EP1740680A2 - Use of polyalkyl(meth)acrylates in lubricating oil compositions - Google Patents

Use of polyalkyl(meth)acrylates in lubricating oil compositions

Info

Publication number
EP1740680A2
EP1740680A2 EP05707597A EP05707597A EP1740680A2 EP 1740680 A2 EP1740680 A2 EP 1740680A2 EP 05707597 A EP05707597 A EP 05707597A EP 05707597 A EP05707597 A EP 05707597A EP 1740680 A2 EP1740680 A2 EP 1740680A2
Authority
EP
European Patent Office
Prior art keywords
lubricating oil
oil composition
polyalkyl
meth
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.)
Granted
Application number
EP05707597A
Other languages
German (de)
French (fr)
Other versions
EP1740680B1 (en
Inventor
Markus Scherer
Klaus Hedrich
Michael Alibert
Michael Müller
Roland Schweder
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
RohMax 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 RohMax Additives GmbH filed Critical RohMax Additives GmbH
Publication of EP1740680A2 publication Critical patent/EP1740680A2/en
Application granted granted Critical
Publication of EP1740680B1 publication Critical patent/EP1740680B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • 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
    • C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/22—Polyesters
    • 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
    • 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
    • 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
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • 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

Definitions

  • the present invention relates to the use of polyalkyl (meth) acrylates in lubricating oil compositions.
  • Air - oil heat exchangers, convection and heat radiation of the system components counteract a temperature increase at the same time.
  • the structural design of individual system components, ambient conditions, operating mode and duration affect the resulting operating temperature of the hydraulic fluid used.
  • the structural design is based on the type of device intermittent operation with appropriate downtime and the resulting liquid cooling. Similarly, assumptions must be made when estimating the ambient temperature.
  • the use of the invention allows high performance of the hydraulic systems without the temperature rising to a critical range.
  • the present use contributes to an increase in performance of these systems and a reduction in the temperature of the hydraulic fluid.
  • the use of the present invention can be carried out particularly easily and simply.
  • the present inventive use shows a high environmental compatibility.
  • polyalkyl esters are used in a lubricating oil composition.
  • Polyalkyl esters in the context of the present invention are polymers derived from olefinic esters. These polymers are known in the art and are commercially available. Particularly preferred polymers of this class can be obtained by polymerization of monomer compositions, which may in particular comprise (meth) acrylates, maleates and / or fumarates which may have different alcohol radicals.
  • (meth) acrylates include methacrylates and acrylates as well as mixtures of both. These monomers are well known.
  • the alkyl radical may be linear, cyclic or branched.
  • Preferred mixtures from which preferred polyalkyl esters are obtainable may be 0 to 50% by weight, in particular 2 to 40% by weight and more preferably 10 to 30% by weight, based on the weight of the monomer compositions for the preparation of the polyalkyl esters 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
  • Cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate
  • compositions to be polymerized for preparing preferred polyalkyl esters may contain from 50 to 100% by weight, in particular from 60 to 98% by weight and particularly preferably from 70 to 90% by weight, based on the weight of the monomer compositions for preparing the polyalkyl esters, one or more ethylenically unsaturated ester compounds of the formula (II)
  • R is hydrogen or methyl
  • R 4 is a linear or branched alkyl radical having 6 to 30 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 30 carbon atoms.
  • Cycloalkyl (meth) acrylates such as 2,4,5-tri-t-butyl-3-vinylcyclohexyl (meth) acrylate,
  • Cycloalkyl (meth) acrylates such as 3-vinylcyclohexyl (meth) acrylate,
  • the ester compounds with 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, generally a mixture of esters, such as (Meth) acrylates with different long-chain Aikohoiresten arises.
  • These fatty alcohols include Oxo Alcohol® 7911 and Oxo Alcohol® 7900, Oxo Alcohol® 1100 from Monsanto; Alphanoi® 79 from ICI; Nafol® 1620, Alibi® 610 and Alfol® 810 from Sasol; Epal® 610 and Epal® 810 from Ethyl Corporation; Linevol® 79, Linevol® 911 and Dobanol® 25L from Shell AG; Lial 125 from Sasol; Dehydad® and Lorol® grades from Cognis.
  • the mixture for the production of preferred polyalkyl esters at least 60 wt .-%, preferably at least 70 wt .-%, based on the weight of the monomer compositions for the preparation of the polyalkyl esters, monomers according to formula (II).
  • 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.
  • At least 50 wt .-%, particularly preferably at least 70 wt .-% of the radicals R 4 according to formula (II) are linear.
  • the ratio of branched to linear side chains of the radicals R 4 according to formula (II) is preferably in the range from 0.0001 to 0.3, particularly preferably in the range from 0.001 to 0.1.
  • a polyalkyl (meth) acrylate may be used wherein at least 60% by weight of the ethylenically unsaturated ester compounds of formula (II) are alkyl (meth) acrylates based on the total weight of the ethylenically unsaturated Ester compounds of the formula (II).
  • the proportion of (meth) acrylates having 6 to 15 carbon atoms in the alcohol moiety is in the range of 20 to 95 wt .-%, based on the weight of the monomer composition for the preparation of the polyalkyl esters.
  • the proportion of (meth) acrylates having 16 to 30 carbon atoms in the alcohol residue is preferably in the range of 0.5 to 60 wt .-%, based on the weight of the monomer composition for the preparation of the polyalkyl esters.
  • the proportion of olefinically unsaturated esters having 8 to 14 carbon atoms is preferably greater than or equal to the proportion of olefinically unsaturated esters having 16 to 18 carbon atoms.
  • Preferred mixtures for preparing preferred polyalkyl esters may further include, in particular, ethylenically unsaturated monomers which can be copolymerized with the ethylenically unsaturated ester compounds of formulas (I) and / or (II).
  • the proportion of comonomers is preferably in the range from 0 to 50 wt .-%, in particular 2 to 40 wt .-% and particularly preferably 5 to 30 wt .-%, based on the weight of the monomer compositions for the preparation of the polyalkyl esters.
  • comonomers for the polymerization according to the present invention are particularly suitable, which correspond to the formula:
  • R and R 2 * are independently selected from the group consisting of hydrogen, halogens, CN, linear or branched alkyl groups having 1 to 20, preferably 1 to 6 and particularly preferably 1 to 4 carbon atoms, which have 1 to (2n + 1)
  • 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 the formula
  • Vinyl esters such as vinyl acetate
  • Styrene substituted styrenes having an alkyl substituent in the side chain, such as.
  • alkyl substituent in the side chain such as.
  • ⁇ -methylstyrene and ⁇ -ethylstyrene substituted styrenes with a
  • Alkyl substituents on the ring such as vinyltoluene and p-methylstyrene, halogenated
  • Styrenes such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and
  • Heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl
  • N-vinylpyrrolidine 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam,
  • Maleic acid and maleic acid derivatives such as maleic anhydride, Methylmaleic anhydride, maleimide, methylmaleimide; Fumaric acid and fumaric acid derivatives; Acrylic acid and (meth) acrylic acid; Dienes such as divinylbenzene.
  • compositions for preparing preferred polyalkyl esters comprise monomers which can be represented by the formula (III)
  • R is independently hydrogen or methyl
  • R 7 is independently a 2 to 1000 carbon group. with at least one heteroatom
  • X independently a sulfur or oxygen atom or a group of the formula NR 11 , wherein R 11 is independently hydrogen or a group having 1 to 20 carbon atoms and n is an integer greater than or equal to 3.
  • the radical R 7 represents a group comprising 2 to 1000, in particular 2 to 100, preferably 2 to 20 carbon atoms.
  • the term "2 to 1000 carbon group” denotes radicals of organic compounds having 2 to 1000 carbon atoms. It includes aromatic and heteroaromatic groups as well as alkyl, cycloalkyl, alkoxy, cycloalkoxy, alkenyl, alkanoyl, alkoxycarbonyl and heteroaliphatic groups.
  • the groups mentioned can be branched or unbranched. Furthermore, these groups may have conventional substituents.
  • Substituents are, for example, linear and branched alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, 2-methylbutyl or hexyl; Cycloalkyl groups such as cyclopentyl and Cyciohexyl; aromatic groups, such as phenyl or naphthyl; Amino groups, ether groups, ester groups and halides.
  • aromatic groups are radicals of mononuclear or polynuclear aromatic compounds having preferably 6 to 20, in particular 6 to 12, carbon atoms.
  • Heteroaromatic groups denote aryl radicals in which at least one CH group has been replaced by N and / or at least two adjacent CH groups have been replaced by S, NH or O, heteroaromatic groups having from 3 to 19 carbon atoms.
  • Preferred aromatic or heteroaromatic groups according to the invention are derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane, diphenyldimethylmethane, bisphenone, diphenylsulfone, thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole, isoxazole, pyrazole, 1,3,4-oxadiazole , 2,5-diphenyl-1, 3,4-oxadiazole, 1, 3,4-thiadiazole, 1, 3,4-triazole, 2,5-diphenyl-1,3,4-triazole, 1, 2.5 -Triphenyl-1, 3,4-triazole, 1, 2,4-oxadiazole, 1, 2,4-thiadiazole, 1, 2,4-triazole, 1, 2,3-triazole, 1, 2,3,4 Tetrazole, benzofbjthiophene, be
  • the preferred alkyl groups include the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl, tert-butyl, pentyl, 2-methylbutyl, 1, 1 Dimethylpropyl, hexyl, heptyl, octyl, 1, 1,3,3-tetramethylbutyl, nonyl, 1-decyl, 2-decyl, undecyl, dodecyl, pentadecyl and the eicosyl group.
  • Preferred cycloalkyl groups include the cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups, optionally substituted with branched or unbranched alkyl groups.
  • Preferred alkenyl groups include the vinyl, allyl, 2-methyl-2-propylene, 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.
  • the preferred alkoxycarbonyl groups include the methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, tert-butoxycarbonyl, hexyloxycarbonyl, 2-methylhexyloxycarbonyl, decyloxycarbonyl or dodecyloxycarbonyl group.
  • the preferred alkoxy groups include alkoxy groups whose hydrocarbon radical is one of the aforementioned preferred alkyl groups.
  • 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, nitrogen, sulfur, boron, silicon and phosphorus.
  • the radical R 7 in formula (III) has at least one group of the formula -OH or -NR 8 R 8 , in which R 8 independently comprises hydrogen or a group having 1 to 20 carbon atoms.
  • the group X in formula (III) can be represented by the formula NH.
  • the number ratio of heteroatoms to carbon atoms in the radical R 7 of the formula (III) can be within wide limits. This ratio is preferably in the range from 1: 1 to 1:10, in particular from 1: 1 to 1: 5 and particularly preferably from 1: 2 to 1: 4.
  • the radical R 7 of the formula (III) comprises 2 to 1000 carbon atoms. In a particular aspect, R 7 has at most 10 carbon atoms.
  • the most preferred comonomers include, among others
  • Aryl (meth) acrylates such as benzyl methacrylate or
  • Phenyl methacrylate 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 preferably 1 to
  • 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,
  • Phosphorus, boron and / or silicon-containing methacrylates such as
  • the ethoxylated (meth) acrylates can be obtained, for example, by transesterification of alkyl (meth) acrylates with ethoxylated alcohols, which more preferably have from 1 to 20, in particular from 2 to 8, ethoxy groups.
  • the hydrophobic radical of the ethoxylated alcohols may preferably comprise 1 to 40, in particular 4 to 22, carbon atoms, it being possible to use both linear and branched alcohol radicals.
  • the ethoxylated (meth) acrylates have an OH end group.
  • Lutensol ® A- brands especially Lutensol ® A 3 N, Lutensol ® A 4 N, N Lutensol ® A 7 and A 8 Lutensol ® N
  • ethers of the Lutensol ® TO brands especially Lutensol ® TO 2, Lutensol ® TO 3, Lutensol ® TO 5, Lutensol ® TO 6, Lutensol ® TO 65, Lutensol ® TO 69, Lutensol ® TO 7, Lutensol ® TO 79 , Lutensol ® 8 and Lutensol ® 89
  • ethers of the Lutensol ® AO brands especially Lutensol ® AO 3, Lutensol ® AO 4, Lutensol ® AO 5, Lutensol ® AO 6, Lutensol ® AO 7, Lutensol ® AO 79, Lutensol ® AO 8 and Lutensol ® ®
  • aminoalkyl (meth) acrylates and aminoalkyl (meth) acrylamides for example, N- (3-dimethylaminopropyl) methacrylamide (DMAPMAM), and hydroxyalkyl (meth) acrylates, for example, 2-hydroxyethyl methacrylate (HEMA) are particularly preferred.
  • Very particularly preferred mixtures for the preparation of the polyalkyl esters include methyl methacrylate, butyl methacrylate, lauryl methacrylate, stearyl methacrylate and / or styrene.
  • the polyalkyl ester has a specific viscosity ⁇ sp / c measured in chloroform at 25 ° C. in the range from 5 to 30 ml / g, preferably in the range from 10 to 25 ml / g, measured according to ISO 1628-6.
  • the preferred polyalkyl esters which can be obtained by polymerization of unsaturated ester compounds preferably have a polydispersity M w / M n in the range of 1.2 to 4.0. This size can be determined by gel permeation chromatography (GPC).
  • polyalkyl esters from the above-described compositions.
  • ATRP atom transfer radical polymerization
  • RAFT reversible addition fragmentation chain transfer
  • 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, ketone peroxide, tert-butyl peroctoate, methyl isobutyl ketone peroxide , Cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, part.- Butyiperoxyisopropyl carbonate, 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethyihexane, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy-3,5,5-trimethylhexanoate, di
  • chain transfer agents are oil-soluble mercaptans such as, for example, tert-dodecylmercaptan or 2-mercaptoethanol or else chain transfer agents from the class of terpenes, for example terpinolene.
  • the ATRP method is known per se. It is believed that this is a "living" radical polymerization without any limitation to the description of the mechanism.
  • a transition metal compound is reacted with a compound having a transferable atomic group.
  • the transferable atomic group is transferred to the transition metal compound, whereby the metal is oxidized.
  • This reaction forms a radical that adds to ethylenic groups.
  • the transfer of the atomic group to the transition metal compound is reversible so that the atomic group is re-transferred to the growing polymer chain, forming a controlled polymerization system. Accordingly, the structure of the polymer, the molecular weight and the molecular weight distribution can be controlled.
  • polymers according to the invention can also be obtained, for example, by RAFT methods. This process is described in detail, for example, in WO 98/01478, which is expressly referred to for purposes of the disclosure.
  • the polymerization can be carried out at atmospheric pressure, lower or higher pressure.
  • the polymerization temperature is not critical. In general, however, it is in the range of -20 ° - 200 ° C, preferably 0 ° - 130 ° C and particularly preferably 60 ° - 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.
  • 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.
  • 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.
  • mineral oils are also produced from raw materials of plant origin (eg from jojoba, rapeseed) or animal (eg claw oil) of origin. Accordingly, mineral oils, depending on the origin of different proportions of aromatic, cyclic, branched and linear hydrocarbons.
  • paraffin-based, naphthenic and aromatic fractions in crude oils or mineral oils, the terms paraffin-based fraction being longer-chain or highly branched isoalkanes and naphthenic fraction being cycloalkanes.
  • mineral oils depending on their origin and refinement, have different proportions of n-alkanes, isoalkanes with a low degree of branching, so-called monomethyl-branched paraffins, and compounds 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.
  • Liquid chromatography on silica gel shows the following constituents, wherein the percentages relate to the total weight of the mineral oil used in each case: n-alkanes having about 18 to 31 carbon atoms:
  • 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 polyalkyl ester in the lubricating oil composition is preferably in the range of 2 to 40% by weight, more preferably in the range of 4 to 20% by weight, based on the total weight of the composition.
  • a lubricating oil composition may contain other additives and additives.
  • the lubricating oil composition comprising at least one polyalkyl ester is preferably used as the hydraulic fluid.
  • the lubricating oil composition can be used in a vane pump, a gear pump, a radial piston pump or an axial piston pump.
  • the lubricating oil composition can preferably be used at a pressure of 50 to 450 bar, in particular in a pressure range of 100 to 350 bar and very particularly preferably in a pressure range of 120 to 200 bar.
  • Lubricating oil compositions comprising at least one polyalkyl ester which can be obtained by polymerization of monomer compositions consisting of
  • R is hydrogen or methyl
  • R 1 is hydrogen, 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
  • R is hydrogen or methyl
  • R 4 is a linear or branched alkyl radical having 6 to 30 carbon atoms
  • R 5 and R ⁇ are independently hydrogen or a group of the formula -COOR ", where R" is hydrogen or an alkyl group having 6 to 30 carbon atoms means
  • polyalkyl ester has a specific viscosity ⁇ sp / c of between 5 and 30 ml / g, but in particular 10 - 25 ml / g, measured in chloroform at 25 ° C.,
  • the lubricating oil composition by the addition of polyalkylester a hydraulic power P a at a temperature T-i + x, wherein Ti is greater than or equal to 20 ° C, wherein Ti is preferably in the range of 50 to 120 ° C and x is greater than or equal to 5 ° C is, wherein x is preferably in the range of 10 to 90 ° C, which is at least as large as the hydraulic line Pb of the hydraulic fluid without addition of polyalkyl esters at the temperature Ti,
  • thermo-induced degradation d (P a ) / dT of the polyalkylester lubricating oil composition is less than the temperature-induced degradation d (P b ) / dT of the lubricating oil composition without polyalkyl ester.
  • polyalkyl esters in particular of the new compounds leads to an improvement in hydraulic performance at elevated temperature, which is at least 60, preferably at least 80 ° C and most preferably at least 90 ° C.
  • the polyalkyl ester retards undesirable overheating of the lubricating oil composition at high hydraulic power.
  • the high hydraulic power is preferably at least 60%, in particular at least 70% and particularly preferably at least 80%, based on the short-term maximum power.
  • Preferred lubricating oil compositions have a viscosity measured in accordance with ASTM D 445 at 40 ° C in the range of 10 to 120 mm 2 / s, more preferably in the range of 22 to 100 mm 2 / s.
  • preferred lubricating oil compositions have a viscosity index determined in accordance with ASTM D 2270 in the range from 120 to 350, in particular from 140 to 200.
  • Rinse up Fill the storage container with 55 kg test liquid. Subsequent operation at: pump speed 750 rpm, pressure 50 bar, liquid intake temperature 80 ° C, 2 hours.
  • Heating test pump speed 1500 rpm, pressure 150 bar, cooling and heating switched off, ambient temperature 20 ° C, liquid intake temperature beginning approx. 40 ° C, end approx. 90 ° C.
  • Efficiency test pump speed 1500 1 / min, pressure beginning 50 bar, end 250 bar, in 50 bar stages, liquid intake temperature constant 80 ° C.
  • Cooling cycle pump speed 750 rpm, pressure 0 bar, liquid intake temperature start approx. 90 ° C, end approx. 40 ° C.
  • Heating test pump speed 1500 rpm, pressure 250 bar, cooling and heating switched off, ambient temperature 20 ° C, liquid intake temperature beginning approx. 40 ° C, end approx. 90 ° C.
  • Efficiency test pump speed of 1500 1 / min, pressure start 50 bar, end 250 bar, in 50 bar stages, liquid intake temperature constant 80 ° C.
  • step 6 and 9 of the test program described above were in step 6 and 9 of the test program described above. These are in each case test phases, which took place with shutdown of the cooling. Thus, the temperature increase in the pump could be determined. A lower temperature increase, which has a hydraulic fluid with an additive, is therefore a reduction in temperature compared to a hydraulic fluid without additive equate.
  • Step 6 was carried out at a pressure of 150 bar, step 9 at a pressure of 250 bar.
  • the hydraulic power can be derived directly from the current flow rate of a hydraulic pump.
  • the current flow rate could be read directly in the hydraulic circuit described above with the mentioned flow meter.
  • the hydraulic performance could be determined directly by the relationship described in the literature (see, for example, F.W. Höfer et al., Memento de Technologie Automobile, 1 Edition, p. 650, Robert Bosch GmbH, 1988):
  • the synthesis of the polymer solutions AD was carried out in each case in a mineral oil by means of conventional free-radical polymerization, as set forth, inter alia, in Ullmanns Encyclopedia of Industrial Chemistry, Sixth Edition.
  • the polymerization initiator used was tert-butyl peroctoate and the chain transfer agent dodecylmercaptan.
  • the mineral oil used as solvent was a 100 solvent neutral oil from Kuwait Petroleum. It was polymerized at a temperature of 100 ° C, nach hypottert with tert-butyl peroctoate and thereafter polymerized until the residual monomer content of the polymer solutions prepared were less than 2 wt .-%. This was usually the case after a total process time of 6h.
  • the polymers AD contained between 11 and 27 wt .-% methyl methacrylate and between 63 and 89 wt .-% of a mixture of long-chain alkyl-substituted C 12 - 1 8 methacrylates, each based on the total weight of the monomers used.
  • the specific viscosity ⁇ sp / c measured in chloroform at 25 ° C. was 17 ml / g for polymer A, 21 ml / g for polymer B, 25 ml / g for polymer C and 40 ml for polymer D /G.
  • Composition Monomer mixture 54.375 kg C12-18-alkyl methacrylate mixture 18.125 kg methyl methacrylate
  • Post-feeder step 0.126 kg of tert-butyl-per-2-ethyl-hexanoate
  • a 150 l polymerization reactor equipped with reflux condenser and stirrer is charged at room temperature with the components listed above (original). Subsequently, the template is degassed with 0.62 kg of dry ice and heated to a temperature of 100 ° C. After 5 minutes, the amount of initiator calculated for the template is added and the feed started at the same time. The entire amount of feed is metered into the reactor in 3.5 hours. Thereafter, stirring is continued for 2 hours at 100.degree. Subsequently, the product is re-fed with initiator and stirred for a further 2 hours at 100 ° C.
  • Composition Monomer mixture 62.35 kg C12-18-alkyl methacrylate mixture 10.15 kg methyl methacrylate
  • Post-feeder step 0.126 kg of tert-butyl-per-2-ethyl-hexanoate
  • the preparation is carried out as described for polymer A).
  • Composition Monomer mixture 60.9 kg C12-18-alkyl methacrylate mixture 9.1 kg methyl methacrylate
  • Post-feeder step 0.126 kg of tert-butyl-per-2-ethyl-hexanoate
  • the preparation is carried out as described for polymer A).
  • Composition Monomer mixture 54.8 kg C12-18-alkyl methacrylate mixture 8.2 kg methyl methacrylate
  • Feed 58.9 kg of monomer mixture 0.15 kg of tert-butyl-per-2-ethyl-hexanoate 0.12 kg of dodecylmercaptan
  • Post-feeder step 0.126 kg of tert-butyl-per-2-ethyl-hexanoate
  • the preparation is carried out as described for polymer A).
  • polymer solutions in Tab. 1 precursors dissolved in mineral oil (referred to as polymer solutions in Tab. 1) were used.
  • the polymer concentrations of the polymer solutions used were 72.5% by weight in the case of polymers A and B, 70% by weight in the case of polymer C and 63% by weight in the case of polymer D.
  • the commercially available product Oloa 4992 from Oronite was used as the D1 package for all formulations shown in Table 1.
  • the concentration of Oloa 4992 was kept constant at 0.6% by weight for all the formulations investigated.
  • the oils used were all mineral oils whose viscosity index is within a narrow range of about 100 (+/- 5).
  • the mineral oils used can be obtained commercially.
  • Esso 80 is a SN 80 oil from ExxonMobil
  • KPE100 is a SN 100 oil from Kuwait Petroleum
  • Esso 600 is an SN 600 oil from ExxonMobil.
  • the Nexbase 3020 is a hydro- treated oil from Fortum.
  • the choice of the oil or oil mixtures in the preparation of the formulations plays no role in this context, as long as oils in a tightly staked Vl- Range are used and all formulations are set to identical kinematic viscosities.
  • the choice of different oil compositions as shown in Table 1 was merely based on the kinematic viscosities measured at 40 ° C at constant values of 46 mm2 / s (+/- 10%) for ISO 46 fluids and 68 mm2 / s (+ / - 10%) for ISO 68 fluids. This was necessary because formulations with different polymer concentrations and polymers of different molecular weights were used.
  • Table 2 Hydraulic performance of different hydraulic fluids measured at different temperatures at a pressure of 150 bar
  • Examples 7 and 8 show, in comparison with Comparative Example 4, that an unexpected increase in performance can also be achieved with ISO 68 fluids (see Comparative Example 4 and Examples 7 and 8 in Table 3). This could be shown both at 150 bar and at 250 bar.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention relates to the use of polyalkyl ester for reducing the temperature in a lubricating oil composition. The polyalkyl ester has a specific viscosity eta sp/c of between 5 and 30 ml/g, measured in chloroform at 25 DEG C.

Description

Verwendung von Polyalkyl(meth)acrylaten in SchmierölzusammensetzungenUse of polyalkyl (meth) acrylates in lubricating oil compositions
Die vorliegende Erfindung betrifft die Verwendung von Polyalkyl(meth)acrylaten in Schmierölzusammensetzungen.The present invention relates to the use of polyalkyl (meth) acrylates in lubricating oil compositions.
Die Überhitzung von mobilen Hydraulikanlagen unter erschwerten Betriebsbedingungen stellt ein bekanntes Problem dar. Reibung einzelner Bauteile des Hydrauliksystems, Volumenströme mit hohem Druckabfall und die Strömungswiderstände im Leitungssystem führen zu einer Temperaturerhöhung der Hydraulikflüssigkeit.The overheating of mobile hydraulic systems under difficult operating conditions is a known problem. Friction of individual components of the hydraulic system, high pressure drop volume flows and the flow resistance in the piping lead to an increase in the temperature of the hydraulic fluid.
Luft - Ölwärmetauscher, Konvektion und Wärmeabstrahlung der Anlagenkomponenten wirken einer Temperaturerhöhung gleichzeitig entgegen. Die konstruktive Auslegung einzelner Anlagekomponenten, Umgebungsbedingungen, Betriebsart und Dauer wirken sich auf die resultierende Betriebstemperatur der eingesetzten Hydraulikflüssigkeit aus. Bei der konstruktiven Auslegung wird je nach Gerätetyp von intermittierendem Betrieb mit entsprechenden Stillstandszeiten und der resultierenden Flüssigkeitsabkühlung ausgegangen. Ebenso sind bei der Abschätzung der Umgebungstemperatur Annahmen zu treffen.Air - oil heat exchangers, convection and heat radiation of the system components counteract a temperature increase at the same time. The structural design of individual system components, ambient conditions, operating mode and duration affect the resulting operating temperature of the hydraulic fluid used. The structural design is based on the type of device intermittent operation with appropriate downtime and the resulting liquid cooling. Similarly, assumptions must be made when estimating the ambient temperature.
Weicht der Betrieb von diesen konstruktiven Annahmen ab (höherer Zeitanteil des Betriebs unter Höchstleistung und höhere Umgebungstemperatur) resultiert daraus eine stetig steigende Flüssigkeitstemperatur. Der Anstieg der Flüssigkeitstemperatur reduziert die Viskosität der Hydraulikflüssigkeit und die Funktion und Lebensdauer einzelner Anlagekomponenten, insbesondere der Hydraulikpumpen und -Motoren.If the operation deviates from these constructive assumptions (higher proportion of time of operation under maximum power and higher ambient temperature), this results in a steadily rising fluid temperature. The increase in liquid temperature reduces the viscosity of the hydraulic fluid and the function and life of individual plant components, especially the hydraulic pumps and motors.
Zum Schutz der Anlagekomponenten wird bei Erreichen einer kritischen Flüssigkeitstemperatur zunächst eine akustische oder optische Warnung ausgelöst. Bei einer weiteren Temperatursteigerung erfolgt eine Abschaltung der Anlage. Solche Ereignisse sind für die Fertigstellung von Baumaßnahmen oder vergleichbarer Termin gebundener Arbeitsabläufe schwer vorherzusehen und damit äußerst hinderlich.To protect the system components is when reaching a critical Liquid temperature initially triggered an audible or visual warning. If the temperature increases further, the system is switched off. Such events are difficult to predict for the completion of construction projects or comparable dates bound work and thus extremely cumbersome.
Einfache konstruktive Lösungen wie vergrößerte Flüssigkeitsvorratsbehälter, wirkungsvollere Kühleinrichtungen bzw. größere, bei niedrigerem Druck arbeitende Hydraulikpumpen sind jedoch ebenfalls mit Nachteilen behaftet, da hiermit Geräteabmessungen, Anlagenkosten und damit höhere Gerätepreise verbunden sind, die sich im Markt nicht durchsetzen konnten. Im Gegenteil, die historische Betrachtung von Abmessungen, Arbeitsdrücken und insbesondere Größe der Vorratsbehälter für Hydraulikflüssigkeiten zeigt, dass sich Gerätekonstruktionen zu höheren Drücken, deutlich kleineren Vorratsbehältern und mangelnden Kühlleistungen entwickeln. Zusätzlich schränken akustische Kapselungen von Motor und Hydraulikpumpe die natürliche Wärmeabfuhr an die Umgebung ein.However, simple design solutions such as enlarged fluid reservoir, more effective cooling devices or larger, working at lower pressure hydraulic pumps are also associated with disadvantages, since this equipment dimensions, system costs and thus higher equipment prices are connected, which could not prevail in the market. On the contrary, the historical consideration of dimensions, working pressures and, in particular, size of hydraulic fluid reservoirs shows that equipment designs are developing to higher pressures, much smaller reservoirs, and poor cooling performance. In addition, acoustic encapsulation of the motor and hydraulic pump limits the natural heat dissipation to the environment.
Dieses Problem wird von Gerätebetreibern und Komponentenlieferanten häufig beklagt. Typische Arbeitgeräte sind beispielsweise Bagger, Radlader, Traktoren und Sondergeräte für Landwirtschaft, Forstwirtschaft und Tagebau. In Anbetracht des Standes der Technik war es somit eine Aufgabe der vorliegenden Erfindung eine einfache Lösung für das zuvor diskutierte Problem der Überhitzung von Hydraulikanlagen anzugeben. Insbesondere sollte die Lösung ohne eine spürbare Leistungsbeeinträchtigung erzielt werden. Des Weiteren war eine Aufgabe der vorliegenden Erfindung eine Lösung zur Verfügung zu stellen, die auch bei Hydraulikanlagen eingesetzt werden kann, die sich bereits in Betrieb befinden.This problem is often lamented by device operators and component suppliers. Typical tools include excavators, wheel loaders, tractors and special equipment for agriculture, forestry and open pit mining. In view of the prior art, it was therefore an object of the present invention to provide a simple solution to the previously discussed problem of overheating hydraulic systems. In particular, the solution should be achieved without any noticeable performance degradation. Furthermore, it was an object of the present invention to provide a solution that can also be used in hydraulic systems that are already in operation.
Darüber hinaus kann es als eine Aufgabe angesehen werden eine Lösung zu finden, die besonders preisgünstig umgesetzt werden kann. Hierbei sollte insbesondere eine Umweltbelastung vermieden werden.In addition, it can be regarded as an object to find a solution that can be implemented particularly inexpensive. This should be In particular, an environmental impact can be avoided.
Gelöst werden diese sowie weitere nicht explizit genannten Aufgaben, die jedoch aus den hierin einleitend diskutierten Zusammenhängen ohne weiteres ableitbar oder erschließbar sind, durch die Verwendung von Polyalkyl(meth)acrylaten mit allen Merkmalen des Patentanspruchs 1. Zweckmäßige Abwandlungen der erfindungsgemäßen Verwendung werden in den auf Anspruch 1 rückbezogenen Unteransprüchen unter Schutz gestellt. Hinsichtlich besonderer Schmierölzusammensetzungen liefert der Anspruch 14 eine Lösung der zugrundeliegenden Aufgabe.These and other objects which are not explicitly mentioned, but which can be readily deduced or deduced from the contexts discussed hereinbelow, are achieved by the use of polyalkyl (meth) acrylates having all the features of claim 1. Advantageous modifications of the use according to the invention are disclosed in US Pat Claim 1 related back claims protected. With regard to particular lubricating oil compositions, claim 14 provides a solution to the underlying problem.
Durch die Verwendung von Polyalkyl(meth)acrylaten zur Verminderung der Temperatur in einer Schmierölzusammensetzung, gelingt es auf nicht ohne Weiteres vorhersehbare Weise Hydraulikflüssigkeiten zur Verfügung zu stellen, mit denen die zuvor dargestellten Problem auf einfache Weise vermindert werden können.The use of polyalkyl (meth) acrylates to reduce the temperature in a lubricating oil composition makes it possible to provide hydraulic fluids which can not be foreseen in a readily foreseeable manner, with which the problems described above can be reduced in a simple manner.
Zugleich lassen sich durch die erfindungsgemäße Verwendung eine Reihe weiterer Vorteile erzielen. Hierzu gehören unter anderem:At the same time can be achieved by the inventive use a number of other benefits. These include:
> Die erfindungsgemäße Verwendung kann in bereits hergestellten Hydraulikanlagen eingesetzt werden.> The use according to the invention can be used in already produced hydraulic systems.
> Die erfindungsgemäße Verwendung verhindert eine Überhitzung von Hydraulikanlagen.> The use according to the invention prevents overheating of hydraulic systems.
> Die erfindungsgemäße Verwendung erlaubt eine hohe Leistung der Hydraulikanlagen, ohne dass die Temperatur in einen kritischen Bereich steigt. Somit trägt die vorliegende Verwendung zu einer Leistungssteigerung dieser Anlagen und einer Senkung der Temperatur der Hydraulikflüssigkeit bei. > Die Verwendung der vorliegenden Erfindung kann besonders leicht und einfach durchgeführt werden.> The use of the invention allows high performance of the hydraulic systems without the temperature rising to a critical range. Thus, the present use contributes to an increase in performance of these systems and a reduction in the temperature of the hydraulic fluid. The use of the present invention can be carried out particularly easily and simply.
> Die vorliegende erfindungsgemäße Verwendung zeigt eine hohe Umweltverträglichkeit.The present inventive use shows a high environmental compatibility.
Erfindungsgemäß werden Polyalkylester in einer Schmierölzusammensetzung verwendet.According to the invention, polyalkyl esters are used in a lubricating oil composition.
Polyalkylester sind im Rahmen der vorliegenden Erfindung Polymere, die von olefinischen Estern abgeleitet sind. Diese Polymere sind in der Fachwelt bekannt und kommerziell erhältlich. Besonders bevorzugte Polymere dieser Klasse können durch Polymerisation von Monomerenzusammensetzungen erhalten werden, die insbesondere (Meth)acrylate, Maleate und/oder Fumarate aufweisen können, die unterschiedliche Alkoholreste aufweisen können.Polyalkyl esters in the context of the present invention are polymers derived from olefinic esters. These polymers are known in the art and are commercially available. Particularly preferred polymers of this class can be obtained by polymerization of monomer compositions, which may in particular comprise (meth) acrylates, maleates and / or fumarates which may have different alcohol radicals.
Der Ausdruck (Meth)acrylate umfaßt Methacrylate und Acrylate sowie Mischungen aus beiden. Diese Monomere sind weithin bekannt. Hierbei kann derAlkylrest linear, cyclisch oder verzweigt sein.The term (meth) acrylates include methacrylates and acrylates as well as mixtures of both. These monomers are well known. Here, the alkyl radical may be linear, cyclic or branched.
Bevorzugte Mischungen, aus denen bevorzugte Polyalkylester erhältlich sind, können 0 bis 50 Gew.-%, insbesondere 2 bis 40 Gew.-% und besonders bevorzugt 10 bis 30 Gew.-%, bezogen auf das Gewicht der Monomerenzusammensetzungen zur Herstellung der Polyalkylester, einer oder mehreren ethylenisch ungesättigten Esterverbindungen der Formel (I) enthaltenPreferred mixtures from which preferred polyalkyl esters are obtainable may be 0 to 50% by weight, in particular 2 to 40% by weight and more preferably 10 to 30% by weight, based on the weight of the monomer compositions for the preparation of the polyalkyl esters or more ethylenically unsaturated ester compounds of the formula (I)
worin R Wasserstoff oder Methyl darstellt, R1 einen linearen oder verzweigten Alkylrest mit 1 bis 5 Kohlenstoffatomen bedeutet, R2 und R3 unabhängig Wasserstoff oder eine Gruppe der Formel -COOR' darstellen, worin R' Wasserstoff oder eine Alkylgruppe mit 1 bis 5 Kohlenstoffatomen bedeutet. wherein 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.
Beispiele für Komponente a) sind unter anderemExamples of component a) include
(Meth)acrylate, Fumarate und Maleate, die sich von gesättigten Alkoholen ableiten, wie Methyl(meth)acrylat, Ethyl(meth)acrylat, n-Propyl(meth)acrylat, iso-Propyl(meth)acrylat, n-Butyl(meth)acrylat, tert-Butyi(meth)acrylat und(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)acrylat;Pentyl (meth) acrylate;
Cycloalkyl(meth)acrylate, wie Cyclopentyl(meth)acrylat;Cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate;
(Meth)acrylate, die sich von ungesättigten Alkoholen ableiten, wie 2-(Meth) acrylates derived from unsaturated alcohols, such as
Propinyl(meth)acrylat, Allyl(meth)acrylat und Vinyl(meth)acrylat.Propynyl (meth) acrylate, allyl (meth) acrylate and vinyl (meth) acrylate.
Als weiteren Bestandteil können die zur Herstellung bevorzugter Polyalkylester zu polymerisierenden Zusammensetzungen 50 bis 100 Gew.-%, insbesondere 60 bis 98 Gew.-% und besonders bevorzugt 70 bis 90 Gew.-%, bezogen auf das Gewicht der Monomerenzusammensetzungen zur Herstellung der Polyalkylester, einer oder mehreren ethylenisch ungesättigten Esterverbindungen der Formel (II)As a further constituent, the compositions to be polymerized for preparing preferred polyalkyl esters may contain from 50 to 100% by weight, in particular from 60 to 98% by weight and particularly preferably from 70 to 90% by weight, based on the weight of the monomer compositions for preparing the polyalkyl esters, one or more ethylenically unsaturated ester compounds of the formula (II)
worin R Wasserstoff oder Methyl darstellt, R4 einen linearen oder verzweigten Alkylrest mit 6 bis 30 Kohlenstoffatomen bedeutet, R5 und R6 unabhängig Wasserstoff oder eine Gruppe der Formel -COOR" darstellen, worin R" Wasserstoff oder eine Alkylgruppe mit 6 bis 30 Kohlenstoffatomen bedeutet, enthalten.wherein R is hydrogen or methyl, R 4 is a linear or branched alkyl radical having 6 to 30 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 30 carbon atoms.
Zu diesen gehören unter anderemThese include, among others
(Meth)acrylate, Fumarate und Maleate, die sich von gesättigten Alkoholen ableiten, wie Hexyl(meth)acrylat, 2-Ethylhexyl(meth)acrylat,(Meth) acrylates, fumarates and maleates derived from saturated alcohols, such as hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
Heptyl(meth)acrylat, 2-tert.-Butylheptyl(meth)acrylat, Octyl(meth)acrylat, 3-iso-Heptyl (meth) acrylate, 2-tert-butylheptyl (meth) acrylate, octyl (meth) acrylate, 3-iso-
Propylheptyl(meth)acrylat, Nonyl(meth)acrylat, Decyl(meth)acrylat,Propylheptyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate,
Undecyl(meth)acrylat, 5-Methylundecyl(meth)acrylat, Dodecyl(meth)acrylat,Undecyl (meth) acrylate, 5-methylundecyl (meth) acrylate, dodecyl (meth) acrylate,
2-Methyldodecyl(meth)acrylat, Tridecyl(meth)acrylat,2-methyldodecyl (meth) acrylate, tridecyl (meth) acrylate,
5-Methyltridecyl(meth)acrylat, Tetradecyl(meth)acrylat, Pentadecyl(meth)acrylat,5-methyltridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate,
Hexadecyl(meth)acrylat, 2-Methylhexadecyl(meth)acrylat,Hexadecyl (meth) acrylate, 2-methylhexadecyl (meth) acrylate,
Heptadecyl(meth)acrylat, 5-iso-Propylheptadecyl(meth)acrylat,Heptadecyl (meth) acrylate, 5-iso-propylheptadecyl (meth) acrylate,
4-tert.-Butyloctadecyl(meth)acrylat, 5-Ethyloctadecyl(meth)acrylat,4-tert-butyl octadecyl (meth) acrylate, 5-ethyloctadecyl (meth) acrylate,
3-iso-Propyloctadecyl(meth)acrylat, Octadecyl(meth)acry!at,3-iso-propyloctadecyl (meth) acrylate, octadecyl (meth) acrylate,
Nonadecyl(meth)acrylat, Eicosyl(meth)acrylat, Cetyleicosyl(meth)acrylat,Nonadecyl (meth) acrylate, eicosyl (meth) acrylate, cetyleicosyl (meth) acrylate,
Stearyleicosyl(meth)acrylat, Docosyl(meth)acrylat und/oderStearyleicosyl (meth) acrylate, docosyl (meth) acrylate and / or
Eicosyltetratriacontyl(meth)acrylat;Eicosyltetratriacontyl (meth) acrylate;
Cycloalkyl(meth)acrylate, wie 2,4,5-Tri-t-butyl-3-Vinylcyclohexyl(meth)acrylat,Cycloalkyl (meth) acrylates, such as 2,4,5-tri-t-butyl-3-vinylcyclohexyl (meth) acrylate,
2,3,4,5-Tetra-t-butylcyclohexyl(meth)acrylat;2,3,4,5-tetra-t-butylcyclohexyl (meth) acrylate;
(Meth)acrylate, die sich von ungesättigten Alkoholen ableiten, wie z. B.(Meth) acrylates derived from unsaturated alcohols, such as. B.
Oleyl(meth)acrylat;Oleyl (meth) acrylate;
Cycloalkyl(meth)acrylate, wie 3-Vinylcyclohexyl(meth)acrylat,Cycloalkyl (meth) acrylates, such as 3-vinylcyclohexyl (meth) acrylate,
Cyclohexyl(meth)acrylat, Bornyl(meth)acrylat; sowie die entsprechendenCyclohexyl (meth) acrylate, bornyl (meth) acrylate; as well as the corresponding ones
Fumarate und Maleate.Fumarates and maleates.
Die Esterverbindungen mit langkettigem Alkoholrest, insbesondere die Verbindungen gemäß Komponente (b), lassen sich beispielsweise durch Umsetzen von (Meth)acrylaten, Fumaraten, Maleaten und/oder den entsprechenden Säuren mit langkettigen Fettalkoholen erhalten, wobei im allgemeinen eine Mischung von Estern, wie beispielsweise (Meth)acrylaten mit verschieden langkettigen Aikohoiresten entsteht. Zu diesen Fettalkoholen gehören unter anderem Oxo Alcohol® 7911 und Oxo Alcohol® 7900, Oxo Alcohol® 1100 von Monsanto; Alphanoi® 79 von ICI; Nafol® 1620, Alibi® 610 und Alfol® 810 von Sasol; Epal® 610 und Epal® 810 von Ethyl Corporation; Linevol® 79, Linevol® 911 und Dobanol® 25L von Shell AG; Lial 125 von Sasol; Dehydad®- und Lorol®-Typen von Cognis.The ester compounds with 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, generally a mixture of esters, such as (Meth) acrylates with different long-chain Aikohoiresten arises. These fatty alcohols include Oxo Alcohol® 7911 and Oxo Alcohol® 7900, Oxo Alcohol® 1100 from Monsanto; Alphanoi® 79 from ICI; Nafol® 1620, Alibi® 610 and Alfol® 810 from Sasol; Epal® 610 and Epal® 810 from Ethyl Corporation; Linevol® 79, Linevol® 911 and Dobanol® 25L from Shell AG; Lial 125 from Sasol; Dehydad® and Lorol® grades from Cognis.
Gemäß einem besonderen Aspekt der vorliegenden Erfindung weist die Mischung zur Herstellung bevorzugter Polyalkylester mindestens 60 Gew.-%, vorzugsweise mindestens 70 Gew.-%, bezogen auf das Gewicht der Monomerenzusammensetzungen zur Herstellung der Polyalkylester, Monomere gemäß Formel (II) auf.According to a particular aspect of the present invention, the mixture for the production of preferred polyalkyl esters at least 60 wt .-%, preferably at least 70 wt .-%, based on the weight of the monomer compositions for the preparation of the polyalkyl esters, monomers according to formula (II).
Von den ethylenisch ungesättigten Esterverbindungen sind die (Meth)acrylate gegenüber den Maleaten und Fumaraten besonders bevorzugt, d.h. R2, R3, R5 und R6 der Formeln (I) und (II) stellen in besonders bevorzugten Ausführungsformen Wasserstoff dar. Im allgemeinen sind die Methacrylaten den Acrylaten bevorzugt.Of the ethylenically unsaturated ester compounds, 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. In general the methacrylates are preferred to the acrylates.
Gemäß einer besonderen Ausführungsform der vorliegenden Erfindung sind vorzugsweise mindestens 50 Gew.-%, besonders bevorzugt mindestens 70 Gew.-% der Reste R4 gemäß Formel (II) linear.According to a particular embodiment of the present invention preferably at least 50 wt .-%, particularly preferably at least 70 wt .-% of the radicals R 4 according to formula (II) are linear.
Vorzugsweise liegt das Verhältnis von verzweigten zu den linearen Seitenketten der Reste R4 gemäß Formel (II) im Bereich von 0,0001 bis 0,3, besonders bevorzugt im Bereich von 0,001 bis 0,1.The ratio of branched to linear side chains of the radicals R 4 according to formula (II) is preferably in the range from 0.0001 to 0.3, particularly preferably in the range from 0.001 to 0.1.
Gemäß einem besonderen Aspekt der vorliegenden Erfindung kann ein Polyalkyl(meth)acrylat verwendet werden, wobei mindestens 60 Gew.-% der ethylenisch ungesättigten Esterverbindungen der Formel (II) Alkyl(meth)acrylate darstellen, bezogen auf das Gesamtgewicht der ethylenisch ungesättigten Esterverbindungen der Formel (II).According to a particular aspect of the present invention, a polyalkyl (meth) acrylate may be used wherein at least 60% by weight of the ethylenically unsaturated ester compounds of formula (II) are alkyl (meth) acrylates based on the total weight of the ethylenically unsaturated Ester compounds of the formula (II).
Gemäß einem besonderen Aspekt der vorliegenden Erfindung werden vorzugsweise Mischungen von langkettigen Alkyl(meth)acrylaten gemäß Komponente der Formel (II) eingesetzt, wobei die Mischungen mindestens ein (Meth)acrylat mit 6 bis 15 Kohlenstoffatomen im Alkoholrest sowie mindestens ein (Meth)acrylat mit 16 bis 30 Kohlenstoffatomen im Alkoholrest aufweisen. Vorzugsweise liegt der Anteil der (Meth)acrylate mit 6 bis 15 Kohlenstoffatomen im Alkoholrest im Bereich von 20 bis 95 Gew.-%, bezogen auf das Gewicht der Monomerenzusammensetzung zur Herstellung der Polyalkylester. Der Anteil der (Meth)acrylate mit 16 bis 30 Kohlenstoffatomen im Alkoholrest liegt vorzugsweise im Bereich von 0,5 bis 60 Gew.-%, bezogen auf das Gewicht der Monomerenzusammensetzung zur Herstellung der Polyalkylester.According to a particular aspect of the present invention, preference is given to using mixtures of long-chain alkyl (meth) acrylates according to the component of the formula (II), where the mixtures comprise at least one (meth) acrylate having 6 to 15 carbon atoms in the alcohol radical and at least one (meth) acrylate Have 16 to 30 carbon atoms in the alcohol radical. Preferably, the proportion of (meth) acrylates having 6 to 15 carbon atoms in the alcohol moiety is in the range of 20 to 95 wt .-%, based on the weight of the monomer composition for the preparation of the polyalkyl esters. The proportion of (meth) acrylates having 16 to 30 carbon atoms in the alcohol residue is preferably in the range of 0.5 to 60 wt .-%, based on the weight of the monomer composition for the preparation of the polyalkyl esters.
Gemäß einem weiteren Aspekt der vorliegenden Erfindung ist der Anteil an olefinisch ungesättigten Estern mit 8 bis 14 Kohlenstoffatomen vorzugsweise größer oder gleich dem Anteil an olefinisch ungesättigten Estern mit 16 bis 18 Kohlenstoffatomen.According to a further aspect of the present invention, the proportion of olefinically unsaturated esters having 8 to 14 carbon atoms is preferably greater than or equal to the proportion of olefinically unsaturated esters having 16 to 18 carbon atoms.
Bevorzugte Mischungen zur Herstellung bevorzugter Polyalkylester können des weiteren insbesondere ethylenisch ungesättigte Monomere, die sich mit den ethylenisch ungesättigten Esterverbindungen der Formeln (I) und/oder (II) copolymerisieren lassen, umfassen. Der Anteil an Comonomere liegt bevorzugt im Bereich von 0 bis 50 Gew.-%, insbesondere 2 bis 40 Gew.-% und besonders bevorzugt 5 bis 30 Gew.-%, bezogen auf das Gewicht der Monomerenzusammensetzungen zur Herstellung der Polyalkylester.Preferred mixtures for preparing preferred polyalkyl esters may further include, in particular, ethylenically unsaturated monomers which can be copolymerized with the ethylenically unsaturated ester compounds of formulas (I) and / or (II). The proportion of comonomers is preferably in the range from 0 to 50 wt .-%, in particular 2 to 40 wt .-% and particularly preferably 5 to 30 wt .-%, based on the weight of the monomer compositions for the preparation of the polyalkyl esters.
Hierbei sind Comonomere zur Polymerisation gemäß der vorliegenden Erfindung besonders geeignet, die der Formel entsprechen: Here, comonomers for the polymerization according to the present invention are particularly suitable, which correspond to the formula:
worin R und R2* unabhängig ausgewählt sind aus der Gruppe bestehend aus Wasserstoff, Halogene, CN, lineare oder verzweigte Alkylgruppen mit 1 bis 20, vorzugsweise 1 bis 6 und besonders bevorzugt 1 bis 4 Kohlenstoffatomen, welche mit 1 bis (2n+1) Halogenatomen substituiert sein können, wobei n die Zahl der Kohlenstoffatome der Alkylgruppe ist (beispielsweise CF3), α, ß- ungesättigte lineare oder verzweigte Alkenyl- oder Alkynylgruppen mit 2 bis 10, vorzugsweise von 2 bis 6 und besonders bevorzugt von 2 bis 4 Kohlenstoffatomen, welche mit 1 bis (2n-1) Halogenatomen, vorzugsweise Chlor, substituiert sein können, wobei n die Zahl der Kohlenstoffatome der Alkylgruppe, beispielsweise CH2=CCI-, ist, Cycloalkylgruppen mit 3 bis 8 Kohlenstoffatomen, welche mit 1 bis (2n-1 ) Halogenatomen, vorzugsweise Chlor, substituiert sein können, wobei n die Zahl der Kohlenstoffatome der Cycloalkylgruppe ist; Arylgruppen mit 6 bis 24 Kohlenstoffatomen, welche mit 1 bis (2n-1 ) Halogenatomen, vorzugsweise Chlor, und/oder Alkylgruppen mit 1 bis 6 Kohlenstoffatomen substituiert sein können, wobei n die Zahl der Kohlenstoffatome der Arylgruppe ist; C(=Y*)R5*, C(=Y*)NR6*R7\ Y*C(=Y*)R5\ SOR5*, S02R5\ OS02R5\ NR8*S02R5*, PR5* 2, P(=Y*)R5* 2, Y*PR5* 2, Y*P(=Y*)R5* 2, NR8* 2 welche mit einer zusätzlichen R8*-, Aryl- oder Heterocyclyl- Gruppe quaternärisiert sein kann, wobei Y* NR8*, S oder O, vorzugsweise O sein kann; R5*eine Alkylgruppe mit 1 bis 20 Kohlenstoffatomen, eine Alkylthio mit 1 bis 20 Kohlenstoffatomen, OR15 (R15 ist Wasserstoff oder ein Alkalimetall), Alkoxy von 1 bis 20 Kohlenstoffatomen, Aryloxy oder Heterocyklyloxy ist; R6* und R7* unabhängig Wasserstoff oder eine Alkylgruppe mit 1 bis 20 Kohlenstoffatomen sind, oder R6* und R7* können zusammen eine Alkylengruppe mit 2 bis 7 vorzugsweise 2 bis 5 Kohlenstoffatomen bilden, wobei sie einen 3 bis 8-gliedrigen, vorzugsweise 3 bis 6-gliedrigen Ring bilden, und R8* Wasserstoff, lineare oder verzweigte Aikyl- oder Arylgruppen mit 1 bis 20 Kohlenstoffatomen sind;in which R and R 2 * are independently selected from the group consisting of hydrogen, halogens, CN, linear or branched alkyl groups having 1 to 20, preferably 1 to 6 and particularly preferably 1 to 4 carbon atoms, which have 1 to (2n + 1) Where n is the number of carbon atoms of the alkyl group (for example CF 3 ), α, β-unsaturated linear or branched alkenyl or alkynyl groups having 2 to 10, preferably 2 to 6 and particularly preferably 2 to 4 carbon atoms which may be substituted with 1 to (2n-1) halogen atoms, preferably chlorine, where n is the number of carbon atoms of the alkyl group, for example CH 2 = CCI-, cycloalkyl groups of 3 to 8 carbon atoms, containing 1 to (2n 1) halogen atoms, preferably chlorine, may be substituted, where n is the number of carbon atoms of the cycloalkyl group; Aryl groups of 6 to 24 carbon atoms which may be substituted with 1 to (2n-1) halogen atoms, preferably chlorine, and / or alkyl groups of 1 to 6 carbon atoms, where n is the number of carbon atoms of the aryl group; C (= Y *) R 5 * , C (= Y *) NR 6 * R 7 \ Y * C (= Y *) R 5 \ SOR 5 * , S0 2 R 5 \ OS0 2 R 5 \ NR 8 * S0 2 R 5 * , PR 5 * 2 , P (= Y *) R 5 * 2 , Y * PR 5 * 2 , Y * P (= Y *) R 5 * 2 , NR 8 * 2 which with an additional R 8 * -, aryl or heterocyclyl group may be quaternized, where Y * NR 8 * , S or O, preferably O may be; R 5 * is an alkyl group having 1 to 20 carbon atoms, an alkylthio having 1 to 20 carbon atoms, OR 15 (R 15 is hydrogen or an alkali metal), alkoxy of 1 to 20 carbon atoms, aryloxy or heterocyclyloxy; R 6 * and R 7 * are independently hydrogen or an alkyl group having 1 to 20 carbon atoms, or R 6 * and R 7 * may together form an alkylene group having 2 to 7, preferably 2 to 5, carbon atoms, having a 3 to 8 membered one , preferably form 3 to 6-membered ring, and R 8 * are hydrogen, linear or branched acyl or aryl groups of 1 to 20 carbon atoms;
R3* und R4* unabhängig ausgewählt aus der Gruppe bestehend aus Wasserstoff, Halogen (vorzugsweise Fluor oder Chlor), Alkylgruppen mit 1 bis 6 Kohlenstoffatomen und COOR9*, worin R9* Wasserstoff, ein Alkalimetall oder eine Alkylgruppe mit 1 bis 40 Kohlenstoffatomen ist, sind, oder R3* und R4* können zusammen eine Gruppe der Formel (CH2)n- bilden, welche mit 1 bis 2n' Halogenatomen oder Ci bis C4 Alkylgruppen substituiert sein kann, oder der Formel C(=0)-Y*-C(=0) bilden, wobei n' von 2 bis 6, vorzugsweise 3 oder 4 ist und Y* wie zuvor definiert ist; und wobei zumindest 2 der Reste R1*, R2*, R3* und R4* Wasserstoff oder Halogen sind.R 3 * and R 4 * are independently selected from the group consisting of hydrogen, halogen (preferably fluoro or chloro), alkyl groups of 1 to 6 carbon atoms and COOR 9 * , where R 9 * is hydrogen, an alkali metal or an alkyl group of 1 to 40 Carbon atoms, or R 3 * and R 4 * may together form a group of the formula (CH 2 ) n - which may be substituted by 1 to 2n 'halogen atoms or C 1 to C 4 alkyl groups, or the formula C (= 0) -Y * -C (= 0) where n 'is from 2 to 6, preferably 3 or 4, and Y * is as previously defined; and wherein at least 2 of the radicals R 1 * , R 2 * , R 3 * and R 4 * are hydrogen or halogen.
Hierzu gehören unter anderem Vinylhalogenide, wie beispielsweise Vinylchlorid,These include, but are not limited to, vinyl halides such as vinyl chloride,
Vinylfluorid, Vinylidenchlorid und Vinylidenfluorid;Vinyl fluoride, vinylidene chloride and vinylidene fluoride;
Vinylester, wie Vinylacetat;Vinyl esters, such as vinyl acetate;
Styrol, substituierte Styrole mit einem Alkylsubstituenten in der Seitenkette, wie z. B. α-Methylstyrol und α-Ethylstyrol, substituierte Styrole mit einemStyrene, substituted styrenes having an alkyl substituent in the side chain, such as. For example, α-methylstyrene and α-ethylstyrene, substituted styrenes with a
Alkylsubstitutenten am Ring, wie Vinyltuluol und p-Methylstyrol, halogenierteAlkyl substituents on the ring, such as vinyltoluene and p-methylstyrene, halogenated
Styrole, wie beispielsweise Monochlorstyrole, Dichlorstyrole, Tribromstyrole undStyrenes such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and
Tetrabromstyrole;tetrabromostyrenes;
Heterocyclische Vinylverbindungen, wie 2-Vinylpyridin, 3-Vinylpyridin, 2-Methyl-Heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl
5-vinylpyridin, 3-Ethyl-4-vi nyl pyrid in , 2,3-Dimethyl-5-vinylpyridin, Vinylpyrimidin,5-vinylpyridine, 3-ethyl-4-viinyl pyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine,
Vinylpiperidin, 9-Vinylcarbazol, 3-Vinylcarbazol, 4-Vinylcarbazol,Vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole,
1-Vinylimidazol, 2-Methyl-1-vinylimidazol, N-Vinylpyrrolidon, 2-Vinylpyrrolidon,1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone,
N-Vinylpyrrolidin, 3-Vinylpyrrolidin, N-Vinylcaprolactam, N-Vinylbutyrolactam,N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam,
Vinyloxolan, Vinylfuran, Vinylthiophen, Vinylthiolan, Vinylthiazole und hydrierteVinyloxolane, vinylfuran, vinylthiophene, vinylthiolane, vinylthiazole and hydrogenated
Vinylthiazole, Vinyloxazole und hydrierte Vinyloxazole;Vinyl thiazoles, vinyloxazoles and hydrogenated vinyloxazoles;
Vinyl- und Isoprenylether;Vinyl and isoprenyl ethers;
Maleinsäure und Maleinsäurederivate, wie beispielsweise Maleinsäureanhydrid, Methylmaleinsäureanhydrid, Maleinimid, Methylmaieinimid; Fumarsäure und Fumarsäurederivate; Acrylsäure und (Meth)acrylsäure; Diene wie beispielsweise Divinylbenzol.Maleic acid and maleic acid derivatives, such as maleic anhydride, Methylmaleic anhydride, maleimide, methylmaleimide; Fumaric acid and fumaric acid derivatives; Acrylic acid and (meth) acrylic acid; Dienes such as divinylbenzene.
Besonders bevorzugt umfassen die Zusammensetzungen zur Herstellung bevorzugter Polyalkylester Monomere, die durch die Formel (III) darstellbar sind,Most preferably, the compositions for preparing preferred polyalkyl esters comprise monomers which can be represented by the formula (III)
worin R unabhängig Wasserstoff oder Methyl, R7 unabhängig eine 2 bis 1000 Kohlenstoffatome umfassende Gruppe. mit mindestens einem Heteroatom, X unabhängig ein Schwefel- oder Sauerstoffatom oder eine Gruppe der Formel NR11, worin R11 unabhängig Wasserstoff oder eine Gruppe mit 1 bis 20 Kohlenstoffatomen und n eine ganze Zahl größer oder gleich 3 darstellt.wherein R is independently hydrogen or methyl, R 7 is independently a 2 to 1000 carbon group. with at least one heteroatom, X independently a sulfur or oxygen atom or a group of the formula NR 11 , wherein R 11 is independently hydrogen or a group having 1 to 20 carbon atoms and n is an integer greater than or equal to 3.
Der Rest R7 stellt eine 2 bis 1000, insbesondere 2 bis 100, vorzugsweise 2 bis 20 Kohlenstoffatome umfassende Gruppe dar. Der Ausdruck "2 bis 1000 Kohlenstoff aufweisende Gruppe" kennzeichnet Reste organischer Verbindungen mit 2 bis 1000 Kohlenstoffatomen. Er umfasst aromatische und heteroaromatische Gruppen sowie Alkyl-, Cycloalkyl-, Alkoxy-, Cycloalkoxy-, Alkenyl-, Alkanoyl-, Alkoxycarbonylgruppen sowie heteroalipatische Gruppen. Dabei können die genannten Gruppen verzweigt oder nicht verzweigt sein. Des weiteren können diese Gruppen übliche Substituenten aufweisen. Substituenten sind beispielsweise lineare und verzweigte Alkylgruppen mit 1 bis 6 Kohlenstoffatome, wie beispielsweise Methyl, Ethyl, Propyl, Butyl, Pentyl, 2- Methylbutyl oder Hexyl; Cycloalkylgruppen, wie beispielsweise Cyclopentyl und Cyciohexyl; aromatische Gruppen, wie Phenyl oder Naphthyl; Aminogruppen, Ethergruppen, Estergruppen sowie Halogenide.The radical R 7 represents a group comprising 2 to 1000, in particular 2 to 100, preferably 2 to 20 carbon atoms. The term "2 to 1000 carbon group" denotes radicals of organic compounds having 2 to 1000 carbon atoms. It includes aromatic and heteroaromatic groups as well as alkyl, cycloalkyl, alkoxy, cycloalkoxy, alkenyl, alkanoyl, alkoxycarbonyl and heteroaliphatic groups. The groups mentioned can be branched or unbranched. Furthermore, these groups may have conventional substituents. Substituents are, for example, linear and branched alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, 2-methylbutyl or hexyl; Cycloalkyl groups such as cyclopentyl and Cyciohexyl; aromatic groups, such as phenyl or naphthyl; Amino groups, ether groups, ester groups and halides.
Erfindungsgemäß bezeichnen aromatische Gruppen Reste ein oder mehrkerniger aromatischer Verbindungen mit vorzugsweise 6 bis 20, insbesondere 6 bis 12 C-Atomen. Heteroaromatische Gruppen kennzeichnen Arylreste, worin mindestens eine CH-Gruppe durch N ersetzt ist und/oder mindestens zwei benachbarte CH-Gruppen durch S, NH oder O ersetzt sind, wobei heteroaromatische Gruppen 3 bis 19 Kohlenstoffatome aufweisen.According to the invention, aromatic groups are radicals of mononuclear or polynuclear aromatic compounds having preferably 6 to 20, in particular 6 to 12, carbon atoms. Heteroaromatic groups denote aryl radicals in which at least one CH group has been replaced by N and / or at least two adjacent CH groups have been replaced by S, NH or O, heteroaromatic groups having from 3 to 19 carbon atoms.
Erfindungsgemäß bevorzugte aromatische oder heteroaromatische Gruppen leiten sich von Benzol, Naphthalin, Biphenyl, Diphenylether, Diphenylmethan, Diphenyldimethylmethan, Bisphenon, Diphenylsulfon, Thiophen, Furan, Pyrrol, Thiazol, Oxazol, Imidazol, Isothiazol, Isoxazol, Pyrazol, 1 ,3,4-Oxadiazol, 2,5- Diphenyl-1 ,3,4-oxadiazol, 1 ,3,4-Thiadiazol, 1 ,3,4-Triazol, 2,5-Diphenyl-1,3,4- triazol, 1 ,2,5-Triphenyl-1 ,3,4-triazol, 1 ,2,4-Oxadiazol, 1 ,2,4-Thiadiazol, 1 ,2,4- Triazol, 1 ,2,3-Triazol, 1 ,2,3,4-Tetrazol, Benzofbjthiophen, Benzo[b]furan, Indol, Benzo[c]thiophen, Benzo[c]furan, Isoindol, Benzoxazol, Benzothiazol, Benzimidazol, Benzisoxazol, Benzisothiazol, Benzopyrazol, Benzothiadiazol, Benzotriazol, Dibenzofuran, Dibenzothiophen, Carbazol, Pyridin, Bipyridin, Pyrazin, Pyrazol, Pyrimidin, Pyridazin, 1,3,5-Triazin, 1 ,2,4-Triazin, 1 ,2,4,5- Triazin, Tetrazin, Chinolin, Isochinolin, Chinoxalin, Chinazolin, Cinnolin, 1 ,8- Naphthyridin, 1 ,5-Naphthyridin, 1 ,6-Naphthyridin, 1 ,7-Naphthyridin, Phthalazin, Pyridopyrimidin, Purin, Pteridin oder Chinolizin, 4H-Chinolizin, Diphenylether, Anthracen, Benzopyrrol, Benzooxathiadiazol, Benzooxadiazol, Benzopyridin, Benzopyrazin, Benzopyrazidin, Benzopyrimidin, Benzotriazin, Indolizin, Pyridopyridin, Imidazopyrimidin, Pyrazinopyrimidin, Carbazol, Aciridin, Phenazin, Benzochinolin, Phenoxazin, Phenothiazin, Acridizin, Benzopteridin, Phenanthrolin und Phenanthren ab, die gegebenenfalls auch substituiert sein können. Zu den bevorzugten Alkylgruppen gehören die Methyl-, Ethyl-, Propyi-, Isopropyl-, 1-Butyl-, 2-Butyl-, 2-Methylpropyl-, tert.-Butylrest, Pentyl-, 2- Methylbutyl-, 1 ,1-Dimethylpropyl-, Hexyl-, Heptyl-, Octyl-, 1 ,1,3,3- Tetramethylbutyl, Nonyl-, 1-Decyl-, 2-Decyl-, Undecyl-, Dodecyl-, Pentadecyl- und die Eicosyl-Gruppe.Preferred aromatic or heteroaromatic groups according to the invention are derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane, diphenyldimethylmethane, bisphenone, diphenylsulfone, thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole, isoxazole, pyrazole, 1,3,4-oxadiazole , 2,5-diphenyl-1, 3,4-oxadiazole, 1, 3,4-thiadiazole, 1, 3,4-triazole, 2,5-diphenyl-1,3,4-triazole, 1, 2.5 -Triphenyl-1, 3,4-triazole, 1, 2,4-oxadiazole, 1, 2,4-thiadiazole, 1, 2,4-triazole, 1, 2,3-triazole, 1, 2,3,4 Tetrazole, benzofbjthiophene, benzo [b] furan, indole, benzo [c] thiophene, benzo [c] furan, isoindole, benzoxazole, benzothiazole, benzimidazole, benzisoxazole, benzisothiazole, benzopyrazole, benzothiadiazole, benzotriazole, dibenzofuran, dibenzothiophene, carbazole, pyridine , Bipyridine, pyrazine, pyrazole, pyrimidine, pyridazine, 1,3,5-triazine, 1, 2,4-triazine, 1, 2,4,5-triazine, tetrazine, quinoline, isoquinoline, quinoxaline, quinazoline, cinnoline, 1 , 8-Naphthyridine, 1, 5-naphthyridine, 1, 6-naphthyridine, 1, 7-Na phthyridine, phthalazine, pyridopyrimidine, purine, pteridine or quinolizine, 4H-quinolizine, diphenyl ether, anthracene, benzopyrrole, benzooxathiadiazole, benzooxadiazole, benzopyridine, benzopyrazine, benzopyrazidine, benzopyrimidine, benzotriazine, indolizine, pyridopyridine, imidazopyrimidine, pyrazinopyrimidine, carbazole, aciridine, phenazine, Benzoquinoline, phenoxazine, phenothiazine, acridizine, benzopteridine, phenanthroline and phenanthrene, which may optionally be substituted. The preferred alkyl groups include the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl, tert-butyl, pentyl, 2-methylbutyl, 1, 1 Dimethylpropyl, hexyl, heptyl, octyl, 1, 1,3,3-tetramethylbutyl, nonyl, 1-decyl, 2-decyl, undecyl, dodecyl, pentadecyl and the eicosyl group.
Zu den bevorzugten Cycloalkylgruppen gehören die Cyclopropyl-, Cyclobutyl-, Cyclopentyl-, Cyclohexyl-, Cycloheptyl- und die Cyclooctyl-Gruppe, die gegebenenfalls mit verzweigten oder nicht verzweigten Alkylgruppen substituiert sind.Preferred cycloalkyl groups include the cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups, optionally substituted with branched or unbranched alkyl groups.
Zu den bevorzugten Alkenylgruppen gehören die Vinyl-, Allyl-, 2-Methyl-2- propen-, 2-Butenyl-, 2-Pentenyl-, 2-Decenyl- und die 2-Eicosenyl-Gruppe.Preferred alkenyl groups include the vinyl, allyl, 2-methyl-2-propylene, 2-butenyl, 2-pentenyl, 2-decenyl and 2-eicosenyl groups.
Zu den bevorzugten Alkinylgruppen gehören die Ethinyl-, Propargyl-, 2-Methyl- 2- propin, 2-Butinyl-, 2-Pentinyl- und die 2-Decinyl-Gruppe.The preferred alkynyl groups include the ethynyl, propargyl, 2-methyl-2-propyne, 2-butynyl, 2-pentynyl and 2-decynyl groups.
Zu den bevorzugten Alkanoylgruppen gehören die Formyl-, Acetyl-, Propionyl-, 2-Methylpropionyl-, Butyryl-, Valeroyl-, Pivaloyl-, Hexanoyl-, Decanoyl- und die Dodecanoyl-Gruppe.Preferred alkanoyl groups include the formyl, acetyl, propionyl, 2-methylpropionyl, butyryl, valeroyl, pivaloyl, hexanoyl, decanoyl and dodecanoyl groups.
Zu den bevorzugten Alkoxycarbonylgruppen gehören die Methoxycarbonyl-, Ethoxycarbonyl-, Propoxycarbonyl-, Butoxycarbonyl-, tert.-Butoxycarbonyl- Gruppe, Hexyloxycarbonyl-, 2-Methylhexyloxycarbonyl-, Decyloxycarbonyl- oder Dodecyloxycarbonyl-Gruppe.The preferred alkoxycarbonyl groups include the methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, tert-butoxycarbonyl, hexyloxycarbonyl, 2-methylhexyloxycarbonyl, decyloxycarbonyl or dodecyloxycarbonyl group.
Zu den bevorzugten Alkoxygruppen gehören Alkoxygruppen, deren Kohlenwasserstoffrest eine der vorstehend genannten bevorzugten Alkylgruppen ist. Zu den bevorzugten Cycloalkoxygruppen gehören Cycloalkoxygruppen, deren Kohlenwasserstoffrest eine der vorstehend genannten bevorzugten Cycloalkylgruppen ist.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.
Zu den bevorzugten Heteroatomen, die im Rest R10 enthalten sind gehören unter anderem Sauerstoff, Stickstoff, Schwefel, Bor, Silicium und Phosphor.The preferred heteroatoms contained in R 10 include, among others, oxygen, nitrogen, sulfur, boron, silicon and phosphorus.
Gemäß einer besonderen Ausführungsform der vorliegenden Erfindung weist der Rest R7 in Formel (III) mindestens eine Gruppe der Formel -OH oder - NR8R8 auf, worin R8 unabhängig Wasserstoff oder eine Gruppe mit 1 bis 20 Kohlenstoffatomen umfasst.According to a particular embodiment of the present invention, the radical R 7 in formula (III) has at least one group of the formula -OH or -NR 8 R 8 , in which R 8 independently comprises hydrogen or a group having 1 to 20 carbon atoms.
Vorzugsweise ist die Gruppe X in Formel (III) durch die Formel NH darstellbar.Preferably, the group X in formula (III) can be represented by the formula NH.
Das Zahlenverhältnis von Heteroatomen zu Kohlenstoffatomen im Rest R7 der Formel (III) kann in weiten Bereichen liegen. Vorzugsweise liegt dieses Verhältnis im Bereich von 1 :1 bis 1 :10, insbesondere 1 :1 bis 1 :5 und besonders bevorzugt 1 :2 bis 1 :4.The number ratio of heteroatoms to carbon atoms in the radical R 7 of the formula (III) can be within wide limits. This ratio is preferably in the range from 1: 1 to 1:10, in particular from 1: 1 to 1: 5 and particularly preferably from 1: 2 to 1: 4.
Der Rest R7 der Formel (III) umfasst 2 bis 1000 Kohlenstoffatome. Gemäß einem besonderen Aspekt weist der Rest R7 höchstens 10 Kohlenstoffatome auf.The radical R 7 of the formula (III) comprises 2 to 1000 carbon atoms. In a particular aspect, R 7 has at most 10 carbon atoms.
Zu den besonders bevorzugten Comonomeren gehören unter anderemThe most preferred comonomers include, among others
Aryl(meth)acrylate, wie Benzylmethacrylat oderAryl (meth) acrylates, such as benzyl methacrylate or
Phenylmethacrylat, wobei die Arylreste jeweils unsubstituiert oder bis zu vierfach substituiert sein können;Phenyl methacrylate, wherein the aryl radicals may each be unsubstituted or substituted up to four times;
Methacrylate von halogenierten Alkoholen, wieMethacrylates of halogenated alcohols, such as
2,3-Dibromopropylmethacrylat,2,3-Dibromopropylmethacrylat,
4-Bromophenylmethacrylat,4-Bromophenylmethacrylat,
1 ,3-Dichloro-2-propylmethacrylat, 2-Bromoethylmethacryiat,1, 3-dichloro-2-propyl methacrylate, 2-Bromoethylmethacryiat,
2-lodoethylmethacrylat,2-lodoethylmethacrylat,
Chloromethylmethacrylat;Chloromethylmethacrylat;
Hydroxyalkyl(meth)acrylate, wieHydroxyalkyl (meth) acrylates, such as
3-Hydroxypropylmethacrylat,3-hydroxypropyl methacrylate,
3,4-Dihydroxybutylmethacrylat,3,4-dihydroxybutyl,
2-Hydroxyethylmethacrylat,2-hydroxyethyl methacrylate,
2-Hydroxypropylmethacrylat,2-hydroxypropyl methacrylate,
2,5-Dimethyl-1,6-hexandiol(meth)acrylat,2,5-dimethyl-1,6-hexanediol (meth) acrylate,
1 ,10-Decandiol(meth)acrylat; carbonylhaltige Methacrylate, wie1, 10-decanediol (meth) acrylate; carbonyl-containing methacrylates, such as
2-Carboxyethylmethacrylat,2-carboxyethyl methacrylate,
Carboxymethylmethacrylat,Carboxymethylmethacrylat,
Oxazolidinylethylmethacrylat,oxazolidinylethyl,
N-(Methacryloyloxy)formamid,N- (methacryloyloxy) formamide,
Acetonylmethacrylat,Acetonylmethacrylat,
N-Methacryloylmorpholin,N-methacryloylmorpholine,
N-Methacryloyl-2-pyrrolid inon ,N-methacryloyl-2-pyrrolidone,
N-(2-Methacryloyloxyethyl)-2-pyrrolidinon,N- (2-methacryloyloxyethyl) -2-pyrrolidinone,
N-(3-Methacryloyloxypropyl)-2-pyrrolidinon,N- (3-methacryloyloxypropyl) -2-pyrrolidinone,
N-(2-Methacryloyloxypentadecyl)-2-pyrrolidinon,N- (2-Methacryloyloxypentadecyl) -2-pyrrolidinone,
N-(3-Methacryloyloxyheptadecyl)-2-pyrrolidinon;N- (3-Methacryloyloxyheptadecyl) -2-pyrrolidinone;
Glycoldimethacrylate, wie 1,4-Butandiolmethacrylat, 2-Butoxyethylmethacrylat,Glycol dimethacrylates, such as 1,4-butanediol methacrylate, 2-butoxyethyl methacrylate,
2-Ethoxyethoxymethyl methacrylat,2-ethoxyethoxymethyl methacrylate,
2-Ethoxyethylmethacrylat;2-ethoxyethyl;
Methacrylate von Etheralkoholen, wieMethacrylates of ether alcohols, such as
Tetrahydrofurfu ryl methacrylat,Tetrahydrofurfuryl methacrylate,
Vinyloxyethoxyethylmethacrylat,Vinyloxyethoxyethylmethacrylat,
Methoxyethoxyethylmethacrylat,methoxyethoxyethyl,
1 -Butoxypropylmethacrylat, 1-Methyl-(2-vinyloxy)ethylmethacrylat,1-butoxypropyl methacrylate, 1-methyl- (2-vinyloxy) ethyl methacrylate,
Cyclohexyloxymethylmethacrylat,Cyclohexyloxymethylmethacrylat,
Methoxymethoxyethylmethacrylat,Methoxymethoxyethylmethacrylat,
Benzyloxymethylmethacrylat,Benzyloxymethylmethacrylat,
Furfurylmethacrylat,furfuryl,
2-Butoxyethylmethacrylat,2-butoxyethyl methacrylate,
2-Ethoxyethoxymethyl methacrylat,2-ethoxyethoxymethyl methacrylate,
2-Ethoxyethylmethacrylat,2-ethoxyethyl methacrylate,
Allyloxymethylmethacrylat,Allyloxymethylmethacrylat,
1 -Ethoxybutylmethacrylat,1-ethoxybutyl methacrylate,
Methoxymethylmethacrylat,methoxymethyl,
1 -Ethoxyethylmethacrylat,1-ethoxyethyl methacrylate,
Ethoxymethylmethacrylat und ethoxylierte (Meth)acrylate, die bevorzugt 1 bisEthoxymethyl methacrylate and ethoxylated (meth) acrylates, preferably 1 to
20, insbesondere 2 bis 8 Ethoxygruppen aufweisen;20, in particular 2 to 8 ethoxy groups have;
Aminoalkyl(meth)acrylate und Aminoalkyl(meth)acrylatamide, wieAminoalkyl (meth) acrylates and aminoalkyl (meth) acrylatamides, such as
N-(3-Dimethylaminopropyl)methacrylamid,N- (3-dimethylaminopropyl) methacrylamide,
Dimethylaminopropylmethacrylat,dimethylaminopropyl,
3-Diethylaminopentylmethacrylat,3-Diethylaminopentylmethacrylat,
3-Dibutylaminohexadecyl(meth)acrylat;3-Dibutylaminohexadecyl (meth) acrylate;
Nitrile der (Meth)acrylsäure und andere stickstoffhaltige Methacrylate, wieNitriles of (meth) acrylic acid and other nitrogen-containing methacrylates, such as
N-(Methacryloyloxyethyl)diisobutylketimin,N- (methacryloyloxyethyl) diisobutylketimin,
N-(Methacryloyloxyethyl)dihexadecylketimin,N- (methacryloyloxyethyl) dihexadecylketimin,
Methacryloylamidoacetonitril,methacryloylamidoacetonitrile,
2-Methacryloyloxyethylmethylcyanamid,2-Methacryloyloxyethylmethylcyanamid,
Cyanomethylmethacrylat; heterocyclische (Meth)acrylate, wie 2-(1-lmidazolyl)ethyl(meth)acrylat,cyanomethyl; heterocyclic (meth) acrylates, such as 2- (1-imidazolyl) ethyl (meth) acrylate,
2-(4-Morpholinyl)ethyl(meth)acrylat und 1 -(2-Methacryloyloxyethyl)-2-pyrrolidon;2- (4-morpholinyl) ethyl (meth) acrylate and 1- (2-methacryloyloxyethyl) -2-pyrrolidone;
Oxiranylmethacrylate, wieOxiranyl methacrylates, as
2,3-Epoxybutylmethacrylat,2,3-epoxybutyl methacrylate,
3,4-Epoxybutylmethacrylat, 10,11-Epoxyundecylmethacrylat,3,4-epoxybutyl, 10,11-epoxyundecyl methacrylate,
2,3-Epoxycyclohexylmethacrylat,2,3-epoxycyclohexyl methacrylate,
10,11-Epoxyhexadecylmethacrylat;;10,11-Epoxyhexadecylmethacrylat ;;
Glycidylmethacrylat; schwefelhaltige Methacrylate, wieglycidyl methacrylate; Sulfur-containing methacrylates, such as
Ethylsulfinylethylmethacrylat,Ethylsulfinylethylmethacrylat,
4-Thiocyanatobutylmethacrylat,4-Thiocyanatobutylmethacrylat,
Ethylsulfonylethylmethacrylat,Ethylsulfonylethylmethacrylat,
Thiocyanatomethylmethacrylat,Thiocyanatomethylmethacrylat,
Methylsulfinylmethylmethacrylat,Methylsulfinylmethylmethacrylat,
Bis(methacryloyloxyethyl)sulfid;Bis (methacryloyloxyethyl) sulfide;
Phosphor-, Bor- und/oder Silicium-haltige Methacrylate, wiePhosphorus, boron and / or silicon-containing methacrylates, such as
2-(Dimethylphosphato)propylmethacrylat,2- (Dimethylphosphato) propyl methacrylate,
2-(Ethylenphosphito)propylmethacrylat,2- (Ethylenphosphito) propyl methacrylate,
Dimethylphosphinomethylmethacrylat,Dimethylphosphinomethylmethacrylat,
Dimethylphosphonoethylmethacrylat,Dimethylphosphonoethylmethacrylat,
Diethylmethacryloylphosphonat,Diethylmethacryloylphosphonat,
Dipropylmethacryloylphosphat, 2-(Dibutylphosphono)ethylmethacrylat,Dipropylmethacryloyl phosphate, 2- (dibutylphosphono) ethyl methacrylate,
2,3-Butylenmethacryloylethylborat,2,3-Butylenmethacryloylethylborat,
Methyldiethoxymethacryloylethoxysilan,Methyldiethoxymethacryloylethoxysilan,
Diethylphosphatoethylmethacrylat.Diethylphosphatoethylmethacrylat.
Diese Monomere können einzeln oder als Mischung eingesetzt werden. Die ethoxylierten (Meth)acrylate können beispielsweise durch Umesterung von Alkyl(Meth)acrylaten mit ethoxylierten Alkoholen, die besonders bevorzugt 1 bis 20, insbesondere 2 bis 8 Ethoxygruppen aufweisen erhalten werden. Der hydrophobe Rest der ethoxylierten Alkohole kann vorzugsweise 1 bis 40, insbesondere 4 bis 22 Kohlenstoffatome umfassen, wobei sowohl lineare als auch verzweigte Alkoholreste eingesetzt werden können. Gemäß einer weiteren bevorzugten Ausführungsform weisen die ethoxylierten (Meth)acrylate eine OH- Endgruppe auf. Beispiele für käufliche Ethoxylate, welche zur Herstellung von ethoxylierten (Meth)acrylaten herangezogen werden können, sind Ether der Lutensol® A- Marken, insbesondere Lutensol® A 3 N, Lutensol® A 4 N, Lutensol® A 7 N und Lutensol® A 8 N, Ether der Lutensol® TO-Marken , insbesondere Lutensol® TO 2, Lutensol® TO 3, Lutensol® TO 5, Lutensol® TO 6, Lutensol® TO 65, Lutensol® TO 69, Lutensol® TO 7, Lutensol® TO 79, Lutensol® 8 und Lutensol® 89, Ether der Lutensol® AO-Marken, insbesondere Lutensol® AO 3, Lutensol® AO 4, Lutensol® AO 5, Lutensol® AO 6, Lutensol® AO 7, Lutensol® AO 79, Lutensol® AO 8 und Lutensol® AO 89, Ether der Lutensol® ON-Marken, insbesondere Lutensol® ON 30, Lutensol® ON 50, Lutensol® ON 60, Lutensol® ON 65, Lutensol® ON 66, Lutensol® ON 70, Lutensol® ON 79 und Lutensol® ON 80, Ether der Lutensol® XL-Marken, insbesondere Lutensol® XL 300, Lutensol® XL 400, Lutensol® XL 500, Lutensol® XL 600, Lutensol® XL 700, Lutensol® XL 800, Lutensol® XL 900 und Lutensol® XL 1000, Ether der Lutensol® AP-Marken, insbesondere Lutensol® AP 6, Lutensol® AP 7, Lutensol® AP 8, Lutensol® AP 9, Lutensol® AP 10, Lutensol® AP 14 und Lutensol® AP 20, Ether der IMBENTIN®- Marken, insbesondere der IMBENTIN®-AG-Marken, der IMBENTIN®-U-Marken, der IMBENTIN®-C-Marken, der IMBENTIN®-T-Marken, der IMBENTIN®-OA- Marken, der IMBENTIN®-POA-Marken, der IMBENTIN®-N-Marken sowie der IMBENTIN®-0-Marken sowie Ether der Marlipal®-Marken, insbesondere Marlipal® 1/7, Marlipal® 1012/6, Marlipal® 1618/1 , Marlipal® 24/20, Marlipal® 24/30, Marlipal® 24/40, Marlipal® 013/20, Marlipal® 013/30, Marlipal® 013/40, Marlipal® 025/30, Marlipal® 025/70, Marlipal® 045/30, Marlipal® 045/40, Marlipal® 045/50, Marlipal® 045/70 und Marlipal® 045/80.These monomers can be used singly or as a mixture. The ethoxylated (meth) acrylates can be obtained, for example, by transesterification of alkyl (meth) acrylates with ethoxylated alcohols, which more preferably have from 1 to 20, in particular from 2 to 8, ethoxy groups. The hydrophobic radical of the ethoxylated alcohols may preferably comprise 1 to 40, in particular 4 to 22, carbon atoms, it being possible to use both linear and branched alcohol radicals. According to a further preferred embodiment, the ethoxylated (meth) acrylates have an OH end group. Examples of commercially available ethoxylates which can be used for the preparation of acrylates of ethoxylated (meth) ethers are the Lutensol ® A- brands, especially Lutensol ® A 3 N, Lutensol ® A 4 N, N Lutensol ® A 7 and A 8 Lutensol ® N, ethers of the Lutensol ® TO brands, especially Lutensol ® TO 2, Lutensol ® TO 3, Lutensol ® TO 5, Lutensol ® TO 6, Lutensol ® TO 65, Lutensol ® TO 69, Lutensol ® TO 7, Lutensol ® TO 79 , Lutensol ® 8 and Lutensol ® 89, ethers of the Lutensol ® AO brands, especially Lutensol ® AO 3, Lutensol ® AO 4, Lutensol ® AO 5, Lutensol ® AO 6, Lutensol ® AO 7, Lutensol ® AO 79, Lutensol ® AO 8 and Lutensol ® AO 89, ethers of the Lutensol ® ON brands, especially Lutensol ® ON 30, Lutensol ® ON 50, Lutensol ® ON 60, Lutensol ® ON 65, Lutensol ® ON 66, Lutensol ® ON 70, Lutensol ® ON 79 and Lutensol ® ON 80 ethers of Lutensol ® XL brands, especially Lutensol ® XL 300, Lutensol ® XL 400, Lutensol ® XL 500, Lutensol ® XL 6 00, Lutensol ® XL 700, Lutensol ® XL 800, Lutensol ® XL 900 and Lutensol ® XL 1000 ethers of the Lutensol ® AP brands, especially Lutensol ® AP 6, Lutensol ® AP 7, Lutensol ® AP 8, Lutensol ® AP 9 , Lutensol ® AP 10, Lutensol ® AP 14 and Lutensol ® AP 20, ethers of IMBENTIN ® - brands, especially IMBENTIN -AG ® brands, the IMBENTIN ® -U-marks, the IMBENTIN -C ® brands, the IMBENTIN ® -T-brands, the IMBENTIN ® -OA-brands, the IMBENTIN ® -POA-brands, the IMBENTIN ® -N-brands as well as the IMBENTIN ® -0-brands as well as ethers of the Marlipal ® brands, in particular Marlipal ® 1 / 7, Marlipal ® 1012/6, 1618/1 Marlipal ®, Marlipal ® 24/20, Marlipal ® 24/30, Marlipal ® 24/40, Marlipal ® 013/20, 013/30 Marlipal ®, Marlipal ® 013/40, Marlipal ® 025/30, 025/70 Marlipal ®, Marlipal ® 045/30, 045/40 Marlipal ®, Marlipal ® 045/50, 045/70 and Marlipal ® Marlipal ® 045/80.
Hiervon sind Aminoalkyl(meth)acrylate und Aminoalkyl(meth)acrylamide, beispielsweise N-(3-Dimethylaminopropyl)methacrylamid (DMAPMAM), und Hydroxyalkyl(meth)acrylate, beispielsweise 2-Hydroxyethylmethacrylat (HEMA) besonders bevorzugt. Ganz besonders bevorzugte Mischungen zur Herstellung der Polyalkylester weisen Methylmethacrylat, Butylmethacrylat, Laurylmethacrylat, Stearylmethacrylat und/oder Styrol auf.Of these, aminoalkyl (meth) acrylates and aminoalkyl (meth) acrylamides, for example, N- (3-dimethylaminopropyl) methacrylamide (DMAPMAM), and hydroxyalkyl (meth) acrylates, for example, 2-hydroxyethyl methacrylate (HEMA) are particularly preferred. Very particularly preferred mixtures for the preparation of the polyalkyl esters include methyl methacrylate, butyl methacrylate, lauryl methacrylate, stearyl methacrylate and / or styrene.
Diese Komponenten können einzeln oder als Mischungen eingesetzt werden.These components can be used individually or as mixtures.
Der Polyalkylester weist eine in Chloroform bei 25°C gemessene spezifische Viskosität ηsp/c im Bereich von 5 bis 30 ml/g, vorzugsweise im Bereich von 10 bis 25 ml/g, gemessen gemäß ISO 1628-6.The polyalkyl ester has a specific viscosity η sp / c measured in chloroform at 25 ° C. in the range from 5 to 30 ml / g, preferably in the range from 10 to 25 ml / g, measured according to ISO 1628-6.
Die bevorzugten Polyalkylester, die durch Polymerisation von ungesättigten Esterverbindungen erhalten werden können, weisen vorzugsweise eine Polydispersität Mw/Mn im Bereich von 1,2 bis 4,0 auf. Diese Größe kann durch Gelpermeationschromatographie (GPC) ermittelt werden.The preferred polyalkyl esters which can be obtained by polymerization of unsaturated ester compounds preferably have a polydispersity M w / M n in the range of 1.2 to 4.0. This size can be determined by gel permeation chromatography (GPC).
Die Herstellung der Polyalkylester aus den zuvor beschriebenen Zusammensetzungen ist an sich bekannt. So können diese Polymere insbesondere durch radikalische Polymerisation, sowie verwandte Verfahren, wie beispielsweise ATRP (=Atom Transfer Radical Polymerisation) oder RAFT (=Reversible Addition Fragmentation Chain Transfer) erfolgen.The preparation of the polyalkyl esters from the above-described compositions is known per se. Thus, these polymers can be carried out in particular by radical polymerization, as well as related processes, such as ATRP (= atom transfer radical polymerization) or RAFT (= reversible addition fragmentation chain transfer).
Die übliche freie radikalische Polymerisation ist u.a. in Ullmanns's Encyclopedia of Industrial Chemistry, Sixth Edition dargelegt. Im Allgemeinen werden hierzu ein Polymerisationsinitiator sowie ein Kettenüberträger eingesetzt.The usual free radical polymerization is i.a. in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition. In general, a polymerization initiator and a chain transfer agent are used for this purpose.
Zu den verwendbaren Initiatoren gehören unter anderem die in der Fachwelt weithin bekannten Azoinitiatoren, wie AIBN und 1 ,1-Azobiscyclohexancarbonitril, sowie Peroxyverbindungen, wie Methylethylketonperoxid, Acetylacetonperoxid, Dilaurylperoxyd, tert.-Butylper-2- ethylhexanoat, Ketonperoxid, tert-Butylperoctoat, Methylisobutylketonperoxid, Cyclohexanonperoxid, Dibenzoylperoxid, tert.-Butylperoxybenzoat, teil.- Butyiperoxyisopropylcarbonat, 2,5-Bis(2-ethylhexanoyl-peroxy)-2,5- dimethyihexan, tert.-Butylperoxy-2-ethylhexanoat, tert.-Butylperoxy-3,5,5- trimethylhexanoat, Dicumylperoxid, 1 ,1-Bis(tert.-butylperoxy)cyclohexan, 1 ,1-Bis(tert.-butylperoxy)3,3,5-trimethylcyclohexan, Cumylhydroperoxid, tert.- Butylhydroperoxid, Bis(4-tert.-butylcyclohexyl)peroxydicarbonat, Mischungen von zwei oder mehr der vorgenannten Verbindungen miteinander sowie Mischungen der vorgenannten Verbindungen mit nicht genannten Verbindungen, die ebenfalls Radikale bilden können. Als Kettenüberträger eignen sich insbesondere öllösliche Mercaptane wie beispielsweise tert- Dodecylmercaptan oder 2-Mercaptoethanol oder auch Kettenüberträger aus der Klasse der Terpene, wie beispielsweise Terpinolen.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, ketone peroxide, tert-butyl peroctoate, methyl isobutyl ketone peroxide , Cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, part.- Butyiperoxyisopropyl carbonate, 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethyihexane, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy-3,5,5-trimethylhexanoate, dicumylperoxide, 1, 1-bis (tert-butylperoxy) cyclohexane, 1,1-bis (tert-butylperoxy) 3,3,5-trimethylcyclohexane, cumyl hydroperoxide, tert-butyl hydroperoxide, bis (4-tert-butylcyclohexyl) peroxydicarbonate, mixtures of two or more the aforementioned compounds with one another and mixtures of the abovementioned compounds with unspecified compounds which can also form radicals. Particularly suitable as chain transfer agents are oil-soluble mercaptans such as, for example, tert-dodecylmercaptan or 2-mercaptoethanol or else chain transfer agents from the class of terpenes, for example terpinolene.
Das ATRP-Verfahren ist an sich bekannt. Es wird angenommen, dass es sich hierbei um eine "lebende" radikalische Polymerisation handelt, ohne dass durch die Beschreibung des Mechanismus eine Beschränkung erfolgen soll. In diesen Verfahren wird eine Übergangsmetallverbindung mit einer Verbindung umgesetzt, welche eine übertragbare Atomgruppe aufweist. Hierbei wird die übertragbare Atomgruppe auf die Übergangsmetallverbindung transferiert, wodurch das Metall oxidiert wird. Bei dieser Reaktion bildet sich ein Radikal, das an ethylenische Gruppen addiert. Die Übertragung der Atomgruppe auf die Übergangsmetallverbindung ist jedoch reversibel, so dass die Atomgruppe auf die wachsende Polymerkette rückübertragen wird, wodurch ein kontrolliertes Polymerisationssystem gebildet wird. Dementsprechend kann der Aufbau des Polymers, das Molekulargewicht und die Molekulargewichtsverteilung gesteuert werden.The ATRP method is known per se. It is believed that this is a "living" radical polymerization without any limitation to the description of the mechanism. In these methods, a transition metal compound is reacted with a compound having a transferable atomic group. Here, the transferable atomic group is transferred to the transition metal compound, whereby the metal is oxidized. This reaction forms a radical that adds to ethylenic groups. However, the transfer of the atomic group to the transition metal compound is reversible so that the atomic group is re-transferred to the growing polymer chain, forming a controlled polymerization system. Accordingly, the structure of the polymer, the molecular weight and the molecular weight distribution can be controlled.
Diese Reaktionsführung wird beispielsweise von J-S. Wang, et al., J.Am.Chem.Soα, vol.117, p.5614-5615 (1995), von Matyjaszewski, Macromolecules, vol.28, p.7901 - 7910 (1995) beschrieben. Darüber hinaus offenbaren die Patentanmeldungen WO 96/30421 , WO 97/47661 , WO 97/18247, WO 98/40415 und WO 99/10387 Varianten der zuvor erläuterten ATRP.This reaction procedure is described for example by JS. Wang, et al., J. Am. Chem. Soo, vol.117, p.5614-5615 (1995), by Matyjaszewski, Macromolecules, vol.28, p.7901-7910 (1995). In addition, the patent applications WO 96/30421, WO 97/47661, WO 97/18247, WO 98/40415 and WO 99/10387 disclose variants of the previously discussed ATRP.
Des Weiteren können die erfindungsgemäßen Polymere beispielsweise auch über RAFT-Methoden erhalten werden. Dieses Verfahren ist beispielsweise in WO 98/01478 ausführlich dargestellt, worauf für Zwecke der Offenbarung ausdrücklich Bezug genommen wird.Furthermore, the polymers according to the invention can also be obtained, for example, by RAFT methods. This process is described in detail, for example, in WO 98/01478, which is expressly referred to for purposes of the disclosure.
Die Polymerisation kann bei Normaldruck, Unter- od. Überdruck durchgeführt werden. Auch die Polymerisationstemperatur ist unkritisch. Im allgemeinen liegt sie jedoch im Bereich von -20° - 200°C, vorzugsweise 0° - 130°C und besonders bevorzugt 60° - 120°C.The polymerization can be carried out at atmospheric pressure, lower or higher pressure. The polymerization temperature is not critical. In general, however, it is in the range of -20 ° - 200 ° C, preferably 0 ° - 130 ° C and particularly preferably 60 ° - 120 ° C.
Die Polymerisation kann mit oder ohne Lösungsmittel durchgeführt werden. Der Begriff des Lösungsmittels ist hierbei weit zu verstehen.The polymerization can be carried out with or without solvent. The term of the solvent is to be understood here broadly.
Vorzugsweise wird die Polymerisation in einem unpolaren Lösungsmittel durchgeführt. Hierzu gehören Kohlenwasserstofflösungsmittel, wie beispielsweise aromatische Lösungsmittel, wie Toluol, Benzol und Xylol, gesättigte Kohlenwasserstoffe, wie beispielsweise Cyclohexan, Heptan, Octan, Nonan, Decan, Dodecan, die auch verzweigt vorliegen können. Diese Lösungsmittel können einzeln sowie als Mischung verwendet werden. Besonders bevorzugte Lösungsmittel sind Mineralöle, natürliche Öle und synthetische Öle sowie Mischungen hiervon. Von diesen sind Mineralöle ganz besonders bevorzugt.Preferably, the polymerization is carried out in a nonpolar solvent. These 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. These 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.
Des Weiteren wird der Polyalkylester in einer Schmierölzusammensetzung eingesetzt. Eine Schmierölzusammensetzung umfasst mindestens ein Schmieröl.Furthermore, the polyalkyl ester is used in a lubricating oil composition. A lubricating oil composition comprises at least one lubricating oil.
Zu den Schmierölen gehören insbesondere Mineralöle, synthetische Öle und natürliche Öle. Mineralöle sind an sich bekannt und kommerziell erhältlich. Sie werden im Allgemeinen aus Erdöl oder Rohöl durch Destillation und/oder Raffination und gegebenenfalls weitere Reinigungs- und Veredelungsverfahren gewonnen, wobei unter den Begriff Mineralöl insbesondere die höhersiedenden Anteile des Roh- oder Erdöls fallen. Im Allgemeinen liegt der Siedepunkt von Mineralöl höher als 200 °C, vorzugsweise höher als 300 °C, bei 5000 Pa. Die Herstellung durch Schwelen von Schieferöl, Verkoken von Steinkohle, Destillation unter Luftabschluß von Braunkohle sowie Hydrieren von Stein- oder Braunkohle ist ebenfalls möglich. Zu einem geringen Anteil werden Mineralöle auch aus Rohstoffen pflanzlichen (z. B. aus Jojoba, Raps) od. tierischen (z. B. Klauenöl) Ursprungs hergestellt. Dementsprechend weisen Mineralöle, je nach Herkunft unterschiedliche Anteile an aromatischen, cyclischen, verzweigten und linearen Kohlenwasserstoffen auf.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 produced from raw materials of plant origin (eg from jojoba, rapeseed) or animal (eg claw oil) of origin. Accordingly, mineral oils, depending on the origin of different proportions of aromatic, cyclic, branched and linear hydrocarbons.
Im Allgemeinen unterscheidet man paraffinbasische, naphthenische und aromatische Anteile in Rohölen bzw. Mineralölen, wobei die Begriffe paraffinbasischer Anteil für längerkettig bzw. stark verzweigte iso-Alkane und naphtenischer Anteil für Cycloalkane stehen. Darüber hinaus weisen Mineralöle, je nach Herkunft und Veredelung unterschiedliche Anteile an n- Alkanen, iso-Alkanen mit einem geringen Verzweigungsgrad, sogenannte monomethylverzweigten Paraffine, und Verbindungen mit Heteroatomen, insbesondere O, N und/oder S auf, denen bedingt polare Eigenschaften zugesprochen werden. Die Zuordnung ist jedoch schwierig, da einzelne Alkanmoleküle sowohl langkettig verzweigte Gruppen als auch Cycloalkanreste und aromatische Anteile aufweisen können. Für die Zwecke der vorliegenden Erfindung kann die Zuordnung beispielsweise gemäß DIN 51 378 erfolgen. Polare Anteile können auch gemäß ASTM D 2007 bestimmt werden.In general, a distinction is made between 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. In addition, 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. For the purposes of the present invention, the assignment can be made, for example, according to DIN 51 378. Polar proportions may also be determined according to ASTM D 2007.
Der Anteil der n-Alkane beträgt in bevorzugten Mineralölen weniger als 3 Gew.-%, der Anteil der O, N und/oder S-haltigen Verbindungen weniger als 6 Gew.-%. Der Anteil der Aromaten und der monomethylverzweigten Paraffine liegt im Allgemeinen jeweils im Bereich von 0 bis 40 Gew.-%. Gemäß einem interssanten Aspekt umfaßt Mineralöl hauptsächlich naphtenische und paraffinbasische Alkane, die im allgemeinen mehr als 13, bevorzugt mehr als 18 und ganz besonders bevorzugt mehr als 20 Kohlenstoffatome aufweisen. Der Anteil dieser Verbindungen ist im allgemeinen > 60 Gew.-%, vorzugsweise > 80 Gew.-%, ohne dass hierdurch eine Beschränkung erfolgen soll. Ein bevorzugtes Mineralöl enthält 0,5 bis 30 Gew.-% aromatische Anteile, 15 bis 40 Gew.-% naphthenische Anteile, 35 bis 80 Gew.-% paraffinbasische Anteile, bis zu 3 Gew.-% n-Alkane und 0,05 bis 5 Gew.-% polare Verbindungen, jeweils bezogen auf das Gesamtgewicht des Mineralöls.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 .-%. According to an interesting aspect, 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.
Eine Analyse von besonders bevorzugten Mineralölen, die mittels herkömmlicher Verfahren, wie Harnstofftrennung undAn analysis of particularly preferred mineral oils obtained by conventional methods such as urea separation and
Flüssigkeitschromatographie an Kieselgel, erfolgte, zeigt beispielsweise folgende Bestandteile, wobei sich die Prozentangaben auf das Gesamtgewicht des jeweils eingesetzten Mineralöls beziehen: n-Alkane mit ca. 18 bis 31 C-Atome:Liquid chromatography on silica gel, for example, shows the following constituents, wherein the percentages relate to the total weight of the mineral oil used in each case: n-alkanes having about 18 to 31 carbon atoms:
0,7 - 1,0 %, gering verzweigte Alkane mit 18 bis 31 C-Atome:0.7-1.0%, low branched alkanes having 18 to 31 C atoms:
1 ,0 - 8,0 %,1, 0 - 8.0%,
Aromaten mit 14 bis 32 C-Atomen:Aromatics with 14 to 32 C atoms:
0,4 - 10,7 %,0.4-10.7%,
Iso- und Cyclo-Alkane mit 20 bis 32 C-Atomen:Iso- and cycloalkanes with 20 to 32 carbon atoms:
60,7- 82,4 %, polare Verbindungen:60.7- 82.4%, polar compounds:
0,1 - 0,8 %,0.1 - 0.8%,
Verlust:Loss:
6,9 - 19,4 %.6.9 - 19.4%.
Wertvolle Hinweise hinsichtlich der Analyse von Mineralölen sowie eine Aufzählung von Mineralölen, die eine abweichende Zusammensetzung aufweisen, findet sich beispielsweise in Ulimanns Encyclopedia of Industrial Chemistry, 5th Edition on CD-ROM, 1997, Stichwort "lubricants and related products".Valuable information regarding the analysis of mineral oils and a Enumeration of mineral oils which have a different composition can be found for example in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition on CD-ROM, 1997, keyword "lubricants and related products".
Synthetische Öle umfassen unter anderem organische Ester, beispielsweise Diester und Polyester, Polyalkylenglykole, Polyether, synthetische Kohlenwasserstoffe, insbesondere Polyolefine, von denen Polyalphaolefine (PAO) bevorzugt sind, Silikonöle und Perfluoralkylether. Sie sind meist etwas teurer als die mineralischen Öle, haben aber Vorteile hinsichtlich ihrer Leistungsfähigkeit.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.
Natürliche Öle sind tierische oder pflanzliche Öle, wie beispielsweise Klauenöle oder Jojobaöle.Natural oils are animal or vegetable oils, such as claw oils or jojoba oils.
Diese Schmieröle können auch als Mischungen eingesetzt werden und sind vielfach kommerziell erhältlich.These lubricating oils can also be used as mixtures and are often commercially available.
Die Konzentration des Polyalkylesters in der Schmierölzusammensetzung liegt vorzugsweise im Bereich von 2 bis 40 Gew.-%, besonders bevorzugt im Bereich von 4 bis 20 Gew.-%, bezogen auf das Gesamtgewicht der Zusammensetzung.The concentration of the polyalkyl ester in the lubricating oil composition is preferably in the range of 2 to 40% by weight, more preferably in the range of 4 to 20% by weight, based on the total weight of the composition.
Neben den zuvor genannten Komponenten kann eine Schmierölzusammensetzung weitere Additive und Zusatzstoffe enthalten.Besides the aforementioned components, a lubricating oil composition may contain other additives and additives.
Zu diesen Additiven gehören unter anderem Antioxidantien, Korrosionsinhibitoren, Antischaummittel, Anti-Wear-Komponenten, Farbstoffe, Farbstabilisatoren, Detergentien, Stockpunkterniedriger und/oder Dl-Additive. Die Schmierölzusammensetzung, die mindestens einen Polyalkylester umfasst, wird vorzugsweise als Hydraulikflüssigkeit eingesetzt. Besonders bevorzugt kann die Schmierölzusammensetzung in einer Flügelzellenpumpe, einer Zahnradpumpe, Radialkolbenpumpe oder einer Axialkolbenpumpe eingesetzt werden.These additives include antioxidants, corrosion inhibitors, anti-foaming agents, anti-wear components, dyes, color stabilizers, detergents, pour point depressants and / or Dl additives. The lubricating oil composition comprising at least one polyalkyl ester is preferably used as the hydraulic fluid. Particularly preferably, the lubricating oil composition can be used in a vane pump, a gear pump, a radial piston pump or an axial piston pump.
Vorzugsweise kann die Schmierölzusammensetzung bei einem Druck von 50 bis 450 bar, insbesondere in einem Druckbereich von 100 - 350 bar und ganz besonders bevorzugt in einem Druckbereich von 120 - 200 bar, eingesetzt werden.The lubricating oil composition can preferably be used at a pressure of 50 to 450 bar, in particular in a pressure range of 100 to 350 bar and very particularly preferably in a pressure range of 120 to 200 bar.
Des Weiteren betrifft die vorliegende Erfindung neueFurthermore, the present invention relates to new
Schmierölzusammensetzungen umfassend mindestens ein Polyalkylester, der durch Polymerisation von Monomerenzusammensetzungen erhalten werden kann, die ausLubricating oil compositions comprising at least one polyalkyl ester which can be obtained by polymerization of monomer compositions consisting of
a) 0 bis 50 Gew.-%, bevorzugt 2 bis 40 Gew.-% und besonders bevorzugt 10 bis 30 Gew.-%, bezogen auf das Gewicht der Monomerenzusammensetzungen zur Herstellung der Polyalkylester, einer oder mehreren ethylenisch ungesättigten Esterverbindungen der Formel (I)a) 0 to 50 wt .-%, preferably 2 to 40 wt .-% and particularly preferably 10 to 30 wt .-%, based on the weight of the monomer compositions for the preparation of the polyalkyl esters, one or more ethylenically unsaturated ester compounds of the formula (I )
worin R Wasserstoff oder Methyl darstellt, R1 Wasserstoff, einen linearen oder verzweigten Alkylrest mit 1 bis 5 Kohlenstoffatomen bedeutet, R2 und R3 unabhängig Wasserstoff oder eine Gruppe der Formel -COOR' darstellen, worin R' Wasserstoff oder eine Alkylgruppe mit 1 bis 5 Kohlenstoffatomen bedeutet,wherein R is hydrogen or methyl, R 1 is hydrogen, 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
b) 50 bis 100 Gew.-%, bevorzugt 60 bis 98 Gew.-% und besonders bevorzugt 70 bis 90 Gew.-%, bezogen auf das Gewicht der Monomerenzusammensetzungen zur Herstellung der Polyalkylester, einer oder mehreren ethylenisch ungesättigten Esterverbindungen der Formel (II)b) 50 to 100 wt .-%, preferably 60 to 98 wt .-% and particularly preferably 70 to 90 wt .-%, based on the weight of Monomer compositions for preparing the polyalkyl esters, one or more ethylenically unsaturated ester compounds of the formula (II)
worin R Wasserstoff oder Methyl darstellt, R4 einen linearen oder verzweigten Alkylrest mit 6 bis 30 Kohlenstoffatomen bedeutet, R5 und Rδ unabhängig Wasserstoff oder eine Gruppe der Formel -COOR" darstellen, worin R" Wasserstoff oder eine Alkylgruppe mit 6 bis 30 Kohlenstoffatomen bedeutet,wherein R is hydrogen or methyl, R 4 is a linear or branched alkyl radical having 6 to 30 carbon atoms, R 5 and R δ are independently hydrogen or a group of the formula -COOR ", where R" is hydrogen or an alkyl group having 6 to 30 carbon atoms means
c) 0 bis 50 Gew.-%, bevorzugt 2 bis 40 Gew.-% und besonders bevorzugt 5 bis 30 Gew.-%, bezogen auf das Gewicht der Monomerenzusammensetzungen zur Herstellung der Polyalkylester, Comonomer besteht,c) 0 to 50 wt .-%, preferably 2 to 40 wt .-% and particularly preferably 5 to 30 wt .-%, based on the weight of the monomer compositions for the preparation of the polyalkyl esters, comonomer,
wobei der Polyalkylester eine in Chloroform bei 25°C gemessene spezifische Viskosität ηsp/c zwischen 5 und 30 ml/g, insbesondere aber 10 - 25 ml/g, aufweist,wherein the polyalkyl ester has a specific viscosity η sp / c of between 5 and 30 ml / g, but in particular 10 - 25 ml / g, measured in chloroform at 25 ° C.,
wobei die Schmierölzusammensetzung durch Zusatz von Polyalkylester eine hydraulische Leistung Pa bei einer Temperatur T-i+x aufweist, wobei Ti größer oder gleich 20°C, wobei Ti vorzugsweise im Bereich von 50 bis 120°C liegt und x größer oder gleich 5°C ist, wobei x vorzugsweise im Bereich von 10 bis 90°C liegt, die mindestens so groß ist wie die hydraulischen Leitung Pb der Hydaulikflüssigkeit ohne Zusatz von Polyalkylestem bei der Temperatur Ti,wherein the lubricating oil composition by the addition of polyalkylester a hydraulic power P a at a temperature T-i + x, wherein Ti is greater than or equal to 20 ° C, wherein Ti is preferably in the range of 50 to 120 ° C and x is greater than or equal to 5 ° C is, wherein x is preferably in the range of 10 to 90 ° C, which is at least as large as the hydraulic line Pb of the hydraulic fluid without addition of polyalkyl esters at the temperature Ti,
wobei der temperaturbedingte Leistungsabfall d(Pa)/dT der Schmierölzusammensetzung mit Polyalkylester kleiner ist als der temperaturbedingte Leistungsabfall d(Pb)/dT der Schmierölzusammensetzung ohne Polyalkylester.wherein the temperature-induced degradation d (P a ) / dT of the polyalkylester lubricating oil composition is less than the temperature-induced degradation d (P b ) / dT of the lubricating oil composition without polyalkyl ester.
Die Verwendung der Polyalkylester, insbesondere der neuen Verbindungen führt zu einer Verbesserung der hydraulischen Leistung bei erhöhter Temperatur, die mindestens 60, bevorzugt mindestens 80°C und ganz besonders bevorzugt mindestens 90°C beträgt.The use of the polyalkyl esters, in particular of the new compounds leads to an improvement in hydraulic performance at elevated temperature, which is at least 60, preferably at least 80 ° C and most preferably at least 90 ° C.
Vorzugsweise verzögert der Polyalkylester eine unerwünschte Überhitzung der Schmierölzusammensetzung bei einer hohen hydraulischen Leistung. Die hohe hydraulische Leistung beträgt vorzugsweise mindestens 60%, insbesondere mindestens 70% und besonders bevorzugt mindestens 80%, bezogen auf die kurzfristige Maximalleistung.Preferably, the polyalkyl ester retards undesirable overheating of the lubricating oil composition at high hydraulic power. The high hydraulic power is preferably at least 60%, in particular at least 70% and particularly preferably at least 80%, based on the short-term maximum power.
Bevorzugte Schmierölzusammensetzungen weisen eine gemäß ASTM D 445 bei 40°C gemessenen Viskosität im Bereich von 10 bis 120 mm2/s, besonders bevorzugt im Bereich von 22 bis 100 mm2/s auf.Preferred lubricating oil compositions have a viscosity measured in accordance with ASTM D 445 at 40 ° C in the range of 10 to 120 mm 2 / s, more preferably in the range of 22 to 100 mm 2 / s.
Gemäß einem besonderen Aspekt der vorliegenden Erfindung weisen bevorzugte Schmierölzusammensetzung einen gemäß ASTM D 2270 bestimmmten Viskositätsindex im Bereich von 120 bis 350, insbesondere von 140 bis 200 auf.According to a particular aspect of the present invention, preferred lubricating oil compositions have a viscosity index determined in accordance with ASTM D 2270 in the range from 120 to 350, in particular from 140 to 200.
Nachfolgend wird die Erfindung durch Beispiele und Vergleichsbeispiele eingehender erläutert, ohne dass die Erfindung auf diese Beispiele beschränkt werden soll.In the following, the invention will be explained in more detail by means of examples and comparative examples, without the invention being restricted to these examples.
A) MessmethodenA) Measuring methods
Zur Bestimmung des Einflusses der Hydraulikflüssigkeit auf das Leistungs- / Temperaturverhalten von Hydraulikanlagen wurde ein Leistungsprüfstand für Hydraulikpumpen gewählt, um Wetter bedingte Variationen der Betriebsbedingungen auszuschließen. Folgende konstruktive Vorgaben zu Ausführung des Leistungsprüfstands wurden festgelegt:In order to determine the influence of the hydraulic fluid on the performance / temperature behavior of hydraulic systems, a hydraulic pump performance test bench was chosen to measure variations in the weather conditions To exclude operating conditions. The following constructive specifications for the design of the dynamometer were defined:
> Aufbau in einer räumlich geschlossenen Prüfstandszelle mit Temperatur und Durchsatz geregelter regelbarer Zu- und Abluft> Design in a spatially closed test cell with temperature and flow rate of regulated controllable supply and exhaust air
> Antrieb der Hydraulikpumpe mit Drehzahl geregeltem Elektromotor, Leistung 22 kW, Messeinrichtung Drehzahl und Abtriebsdrehmoment> Drive of the hydraulic pump with speed controlled electric motor, power 22 kW, measuring device speed and output torque
> Hydrauliksystem mit Flügelzellenpumpe, Druckbereich bis 270 bar> Hydraulic system with vane pump, pressure range up to 270 bar
> Wärme isolierter Vorratsbehälter für die Hydraulikflüssigkeit (HF)> Heat isolated hydraulic fluid reservoir (HF)
> Automatisierter Betrieb für verschiedene Betriebsarten> Automated operation for different operating modes
> Automatisierte Messdatenerfassung, Möglichkeit der statistischen Auswertung der Messdaten> Automated data acquisition, possibility of statistical evaluation of the measured data
Der Leistungsprüfstandsaufbau ist in Figur 1 beschrieben, die Bedeutung der darin verwendeten Nummern und Komponenten können den ersten beiden Spalten der nachfolgenden Tabelle entnommen werdenThe dynamometer design is described in Figure 1, the meaning of the numbers and components used therein can be found in the first two columns of the following table
Es wurde eine Ansaugleitung mit Wärmetauscher zum Aufheizen und Abkühlen der Hydraulikflüssigkeit eingesetzt. Es wurden sowohl Hochdruck-Feinfilter als auch Niederdruck-Feinfilter benutzt, sowie ein elektrisch angesteuertes Druckregelventil bis 270 bar.It was a suction with heat exchanger for heating and cooling of the hydraulic fluid used. Both high-pressure fine filter and low-pressure fine filter were used, as well as an electrically controlled pressure regulating valve up to 270 bar.
Zwecks Reproduzierbarkeit der generierten Ergebnisse wurde nach einem streng definierten Prüfprogramm vorgegangen.For the reproducibility of the generated results, a strictly defined test program was used.
Nach Inbetriebnahme des Prüfstands erfolgte zunächst ein eintägiger Einlauf der neuen Flügelzellenpumpe bei wechselnden Drehzahlen und Lasten. Hierzu wurde eine handelsübliche Hydraulikflüssigkeit der Klasse ISO 46 oder ISO 68 verwendet. Danach wurden alle Testflüssigkeiten folgendem Prüfprogramm unterzogen:After commissioning the test bench, a one-day intake was initially carried out the new vane pump with changing speeds and loads. For this purpose, a commercial hydraulic fluid class ISO 46 or ISO 68 was used. Thereafter, all test liquids were subjected to the following test program:
1. Konditionierung der Prüfstandszelle und aller Anlagenteile auf 20°C (über Nacht).1. Condition the test cell and all parts of the system to 20 ° C (overnight).
2. Einbau gereinigter Hoch- und Niederdruckfeinfilter (erster Satz Filter).2. Installation of cleaned high and low pressure fine filters (first set of filters).
3. Spüllauf: Füllen des Vorratsbehälters mit 55 kg Testflüssigkeit. Anschließender Betrieb bei: Pumpendrehzahl 750 1/min, Druck 50 bar, Flüssigkeit Ansaugtemperatur 80°C, 2h.3. Rinse up: Fill the storage container with 55 kg test liquid. Subsequent operation at: pump speed 750 rpm, pressure 50 bar, liquid intake temperature 80 ° C, 2 hours.
4. Ablassen der Testflüssigkeit, Ausbau der Hoch- und Niederdruckfilter.4. Drain the test fluid, remove the high and low pressure filters.
5. Einbau gereinigter Hoch- und Niederdruckfeinfilter (zweiter Satz Filter), Füllen des Vorratsbehälters mit 80 kg Testflüssigkeit.5. Install cleaned high and low pressure fine filter (second set of filters), fill reservoir with 80 kg test fluid.
6. Aufheiztest: Pumpendrehzahl 1500 1/min, Druck 150 bar, Kühlung und Heizung abgeschaltet, Umgebungstemperatur 20°C, Flüssigkeit Ansaugtemperatur Beginn ca. 40°C, Ende ca. 90°C.6. Heating test: pump speed 1500 rpm, pressure 150 bar, cooling and heating switched off, ambient temperature 20 ° C, liquid intake temperature beginning approx. 40 ° C, end approx. 90 ° C.
7. Wirkungsgradtest: Pumpendrehzahl 1500 1/min, Druck Beginn 50 bar, Ende 250 bar, in 50 bar Stufen, Flüssigkeit Ansaugtemperatur konstant 80°C.7. Efficiency test: pump speed 1500 1 / min, pressure beginning 50 bar, end 250 bar, in 50 bar stages, liquid intake temperature constant 80 ° C.
8. Abkühlzyklus: Pumpendrehzahl 750 1/min, Druck 0 bar, Flüssigkeit Ansaugtemperatur Beginn ca. 90°C, Ende ca. 40°C.8. Cooling cycle: pump speed 750 rpm, pressure 0 bar, liquid intake temperature start approx. 90 ° C, end approx. 40 ° C.
9. Aufheiztest: Pumpendrehzahl 1500 1/min, Druck 250 bar, Kühlung und Heizung abgeschaltet, Umgebungstemperatur 20°C, Flüssigkeit Ansaugtemperatur Beginn ca. 40°C, Ende ca. 90°C.9. Heating test: pump speed 1500 rpm, pressure 250 bar, cooling and heating switched off, ambient temperature 20 ° C, liquid intake temperature beginning approx. 40 ° C, end approx. 90 ° C.
10. Wirkungsgradtest Pumpendrehzahl von 1500 1/min, Druck Start 50 bar, Ende 250 bar, in 50 bar Stufen, Flüssigkeit Ansaugtemperatur konstant 80°C.10. Efficiency test pump speed of 1500 1 / min, pressure start 50 bar, end 250 bar, in 50 bar stages, liquid intake temperature constant 80 ° C.
11. Ablassen des Testflüssigkeit, Ausbau der Hoch- und Niederdruckfilter.11. Drain the test fluid, remove the high and low pressure filters.
Die der vorliegenden Erfindung zugrunde liegenden Daten wurden in Schritt 6 und 9 des oben beschriebenen Prüfprogramms vermessen. Es handelt sich jeweils um Testphasen, die unter Abschaltung der Kühlung verliefen. Somit ließ sich die Temperaturerhöhung in der Pumpe bestimmen. Eine geringere Temperaturerhöhung, die eine Hydraulikflüssigkeit mit einem Zusatzstoff aufweist, ist daher einer Verminderung der Temperatur gegenüber einer Hydraulikflüssigkeit ohne Zusatzstoff gleichzusetzen. Schritt 6 wurde bei einem Druck von 150 bar, Schritt 9 bei einem Druck von 250 bar durchgeführt.The data underlying the present invention were in step 6 and 9 of the test program described above. These are in each case test phases, which took place with shutdown of the cooling. Thus, the temperature increase in the pump could be determined. A lower temperature increase, which has a hydraulic fluid with an additive, is therefore a reduction in temperature compared to a hydraulic fluid without additive equate. Step 6 was carried out at a pressure of 150 bar, step 9 at a pressure of 250 bar.
Die hydraulische Leistung kann direkt über die aktuelle Fließrate einer Hydraulikpumpe abgeleitet werde. Allgemein gilt: Je höher die aktuelle Fließrate Qa und der damit verbundene Volumenstrom in einer Hydraulikanlage, desto höher die hydraulische Leistung. Die aktuelle Fließrate konnte im oben beschriebenen Hydraulikkreislauf mit der erwähnten Durchflussmesseinrichtung direkt abgelesen werden. Die hydraulische Leistung konnte direkt über den in der Literatur (s. beispielsweise: F. -W. Höfer et al., Memento de Technologie Automobile, lere Edition, p. 650, Robert Bosch GmbH, 1988) beschriebenen Zusammenhang bestimmt werden:The hydraulic power can be derived directly from the current flow rate of a hydraulic pump. In general, the higher the actual flow rate Qa and the associated volume flow in a hydraulic system, the higher the hydraulic power. The current flow rate could be read directly in the hydraulic circuit described above with the mentioned flow meter. The hydraulic performance could be determined directly by the relationship described in the literature (see, for example, F.W. Höfer et al., Memento de Technologie Automobile, 1 Edition, p. 650, Robert Bosch GmbH, 1988):
PH (in kW) = (Pout * Qa) / 600PH (in kW) = (Pout * Qa) / 600
wobei Pout = Druck Pumpenausgang in bar sowie Qa = aktuelle Fließrate in l/min.where Pout = pressure pump output in bar and Qa = current flow rate in l / min.
Die Tests bestanden darin, die aktuellen Fließraten in Abhängigkeit von den gemessenen Flüssigkeitstemperaturen bei einem Druck von 150 bzw. 250 bar (Pumpenausgang) zu bestimmen. Über den oben genannten Zusammenhang lässt sich direkt auf die hydraulische Leistung bei einer bestimmten Flüssigkeitstemperatur schließen. B) Herstellung von PolyalkylestemThe tests consisted of determining the actual flow rates as a function of the measured liquid temperatures at a pressure of 150 or 250 bar (pump outlet). The above relationship makes it possible to directly deduce the hydraulic performance at a given liquid temperature. B) Preparation of polyalkyl esters
Die Synthese der Polymerlösungen A-D erfolgte jeweils in einem Mineralöl mittels üblicher freier radikalischer Polymerisation wie sie u.a. in Ullmanns's Encyclopedia of Industrial Chemistry, Sixth Edition dargelegt ist. Als Polymerisationsinitiator wurde tert-Butylperoctoat sowie als Kettenüberträger Dodecylmercaptan eingesetzt. Bei dem als Lösemittel eingesetzten Mineralöl handelte es sich um ein 100 Solvent Neutral-Öl der Firma Kuwait Petroleum. Es wurde bei einer Temperatur von 100°C polymerisiert, mit tert-Butylperoctoat nachgefüttert und hiernach solange polymerisiert bis die Restmonomergehalte der hergestellten Polymerlösungen weniger als 2 Gew.-% betrugen. Dies war i.d.R. nach einer Gesamtprozessdauer von 6h der Fall. Die Polymere A-D enthielten zwischen 11 und 27 Gew.-% Methylmethacrylat sowie zwischen 63 und 89 Gew.-% einer Mischung aus langkettig alkylsubstituierten C12-18- Methacrylaten, jeweils bezogen auf das Gesamtgewicht der eingesetzten Monomere. Die in Chloroform bei 25°C gemessene spezifische Viskosität ηsp/c lag für Polymer A bei 17 ml/g, für Polymer B bei 21 ml/g, für Polymer C bei 25 ml/g sowie im Falle von Polymer D bei 40 ml/g.The synthesis of the polymer solutions AD was carried out in each case in a mineral oil by means of conventional free-radical polymerization, as set forth, inter alia, in Ullmanns Encyclopedia of Industrial Chemistry, Sixth Edition. The polymerization initiator used was tert-butyl peroctoate and the chain transfer agent dodecylmercaptan. The mineral oil used as solvent was a 100 solvent neutral oil from Kuwait Petroleum. It was polymerized at a temperature of 100 ° C, nachfüttert with tert-butyl peroctoate and thereafter polymerized until the residual monomer content of the polymer solutions prepared were less than 2 wt .-%. This was usually the case after a total process time of 6h. The polymers AD contained between 11 and 27 wt .-% methyl methacrylate and between 63 and 89 wt .-% of a mixture of long-chain alkyl-substituted C 12 - 1 8 methacrylates, each based on the total weight of the monomers used. The specific viscosity η sp / c measured in chloroform at 25 ° C. was 17 ml / g for polymer A, 21 ml / g for polymer B, 25 ml / g for polymer C and 40 ml for polymer D /G.
a) Herstellung von Polymer Aa) Preparation of polymer A
Zusammensetzung Monomermischung: 54,375 kg C12-18-Alkylmethacrylat-Mischung 18,125 kg MethylmethacrylatComposition Monomer mixture: 54.375 kg C12-18-alkyl methacrylate mixture 18.125 kg methyl methacrylate
Vorlage: 27,5 kg 100N Mineralöl 4,1 kg Monomermischung 0,01 kg DodecylmercaptanOriginal: 27.5 kg 100N mineral oil 4.1 kg monomer mixture 0.01 kg dodecylmercaptan
0,026 kg tert-Butyl-per-2-ethyl-hexanoat Zulauf: 68,4 kg Monomermischung 0,20 kg tert-Butyl-per-2-ethyl-hexanoat 0,86 kg Dodecylmercaptan0.026 kg of tert-butyl per-2-ethyl-hexanoate Feed: 68.4 kg of monomer mixture 0.20 kg of tert-butyl-per-2-ethyl-hexanoate 0.86 kg of dodecylmercaptan
Nachfütter-Schritt: 0,126 kg tert-Butyl-per-2-ethyl-hexanoatPost-feeder step: 0.126 kg of tert-butyl-per-2-ethyl-hexanoate
Prozessbeschreibung:Process description:
Ein 150 I Polymerisationsreaktor ausgestattet mit Rückflusskühler und Rührwerk wird bei Raumtemperatur mit den oben aufgeführten Komponenten (Vorlage) befüllt. Anschließend wird die Vorlage mit 0,62 kg Trockeneis entgast und auf eine Temperatur von 100°C erwärmt. Nach 5 Minuten wird die für die Vorlage berechnete Initiatormenge zugegeben und zeitgleich der Zulauf gestartet. Die gesamte Zulauf-Menge wird in 3,5 Stunden in den Reaktor dosiert. Danach wird 2 Stunden bei 100°C nachgerührt. Anschließend wird das Produkt mit Initiator nachgefüttert und für weitere 2 Stunden bei 100°C nachgerührt.A 150 l polymerization reactor equipped with reflux condenser and stirrer is charged at room temperature with the components listed above (original). Subsequently, the template is degassed with 0.62 kg of dry ice and heated to a temperature of 100 ° C. After 5 minutes, the amount of initiator calculated for the template is added and the feed started at the same time. The entire amount of feed is metered into the reactor in 3.5 hours. Thereafter, stirring is continued for 2 hours at 100.degree. Subsequently, the product is re-fed with initiator and stirred for a further 2 hours at 100 ° C.
ηs /c= 17 ml/gη s / c = 17 ml / g
b) Herstellung von Polymer Bb) Preparation of Polymer B
Zusammensetzung Monomermischung: 62,35 kg C12-18-Alkylmethacrylat-Mischung 10,15 kg MethylmethacrylatComposition Monomer mixture: 62.35 kg C12-18-alkyl methacrylate mixture 10.15 kg methyl methacrylate
Vorlage: 27,5 kg 100N Mineralöl 4,1 kg Monomermischung 0,01 kg DodecylmercaptanTemplate: 27.5 kg of 100N mineral oil 4.1 kg monomer mixture 0.01 kg dodecylmercaptan
0,026 kg tert-Butyl-per-2-ethyl-hexanoat Zulauf: 68,4 kg Monomermischung 0,19 kg tert-Butyl-per-2-ethyl-hexanoat 0,53 kg Dodecylmercaptan0.026 kg of tert-butyl-per-2-ethyl-hexanoate Feed: 68.4 kg of monomer mixture 0.19 kg of tert-butyl-per-2-ethyl-hexanoate 0.53 kg of dodecylmercaptan
Nachfütter-Schritt: 0,126 kg tert-Butyl-per-2-ethyl-hexanoatPost-feeder step: 0.126 kg of tert-butyl-per-2-ethyl-hexanoate
Prozessbeschreibung:Process description:
Die Herstellung erfolgt wie bei Polymer A) beschrieben.The preparation is carried out as described for polymer A).
ηsp/c= 21 ml/gη sp / c = 21 ml / g
c) Herstellung von Polymer Cc) Preparation of Polymer C
Zusammensetzung Monomermischung: 60,9 kg C12-18-Alkylmethacrylat-Mischung 9,1 kg MethylmethacrylatComposition Monomer mixture: 60.9 kg C12-18-alkyl methacrylate mixture 9.1 kg methyl methacrylate
Vorlage: 30,0 kg 100N Mineralöl 4,1 kg Monomermischung 0,01 kg DodecylmercaptanOriginal: 30.0 kg 100N mineral oil 4.1 kg monomer mixture 0.01 kg dodecylmercaptan
0,026 kg tert-Butyl-per-2-ethyl-hexanoat Zulauf: 65,9 kg Monomermischung 0,22 kg tert-Butyl-per-2-ethyl-hexanoat 0,27 kg Dodecylmercaptan0.026 kg of tert-butyl per-2-ethyl-hexanoate Feed: 65.9 kg of monomer mixture 0.22 kg of tert-butyl-per-2-ethyl-hexanoate 0.27 kg of dodecylmercaptan
Nachfütter-Schritt: 0,126 kg tert-Butyl-per-2-ethyl-hexanoatPost-feeder step: 0.126 kg of tert-butyl-per-2-ethyl-hexanoate
Prozessbeschreibung:Process description:
Die Herstellung erfolgt wie bei Polymer A) beschrieben.The preparation is carried out as described for polymer A).
ηSp/c= 25 ml/gη S p / c = 25 ml / g
d) Herstellung von Polymer Dd) Preparation of Polymer D
Zusammensetzung Monomermischung: 54.8 kg C12-18-Alkylmethacrylat-Mischung 8,2 kg MethylmethacrylatComposition Monomer mixture: 54.8 kg C12-18-alkyl methacrylate mixture 8.2 kg methyl methacrylate
Vorlage: 37,0 kg 100N Mineralöl 4,1 kg Monomermischung 0,01 kg DodecylmercaptanOriginal: 37.0 kg 100N mineral oil 4.1 kg monomer mixture 0.01 kg dodecylmercaptan
0,026 kg tert-Butyl-per-2-ethyl-hexanoat0.026 kg of tert-butyl per-2-ethyl-hexanoate
Zulauf: 58.9 kg Monomermischung 0,15 kg tert-Butyl-per-2-ethyl-hexanoat 0,12 kg Dodecylmercaptan Nachfütter-Schritt: 0,126 kg tert-Butyl-per-2-ethyl-hexanoatFeed: 58.9 kg of monomer mixture 0.15 kg of tert-butyl-per-2-ethyl-hexanoate 0.12 kg of dodecylmercaptan Post-feeder step: 0.126 kg of tert-butyl-per-2-ethyl-hexanoate
Prozessbeschreibung:Process description:
Die Herstellung erfolgt wie bei Polymer A) beschrieben.The preparation is carried out as described for polymer A).
ηSp/c= 40 ml/gη S p / c = 40 ml / g
C) Ausführungsbeispiele 1 bis 7 und Vergleichsbeispiele 1 bis 4C) Embodiments 1 to 7 and Comparative Examples 1 to 4
Aus den Polymeren wurden verschiedene Hydrauliköle hergestellt. Die Zusammensetzung der Hydrauliköle ist in Tabelle 1 widergegeben. Die Formulierungen wurden gemäß DIN 51524 hergestellt. Die kinematischen Viskositäten der Öle des ISO-Grades 46 lagen demnach in einem Viskositätsbereich von 46 mm2/s +/- 10% sowie die Viskositäten der Öle des ISO 68-Grades in einem Bereich von 68 mm2/s +/- 10%.From the polymers, various hydraulic oils were produced. The composition of the hydraulic oils is shown in Table 1. The formulations were prepared according to DIN 51524. Accordingly, the kinematic viscosities of ISO grade 46 oils were in a viscosity range of 46 mm 2 / s +/- 10% and the viscosities of ISO 68 grade oils in the range of 68 mm 2 / s +/- 10%.
Zur Herstellung der Formulierungen wurden in Mineralöl vorgelöste Polymere (in Tab. 1 als Polymerlösungen bezeichnet) eingesetzt. Die Polymerkonzentrationen der eingesetzten Polymerlösungen lagen bei 72,5 Gew.% im Falle der Polymere A und B, bei 70 Gew.% im Falle des Polymeren C sowie bei 63 Gew.% im Falle des Polymeren D.To prepare the formulations, precursors dissolved in mineral oil (referred to as polymer solutions in Tab. 1) were used. The polymer concentrations of the polymer solutions used were 72.5% by weight in the case of polymers A and B, 70% by weight in the case of polymer C and 63% by weight in the case of polymer D.
Als Dl-Paket wurde für alle in Tab. 1 gezeigten Formulierungen das handelsübliche Produkt Oloa 4992 der Firma Oronite eingesetzt. Die Konzentration an Oloa 4992 wurde für alle untersuchten Formulierungen mit 0,6 Gew.% konstant gehalten. Die eingesetzten Öle waren allesamt Mineralöle, deren Viskositätsindex sich in einem engen Bereich um ca. 100 (+/- 5) bewegt. Die eingesetzten Mineralöle können kommerziell erhalten werden. So stellt Esso 80 ein SN 80-ÖI der Firma ExxonMobil, KPE100 ein SN 100-ÖI der Firma Kuwait Petroleum und Esso 600 ein SN 600-ÖI der Firma ExxonMobil dar. Das Nexbase 3020 ist im Gegensatz zu den vorher genannten Ölen ein hydro-behandeltes Öl der Firma Fortum.The commercially available product Oloa 4992 from Oronite was used as the D1 package for all formulations shown in Table 1. The concentration of Oloa 4992 was kept constant at 0.6% by weight for all the formulations investigated. The oils used were all mineral oils whose viscosity index is within a narrow range of about 100 (+/- 5). The mineral oils used can be obtained commercially. For example, Esso 80 is a SN 80 oil from ExxonMobil, KPE100 is a SN 100 oil from Kuwait Petroleum and Esso 600 is an SN 600 oil from ExxonMobil. The Nexbase 3020 is a hydro- treated oil from Fortum.
Tabelle 1Table 1
Tabelle 1 (Fortsetzung) Table 1 (continued)
Die Wahl des Öles bzw. der Ölmischungen bei der Herstellung der Formulierungen (in obigen Beispiel- und Vergleichsformulierungen das Gewichtsverhältnis zwischen Esso 80, KPE 100, Esso 600 sowie Nexbase 3020) spielt in diesem Zusammenhang keine Rolle, solange Öle in einem eng abgesteckten Vl-Bereich eingesetzt werden und alle Formulierungen auf identische kinematische Viskositäten eingestellt werden. Die Wahl unterschiedlicher Ölzusammensetzungen wie in Tabelle 1 gezeigt beruhte lediglich darauf, die bei 40°C gemessenen kinematischen Viskositäten auf konstanten Werten von 46 mm2/s (+/- 10%) für ISO 46-Flüssigkeiten sowie von 68 mm2/s (+/- 10%) für ISO 68-Flüssigkeiten zu halten. Dies war notwendig, da Formulierungen mit unterschiedlichen Polymerkonzentrationen sowie Polymere unterschiedlicher Molekulargewichte eingesetzt wurden.The choice of the oil or oil mixtures in the preparation of the formulations (in the above example and comparative formulations, the weight ratio between Esso 80, KPE 100, Esso 600 and Nexbase 3020) plays no role in this context, as long as oils in a tightly staked Vl- Range are used and all formulations are set to identical kinematic viscosities. The choice of different oil compositions as shown in Table 1 was merely based on the kinematic viscosities measured at 40 ° C at constant values of 46 mm2 / s (+/- 10%) for ISO 46 fluids and 68 mm2 / s (+ / - 10%) for ISO 68 fluids. This was necessary because formulations with different polymer concentrations and polymers of different molecular weights were used.
Die bei unterschiedlichen Temperaturen gemessenen hydraulischen Leistungen können den nachfolgenden Tabellen 2 und 3 entnommen werden.The hydraulic performances measured at different temperatures can be found in Tables 2 and 3 below.
Tabelle 2: Bei unterschiedlichen Temperaturen gemessene hydraulische Leistung der verschiedenen Hydraulikflüssigkeiten bei einem Druck 150 barTable 2: Hydraulic performance of different hydraulic fluids measured at different temperatures at a pressure of 150 bar
Tabelle 2 (Fortsetzung) Table 2 (continued)
Tabelle 3: Bei unterschiedlichen Temperaturen gemessene hydraulische Leistung der verschiedenen Hydraulikflüssigkeiten bei einem Druck 250 barTable 3: Hydraulic performance of different hydraulic fluids measured at different temperatures at a pressure of 250 bar
Tabelle 3 (Fortsetzung) Table 3 (continued)
Tabelle 3 (Fortsetzung)Table 3 (continued)
Tabelle 3 (Fortsetzung)Table 3 (continued)
Bei allen Versuchen, welche mit Flüssigkeiten der Klasse ISO 46 bei einem Druck von 150 bar durchgeführt wurden, zeigte sich im Vergleich zu einer polymerfreien Flüssigkeit (Vgl. 1), dass bessere Leistungs- / Temperaturverhältnisse erreicht wurden, sofern die Polymerlösung A, B oder C enthaltenden Formulierungen gemäß den Beispielen 1 bis 6 eingesetzt wurden. Dies wurde insbesondere bei höheren Flüssigkeitstemperaturen (oberhalb beispielsweise 60°C) deutlich. Ebenso zeigen die im Anhang zu findenden Daten, dass dies unabhängig davon erreicht werden konnte, ob relativ niedrige (4,9 - 8,4 Gew.% im Falle der Beispielstudien 1 , 2 und 3) oder relativ hohe (11,0 - 19,6 Gew.% im Falle der Beispielstudien 4, 5 und 6) Konzentrationen der jeweiligen Polymerlösung A, B oder C verwendet wurden. Kam allerdings die Polymerlösung D zum Einsatz, welche dadurch gekennzeichnet war, dass sie ein höheres Molekulargewicht des Polymeren im Vergleich zu Lösung A, B oder C besaß, wurden schlechtere Leistungs- / Temperaturverhältnisse im direkten Vergleich mit der polymerfreien Formulierung beobachtet. In all experiments, which were carried out with liquids of class ISO 46 at a pressure of 150 bar, it was found that better performance / temperature conditions were achieved compared to a polymer-free liquid (see FIG. 1), provided that the polymer solution A, B or C containing formulations according to Examples 1 to 6 were used. This became particularly clear at higher liquid temperatures (above, for example, 60 ° C). Similarly, the data in the appendix show that this could be achieved independently, whether relatively low (4.9 - 8.4 wt% in the case of Example 1, 2 and 3) or relatively high (11.0 - 19 , 6% by weight in the case of Example Studies 4, 5 and 6) concentrations of the respective polymer solution A, B or C were used. However, when polymer solution D was used, which was characterized as having a higher molecular weight of the polymer as compared to solution A, B or C, poorer performance / temperature ratios were observed in direct comparison with the polymer-free formulation.
Wurden gleiche Versuche mit ISO 46-Flüssigkeiten bei einem Druck von 250 bar anstatt 150 bar durchgeführt, so nahm die Verbesserung durch die Formulierung gemäß Beispiel 3, welche 4,9 Gew.% Polymerlösung C enthielt, gegenüber dem polymerfreien Öl ab. Die das Polymer D enthaltende Formulierung gemäß Vergleichsbeispiel 2 war hingegen dem polymerfreien Öl gemäß Vergleichsbeispiel 1 deutlich unterlegen, was auch schon bei 150 bar der Fall war. Die Polymerlösung A bzw. B haltigen Öle gemäß den Beispielen 1 und 2 waren bei einem Druck von 250 bar dem polymerfreien Öl gemäß Vergleichsbeispiel 1 deutlich überlegen.When the same tests were carried out with ISO 46 fluids at a pressure of 250 bar instead of 150 bar, the improvement by the formulation according to Example 3, which contained 4.9% by weight of polymer solution C, decreased with respect to the polymer-free oil. The polymer D-containing formulation according to Comparative Example 2, however, was clearly inferior to the polymer-free oil according to Comparative Example 1, which was the case even at 150 bar. The polymer solution A or B-containing oils according to Examples 1 and 2 were at a pressure of 250 bar the polymer-free oil according to Comparative Example 1 clearly superior.
Dieser Effekt ist nicht auf die kinematische Viskosität beschränkt. So zeigen die Beispiele 7 und 8 im Vergleich mit dem Vergleichsbeispiel 4, dass eine unerwartete Leistungssteigerung auch mit ISO 68-Flüssigkeiten erzielt werden kann (s. Vergleichsbeispiel 4 sowie Beispiele 7 und 8 in Tab. 3). Dies konnte sowohl bei 150 bar als auch bei 250 bar gezeigt werden. This effect is not limited to the kinematic viscosity. Thus, Examples 7 and 8 show, in comparison with Comparative Example 4, that an unexpected increase in performance can also be achieved with ISO 68 fluids (see Comparative Example 4 and Examples 7 and 8 in Table 3). This could be shown both at 150 bar and at 250 bar.

Claims

Patentansprüche Patent claims
1. Verwendung von Polyalkylester zur Verminderung der Temperatur in einer Schmierölzusammensetzung, wobei der Polyalkylester eine in Chloroform bei 25°C gemessene spezifische Viskosität ηsp/c zwischen 5 und 30 ml/g aufweist.1. Use of polyalkyl ester to reduce the temperature in a lubricating oil composition, the polyalkyl ester having a specific viscosity η sp/c between 5 and 30 ml/g, measured in chloroform at 25 ° C.
2. Verwendung gemäß Anspruch 1 , dadurch gekennzeichnet, dass der Polyalkylester zu einer Verbesserung der hydraulischen Leistung bei erhöhter Temperatur führt.2. Use according to claim 1, characterized in that the polyalkyl ester leads to an improvement in the hydraulic performance at elevated temperature.
3. Verwendung gemäß Anspruch 2, dadurch gekennzeichnet, dass die Temperatur mindestens 60°C, insbesondere mindestens 80°C, beträgt.3. Use according to claim 2, characterized in that the temperature is at least 60°C, in particular at least 80°C.
4. Verwendung gemäß mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Polyalkylester eine unerwünschte Überhitzung der Schmierölzusammensetzung bei einer hohen hydraulischen Leistung verzögert.4. Use according to at least one of the preceding claims, characterized in that the polyalkyl ester delays undesirable overheating of the lubricating oil composition at high hydraulic performance.
5. Verwendung gemäß mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Schmierölzusammensetzung eine Hydraulikflüssigkeit ist.5. Use according to at least one of the preceding claims, characterized in that the lubricating oil composition is a hydraulic fluid.
6. Verwendung gemäß mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Polyalkylester ein Polyalkyl(meth)acrylat ist.6. Use according to at least one of the preceding claims, characterized in that the polyalkyl ester is a polyalkyl (meth)acrylate.
7. Verwendung gemäß mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Schmierölzusammensetzung eine bei 40°C gemessene kinematische Viskosität im Bereich von 10 bis 120 mm2/s aufweist. 7. Use according to at least one of the preceding claims, characterized in that the lubricating oil composition has a kinematic viscosity measured at 40°C in the range of 10 to 120 mm 2 /s.
8. Verwendung gemäß mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Schmierölzusammensetzung einen Viskositätsindex im Bereich von 120 bis 350 aufweist.8. Use according to at least one of the preceding claims, characterized in that the lubricating oil composition has a viscosity index in the range from 120 to 350.
9. Verwendung gemäß mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Schmierölzusammensetzung 2 bis 40 Gew.-% Polyalkylester umfasst.9. Use according to at least one of the preceding claims, characterized in that the lubricating oil composition comprises 2 to 40% by weight of polyalkyl esters.
10. Verwendung gemäß mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Schmierölzusammensetzung mindestens ein Mineralöl und/oder ein synthetisches Öl umfasst.10. Use according to at least one of the preceding claims, characterized in that the lubricating oil composition comprises at least one mineral oil and/or a synthetic oil.
11. Verwendung gemäß mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Schmierölzusammensetzung Antioxidantien, Korrosionsinhibitoren, Antischaummittel, Anti-Wear- Komponenten, Farbstoffe, Farbstabilisatoren, Detergentien, Stockpunkterniedriger oder Dl-Additive enthält.11. Use according to at least one of the preceding claims, characterized in that the lubricating oil composition contains antioxidants, corrosion inhibitors, anti-foaming agents, anti-wear components, dyes, color stabilizers, detergents, pour point depressants or DI additives.
12. Verwendung gemäß mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Schmierölzusammensetzung in einer Flügelzellenpumpe, einer Zahnradpumpe, Radialkolbenpumpe oder einer Axialkolbenpumpe eingesetzt wird.12. Use according to at least one of the preceding claims, characterized in that the lubricating oil composition is used in a vane pump, a gear pump, radial piston pump or an axial piston pump.
13. Verwendung gemäß mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Schmierölzusammensetzung bei einem Druck von 50 bis 450 bar, insbesondere in einem Druckbereich von 100 - 350 bar, eingesetzt wird. 13. Use according to at least one of the preceding claims, characterized in that the lubricating oil composition is used at a pressure of 50 to 450 bar, in particular in a pressure range of 100 - 350 bar.
4. Schmieröizusammensetzung umfassend mindestens ein Polyalkylester, der durch Polymerisation von Monomerenzusammensetzungen erhalten werden kann, die aus a) 0 bis 50 Gew.-%, bezogen auf das Gewicht der Monomerenzusammensetzungen zur Herstellung der Polyalkylester, einer oder mehreren ethylenisch ungesättigten Esterverbindungen der Formel (I)4. Lubricating oil composition comprising at least one polyalkyl ester, which can be obtained by polymerizing monomer compositions which consist of a) 0 to 50% by weight, based on the weight of the monomer compositions for producing the polyalkyl esters, of one or more ethylenically unsaturated ester compounds of the formula (I )
worin R Wasserstoff oder Methyl darstellt, R1 Wasserstoff, einen linearen oder verzweigten Alkylrest mit 1 bis 5 Kohlenstoffatomen bedeutet, R2 und R3 unabhängig Wasserstoff oder eine Gruppe der Formel -COOR' darstellen, worin R! Wasserstoff oder eine Alkylgruppe mit 1 bis 5 Kohlenstoffatomen bedeutet, b) 50 bis 100 Gew.-%, bezogen auf das Gewicht der Monomerenzusammensetzungen zur Herstellung der Polyalkylester, einer oder mehreren ethylenisch ungesättigten Esterverbindungen der Formel (II) in which R represents hydrogen or methyl, R 1 represents hydrogen, a linear or branched alkyl radical with 1 to 5 carbon atoms, R 2 and R 3 independently represent hydrogen or a group of the formula -COOR', in which R ! Hydrogen or an alkyl group with 1 to 5 carbon atoms means, b) 50 to 100% by weight, based on the weight of the monomer compositions for producing the polyalkyl esters, of one or more ethylenically unsaturated ester compounds of the formula (II)
worin R Wasserstoff oder Methyl darstellt, R4 einen linearen oder verzweigten Alkylrest mit 6 bis 30 Kohlenstoffatomen bedeutet, R5 und R6 unabhängig Wasserstoff oder eine Gruppe der Formel -COOR" darstellen, worin R" Wasserstoff oder eine Alkylgruppe mit 6 bis 30 Kohlenstoffatomen bedeutet, c) 0 bis 50 Gew.-%, bezogen auf das Gewicht der Monomerenzusammensetzungen zur Herstellung der Polyalkylester, Comonomer besteht, wobei der Polyalkylester eine in Chloroform bei 25°C gemessene spezifische Viskosität ηsp/c zwischen 5 und 30 ml/g aufweist, dadurch gekennzeichnet, dass die Schmierölzusammensetzung durch Zusatz von Polyalkylester eine hydraulische Leistung Pa bei einer Temperatur T-i+x aufweist, wobei T1 größer oder gleich 20°C und x größer oder gleich 5°C ist, die mindestens so groß ist wie die hydraulischen Leitung Pb der Hydaulikflüssigkeit ohne Zusatz von Polyalkylestern bei der Temperatur Ti, wobei der temperaturbedingte Leistungsabfall d(Pa)/dT der Schmierölzusammensetzung mit Polyalkylester kleiner ist als der temperaturbedingte Leistungsabfall d(Pb)/dT der Schmierölzusammensetzung ohne Polyalkylester. in which R represents hydrogen or methyl, R 4 represents a linear or branched alkyl radical with 6 to 30 carbon atoms, R 5 and R 6 independently represent hydrogen or a group of the formula -COOR", in which R" represents hydrogen or an alkyl group with 6 to 30 carbon atoms means c) 0 to 50% by weight, based on the weight of the monomer compositions for producing the polyalkyl esters, comonomer, the polyalkyl ester having a specific viscosity η sp / c measured in chloroform at 25 ° C between 5 and 30 ml / g has, characterized in that the lubricating oil composition has a hydraulic power P a at a temperature T-i + x due to the addition of polyalkyl ester, where T1 is greater than or equal to 20 ° C and x is greater than or equal to 5 ° C, which is at least as great like the hydraulic line Pb of the hydraulic fluid without the addition of polyalkyl esters at the temperature Ti, whereby the temperature-related loss in performance d(P a )/dT of the lubricating oil composition with polyalkyl esters is smaller than the temperature-related loss in performance d(P b )/dT of the lubricating oil composition without polyalkyl esters.
15. Schmierölzusammensetzung gemäß Anspruch 14, dadurch gekennzeichnet, dass Ti im Bereich von 50 bis 120°C liegt.15. Lubricating oil composition according to claim 14, characterized in that Ti is in the range of 50 to 120°C.
16. Schmierölzusammensetzung gemäß Anspruch 14 oder 15, dadurch gekennzeichnet, dass x im Bereich von 10 bis 90°C liegt. 16. Lubricating oil composition according to claim 14 or 15, characterized in that x is in the range from 10 to 90 ° C.
17. Schmieröizusammensetzung gemäß mindestens einem der Ansprüche 14 bis 16, dadurch gekennzeichnet, dass mindestens 50 Gew.-% der Reste R4 gemäß Formel (II) linear sind.17. Lubricating oil composition according to at least one of claims 14 to 16, characterized in that at least 50% by weight of the radicals R 4 according to formula (II) are linear.
18. Schmieröizusammensetzung gemäß mindestens einem der Ansprüche 14 bis 17, dadurch gekennzeichnet, dass das Verhältnis von verzweigten zu den linearen Seitenketten der Reste R4 gemäß Formel (II) im Bereich von 0,0001 bis 0,3 liegt.18. Lubricating oil composition according to at least one of claims 14 to 17, characterized in that the ratio of branched to linear side chains of the radicals R 4 according to formula (II) is in the range from 0.0001 to 0.3.
19. Schmieröizusammensetzung gemäß mindestens einem der Ansprüche 14 bis 18, dadurch gekennzeichnet, dass der Anteil an C-8-15 größer oder gleich dem Anteil an C-iβ-iβ ist.19. Lubricating oil composition according to at least one of claims 14 to 18, characterized in that the proportion of C- 8 - 15 is greater than or equal to the proportion of C-iβ-iβ.
20. Schmieröizusammensetzung gemäß mindestens einem der Ansprüche 14 bis 19, dadurch gekennzeichnet, dass der Polyalkyester eine Polydispersität Mw/Mn im Bereich von 1 ,2 bis 4,0 aufweist.20. Lubricating oil composition according to at least one of claims 14 to 19, characterized in that the polyalkyester has a polydispersity M w /M n in the range from 1.2 to 4.0.
21. Schmieröizusammensetzung gemäß mindestens einem der Ansprüche 14 bis 20, dadurch gekennzeichnet, dass der Polyalkyester ein Polyalkyl(meth)acrylat ist, wobei mindestens 60 Gew.-% der ethylenisch ungesättigten Esterverbindungen der Formel (II) Alkyl(meth)acrylate darstellen, bezogen auf das Gesamtgewicht der ethylenisch ungesättigten Esterverbindungen der Formel (II). 21. Lubricating oil composition according to at least one of claims 14 to 20, characterized in that the polyalkyl ester is a polyalkyl (meth) acrylate, at least 60% by weight of the ethylenically unsaturated ester compounds of the formula (II) being alkyl (meth) acrylates on the total weight of the ethylenically unsaturated ester compounds of the formula (II).
EP05707597.0A 2004-04-30 2005-02-24 Use of polyalkyl(meth)acrylates in lubricating oil compositions Not-in-force EP1740680B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004021778A DE102004021778A1 (en) 2004-04-30 2004-04-30 Use of polyalkyl (meth) acrylates in lubricating oil compositions
PCT/EP2005/001907 WO2005108531A2 (en) 2004-04-30 2005-02-24 Use of polyalkyl(meth)acrylates in lubricating oil compositions

Publications (2)

Publication Number Publication Date
EP1740680A2 true EP1740680A2 (en) 2007-01-10
EP1740680B1 EP1740680B1 (en) 2018-06-06

Family

ID=34960531

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05707597.0A Not-in-force EP1740680B1 (en) 2004-04-30 2005-02-24 Use of polyalkyl(meth)acrylates in lubricating oil compositions

Country Status (10)

Country Link
US (1) US8754018B2 (en)
EP (1) EP1740680B1 (en)
JP (1) JP5452863B2 (en)
KR (1) KR101129881B1 (en)
CN (1) CN101142303B (en)
BR (1) BRPI0510456A (en)
CA (1) CA2560125C (en)
DE (1) DE102004021778A1 (en)
MX (1) MXPA06011984A (en)
WO (1) WO2005108531A2 (en)

Families Citing this family (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9096041B2 (en) 2004-02-10 2015-08-04 Evonik Degussa Gmbh Method for coating substrates and carrier substrates
DE102004006612A1 (en) * 2004-02-10 2005-08-25 Degussa Ag Compound ceramic wall coating comprises a carrier layer and at least one ceramic layer containing ceramic particles which are chosen from a group of oxides, nitrides, borides or carbides of metal or semi-metals
DE102004018930A1 (en) * 2004-04-20 2005-11-17 Degussa Ag Use of a ceramic separator in lithium-ion batteries having an electrolyte containing ionic liquids
DE102004036073A1 (en) * 2004-07-24 2006-02-16 Degussa Ag Process for sealing natural stones
KR101146870B1 (en) * 2004-10-21 2012-05-16 에보니크 데구사 게엠베하 Inorganic separator-electrode-unit for lithium-ion batteries, method for the production thereof and use thereof in lithium batteries
JP2006124586A (en) * 2004-10-29 2006-05-18 Sanyo Chem Ind Ltd Viscosity index improver composition and lubricating oil composition
DE102005015931A1 (en) 2005-04-06 2006-10-12 Rohmax Additives Gmbh Polyalkyl (meth) acrylate copolymers with excellent properties
US7648950B2 (en) * 2005-04-22 2010-01-19 Rohmax Additives Gmbh Use of a polyalkylmethacrylate polymer
DE102005031244A1 (en) * 2005-07-01 2007-02-15 Rohmax Additives Gmbh Oil-soluble comb polymers
DE102005041528A1 (en) * 2005-08-31 2007-03-01 Rohmax Additives Gmbh Multi-arm star-shaped polymer for use as lubricating oil additive, e.g. viscosity modifier or dispersant, has at least three arms containing units derived from esters of higher alkanols and unsaturated carboxylic acids
DE102006001640A1 (en) * 2006-01-11 2007-07-12 Degussa Gmbh Coating a substrate, useful as a wall paper, comprises providing a substrate, applying a composition containing metal and/or metalloid on side of the substrate, drying and applying the composition on other side of substrate and drying
DE102006001639A1 (en) * 2006-01-11 2007-07-12 Degussa Gmbh Coating of substrates, useful as wallpaper, comprises supplying a substrate, applying a composition on one side of the substrate, drying the applied composition and applying a coating on the coated side of the substrate
DE102006001641A1 (en) * 2006-01-11 2007-07-12 Degussa Gmbh Coating substrate, particularly wall paper, comprises e.g. applying composition containing inorganic compound comprising metal/half metal, silane-containg coating, coating containing biocidal and/or anti-microbial substances, and drying
US20070197410A1 (en) * 2006-02-21 2007-08-23 Rohmax Additives Gmbh Energy efficiency in hydraulic systems
DE102006016588A1 (en) * 2006-04-06 2007-10-18 Rohmax Additives Gmbh Fuel compositions comprising renewable resources
DE102006039420A1 (en) * 2006-08-23 2008-02-28 Evonik Rohmax Additves Gmbh Process for the preparation of methacrylate esters
US20080302422A1 (en) * 2007-06-07 2008-12-11 Rohmax Additives Gmbh Power output in hydraulic systems
JP5502730B2 (en) 2007-07-09 2014-05-28 エボニック オイル アディティヴス ゲゼルシャフト ミット ベシュレンクテル ハフツング Use of comb polymers to reduce fuel consumption
DE102007036856A1 (en) * 2007-08-06 2009-02-26 Evonik Rohmax Additives Gmbh Use of ester-group-containing polymers as antifatigue additives
JP5623276B2 (en) * 2007-08-23 2014-11-12 シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイＳｈｅｌｌ Ｉｎｔｅｒｎａｔｉｏｎａｌｅ Ｒｅｓｅａｒｃｈ Ｍａａｔｓｃｈａｐｐｉｊ Ｂｅｓｌｏｔｅｎｖｅｎｎｏｏｔｓｈａｐ Lubricating oil composition usage
DE102007045146A1 (en) * 2007-09-20 2009-05-28 Evonik Degussa Gmbh Single-axle vehicle with a platform and / or a seat for a driver
DE102007059805A1 (en) 2007-12-11 2009-06-25 Evonik Degussa Gmbh battery Pack
US20100162693A1 (en) * 2008-12-31 2010-07-01 Michael Paul W Method of reducing torque ripple in hydraulic motors
DE102009001447A1 (en) 2009-03-10 2010-09-16 Evonik Rohmax Additives Gmbh Use of comb polymers to improve the load carrying capacity
EP2440640A1 (en) * 2009-06-12 2012-04-18 Evonik RohMax Additives GmbH A fluid having improved viscosity index
DE102010028195A1 (en) * 2010-04-26 2011-10-27 Evonik Rohmax Additives Gmbh Lubricant for transmissions
CN102295972B (en) * 2010-06-24 2013-06-05 中国石油化工股份有限公司 Polymethacrylate viscosity index improver and preparation method
JP5584049B2 (en) * 2010-08-17 2014-09-03 株式会社Ａｄｅｋａ Extreme pressure agent for lubricating oil and lubricating oil composition containing the same
RU2013147456A (en) 2011-03-25 2015-04-27 Басф Се LUBRICANT COMPOSITION HAVING IMPROVED NON-NEWTONIAN VISCOSITY INDICATORS
CN105294431B (en) * 2015-09-14 2017-08-11 宁波蓝润能源科技股份有限公司 A kind of synthesizing ester thickening agent and the preparation method using its semi-synthetic gear oil
JP7050754B6 (en) * 2016-08-15 2023-12-20 エボニック オペレーションズ ゲーエムベーハー Functionalized polyalkyl (meth)acrylates with enhanced demulsification performance
EP3507350B1 (en) 2016-08-31 2020-05-27 Evonik Operations GmbH Comb polymers for improving noack evaporation loss of engine oil formulations
DE102021000567A1 (en) 2021-02-04 2022-08-04 Mercedes-Benz Group AG Lubricating oil composition for a vehicle transmission

Family Cites Families (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3304260A (en) * 1960-12-30 1967-02-14 Monsanto Co Compositions of improved viscosity index containing alkyl polymethacrylate of high relative syndiotacticity
IT1181905B (en) * 1984-06-15 1987-09-30 Anic Spa MULTIFUNCTIONAL ADDITIVE FOR LUBRICANT OILS AND PROCEDURE FOR ITS PREPARATION
FR2642435B1 (en) * 1989-01-27 1994-02-11 Organo Synthese Ste Fse VISCOSITY ADDITIVE FOR LUBRICATING OILS, PROCESS FOR THE PREPARATION THEREOF, AND LUBRICANT COMPOSITIONS BASED ON SAID ADDITIVE
FR2701036B1 (en) * 1993-02-04 1995-04-21 Great Lakes Chemical France Additive with shear stable viscosity for lubricating oils.
HUT69298A (en) * 1993-07-23 1995-09-28 Rohm & Haas Method of making a copolymer useful as viscosity index improving additive for hydraulic fluids
HUT69323A (en) 1993-07-23 1995-09-28 Rohm & Haas Copolymer useful as viskosity index improving additive for hydraulic fluid
JPH0948988A (en) 1995-08-02 1997-02-18 Sanyo Chem Ind Ltd Viscosity index improver
US5817606A (en) 1996-08-08 1998-10-06 Rohm And Haas Company Viscosity index improving additives for phosphate ester-containing hydraulic fluids
US5939365A (en) * 1996-12-20 1999-08-17 Exxon Chemical Patents Inc. Lubricant with a higher molecular weight copolymer lube oil flow improver
FR2762005B1 (en) * 1997-04-11 2000-03-31 Chevron Res & Tech USE OF LOW MOLECULAR WEIGHT SURFACTANTS AS FILTER-IMPROVING AGENTS IN HYDRAULIC LUBRICANTS
DE19754982A1 (en) * 1997-12-11 1999-06-17 Degussa Process for the production of hydrocyanic acid
JP4338807B2 (en) 1998-02-18 2009-10-07 ザ ルブリゾル コーポレイション Viscosity improver for lubricating oil compositions
US6124249A (en) * 1998-12-22 2000-09-26 The Lubrizol Corporation Viscosity improvers for lubricating oil compositions
US5955405A (en) * 1998-08-10 1999-09-21 Ethyl Corporation (Meth) acrylate copolymers having excellent low temperature properties
US6458750B1 (en) * 1999-03-04 2002-10-01 Rohmax Additives Gmbh Engine oil composition with reduced deposit-formation tendency
US6458789B1 (en) * 1999-09-29 2002-10-01 Lion Bioscience Ag 2-aminopyridine derivatives and combinatorial libraries thereof
US6403745B1 (en) * 1999-11-30 2002-06-11 Rohmax Additives Gmbh Gradient copolymers, as well as a method for their preparation and their use
US6391996B1 (en) * 1999-11-30 2002-05-21 Rohmax Additives Gmbh Copolymers obtainable by the ATRP method and a method for their preparation and their use
CA2340836A1 (en) * 2000-03-18 2001-09-18 Degussa Ag Granular product
US20010036437A1 (en) * 2000-04-03 2001-11-01 Andreas Gutsch Nanoscale pyrogenic oxides
DE10120484A1 (en) * 2001-04-25 2002-10-31 Degussa Method and device for the thermal treatment of powdery substances
US7728093B2 (en) * 2002-03-01 2010-06-01 Evonik Rohmax Additives Gmbh Copolymers as dewaxing additives
DE10235758A1 (en) * 2002-08-05 2004-02-26 Degussa Ag Doped zinc oxide powder in aggregate form for use in e.g. electrically conductive lacquers and coatings, comprises doping component, e.g. aluminum oxide
DE10238943B4 (en) * 2002-08-24 2013-01-03 Evonik Degussa Gmbh Separator-electrode unit for lithium-ion batteries, method for their production and use in lithium batteries and a battery, comprising the separator-electrode unit
DE10249292A1 (en) * 2002-10-22 2004-05-13 Rohmax Additives Gmbh Low viscosity polymer dispersions and process for making them
DE10249294A1 (en) * 2002-10-22 2004-05-13 Rohmax Additives Gmbh Stable polymer dispersions and manufacturing processes
DE10249295A1 (en) * 2002-10-22 2004-05-13 Rohmax Additives Gmbh High stability polymer dispersions and process for making them
US20040092409A1 (en) * 2002-11-11 2004-05-13 Liesen Gregory Peter Alkyl (meth) acrylate copolymers
DE10311645A1 (en) * 2003-03-14 2004-09-23 Degussa Ag Mixed indium and tin oxide powder, used in coatings, solar cells, UV absorbers and medical technology, has increased electrical conductivity
DE10314776A1 (en) * 2003-03-31 2004-10-14 Rohmax Additives Gmbh Lubricating oil composition with good rubbing properties
DE10347568A1 (en) * 2003-10-14 2005-05-12 Degussa Capacitor with ceramic separation layer
DE102004006612A1 (en) * 2004-02-10 2005-08-25 Degussa Ag Compound ceramic wall coating comprises a carrier layer and at least one ceramic layer containing ceramic particles which are chosen from a group of oxides, nitrides, borides or carbides of metal or semi-metals
DE102004018930A1 (en) * 2004-04-20 2005-11-17 Degussa Ag Use of a ceramic separator in lithium-ion batteries having an electrolyte containing ionic liquids
US7429555B2 (en) * 2004-04-30 2008-09-30 Rohmax Additives Gmbh Lubricating grease with high water resistance
DE102004036073A1 (en) * 2004-07-24 2006-02-16 Degussa Ag Process for sealing natural stones
KR101146870B1 (en) * 2004-10-21 2012-05-16 에보니크 데구사 게엠베하 Inorganic separator-electrode-unit for lithium-ion batteries, method for the production thereof and use thereof in lithium batteries
US7648950B2 (en) * 2005-04-22 2010-01-19 Rohmax Additives Gmbh Use of a polyalkylmethacrylate polymer
DE102006001640A1 (en) * 2006-01-11 2007-07-12 Degussa Gmbh Coating a substrate, useful as a wall paper, comprises providing a substrate, applying a composition containing metal and/or metalloid on side of the substrate, drying and applying the composition on other side of substrate and drying
DE102006001639A1 (en) * 2006-01-11 2007-07-12 Degussa Gmbh Coating of substrates, useful as wallpaper, comprises supplying a substrate, applying a composition on one side of the substrate, drying the applied composition and applying a coating on the coated side of the substrate
DE102006001641A1 (en) * 2006-01-11 2007-07-12 Degussa Gmbh Coating substrate, particularly wall paper, comprises e.g. applying composition containing inorganic compound comprising metal/half metal, silane-containg coating, coating containing biocidal and/or anti-microbial substances, and drying
US20070197410A1 (en) * 2006-02-21 2007-08-23 Rohmax Additives Gmbh Energy efficiency in hydraulic systems
DE102006039420A1 (en) * 2006-08-23 2008-02-28 Evonik Rohmax Additves Gmbh Process for the preparation of methacrylate esters
DE202006015495U1 (en) * 2006-10-09 2007-02-01 Degussa Ag Electroluminescence unit for articles equipped with electroluminescence unit e.g. articles of daily use and means of transport, has energy source, electronic control and electroluminescent foil in transparent casing
US20080302422A1 (en) * 2007-06-07 2008-12-11 Rohmax Additives Gmbh Power output in hydraulic systems
DE102007045146A1 (en) * 2007-09-20 2009-05-28 Evonik Degussa Gmbh Single-axle vehicle with a platform and / or a seat for a driver

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005108531A2 *

Also Published As

Publication number Publication date
MXPA06011984A (en) 2007-04-16
WO2005108531A3 (en) 2007-05-10
JP2007535596A (en) 2007-12-06
EP1740680B1 (en) 2018-06-06
US20070219101A1 (en) 2007-09-20
KR20070015557A (en) 2007-02-05
CN101142303B (en) 2011-08-17
CA2560125C (en) 2014-04-29
JP5452863B2 (en) 2014-03-26
BRPI0510456A (en) 2007-11-06
DE102004021778A1 (en) 2005-12-08
US8754018B2 (en) 2014-06-17
CN101142303A (en) 2008-03-12
KR101129881B1 (en) 2012-03-28
CA2560125A1 (en) 2005-11-17
WO2005108531A2 (en) 2005-11-17

Similar Documents

Publication Publication Date Title
EP1740680A2 (en) Use of polyalkyl(meth)acrylates in lubricating oil compositions
EP1753847B1 (en) Lubricating grease having a high water-resistance
WO2004087850A1 (en) Lubricating oil composition with good frictional properties
EP1866351B1 (en) Lubricating oil composition comprising polyalkyl (meth)acrylate copolymers
EP1240219B1 (en) Copolymers which can be obtained using atrp methods, and method for producing and using the same
EP1240218B1 (en) Gradient copolymers and method for the production thereof and their use
WO2005097855A1 (en) Polymers with h-bridge forming functionalities
WO2006094520A1 (en) Process for producing lubricating grease
WO2005097956A1 (en) Polymers with h-bridge forming functionalities for improving anti-wear protection
WO2006007934A1 (en) Use of graft polymers
DE102005041528A1 (en) Multi-arm star-shaped polymer for use as lubricating oil additive, e.g. viscosity modifier or dispersant, has at least three arms containing units derived from esters of higher alkanols and unsaturated carboxylic acids
DE102007036856A1 (en) Use of ester-group-containing polymers as antifatigue additives
EP2686352B1 (en) Copolymers comprising ester groups and use thereof in lubricants
EP1334133B1 (en) Method for the continuous production of polymer compositions and the use thereof
DE102009002730A1 (en) Preparing copolymer, useful as additive for e.g. mineral oil and ester oil, comprises polymerizing a monomer composition (comprising e.g. ethylenically unsaturated ester compounds and comonomer) in the presence of alkyl(ene) compounds

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20060612

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR LV MK YU

PUAK Availability of information related to the publication of the international search report

Free format text: ORIGINAL CODE: 0009015

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: EVONIK ROHMAX ADDITIVES GMBH

17Q First examination report despatched

Effective date: 20120123

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: EVONIK OIL ADDITIVES GMBH

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 502005015843

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: C10M0145000000

Ipc: C10M0145140000

RIC1 Information provided on ipc code assigned before grant

Ipc: C10M 145/14 20060101AFI20171121BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20180111

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 502005015843

Country of ref document: DE

Owner name: EVONIK OPERATIONS GMBH, DE

Free format text: FORMER OWNER: ROHMAX ADDITIVES GMBH, 64293 DARMSTADT, DE

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: AT

Ref legal event code: REF

Ref document number: 1006082

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180615

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502005015843

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180906

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180907

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181006

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502005015843

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20190307

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190224

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190224

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180606

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 1006082

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190224

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190224

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181008

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 502005015843

Country of ref document: DE

Owner name: EVONIK OPERATIONS GMBH, DE

Free format text: FORMER OWNER: EVONIK OIL ADDITIVES GMBH, 64293 DARMSTADT, DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: HC

Owner name: EVONIK OPERATIONS GMBH; DE

Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), CHANGE OF OWNER(S) NAME; FORMER OWNER NAME: EVONIK DEGUSSA GMBH

Effective date: 20210209

Ref country code: NL

Ref legal event code: PD

Owner name: EVONIK DEGUSSA GMBH; DE

Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), MERGE; FORMER OWNER NAME: EVONIK OIL ADDITIVES GMBH

Effective date: 20210209

REG Reference to a national code

Ref country code: CH

Ref legal event code: PFUS

Owner name: EVONIK OPERATIONS GMBH, DE

Free format text: FORMER OWNER: EVONIK OIL ADDITIVES GMBH, DE

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20210325 AND 20210331

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20210217

Year of fee payment: 17

Ref country code: FR

Payment date: 20210224

Year of fee payment: 17

Ref country code: NL

Payment date: 20210217

Year of fee payment: 17

REG Reference to a national code

Ref country code: BE

Ref legal event code: HC

Owner name: EVONIK OPERATIONS GMBH; DE

Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), CHANGE OF OWNER(S) NAME; FORMER OWNER NAME: EVONIK DEGUSSA GMBH

Effective date: 20210223

Ref country code: BE

Ref legal event code: PD

Owner name: EVONIK DEGUSSA GMBH; DE

Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), MERGE; FORMER OWNER NAME: EVONIK OIL ADDITIVES GMBH

Effective date: 20210223

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20210217

Year of fee payment: 17

Ref country code: BE

Payment date: 20210217

Year of fee payment: 17

Ref country code: GB

Payment date: 20210219

Year of fee payment: 17

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20050224

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502005015843

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20220301

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20220228

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20220224

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220301

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220228

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220224

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220901

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220228