pad is covalently bound to the grafting base.
• the grafting can be done in one or more steps.
• the composition of the monomer composition B) can be changed.
• different monomers can be used with nitrogen-containing groups.
• compositions can be grafted in other stages, which no or only a small proportion of nitrogen-containing Have monomers. Such grafts may be carried out before or after grafting with monomers containing nitrogen-containing groups.
• the monomer composition B) comprises at least 20 wt .-%, preferably at least 50 wt .-%, in particular at least 70 wt .-% and particularly preferably 90 wt .-% to 100 wt .-%, based on the weight of the monomer composition B) , at least one monomer having at least one nitrogen-containing group.
• the ratio of the weight of the monomer composition A) to the weight of the monomer composition B) is in the range of 99.7: 0.3 to 80:20, preferably in the range of 99.5: 0.5 to 88:12, in particular in the range of 99: 1 to 91: 9 and more preferably in the range of 98: 2 to 95: 5.
• Monomers having at least one nitrogen-containing group are well known.
• the nitrogen-containing groups have a dispersing action.
• preferred nitrogen-containing groups contained in the monomers exhibit a basic action.
• the pK b value of these bases is preferably in the range of 2 to 7, more preferably 4 to 7.
• Preferred groups are primary, secondary or tertiary amines, saturated and / or unsaturated heterocyclic nitrogen compounds, such as pyridine, pyrimidine, piperidine, carbazole, imidazole, morpholine, pyrrole.
• Preferred monomers having at least one nitrogen-containing group are compounds of the formula (III)
• R 7 , R 8 and R 9 independently of one another may be hydrogen or an alkyl group having 1 to 5 carbon atoms and R 10 is a group containing 1 to 100 carbon atoms and having at least one nitrogen atom.
• R 7 , R 8 and R 9 are hydrogen.
• the radical R 10 represents a group comprising 1 to 100, in particular 2 to 50, preferably 2 to 20 carbon atoms.
• the term t to 100 carbon atoms-containing group "denotes radicals of organic compounds having 1 to 100 carbon atoms and comprises aromatic and heteroaromatic groups and Alkyl, cycloalkyl, alkoxy, cycloalkoxy, alkenyl, alkanoyl, alkoxycarbonyl and heteroaliphatic groups, in which the groups mentioned can be branched or unbranched, furthermore these groups can have customary substituents, substituents being, for example, linear and branched alkyl groups with 1 to 6 carbon atoms, such as, for example, 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
• 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 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, furan, pyrrole, imidazole, isoxazole, pyrazole, 1, 3,4-oxadiazole, 2,5-diphenyl-1, 3,4-oxadiazole, 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-triazole, 1, 2,3-triazole, 1, 2,3,4-tetrazole, benzo [b] furan, indole, benzo [c] furan, isoindole, benzoxazole, benzimidazole, benzisoxazole, benzopyrazole, dibenzofuran
• the preferred alkyl groups include the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methyl propyl, tert-butyl, pentyl, 2-methylbutyl, 1, 1 - Di methyl propyl, hexyl, heptyl, octyl, 1, 1, 3,3-tetramethylbutyl, nonyl, 1-decyl, 2-decyl, undecyl, dodecyl, pentadecyi 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.
• the preferred alkenyl groups include the vinyl, allyl, 2-methyl-2-propene, 2-butenyl, 2-pentenyl, 2-decenyl and 2-eicosenyl groups.
• the preferred alkynyl groups include the ethynyl, propargyl, 2-methyl-2-propyne, 2-butynyl, 2-pentynyl and 2-decynyl groups.
• Preferred alkanoyl groups include the formyl, acetyl, propionyl, 2-methylpropionyl, butyryl, valeroyl, pivaloyl, hexanoyl, decanoyl and dodecanoyl groups.
• Preferred alkoxycarbonyl groups include the methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, tert-butoxycarbonyl group, 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.
• Preferred cycloalkoxy groups include cycloalkoxy groups whose hydrocarbon radical is one of the aforementioned preferred cycloalkyl groups.
• the preferred heteroatoms contained in R 10 include, among others, oxygen and nitrogen.
• R 10 may represent a group which is different from the previously described heteroaromatic or heterocyclic Derived compounds.
• Preferred compounds here include pyridine, pyrimidine, piperidine, carbazole, imidazole, morpholine, pyrrole
• the ratio of nitrogen atoms to carbon atoms in the radical R 10 of the formula (III) may, according to a particular aspect, be in the range from 1: 1 to 1:20, preferably 1: 2 to 1:10.
• the preferred monomers having at least one nitrogen-containing group include, inter alia
• Aminoalkyl (meth) acrylates and aminoalkyl (meth) acrylatamides such as
• 3-Dibutylaminohexadecyl (meth) acrylate 3-Dibutylaminohexadecyl (meth) acrylate; heterocyclic (meth) acrylates, such as 2- (1-imidazolyl) ethyl (meth) acrylate, N-morpholinoethyl (meth) acrylate, in particular 2- (4-morpholinyl) ethyl (meth) acrylate and 1- (2-methacryloyloxyethyl) - 2-pyrrolidone;
• heterocyclic (meth) acrylates such as 2- (1-imidazolyl) ethyl (meth) acrylate, N-morpholinoethyl (meth) acrylate, in particular 2- (4-morpholinyl) ethyl (meth) acrylate and 1- (2-methacryloyloxyethyl) - 2-pyrrolidone;
• 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-vinyl carbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxazoles and hydrogenated vinyloxazoles.
• the monomer composition B) may have comonomers which may be copolymerized with the monomers having at least one nitrogen-containing group. These monomers correspond to the monomers set forth with respect to the monomer composition A). These monomers can be used singly or as a mixture.
• a polymerization initiator is generally used, it being possible to use the initiators mentioned above for the preparation of the graft base. Cumyl hydroperoxide, diisobutyl hydroperoxide or tert-butyl perbenzoate can be used with particular preference.
• the present invention provides additives for reducing wear without having a high sulfur content.
• the sulfur content is at most 200 ppm, preferably at most 100 ppm and more preferably at most 5 ppm, based on the weight of the graft copolymer.
• the low proportion of sulfur can be achieved in particular by the use of sulfur-free components.
• the grafting can be carried out under normal pressure, under- or overpressure.
• the polymerization temperature is not critical. In general, however, it is in the range of -20 ° - 200 0 C, preferably 0 ° - 160 0 C and particularly preferably 110 ° - 140 0 C.
• the graft polymerization may be carried out at a temperature higher than the temperature at which the grafting base was formed.
• the temperature of the grafting by at least 5 ° C, preferably at least 10 0 C and particularly preferably at least 2O 0 C higher than the temperature at which the backbone was formed.
• the graft yield being greater than or equal to (x * 10 -5 mol / g + 35)%, particularly preferably greater than or equal to (x * 10 "5 mol / g + 40)%, where x is the after In the case of a weight-average molecular weight of 100,000, it follows that the grafting yield is preferably greater than or equal to 36% and particularly preferably greater than or equal to 41%. According to a particular aspect of the present invention, the graft yield is greater than or equal to 35%, in particular greater than or equal to 45% and particularly preferably greater than or equal to 50%.
• the mass of the graft base (Mp G ) and the mass of the graft copolymer (MPO can be determined by HPLC chromatography (High Performance Liquid Chromatography), which is carried out as adsorption chromatography.
• the polarity of the solvent is varied. This can be achieved by changing the solvent composition.
• a Hewlett Packard HP 1090 liquid chromatograph with a CN-functionalized silica gel column (Nucleosil CN-25 cm # NI224) is used.
• a solvent gradient is preferably used. This can be eluted over 15 minutes.
• Pure isooctane is used in the first minute. In the range from minute 1 to minute 11, the isooctane content is reduced from 100% to 0% with a constant gradient, whereby the content of tetrahydrofuran and methanol is increased from 0% to 50% with a constant gradient. In the range of minute 11 to minute 15, the content of methanol is increased from 50% to 100%, whereby the content of tetrahydrofuran is reduced from 50% to 0%.
• the preferred solvent composition for elution can be seen in Figure 1.
• the HPLC analysis is preferably carried out at a flow rate of 1 ml / min at room temperature.
• the HPLC column can be charged with as high a loading as possible, ensuring that the entire polymer is bound to the column.
• the graft base is generally eluted before the graft copolymer.
• the detection of the polymers is preferably carried out by the ELSD method (Evaporating Light Scattering Detector), which is known per se and in the above cited literature is described.
• ELSD method Electrode Desorption Detector
• a calibration function is required, which should preferably take place immediately before or after the measurement.
• An Alltech 2000 ELSD detector can be used here.
• the total mass of the polymer (M Gesa mt) can be determined in a known manner, for example by weighing the polymer used for analysis or from the density, the weight fraction and the volume of the polymer solution used for analysis.
• the mass of the graft base (M PG ) results from
• the graft copolymer preferably has a specific viscosity ⁇ sp / c measured in chloroform at 25 ° C. in the range from 5 to 70 ml / g, particularly preferably in the range from 6 to 50 ml / g, measured according to ISO 1628-6.
• the ratio of the specific viscosity of the graft copolymer to the specific viscosity ⁇ of the graft base is in the range from 1:01 to 1 to 1, 30: 1, in particular in the range from 1, 10: 1 to 1, 20: 1.
• the weight-average molecular weight of the graft copolymer is preferably less than or equal to 600,000 g / mol, especially less than or equal to 400,000 g / mol. Particularly preferably, the weight-average molecular weight of the graft copolymer is in the range from 5100 to 250,000, in particular 6500 to 120,000 g / mol.
• the ratio of the weight average molecular weight of the graft copolymer to the weight average molecular weight of the grafting base is in the range of 1:01: 1 to 5: 1, more preferably in the range of 1: 5: 1 to 2: 1.
• a lubricating oil composition comprises at least one lubricating oil.
• the lubricating oils include, in particular, mineral oils, synthetic oils and natural oils.
• Mineral oils are known per se and commercially available. They are generally obtained from petroleum or crude oil by distillation and / or refining and, if appropriate, further purification and refining processes, the term "mineral oil” in particular falling to the relatively high-boiling fractions of crude oil or crude oil. In general, the boiling point of mineral oil is higher than 200 ° C., preferably higher than 300 ° C., at 5000 Pa. The production by smoldering of shale oil, coking of hard coal, distillation under exclusion of lignite and hydration of coal or lignite is also possible. To a small extent, mineral oils are also made from plant-based raw materials (eg from jojoba, rapeseed) or animal (eg claw oil) origin. Accordingly, mineral oils, depending on the origin of different proportions of aromatic, cyclic, branched and linear hydrocarbons.
• plant-based raw materials eg from jojoba, rapeseed
• animal eg claw oil
• 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 with heteroatoms, in particular O, N and / or S, which are attributed to polar properties .
• the assignment is difficult, however, since individual alkane molecules can have both long-chain branched groups and cycloalkane radicals and aromatic moieties.
• the assignment can be made, for example, according to DIN 51 378.
• Polar proportions may also be determined according to ASTM D 2007.
• the proportion of n-alkanes in preferred mineral oils is less than 3 wt .-%, the proportion of O, N and / or S-containing compounds less than 6 wt .-%.
• the proportion of aromatics and monomethyl branched paraffins is generally in the range of 0 to 40 wt .-%.
• mineral oil mainly comprises naphthenic and paraffinic alkanes, which generally have more than 13, preferably more than 18 and most preferably more than 20 carbon atoms.
• the proportion of these compounds is generally> 60 wt .-%, preferably> 80 wt .-%, without this being a restriction.
• a preferred mineral oil contains from 0.5 to 30% by weight of aromatic fractions, from 15 to 40% by weight of naphthenic fractions, from 35 to 80% by weight of paraffinic fractions, up to 3% by weight of n-alkanes and 0.05% to 5 wt .-% polar compounds, each based on the total weight of the mineral oil.
• Aromatics with 14 to 32 C atoms :
• 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. 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.
• lubricating oils can also be used as mixtures and are often commercially available.
• the concentration of the graft copolymer in the lubricating oil composition is preferably in the range of 1 to 40% by weight, more preferably in the range of 2 to 20% by weight, based on the total weight of the composition.
• a lubricating oil composition may contain other additives and additives.
• additives include antioxidants, corrosion inhibitors, anti-foaming agents, anti-wear components, dyes, color stabilizers, detergents, pour point depressants, Dl additives, friction modifiers and / or extreme pressure additives.
• the graft copolymer can be used in particular for reducing wear in internal combustion engines, gearboxes, couplings or pumps.
• the present use may result in a mean cam wear of at most 40 ⁇ m, preferably at most 30 ⁇ m and more preferably at most 20 ⁇ m after 100 hours measured according to CEC-L-51-A-98.
• the determination of wear in the engine by a component comparison before and after wear test by measuring the cam shape was measured.
• This test method is suitable both for the investigation of the wear behavior in a car diesel engine (ACEA category B) and in a truck diesel engine (ACEA category E).
• the circumferential profile of each cam is determined and compared in 1 ° increments on a 2- or 3-D measuring machine before and after testing.
• the profile deviation created in the test corresponds to the cam wear.
• the wear results of the individual cams are averaged and compared with the limit of the corresponding ACEA categories.
• thermometer and reflux condenser 430 g of a 150N oil and 47.8 g of a monomer mixture consisting of C12-C18 alkyl methacrylates and methyl methacrylate (MMA) in a weight ratio 99,0: 1, 0 submitted.
• the temperature is set to 100 0 C.
• tert-butyl peroctoate 0.77 g of tert-butyl peroctoate are added and at the same time a Mo ⁇ omerzulauf consisting of 522.2 g of a mixture of C12-C18-alkyl methacrylates and methyl methacrylate in a weight ratio 99.0: 1, 0 and 3.92 g tert-butyl peroctoate started.
• the feed time is 3.5 hours and the feed rate is uniform. 2 hours after the end of the feed, another 1.14 g of tert-butyl peroctoate are added. The total reaction time is 8 hours. Thereafter, the batch is heated to 130 0 C.
• N-vinylpyrrolidone 0, 056%
• tert-butyl peroctoate After reaching the 90 0 C 1, 75 g of tert-butyl peroctoate are added and simultaneously a feed 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 tert-butyl peroctoate started.
• the feed time is 3.5 hours. The feed rate is even. 2 hours after the end of the feed, another 1.20 g of tert-butyl peroctoate are added.
• the total reaction time is 8 hours.
• the polymer solution is added to a pour point improver, which is then present at 5% by weight. Thereafter, the solution is diluted 79/21 with an ethoxylated iso-C13 alcohol containing 3 ethoxylate units.
• Viscosity index 178
• a motor oil formulation of the category SAE 5W-30 consisting of a commercially available base oil and additives such as e.g. OLOA 4594 (DI package) and Nexbase 3043 mixed as an oil component and tested in the CEC-L-51 -A-98 test.
• SAE 5W-30 consisting of a commercially available base oil and additives such as e.g. OLOA 4594 (DI package) and Nexbase 3043 mixed as an oil component and tested in the CEC-L-51 -A-98 test.
• Oloa 4549 is a typical Dl additive for engine oils.
• the product also contains components to improve the 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 commonly used additives for improving the wear behavior.
• ethylene-propylene copolymer (Paratone 8002) was used. 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 excellent thickening action.
• Comparative Example 1 was substantially repeated. However, to the motor oil formulation was added a polymer composition I according to the invention. Here, the thickening effect of Polymer Composition I with a reduced addition of Paratone 8002 was taken into account to maintain the viscosity adjustment of the engine oil formulation. The content of Paratone 8002 was thus reduced compared to the formulation of Comparative Example 1.
• This formulation according to the invention was also tested in the CEC-L-51-A-98 test. The composition and test results of the test methods set out above are set forth in Table 1.
• Comparative Example 1 was substantially repeated. However, a PAMA polymer of composition II was added to the motor oil formulation. With regard to the molecular weight and its oil-thickening effect, the polymer compositions I and II did not differ. For the preparation of the formulation according to Comparative Example 2, therefore, only the 3% by weight of the nitrogen-containing polymer of the polymer composition I was replaced by 3% by weight of the ethoxylate-containing polymer composition II. Such ethoxylated PAMA types of polymer composition II as well as polymer composition I have been described as dispersible VI improvers.
• N-containing polymers have outstanding wear-reducing effects, which can not be explained by the dispersing action and were not to be expected.
• N-containing polymers clearly differ from O-based (ethoxylated) representatives in terms of their advantageous wear protection function.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Lubricants (AREA)
• Graft Or Block Polymers (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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