EP2563887A1 - Schmiermittel für getriebe - Google Patents

Schmiermittel für getriebe

Info

Publication number
EP2563887A1
EP2563887A1 EP11705871A EP11705871A EP2563887A1 EP 2563887 A1 EP2563887 A1 EP 2563887A1 EP 11705871 A EP11705871 A EP 11705871A EP 11705871 A EP11705871 A EP 11705871A EP 2563887 A1 EP2563887 A1 EP 2563887A1
Authority
EP
European Patent Office
Prior art keywords
meth
acrylate
polyalkyl
formula
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11705871A
Other languages
German (de)
English (en)
French (fr)
Inventor
Reza Ghahary
Michael Müller
Thilo Krapfl
Jürgen Gebhardt
Roland Schweder
Torsten Stöhr
Thomas Schimmel
Christoph Wincierz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Oil Additives GmbH
Original Assignee
Evonik Oil Additives GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Evonik Oil Additives GmbH filed Critical Evonik Oil Additives GmbH
Publication of EP2563887A1 publication Critical patent/EP2563887A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
    • C10M145/14—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/22—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/28—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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03D—WIND MOTORS
    • F03D15/00—Transmission of mechanical power
    • F03D15/10—Transmission of mechanical power using gearing not limited to rotary motion, e.g. with oscillating or reciprocating members
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03D—WIND MOTORS
    • F03D80/00—Details, components or accessories not provided for in groups F03D1/00 - F03D17/00
    • F03D80/70—Bearing or lubricating arrangements
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03D—WIND MOTORS
    • F03D9/00—Adaptations of wind motors for special use; Combinations of wind motors with apparatus driven thereby; Wind motors specially adapted for installation in particular locations
    • F03D9/20—Wind motors characterised by the driven apparatus
    • F03D9/25—Wind motors characterised by the driven apparatus the apparatus being an electrical generator
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03D—WIND MOTORS
    • F03D9/00—Adaptations of wind motors for special use; Combinations of wind motors with apparatus driven thereby; Wind motors specially adapted for installation in particular locations
    • F03D9/20—Wind motors characterised by the driven apparatus
    • F03D9/25—Wind motors characterised by the driven apparatus the apparatus being an electrical generator
    • F03D9/255—Wind motors characterised by the driven apparatus the apparatus being an electrical generator connected to electrical distribution networks; Arrangements therefor
    • F03D9/257—Wind motors characterised by the driven apparatus the apparatus being an electrical generator connected to electrical distribution networks; Arrangements therefor the wind motor being part of a wind farm
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • C10M2209/0845—Acrylate; Methacrylate used as base material
    • 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
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/36—Seal compatibility, e.g. with rubber
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/70—Wind energy
    • Y02E10/72—Wind turbines with rotation axis in wind direction

Definitions

  • the present invention relates to lubricants for
  • Mileage - Relatively short oil change intervals which can be done by default in any workshop, oil changes for wind turbines with a lot of cost, time and material associated because the oil from the ground to the nacelle must be transported and the used oil the gondola in the reverse direction must leave.
  • the oil changes for wind turbines with a lot of cost, time and material associated because the oil from the ground to the nacelle must be transported and the used oil the gondola in the reverse direction must leave.
  • Oil quantity is large and amounts up to 1500 liters depending on plant strength.
  • Wind turbines are.
  • the advantage of less downtime and better protection for the transmission as well as the cost of oil change due to the high amount of gear oil also applies in industrial gear applications outside of wind power.
  • lubricants based on special polyalphaolefins (PAO) are commonly used to power transmissions for wind turbines.
  • Such lubricants are used for example in
  • WO 2007/145924 AI set out. These lubricants usually comprise two base oils of different viscosity.
  • the known lubricants have a useful
  • Providing a lubricant with an improved property profile is a permanent task.
  • the lubricant should have improved seal compatibility, especially when compared to polyalphaolefins.
  • the lubricant should show improved flow behavior at low temperatures.
  • the lubricant should have an increased viscosity index, without this resulting in a decrease in the durability of the lubricant would be connected.
  • Lubricants comprise relatively large amounts of expensive and complex to produce PAO with a high viscosity.
  • the second basic component of the described lubricants is a lower viscosity PAO type and much less expensive. Therefore, it is a special task to replace the amount or type of relatively expensive component with cheaper alternatives.
  • the lubricant should the
  • the lubricant should be compatible with many additives, and to improve compatibility if possible, only small, ideally no additional additives should be necessary because they are associated with further costs.
  • Wind turbines represent the claims 9, 20, 28 and 29 is a solution to the problems.
  • the subject of the present invention is accordingly a lubricant for a transmission, which thereby
  • polyalkyl (meth) acrylate for use in lubricants, comprising
  • R is hydrogen or methyl and R 1 is an alkyl radical having 1 to 5 carbon atoms
  • R is hydrogen or methyl and R is an alkyl radical having 6 to 15 carbon atoms, and c) 0 to 50 wt .-% of repeating units derived from (meth) acrylates of the formula (III)
  • R is hydrogen or methyl and R is an alkyl radical having 16 to 40 carbon atoms, which is characterized in that the polyalkyl (meth) acrylate has a weight average molecular weight in the range of 3000 to 25000 g / mol and
  • the repeating units of the formula (II) represent a mixture of linear and branched radicals, wherein 5 to 80% of the radicals R 2 are branched, based on the weight of the repeating units of the formula (II).
  • the lubricant shows improved seal compatibility, especially when compared to polyalphaolefins.
  • the lubricant has an improved flow behavior at low temperatures.
  • the lubricant shows an increased viscosity index, without thereby a decrease in the
  • the lubricant can be provided relatively inexpensively.
  • the amount of relatively inexpensive components, especially low viscosity base oils can be kept high, without the other properties, in particular the shear stability, the
  • the lubricant can be inexpensive
  • the power loss of the transmission can be kept extremely low due to the low Reinbungskoefizienz the lubricant of the invention.
  • the lubricant is compatible with many additives, with little or no additives to
  • Solvent and can be done within a relatively short time.
  • the present invention describes a lubricant for a transmission.
  • Lubricants in particular lubricating oils serve to reduce friction and wear, as well as for power transmission, cooling, vibration damping,
  • the lubricant according to the invention comprises at least 30% by weight, preferably at least 40% by weight and particularly preferably at least 45% by weight of polyalkyl (meth) acrylates.
  • Polyalkyl (meth) acrylates are polymers through which
  • alkyl (meth) acrylates Polymerization of alkyl (meth) acrylates can be obtained.
  • the term (meth) acrylates include methacrylates and acrylates as well as mixtures of both. These monomers are well known.
  • Polyalkyl (meth) acrylates preferably comprise at least 40% by weight, particularly preferably at least 60% by weight,
  • Polyalkyl (meth) acrylates preferably a
  • the number average molecular weight M n may preferably be in the range of 2,500 to 20,000 g / mol, more preferably 5,000 to 17,500 g / mol, and most preferably 7,000 to 13,000 g / mol.
  • polyalkyl (meth) acrylates whose polydispersity index M w / M n is in the range from 1.1 to 2.5, particularly preferably in the range from 1.4 to 1.9 and very particularly preferably in the range of 1.5, are also useful to 1.8 lies the number average and the weight average
  • GPC gel permeation chromatography
  • Preferred polyalkyl (meth) acrylates include
  • R is hydrogen or methyl and R is an alkyl radical having 1 to 5 carbon atoms, 50 to 100 wt .-%, in particular at least 70 wt .-% and particularly preferably at least 80 wt. ⁇ 6 on
  • R is hydrogen or methyl and R is an alkyl radical having 6 to 15 carbon atoms, and 0 to 50 wt .-%, preferably up to 30 wt.% And particularly preferably up to 20 wt. ⁇ 6 on
  • R represents hydrogen or methyl and R 3 represents an alkyl radical having 16 to 40 carbon atoms.
  • Polyalkyl (meth) acrylate according to the invention preferably at least 0.1% by weight and more preferably at least 0.5% by weight of recurring units derived from
  • Polyalkyl (meth) acrylate according to the invention at least preferably 0.1 wt .-%, and particularly preferably at least 1% by weight of repeat units derived from
  • the polyalkyl (meth) acrylates may preferably by
  • Examples of (meth) acrylates of the formula (I) include linear and branched (meth) acrylates which are derived from saturated alcohols, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate,
  • Cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate.
  • linear and branched (meth) acrylates which are derived from saturated alcohols, such as
  • Tridecyl (meth) acrylate 5-methyltridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate;
  • (Meth) acrylates derived from unsaturated alcohols, such as.
  • unsaturated alcohols such as.
  • Cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate, 3-vinylcyclohexyl (meth) acrylate, bornyl (meth) acrylate;
  • Examples of monomers of the formula (III) include linear and branched (meth) acrylates which differ from
  • hexadecyl (meth) acrylate 2-methylhexadecyl (meth) acrylate, 2-methylpentadecyl (meth) acrylate,
  • Cetyleicosyl (meth) acrylate Stearyleicosyl (meth) acrylate, docosyl (meth) acrylate and / or
  • Cycloalkyl (meth) acrylates such as 2, 4, 5-tri-t-butyl-3-vinylcyclohexyl (meth) acrylate, 2, 3, 4, 5-tetra-t-butylcyclohexyl (meth) acrylate.
  • Alkyl (meth) acrylates with a long-chain alcohol radical Alkyl (meth) acrylates with a long-chain alcohol radical
  • components (II) and (III) can be obtained, for example, by reacting (meth) acrylates and / or the corresponding acids with long-chain fatty alcohols, wherein in general a mixture of esters, such as (meth) acrylates with different
  • Fatty alcohols include Oxo Alcohol® 7911, Oxo Alcohol® 7900, Oxo Alcohol® 1100; Alfol® 610, Alfol® 810, Lial® 125 and Nafol® grades (Sasol); C13-C15 alcohol (BASF); Epal® 610 and Epal® 810 (Afton); Linevol® 79, Linevol® 911 and Neodol® 25 (Shell); Dehydad®, Hydrenol® and Lorol® types (Cognis); Acropol® 35 and Exxal® 10
  • the weight ratio of alkyl (meth) acrylates of the formula (III) to the (meth) acrylates of the formula (II) can be in a wide range. Preferably that is
  • Monomers of the formula (II) which have 6 to 15 carbon atoms in the alcohol radical, less than 5: 1, in particular less than 1: 1, more preferably less than 1: 5 and particularly preferably less than 1:10. According to one
  • Weight ratio of monomers of formula (III) having 16 to 40 carbon atoms in the alcohol radical to the monomers of formula (II) having 6 to 15 carbon atoms in the alcohol radical be less than 1: 100, wherein in preferred embodiments, the polymer is not a monomer of the formula (III) having 16 to 40 carbon atoms in the
  • Alcohol radical comprises.
  • Polyalkyl (meth) acrylate for use in lubricants having a weight average molecular weight in the range of 3000 to 25000 g / mol and a polydispersity in the range of 1.1 to 2.5. Furthermore, these polyalkyl (meth) acrylates are characterized in that the repeat units of the formula (II) represent a mixture of linear and branched radicals, wherein 5 to 80%, preferably 10 to 65% of the radicals R 2 are branched, based on the weight of the repeating units of the formula (II).
  • Polyalkyl (meth) acrylates are used, whose from
  • Units represent a mixture of linear and branched radicals, wherein the proportion by weight of the branched radicals R 2 having 9 to 11 carbon atoms is higher than that
  • Polyalkyl (meth) acrylates whose repeating units of the formula (II) is a mixture of linear and branched
  • repeating units of the formula (II) represent a mixture of branched and linear radicals, wherein the weight ratio of
  • branched to linear R 2 ranges from 60:40 to 20:80.
  • lubricants with polyalkyl (meth) acrylates are preferred, whose
  • Repeating units of the formula (II) have a high proportion of branched radicals R 2 having 10 to 15 carbon atoms.
  • the ratio of branched to linear radicals R are in the range from 70:30 to 50:50, preferably 60:40 to 65:35, wherein the repeating units of the formula (II) at least 50 wt .-%, preferably at least 70 wt .-% of radicals R 2 having 13 to 15 carbon atoms, based on the proportion of repeating units of the formula (II).
  • polyalkyl (meth) acrylates whose repeat units of the formula (II) are a mixture of radicals R 2 having a different number of
  • the proportions of repeat units of the formula (II) with the respective carbon numbers and their isomerism can be determined by customary methods on the basis of the monomers used to prepare the polymers. This includes, in particular, gas chromatography (GC).
  • GC gas chromatography
  • polyalkyl (meth) acrylates having repeating units of the formula (II) where at least 50% by weight, in particular 70% by weight and particularly preferably 90% by weight, of the
  • branched radical R 2 at least one branching at one of the positions 2 to 5, preferably at position 2
  • the alkyl (meth) acrylates of the polyalkyl (meth) acrylates of the present invention may hereby have a short-chain or a long-chain branching. According to one
  • Repeating units of the formula (II) represent a mixture of branched radicals, wherein the mixture
  • Polyalkyl (meth) acrylates are used, whose
  • Repeating units of the formula (II) represent a mixture of branched radicals, wherein the mixture
  • branching as well as the position of the branching can be measured by NMR methods on the basis of the monomers used to prepare the polymers. In particular, 13 C and X H NMR measurements can be carried out and evaluated.
  • butyl Branches of pentyl or Hexylverzweigungen can not be distinguished by the NMR methods outlined, so that the term longer-chain branching in addition to the butyl branches also includes pentyl or Hexyl- branches.
  • the monomer mixture may comprise monomers which can be copolymerized with the (meth) acrylates of the formulas (I), (II) and / or (III). These include, among others
  • Aryl (meth) acrylates such as benzyl methacrylate or
  • Styrene substituted styrenes having an alkyl substituent in the side chain, such as. B. D-methylstyrene and
  • Alkyl substituents on the ring such as vinyl toluene and p-methylstyrene, halogenated styrenes such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and
  • maleic acid and maleic acid derivatives such as maleic acid monoesters, maleic diesters,
  • Itaconic acid and itaconic acid derivatives such as itaconic acid monoesters, itaconic diesters and
  • Fumaric acid and fumaric acid derivatives such as
  • 1-alkenes in particular 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene and 1-pentadecene.
  • dispersing monomers can be used.
  • R is hydrogen or methyl
  • X is oxygen, sulfur or an amino group of the formula -NH- or -NR a -, in which R a is an alkyl radical having 1 to 10, preferably 1 to 4, carbon atoms, R 2 is a 2 to 50, in particular 2 to 30, preferably 2 to 20 carbon atoms
  • dispersing monomers examples include aminoalkyl (meth) acrylates,
  • Aminoalkyl (meth) acrylamides include, inter alia
  • Carbonyl-containing (meth) acrylates include, for example
  • heterocyclic (meth) acrylates include, inter alia, 2- (1-imidazolyl) ethyl (meth) acrylate,
  • aminoalkyl (meth) acrylates include in particular
  • aminoalkyl (meth) acrylamides can be used as
  • dispersing monomers such as
  • phosphorus, boron and / or silicon-containing (meth) acrylates may be used as dispersing monomers
  • heterocyclic vinyl compounds include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2, 3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole,
  • N-vinylpyrrolidine 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxolane, vinylfuran,
  • Particularly preferred dispersing monomers include, in particular, ethylenically unsaturated compounds which comprise at least one nitrogen atom, these being particularly preferably selected from those described above
  • Aminoalkyl (meth) acrylates, aminoalkyl (meth) acrylamides and / or heterocyclic (meth) acrylates are selected.
  • the proportion of comonomers can be varied depending on the purpose and property profile of the polymer. in the
  • this proportion can be in the range from 0 to 30% by weight, preferably 0.01 to 20% by weight and more preferably 0.1 to 10% by weight.
  • the proportion of 1-alkenes may preferably be in proportions of up to 30 wt .-%, preferably up to 20 wt .-% and especially
  • polyalkyl (meth) acrylates preferably be limited to 10, wherein particularly preferred embodiments according to the invention to be used polyalkyl (meth) acrylates have no repeating units derived from 1-alkenes.
  • the aforementioned ethylenically unsaturated monomers can be used individually or as mixtures. It is further possible to vary the monomer composition during the main chain polymerization to obtain defined structures such as block copolymers or graft polymers.
  • compositions is known per se.
  • these polymers can in particular by radical
  • ATRP Atom Transfer Radical Polymerization
  • RAFT Reversible Addition Fragmentation Chain
  • the ATRP method is known per se.
  • polymers according to the invention are obtainable by NMP processes (nitroxide mediated polymerization), which are described, inter alia, in US Pat. No. 4,581,429.
  • Hoboken 2002 which is expressly referred to for purposes of the disclosure.
  • the free-radical polymerization of the ethylenically unsaturated compounds can be carried out in a manner known per se.
  • the usual free-radical polymerization is set forth, inter alia, in Ullmanns Encyclopedia of Industrial Chemistry, Sixth Edition.
  • azo initiators well known in the art, such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and 1,1-azobiscyclohexanecarbonitrile, organic peroxides such as dicumyl peroxide, diacyl peroxides such as Dilauroyl peroxide, peroxydicarbonates, such as
  • Diisopropyl peroxydicarbonate peresters, such as tert.
  • polymerization initiators include in particular the following compounds:
  • Methyl isobutyl ketone peroxide cyclohexanone peroxide
  • Butyl hydroperoxide bis (4-tert-butylcyclohexyl) peroxydicarbonate, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 1,1-azobiscyclohexanecarbonitrile, Diisopropyl peroxydicarbonate, tert.
  • Amyl peroxypivalate di (2, 4-dichlorobenzoyl) peroxide, tert.
  • Butyl peroxypivalate, 2,2'-azobis (2-amidinopropane) dihydrochloride di (3,5,5-trimethylhexanoyl) peroxide, dioctanoyl peroxide,
  • polymerization initiators having a half-life of 1 hour at a temperature in the range from 25 ° C. to 200 ° C., preferably in the range from 50 ° C. to 150 ° C., in particular in the range from 50 ° C. to 100 ° C., are very particularly preferred .
  • peroxidic peroxidic
  • Butyl peroctoate particularly suitable for the present purposes.
  • Polymerization initiators are used. If different initiator species are used, they are preferably added separately in successive steps, the later added
  • Polymerization in at least two steps The addition of the polymerization initiator in each step in undiluted form or in a diluted form, preferably dissolved in a solvent, in particular in the form of a 10 wt .-% to 50 wt .-% solution in at least one
  • the polymerization initiator may preferably be added at once in the first step.
  • it has also proved to be particularly expedient to use the polymerization initiator in the first step
  • the polymerization initiator according to a first embodiment of this preferred method is preferably added all at once.
  • it is also preferred to meter in the polymerization initiator in the second step preferably continuously, in particular at a constant metering rate.
  • the polymerization initiator can be metered in continuously in the first and in the second step, preferably at a constant metering rate, wherein the average metering rate of the second step is preferably greater than the average metering rate of the first step.
  • the ratio of the average metering rate of the second step to the average metering rate of the first step is greater than 1.2: 1, preferably in the range of 1.2: 1 to 10: 1, more preferably greater than 1.5: 1, most preferably greater than 2: 1, in particular greater than 3: 1.
  • the amount of polymerization initiator added in the second step is greater than that in the first
  • Step added amount wherein in the second step, based on the total weight of the polymerization in the first step added, preferably
  • At least 120% suitably from 120% to 1000%, particularly preferably at least 150%, in particular from 150% to 500%, of the amount added in the first step
  • the second step is preferably started at one
  • the polymerization initiator in the third step preferably continuously, in particular with a
  • the polymerization initiator is continuous in the first, in the second and in the third step,
  • step is greater than the average metering rate of the second step and the average metering rate of the second step is preferably greater than the average metering rate of the first step.
  • the ratio of the average metering rate of the third step to the mean metering rate of the second step is preferably greater than 1.2: 1, preferably in the range from 1.2: 1 to 10: 1, particularly preferably greater than 1.5: 1, very particularly preferably greater than 2: 1, in particular greater than 3: 1.
  • the amount of polymerization initiator added in the third step is particularly preferably greater than the amount added in the second step, wherein in the third step, based on the total weight of the polymerization initiator added in the second step, preferably at least 120%, advantageously 120% to 1000%, particularly preferably at least 150%, in particular 150% to 500%, of the amount of polymerization initiator added in the second step is added.
  • the third step is preferably started at one
  • Polymerization initiator can be determined in a known manner or based on the known
  • the temperature profile during the polymerization, the addition profile can be calculated.
  • a dosing with constant speed at a constant temperature applies, for example
  • polymerization initiator referred to the total amount of the polymerization initiator added during the second step, wherein k d the
  • the addition of the polymerization initiator can be carried out in more than three steps, starting with the fourth step in each successive step, adding more polymerization initiator than in the immediately preceding step and adding the polymerization initiator all at once or
  • Polymerization initiator amounts in an infinite number
  • Post-initiation preferably takes place at a time at which at least 75.0% by weight, expediently at least 90.0% by weight, in particular at least 95.0% by weight, of the total amount of the polymerization initiator added during the last step is consumed. It is preferably used at 0.1% by weight to 100.0% by weight,
  • Polymerization initiator based on the total amount added to previously added polymerization initiator.
  • the total amount of initiator is preferably in the range of 0.5 to 1, more preferably in the range of 0.6 to 0.8 wt .-%, based on the weight of the monomers.
  • the process can be carried out either in the presence or absence of a chain transfer agent.
  • chain transfer agents typical, for radical polymerizations
  • the sulfur-free molecular weight regulators include, for example, but without limitation, dimeric methylstyrene (2,4 diphenyl-4-methyl-l-pentene), enol ethers aliphatic and / or
  • Terpinolene 1,4-cyclohexadiene, 1,4-dihydronaphthalene, 1,4,4,5,8-tetrahydronaphthalene, 2,5-dihydrofuran, 2,5-dimethylfuran and / or 3,6-dihydro-2H-pyran dimeric a-methylstyrene.
  • mercapto compounds dialkyl sulfides, Dialkyl disulfides and / or diaryl sulfides are used.
  • the following polymerization regulators are given by way of example: di-n-butyl sulfide, di-n-octyl sulfide, diphenyl sulfide,
  • Diethanol sulfide, di-t-butyl trisulfide and dimethyl sulfoxide Preferably used as molecular weight regulators
  • Compounds are mercapto compounds, dialkyl sulfides, dialkyl disulfides and / or diaryl sulfides. Examples of these compounds are ethyl thioglycolate, 2-
  • Thioacetic acid, thiourea and alkylmercaptans such as n-butylmercaptan, n-hexylmercaptan, t-dodecylmercaptan or n-dodecylmercaptan. Particularly preferably used
  • Polymerization regulators are mercaptoalcohols and
  • n-dodecyl mercaptan and also tert-dodecyl mercaptan as chain transfer agent is very particularly preferred.
  • mixtures of molecular weight regulators may be used, with preferred mixtures in particular
  • sulfur-containing regulators such as the above-mentioned mercaptan derivatives and sulfur-free regulators such as terpinolene, terpinene and their derivatives, as well as suitable transition metal complexes.
  • sulfur-free regulators such as terpinolene, terpinene and their derivatives, as well as suitable transition metal complexes.
  • Particular preference is given to using mixtures of the abovementioned n-dodecylmercaptan, tert-dodecylmercaptan and terpinolene as chain transfer agents.
  • the molecular weight regulators are preferably used in amounts of 0.05 to 10, in particular 1 to 6 wt .-% and particularly preferably 2 to 4.5 wt .-%, based on the in the
  • Initiators are added at the polymerization temperature.
  • the regulators can both be charged and also be added with the initiator, the regulators being presented in preferred processes. Particularly preferred are processes in which at least 50 wt .-%,
  • At least 90 wt .-% of the molecular weight regulators are placed in a reactor.
  • the polymerization can be carried out at atmospheric pressure, sub-od.
  • Polymerization temperature is not critical. In general, however, it is in the range of -20 ° to 200 ° C, preferably 20 ° to 180 ° C, and more preferably 60 ° to 150 ° C. at
  • Stepwise addition of the initiator preferably in the range of 20 to 180 ° C., more preferably 60 to 150 ° C.
  • the polymerization is carried out at a temperature in the
  • Initiator is carried out, in which the half-life of the initiator is 30 minutes.
  • the polymerization can be carried out with or without solvent
  • Solvents 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.
  • Solvents can be used individually or as a mixture. Particularly preferred solvents are mineral oils, natural oils and synthetic oils and mixtures thereof. According to a preferred embodiment, the proportion of solvent can be kept low, wherein preferred embodiments of the method according to the invention are characterized in that after completion of the polymerization no Solvent must be separated from the composition, for example by distillation to obtain a usable polymer mixture. Accordingly, the proportion of solvent used in total is preferably in the range of 0 to 30 wt .-%, particularly preferably 0.5 to 10 wt .-% and most preferably in the range of 1 to 8 wt .-%. In this case, the solvent can be used in particular for dissolving the initiator added over the course of the reaction.
  • Polydispersity index can be obtained without
  • Initiator consumption can be minimized.
  • Polyalkyl (meth) acrylates in the lubricant is at least 30 wt .-%, in particular 35 wt .-%, more preferably at least 40 wt .-% and most preferably at least 45 wt .-%, based on the total weight of the lubricant.
  • Polyalkyl (meth) acrylates in the lubricant is at least 30 wt .-%, in particular 35 wt .-%, more preferably at least 40 wt .-% and most preferably at least 45 wt .-%, based on the total weight of the lubricant.
  • Polyalkyl (meth) acrylate may include preferred lubricants for a transmission at least one further base oil.
  • the preferred base oils include in particular
  • Mineral oils are known per se and commercially available. They are generally made from petroleum or crude oil
  • the boiling point of mineral oil is higher than 200 ° C, preferably higher than 300 ° C, at 5000 Pa.
  • the production by smoldering of shale oil, coking of hard coal, distillation under exclusion of air from brown coal and hydrogenation of hard coal or lignite is also possible. Accordingly, mineral oils, depending on
  • Synthetic oils include, but are not limited to, organic esters such as diesters and polyesters, polyalkylene glycols, polyethers, synthetic hydrocarbons, especially polyolefins, of which polyalphaolefins (PAO) are preferred, silicone oils and perfluoroalkyl ethers.
  • synthetic base oils with origin from gas to liquid (GTL), coal to liquid (CTL) or biomass to liquid (BTL) processes can be used. They are usually slightly more expensive than the mineral oils, but have advantages in terms of their performance.
  • Natural oils are animal or vegetable oils, such as claw oils or jojoba oils.
  • Base oils for lubricating oil formulations are grouped according to API (American Petroleum Institute). Mineral oils are subdivided into Group I (not hydrogen-treated) and, depending on degree of saturation, sulfur content and
  • PAOs correspond to Group IV.
  • Invention include at least one polyalphaolefin (PAO) or a Group III oil having a kinematic viscosity measured at 100 ° C in the range of 3.0 to 10.0 mm 2 / s, preferably in the range of 5.5 to 9.0 mm 2 / s and more preferably in the range of 7.5 to 8.5 mm 2 / s (ASTM D 445).
  • lubricants which are a polyalphaolefin (PAO) or a group III oil with a kinematic viscosity at 100 ° C in the range of 3.0 to 5.5 mm 2 / s, more preferably 3.5 to 5 mm 2 / s included.
  • lubricants containing at least one Group III mineral oil are also of particular interest.
  • Range from 3 to 10 mm 2 / s, more preferably 5.5 to 9 mm 2 / s, measured at 100 ° C according to ASTM D 445.
  • poly (alkyl) methacrylates are used together with a Group III mineral oil as a pour point improver.
  • Polyalphaolefins and / or Group III mineral oils may be at least 10% by weight, more preferably at least 35% by weight and most preferably at least 45% by weight, based on the total weight of the lubricant.
  • Lubricating oil composition containing further additives and additives.
  • additives include, but are not limited to, di-additives (dispersants, detergents, defoamers, corrosion inhibitors, antioxidants,
  • pour point improvers particularly preferably based on polyalkyl (meth) acrylate having 1 to 30 carbon atoms in the alcohol group
  • pour point improvers particularly preferably based on polyalkyl (meth) acrylate having 1 to 30 carbon atoms in the alcohol group
  • Lubricating oil compositions in addition to the polymers according to the invention are also present in mixtures with conventional VI improvers.
  • VI improvers include, in particular, hydrogenated styrene-diene copolymers (HSD, US Pat. No. 4,116,917, US Pat.
  • Useful dispersants include, but are not limited to, poly (isobutylene) derivatives, e.g. Poly (isobutylenes) succinimides (PIBSI); Ethylene-propylene oligomers with N / O functionalities.
  • poly (isobutylene) derivatives e.g. Poly (isobutylenes) succinimides (PIBSI); Ethylene-propylene oligomers with N / O functionalities.
  • PIBSI Poly (isobutylenes) succinimides
  • the preferred detergents include, but are not limited to, metal-containing compounds such as, for example phenoxides; salicylates; Thiophosphonates, in particular
  • Defoamers are also of particular interest, and these are often subdivided into silicone-containing and silicone-free defoamers.
  • Silicone-containing antifoams include, but are not limited to, linear poly (dimethylsiloxane) and cyclic
  • polyethers e.g. Poly (ethylene glycol), polyacrylates or tributyl phosphate can be used.
  • antirust additives include sulfonates, such as
  • Example lanolin (wool grease), oxidized paraffins,
  • Zinc naphthenates acylated succinic acids, 4-nonylphenoxyacetic acid, amides and imides (N-acylsarcosine,
  • Dialkylphosphoric acid ester ; morpholine; Dicycylohexylamine or diethanolamine be used.
  • Metal passivators / deactivators include among others Benzotriazole, tolyltriazole, 2-mercaptobenzothiazole,
  • Disalicylidenpropylendiamin Zinc dialkyldithiophosphates and dialkyldithiocarbamates.
  • Antioxidant represents. To the
  • Antioxidants include, for example, phenols, such as 2, 6-di-tert-butyl-phenol (2,6-DTB),
  • BHT butylated hydroxytoluene
  • PNA N-phenyl-1-naphthylamine
  • TMQ polymeric 2,2,4-trimethyldihydroquinone
  • Zinc dithiophosphates Zinc dithiophosphates (ZnDTP)
  • OOS triesters reaction products of dithiophosphoric acid with activated double bonds of olefins
  • Acrylic acid esters maleic acid esters (ash-free at
  • Organosulfur compounds such as dialkyl sulfides, diaryl sulfides, polysulfides, modified thiols, thiophene derivatives, xanthates, thioglycols,
  • dialkyl dimercaptothiadiazoles especially dialkyl dimercaptothiadiazoles, 2-mercaptobenzimidazoles; Zinc and methylenebis (dialkyldithiocarbamate); Organophosphorus compounds such as triaryl and trialkyl phosphites;
  • Preferred antiwear AW and extreme pressure (EP) additives include, but are not limited to, phosphorus compounds such as
  • Trialkyl phosphates triaryl phosphates, e.g.
  • Dialkylphosphoric acid esters ethoxylated mono- and
  • fatty acid ester fatty acid ester; overbased sulfonates; Chlorine compounds or solids, such as graphite or molybdenum disulfide.
  • Friction modifiers may include, but are not limited to, mechanically active compounds such as molybdenum disulfide, graphite (also fluorinated), poly (trifluoroethylene), polyamide,
  • Adsorption layer-forming compounds such as long-chain carboxylic acids, fatty acid esters, ethers, alcohols, amines, amides, imides; Compounds which form layers by tribochemical reactions, such as, for example, saturated fatty acids, phosphoric acid and Thiophosphoric acid esters, xanthogenates, sulfurized
  • Methacrylates unsaturated fatty acids, sulfurized olefins or organometallic compounds, such as molybdenum compounds (molybdenum dithiophosphates and
  • Molybdenum dithiocarbamates MoDTC Molybdenum dithiocarbamates MoDTC and their combinations with ZnDTP, copper-containing organic compounds.
  • ZnDTP e.g. is primarily a
  • Wear protection additive and extreme pressure additive but also has the character of an antioxidant and
  • Corrosion inhibitor here: metal passivator / deactivator
  • lubricants can be provided which are preferably characterized by a low proportion of ester oils.
  • Particularly preferred lubricants have at most 10% by weight, in particular at most 5% by weight, of ester oils.
  • the inventive Lubricants have no detectable levels of ester oils.
  • Ester oils are known in the art and are characterized by a molecular weight of at most 800 g / mol.
  • Preferred lubricants have a measured in accordance with ASTM D 445 at 40 ° C viscosity in the range of 200 to 2000 mm 2 / s, in particular 250 to 1000 mm 2 / s, more preferably in the range of 300 to 800 mm 2 / s.
  • the kinematic viscosity KVi oo measured at 100 ° C. according to ASTM D 445 is preferably at least 30 mm 2 / s, more preferably at least 35 mm 2 / s and most preferably at least 37 mm 2 / s. Accordingly, preferred
  • Lubricants are ISO viscosity grades (ISO VISCOSITY GRADE; ISO VG) ISO 220, ISO 320, ISO 460, ISO 680 and ISO 1000.
  • the use of the polymers according to the invention is not limited to the preferred lubricants set out above, but can also be used in other applications, in particular other lubricants.
  • preferred lubricating oil compositions have a viscosity index determined in accordance with ASTM D 2270 in the range of 100 to 400, more preferably in the range of 130 to 350, and most preferably in the range of 160 to 275.
  • the present lubricating oils have a very high
  • Shear stability which can be determined inter alia by the so-called tapered roller test (KRL) according to CEC L45-T-93.
  • KRL tapered roller test
  • preferred lubricants show after 20 hours at 5000N load, an oil temperature of 60 ° C and a speed of 1475 / min a decrease in the
  • the permanent shear stability index (PSSI) according to ASTM D2603 Ref. B
  • (12.5 minutes ultrasound treatment) be less than or equal to 35, more preferably less than or equal to 20.
  • lubricating oil compositions can be obtained which have a permanent shear stability index (PSSI) according to DIN 51381 (30 cycles Bosch pump) of at most 5, preferably at most 2 and most preferably at most 1.
  • PSSI permanent shear stability index
  • the change in the volume is preferably at most 0 to + 10%, measured after 168 h and 1000 h at a
  • Specimen volume of at most -2 to + 5%, measured after 168 h and 1000 h at a temperature of 130 ° C according to DIN ISO 1817.
  • the lubricant according to the invention is preferably also very low.
  • the change in the Shore A hardness is preferably between -10 and +5 points Shore A, measured after 168 h and 1000 h at a temperature of 100 ° C. with an SRE NBR 28 / SX elastomer according to DIN ISO 1817.
  • a 72 NBR 902 or 75 FKM 585 elastomer is preferably a change in the Shore A hardness is less than or equal to ⁇ 5 points Shore A, measured after 168 h and 1000 h at a temperature of 100 ° C. according to DIN ISO 1817.
  • a change in the Shore A hardness is less than or equal to ⁇ 5 points Shore A, measured after 168 h and 1000 h at a temperature of 130 ° C according to DIN ISO 1817.
  • the elastomers preferably exhibit a relatively constant tensile-elongation behavior after an action of the lubricant according to the invention. So that takes
  • the tensile strength measured in accordance with DIN 53504 preferably decreases by a maximum of 50% after a 168 h and 1000 h exposure of the lubricant at 100 ° C. (DIN ISO 1817). at
  • Lubricant at 130 ° C (DIN ISO 1817) by a maximum of 50%.
  • the elongation at break measured according to DIN 53504, preferably decreases by at most 40% after a 168 h and 1000 h exposure of the lubricant at 100 ° C. (DIN ISO 1817), this value in particular applying to the elastomer SRE NBR 28 / SX.
  • the elongation at break is measured according to DIN 53504 after a 168 h and 1000 h exposure of the
  • Lubricant at 100 ° C (DIN ISO 1817) preferably at most 60%.
  • Elastomers also preferably takes the tensile strength measured according to DIN 53504 after a 168 h and 1000 h
  • the present lubricants exhibit excellent low temperature flowabilities. So can
  • the viscosity measured at -26 ° C. according to ASTM D2983 is preferably at most 150,000 mPas, preferably at most 100,000 mPas and particularly preferably at most 70,000 mPas.
  • pour point (PP) according to ASTM D97 preferred lubricants values less than or equal to -30 ° C, preferably less than or equal to -35 ° C and particularly preferably less than or equal to -45 ° C.
  • the present lubricants act one
  • SRV tests show a surprisingly low wear factor measured in accordance with DIN 51834-4 (load: 300N, stroke length: 1200 ym, frequency: 50 Hz, duration: 3 h).
  • preferred lubricant reach at a temperature of 60 ° C has a wear factor of preferably more than 1200 mm 3/10 6, especially at most 1100 mm 3/10 6 and more preferably 1000 mm 3/10. 6 Reach at 110 ° C preferred lubricant an abrasion factor of
  • the present lubricants preferably at most 650 mm 3/10 6, in particular at most 550 and particularly preferably 500 mm 3/10. 6 Furthermore, the present lubricants
  • the present lubricants can be used in particular as gear oil.
  • gear oil is the suitable lubricants.
  • Gear units for wind turbines may preferably contain spur gear and / or planetary gear, in particular
  • Spur gear and planetary gear with 2 planetary stages and 1 spur gear are preferred to transmit the high forces that rest on the gears.
  • Wind turbines may preferably have a power of at least 50 kW, in particular at least 300 kW and very particularly preferably at least 2300 kW, wherein the rotor torque is preferably at least 8000 Nm, in particular at least 100,000 Nm and more preferably at least 1,300,000 Nm.
  • thermometer and reflux condenser 760.0 g of a monomer mixture whose composition is set forth in Table 1, for example consisting of C12-C15 alkyl methacrylates for Example 2, together with 14.06 g dodecylmercaptan and 14.06 g tert-dodecyl mercaptan and 32.4 g of the mineral oil Nexbase 3020 presented as a solvent.
  • the temperature was set at 110 ° C.
  • 1.9 g of tert-butyl per-2-ethylhexanoate dissolved in 7.60 g Nexbase 3020 (20% strength sols.) was added in three hours, wherein within the first
  • Polydispersity index PDI of the polymers were determined by GPC. The measurements were carried out in tetrahydrofuran at 35 ° C. against a polymethyl methacrylate calibration curve from a set of> 25 standards (Polymer Standards Service or Polymer Laboratories), whose M ⁇ peak is logarhythmic
  • LMA Alkyl methacrylate containing 12 to 14 carbon atoms in the
  • Alkyl radical where the alkyl radical is a mixture with predominantly linear radicals (proportion of linear radicals about 98% by weight, proportion C12 about 73% by weight, proportion C14 about 25% by weight) Alkyl methacrylate containing about 10 C atoms in the
  • alkyl radical is a mixture with predominantly branched radicals (proportion of branched radicals about 98% by weight, proportion Cio about 89.9% by weight, content Cn about 4, 6% by weight )
  • Alkyl radical wherein the alkyl radical is a mixture with branched and linear radicals (proportion of C 1 2 branched: about 12 wt .-% and C 1 2 linear: about 11.3 wt .-%;
  • Proportion of methyl branching about 14%, proportion of ethyl branching about 10%, proportion of propyl branching about 10%, proportion of longer-chain branching, in particular butyl and higher, about 17%, based on the sum of linear and branched Residues) alkyl methacrylate containing about 13 C atoms in the
  • Alkyl radical wherein the alkyl radical is a mixture with branched and linear radicals (proportion C 13 branched: about 35.6 wt .-% and C 13 linear: about 30.7 wt .-%;
  • Proportion C15 branched about 16.9% by weight and C15 linear: about 13.9% by weight
  • the proportions of linear and branched residues were determined by GC and 13 C and 1 H NMR.
  • the 13 C spectra were carried out at 30 ° C using standard pulse sequences for the quantitative determination of 13 C signals, in particular a relaxation time of 10 s was selected and a broadband decoupling was used to suppress nuclear Overhauser effects.
  • the obtained 13 C-NMR data were processed by mathematical methods to optimize the S / N ratio (line broadening of 3 Hz).
  • the 13 C NMR signals were assigned to 2D NMR experiments, taking into account the effects of incremental chemical shifts of the 13 C signals.
  • the integrals of the following 13 C signal areas were used to calculate the isomer distribution:
  • the viscosity index VI was according to ASTM D 2270.
  • the pour point was measured according to ASTM D97.
  • the low temperature flowability at -26 ° C was determined according to ASTM D2983 (Brookfield, BF). The results obtained are shown in Table 2.
  • the Brookfield viscosity was determined from two measurements, the arithmetic mean being given.
  • a lubricant with about 51.2 wt .-% polymer according to Example 1, 2.65 wt .-% Hitec 307 and 46.15 wt .-% PAO 8 prepared and an SVR test according to DIN 51834-4
  • the lubricant had a wear factor of 987 when measured at 60 ° C with a wear diameter of 608 ym (60 ° C).
  • Wear diameter of 655 ym (110 ° C 300N 1200 ⁇ , 50Hz, 3h).
  • the friction coefficient was 0.072.
  • Running surface is about 3.5 m / s, usually three load levels are selected. Thus, the rolls are first one hour at 1.1 GPa, then one hour, casual, 4 GPa and finally two hours at 1.7 GPa

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CN102858928A (zh) 2013-01-02
RU2568435C2 (ru) 2015-11-20
KR20130081642A (ko) 2013-07-17
JP5795056B2 (ja) 2015-10-14
WO2011134695A1 (de) 2011-11-03
JP2013525552A (ja) 2013-06-20
RU2012150070A (ru) 2014-06-10
US20130229016A1 (en) 2013-09-05
SG185054A1 (en) 2012-12-28
BR112012027310A2 (pt) 2016-08-02
DE102010028195A1 (de) 2011-10-27

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