Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
  • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M149/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
  • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • 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
  • C10M151/00—Lubricating compositions characterised by the additive being a macromolecular compound containing sulfur, selenium or tellurium
  • C10M151/02—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
  • C10M2209/084—Acrylate; Methacrylate
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2217/022—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
  • C10M2217/023—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group the amino group containing an ester bond
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2217/024—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
• • 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
  • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2221/02—Macromolecular compounds obtained by reactions of monomers involving only carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/02—Pour-point; Viscosity index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

• the present invention relates to lubricating oil compositions with good rubbing properties, processes for producing these lubricating oil compositions and use.
• Typical friction reducers forming reaction layers are e.g. saturated fatty acid esters, phosphoric and triphosphoric acid esters, xanthates or sulfur-containing fatty acids.
• This class also includes compounds that do not form solid, but rather liquid reaction products with a high load-bearing capacity under the tribological stress in frictional contact. Examples include unsaturated fatty acids, partial esters of dicarboxylic acids, dialkyl phthalic acid esters and sulphated olefin mixtures.
• the function of such friction-reducing additives is very similar to that of the so-called EP additives, the formation of a reaction layer in the lubricating gap having to take place broadly under milder mixed friction conditions.
• organometallic compounds such as molybdenum dithiophosphonates and dicarbamates
• organic copper compounds and some solid lubricants such as graphite and MoS 2
• the disadvantage of these connections is their very high price.
• many connections are very polar, so that they do not dissolve in fully synthetic lubricating oils.
• JP 05271331 claims the production of polymers and their use in lubricants.
• a copolymer of an ⁇ -olefin and a dibasic ester and its reaction with alkanolamines, cycloalkanolamines, heterocyclic amines and polyalkylene polyamines is described.
• the lubricant containing this statistical copolymer has a coefficient of friction reduced from 0.1104 to 0.07134 compared to a reference, which is shown using the example of a Falex rub test (ASTM D 2714).
• a disadvantage of these polymers is, in particular, their complex production.
• JP 2000355695 (US 6426323) describes lubricant compositions for continuous automatic transmissions (CVT's) which contain dispersing VI improvers.
• CVT's continuous automatic transmissions
• Polyalkyl methacrylates with dispersing comonomers such as dimethylaminoethyl methacrylate, 2-methyl-5-vinylpyridine and N-vinylpyrrolidone are preferably used as VI improvers in order to achieve improved oxidation stability. Friction tests on these lubricants are described by way of example, but no reference is made to the influence of the above. Vl-Improver received.
• EP 570073 describes boron-containing polyalkyl acrylates and methacrylates as lubricant additives which simultaneously have the effect of a Vll and a Have friction modifiers.
• Cyclic boron compounds known as friction-reducing components are statistically incorporated as functional groups in the side chains of conventional PAMA-VI improvers.
• a disadvantage of these copolymers is that they are very complex to produce, so that such products have not been used commercially on a larger scale to date.
• EP 286996 claims lubricant compositions of a certain naphthenic base oil composition which contain 0.01-5% of a friction modifier and are particularly suitable for automatic and continuous transmissions.
• VI improvers in particular PAMA's, are mentioned as additional components, but their type is judged to be uncritical with regard to the friction behavior of the formulation.
• No. 4,699,723 describes dispersing multifunctional VI improvers, built up from ethylene-propylene copolymers (OCP's), onto which a dispersing, antioxidative functional group is grafted. An influence of these Vll's on the friction properties of the resulting lubricants is not described. Statistical copolymers are generally obtained which do not have any friction-improving properties.
• WO 00/58423 describes high-performance motor oils and other lubricants based on a mixture of a high VI polyalphaolefin (HVI-PAO) and a high molecular weight thickener (typically a hydrogenated poly (styrene-co-isoprene), HSI, an ethylene-propylene copolymer (OCP) or a polyisobutylene (PIB) with a weight-average molecular weight M w of 10,000 to 100,000 g / mol.
• HVI-PAO high VI polyalphaolefin
• HSI hydrogenated poly (styrene-co-isoprene)
• OCP ethylene-propylene copolymer
• PIB polyisobutylene
• WO 9524458 (US 5622924) claim viscosity index improvers with a proportion of min. 70% by weight of alkyl methacrylates with no more than 10 carbon atoms.
• the oils formulated with such VI improvers also have improved low friction properties when used in combination with a molybdenum-based friction modifier.
• JP 08157855 describes lubricants which contain VI improvers which maximize the effect of a molybdenum-based friction modifier.
• the same polymers are used as described in WO 9524458.
• traction fluids i.e. Lubricants that, due to their frictional properties in the hydrodynamic range (at high speeds), can transmit forces via the friction contact.
• Particularly high traction or friction coefficients are desirable here in order to make the power transmission as efficient as possible.
• a block copolymer in a lubricating oil is used as an additive with friction-reducing properties
• the block copolymer comprising hydrophobic segments P and polar segments D, the hydrophobic segments being obtained by polymerizing monomer compositions which a) 0 to 40% by weight of one or more ethylenically unsaturated ester compounds of the formula (I)
• R represents hydrogen or methyl
• R 1 represents a linear or branched alkyl radical having 1 to 5 carbon atoms
• R 2 and R 3 independently represent hydrogen or a group of the formula -COOR ', wherein R' is hydrogen or an alkyl group having 1 to 5 carbon atoms b) 50 to 100% by weight of one or more ethylenically unsaturated ester compounds of the formula (II)
• R represents hydrogen or methyl
• R 4 represents a linear or branched alkyl radical having 6 to 30 carbon atoms
• R 5 and R 6 independently represent hydrogen or a group of the formula -COOR ", where R" represents hydrogen or an alkyl group having 6 to 30 carbon atoms means, c) there is 0 to 50% by weight of comonomer
• R ' wherein R is independently hydrogen or methyl, R 7 is independently a group comprising 2 to 1000 carbon atoms with at least one hetero atom, X is independently a sulfur or oxygen atom or a group of the formula NR 8 , wherein R 8 is independently hydrogen or a group with 1 to 20 carbon atoms and n represents an integer greater than or equal to 3, it is possible to provide inexpensive lubricant compositions which have particularly good rubbing properties.
• lubricant compositions comprising the block copolymers of the present invention show excellent properties as a viscosity index improver.
• the viscosity index-improving effect can be seen, for example, from the kinematic viscosities at 40 ° C. and 100 ° C. according to ASTM D 2270
• the lubricant composition according to the invention have excellent low-temperature properties.
• the low temperature properties can be obtained by mini-rotation viscometry (MRV) values that can be obtained in accordance with ASTM D 4684 and scanning Brookfield results as obtained in accordance with ASTM D 5133.
• MMV mini-rotation viscometry
• a pour point-improving effect of the block copolymers to be used according to the invention in lubricating oils can be determined, for example, in accordance with ASTM D 97.
• the amount of additive can be reduced by the present invention.
• the lubricant compositions of the present invention can have a particularly low total additive content for a given property profile.
• the lubricant compositions according to the invention can comprise very large amounts of synthetic oils, since the block copolymers used according to the invention as a friction-reducing additive are also soluble in very non-polar oils.
• the block copolymers contained in the lubricant compositions according to the invention show high oxidation stability and are very chemically stable.
• Block copolymers refer to copolymers that have at least two blocks. Blocks are segments of the copolymer that have a constant composition of one or more monomer units.
• the block copolymers to be used according to the invention as a friction-reducing additive comprise hydrophobic segments which are obtained by polymerizing monomer compositions which, in particular, can have (meth) acrylates, maleates and / or fumarates, which can have different alcohol residues.
• (meth) acrylates encompasses methacrylates and acrylates and mixtures of the two. These monomers are well known.
• the alkyl radical can be linear, cyclic or branched.
• Mixtures from which the hydrophobic segments of the block copolymers can be obtained can be 0 to 40% by weight, in particular 0.5 to 20% by weight, based on the weight of the monomer compositions for producing the hydrophobic segments, of one or more ethylenically unsaturated ester compounds of formula (I) included
• R represents hydrogen or methyl
• R 1 represents a linear or branched alkyl radical having 1 to 5 carbon atoms
• R 2 and R 3 independently represent 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 the production of the hydrophobic segments can be 50 to 100% by weight, in particular 55 to 95% by weight, based on the weight of the monomer compositions for the production of the hydrophobic segments, one or more ethylenically unsaturated ester compounds of the formula (II)
• R represents hydrogen or methyl
• R 4 represents a linear or branched alkyl radical having 6 to 30 carbon atoms
• R 5 and R 6 independently represent hydrogen or a group of the formula -COOR ", where R" represents hydrogen or an alkyl group having 6 to 30 carbon atoms means included.
• (Meth) acrylates, fumarates and maleates derived from saturated alcohols such as hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, 2-tert-butylheptyl (meth) acrylate, octyl ( meth) acrylate, 3-iso-propylheptyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, 5-methylundecyl (meth) acrylate, dodecyl (meth) acrylate, 2-methyldodecyl ( meth) acrylate, tridecyl (meth) acrylate,
• saturated alcohols such as hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (me
• Cycloalkyl (meth) acrylates such as 2,4,5-tri-t-butyl-3-vinylcyclohexyl (meth) acrylate, 2,3,4,5-tetra-t-butylcyclohexyl (meth) acrylate; (Meth) acrylates derived from unsaturated alcohols, such as. B.
• Cycloalkyl (meth) acrylates such as 3-vinylcyclohexyl (meth) acrylate,
• the ester compounds with a long-chain alcohol residue 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, for example (Meth) acrylates with different long-chain alcohol residues are formed.
• These fatty alcohols include, among others, Oxo Alcohol® 7911 and Oxo Alcohol® 7900, Oxo Alcohol® 1100 from Monsanto; Aiphanoi® 79 from ICI; Nafol® 1620, Alfol® 610 and Alfol® 810 from Condea; Epal® 610 and Epal® 810 from Ethyl Corporation; Linevol® 79, Linevol® 911 and Dobanol® 25L from Shell AG; Lial 125 from Augusta® Milan; Dehydad® and Lorol® from Henkel KGaA as well as Linopol® 7- ⁇ 1 and Acropol® 91 Ugine Kuhlmann.
• the mixture for producing the hydrophobic segments has at least 60% by weight, preferably at least 70% by weight, based on the weight of the monomer compositions for producing the hydrophobic segments, of monomers of the 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) are particularly preferred Embodiments represent hydrogen.
• the methacrylates are preferred to the acrylates.
• the proportion of (meth) acrylates having 6 to 15 carbon atoms in the alcohol radical is preferably in the range from 20 to 95% by weight, based on the weight of the monomer composition for the preparation of the hydrophobic segments.
• the proportion of (meth) acrylates with 16 to 30 carbon atoms in the alcohol radical is preferably in the range from 0.5 to 60% by weight, based on the weight of the monomer composition for the preparation of the hydrophobic segments.
• Component c) of the composition to be used to prepare the hydrophobic segments comprises, in particular, ethylenically unsaturated monomers which can be copolymerized with the ethylenically unsaturated ester compounds of the formulas (I) and / or (II).
• comonomers are particularly suitable for the polymerization according to the present invention, which correspond to the formula:
• Aryl (meth) acrylates such as benzyl methacrylate or
• Phenyl methacrylate where the aryl radicals can be unsubstituted or substituted up to four times;
• Halogenated alcohol methacrylates such as
• Vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride;
• Vinyl esters such as vinyl acetate
• Styrene substituted styrenes with an alkyl substituent in the side chain, such as. B. ⁇ -methylstyrene and ⁇ -ethylstyrene, substituted styrenes with an alkyl substituent on the ring, such as vinyltuluol and p-methylstyrene, halogenated styrenes, such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes;
• Heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinyl pyrrolidine, 3-vinyl pyrrolidine, N-vinyl caprolactam, N-vinyl butyrolactam, vinyl oxolane, vinyl furan, vinyl thiophene, vinyl thiolane, vinyl thiazoles and hydrogenated vinyl thiazoles, vinyl oxazoles and hydrogenated vinyl oxazoles; Vinyl and isoprenyl ether; Maleic acid and maleic acid derivatives
• Very particularly preferred mixtures for producing the hydrophobic segments have methyl methacrylate, butyl methacrylate, lauryl methacrylate, stearyl methacrylate and / or styrene.
• block copolymers contained according to the invention as friction-reducing additives in the lubricant composition comprise polar segments D, which can be represented by the formula (III),
• R 7 wherein R is independently hydrogen or methyl, R 7 is independently a group comprising 2 to 1000 carbon atoms with at least one hetero atom, X is independently a sulfur or oxygen atom or a group of the formula NR 8 , in which R 8 is independently hydrogen or a group with 1 to 20 carbon atoms and n represents an integer greater than or equal to 3.
• the different groups X, R and R 7 can be the same or different based on the different repeating units within a polar segment D.
• the radical R 7 represents a group comprising 2 to 1000, in particular 2 to 100, preferably 2 to 20 carbon atoms.
• the expression "2 to 1000 carbon-containing group” denotes residues of organic compounds with 2 to 1000 carbon atoms. It includes aromatic and heteroaromatic groups as well as alkyl, cycloalkyl, alkoxy, cycloalkoxy, alkenyl, alkanoyl, alkoxycarbonyl groups and heteroalipatic groups.
• the groups mentioned can be branched or not branched. Furthermore, these groups can have customary substituents.
• Substituents are, for example, linear and branched alkyl groups with 1 to 6 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, 2-methylbutyl or hexyl; Cycloalkyl groups such as cyclopentyl and cyclohexyl; aromatic groups such as phenyl or naphthyl; Amino groups, ether groups, ester groups and halides.
• aromatic groups denote residues of mono- or polynuclear aromatic compounds with 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 3 to 19 carbon atoms.
• Aromatic or heteroaromatic groups preferred according to the invention are derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane, diphenyldimethylmethane, bisphenone, diphenylsulfone, thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole, isoxazole, 3,4-oxazole, pyrazole , 2,5-diphenyl-1, 3,4-oxadiazole, 1,3,4-thiadiazole, 1,3,4-triazole, 2,5-diphenyl-1,3,4- triazole, 1,2,5-triphenyl-1, 3,4-triazole, 1, 2,4-oxadiazole, 1, 2,4-thiadiazole, 1, 2,4-triazole, 1, 2,3-triazole, 1, 2,3,4-tetrazole, benzo [b] thiophene,
• the preferred alkyl groups include the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl, tert-butyl radical, 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.
• the preferred cycloalkyl groups include the cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and the cyclooctyl group, which are optionally substituted with branched or unbranched alkyl groups.
• the preferred alkenyl groups include the vinyl, allyl, 2-methyl-2-propene, 2-butenyl, 2-pentenyl, 2-decenyl and the 2-eicosenyl groups.
• the preferred alkynyl groups include the ethynyl, propargyl, 2-methyl-2-propyne, 2-butynyl, 2-pentynyl and the 2-decynyl group.
• the 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 group, hexyloxycarbonyl, 2-methylhexyloxycarbonyl, decyloxycarbonyl or dodecyloxycarbonyl group.
• Preferred alkoxy groups include alkoxy groups whose hydrocarbon residue is one of the preferred alkyl groups mentioned above.
• the preferred cycloalkoxy groups include cycloalkoxy groups whose hydrocarbon radical is one of the preferred cycloalkyl groups mentioned above.
• the preferred heteroatoms contained in the R 7 radical include 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 preferably be represented by the formula NH.
• the number ratio of heteroatoms to carbon atoms in the radical R 7 of the formula (IM) can be in wide ranges. This ratio is preferably in the range from 1: 1 to 1:10, in particular 1: 1 to 1: 5 and particularly preferably 1: 2 to 1: 4.
• the radical R 7 of the formula (III) comprises 2 to 1000 carbon atoms. In a particular aspect, the R 7 radical has at most 10 carbon atoms.
• the polar segments D can be produced in particular by polymerizing corresponding (meth) acrylates.
• 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) acrylamides such as N- (3-dimethylaminopropyl) methacrylamide, dimethylaminopropyl methacrylate, 2-dimethylaminoethyl methacrylate 3-diethylaminopentyl methacrylate, 3-dibutylaminohexadecyl (meth) acrylate;
• Nitriles of (meth) acrylic acid and other nitrogen-containing methacrylates such as
• heterocyclic (meth) acrylates such as 2- (1-imidazolyl) ethyl (meth) acrylate,
• Oxiranyl methacrylates such as
• Phosphorus, boron and / or silicon-containing methacrylates such as 2- (dimethylphosphato) propyl methacrylate, 2- (ethylene phosphito) propyl methacrylate, dimethylphosphinomethyl methacrylate, Dimethylphosphonoethylmethacrylat,
• These monomers can be used individually or as a mixture.
• the ethoxylated (meth) acrylates which can be used to prepare the polar segments D can be obtained, for example, by transesterification of alkyl (meth) acrylates with ethoxylated alcohols which particularly preferably have 1 to 20, in particular 2 to 8, ethoxy groups.
• the hydrophobic radical of the ethoxylated alcohols can 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 in particular 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 in particular Lutensol ® AO 3, Lutensol ® AO 4, Lutensol ® AO 5, Lutensol ® AO 6, Lutensol ® AO 7, Lutensol ® AO 79, Lutensol ® AO 8 and Lutensol ® 89
• aminoalkyl (meth) acrylates and aminoalkyl (meth) acrylic amides for example N- (3-dimethylaminopropyl) methacrylamide (DMAPMAM), and hydroxyalkyl (meth) acrylates, for example 2-hydroxyethyl methacrylate (HEMA), are particularly preferred.
• DMAPMAM N- (3-dimethylaminopropyl) methacrylamide
• HEMA 2-hydroxyethyl methacrylate
• the present invention also relates to multiblock copolymers which have at least three, preferably at least four blocks. These block copolymers can have alternating blocks. In addition, the block copolymers can also be present as comb polymers or as star polymers.
• preferred block copolymers having hydrophobic segments P and polar segments D can be represented by the formula
• Pm-Dn (V) in which m and n independently represent integers in the range from 1 to 40, in particular 1 to 5 and preferably 1 or 2, are represented without this is to be a limitation.
• the length of the hydrophobic and polar segments can vary widely.
• the hydrophobic segments P preferably have a degree of polymerization averaged by weight of at least 10, in particular at least 50.
• the weight-average degree of polymerization of the hydrophobic segments is preferably in the range from 20 to 5000, in particular from 60 to 2000.
• the length of the polar segments D is at least 3, preferably at least 5 and particularly preferably at least 10 monomer units, this number being represented by the index x in formula (III).
• the polar segments D preferably have a degree of polymerization averaged over the weight in the range from 10 to 1000.
• the weight ratio of the polar segments D to the hydrophobic segments P is in the range from 1: 1 to 1: 100, preferably 1: 2 to 1:30.
• the lengths of the hydrophobic segments to the polar segments of the copolymer have a ratio in the range from 10 to 1 to 1 to 10, preferably 5 to 1 to 1 to 2 and particularly preferably 3 to 1 to 1 to 1 , although other aspect ratios of the blocks to one another are intended to be encompassed by the present invention.
• the person skilled in the art is aware of the polydispersity of the block copolymers and of the respective segments. The values given relate to the weight average of the respective molecular weight.
• the friction-reducing block copolymers can be obtained, for example, by changing the composition of the monomer mixture to be polymerized during the polymerization. This can be done continuously or discontinuously, with hydrophobic or polar segments being produced in each case.
• the abovementioned monomers can be polymerized using initiators which have a transferable atomic group.
• these initiators can be described by the formula Y- (X), where Y is the core molecule which is believed to form radicals, X represents a transferable atom or group, and m is an integer in the range of 1 to 10, depending on the functionality of group Y. If m> 1, the different transferable atomic groups X can have different meanings. If the functionality of the initiator is> 2, star-shaped polymers are obtained.
• Preferred transferable atoms or atom groups are halogens, such as Cl, Br and / or J.
• group Y is believed to form free radicals which serve as the starting molecule, which free radical attaches to the ethylenically unsaturated monomers. Therefore, group Y preferably has substituents that can stabilize radicals. These substituents include, among others, -CN, -COR and -C0 2 R, where R each represents an alkyl or aryl radical, aryl and / or heteroaryl groups.
• Alkyl radicals are saturated or unsaturated, branched or linear hydrocarbon radicals with 1 to 40 carbon atoms, such as, for example, methyl, ethyl, propyl, butyl, pentyl, 2-methylbutyl, pentenyl, cyclohexyl, heptyl, 2-methylheptenyl, 3-methylheptyl, octyl, nonyl, 3-ethylnonyl, decyl, undecyl, 4-propenylundecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, cetyleicosyl, docosyl and / or eicosyltetratriacontyl.
• Aryl radicals are cyclic, aromatic radicals which have 6 to 14 carbon atoms in the aromatic ring. These radicals can be substituted.
• Substituents are, for example, linear and branched alkyl groups with 1 to 6 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, 2-methylbutyl or hexyl; Cycloalkyl groups such as cyclopentyl and cyclohexyl; aromatic groups such as phenyl or naphthyl; Amino groups, ether groups, ester groups and halides.
• aromatic radicals include, for example, phenyl, xylyl, toluyl, naphthyl or biphenyl.
• heteroaryl denotes a heteroaromatic ring system in which at least one CH group is replaced by N or two adjacent CH groups are replaced by S, O or NH, such as a residue of thiophene, furan, Pyrrole, thiazole, oxazole, pyridine, pyrimidine and benzo [a] furan, which can also have the aforementioned substituents.
• An initiator which can be used according to the invention can be any compound which has one or more atoms or groups of atoms which can be transferred radically under the polymerization conditions.
• Suitable initiators include those of the formulas:
• R 10 is an alkyl group of 1 to 20 carbon atoms, each
• Hydrogen atom independently through a halide, preferably fluride or
• Chloride can be replaced, alkenyl of 2 to 20 carbon atoms, preferably vinyl, alkynyl of 2 to 10 carbon atoms preferably
• Alkyl group is an alkyl of 1 to 6 carbon atoms, such as
• N 3 represents where R 14 is an aryl group or a linear or branched one
• R 5 * , R 6 ' and R 7 * are as previously defined, COCI, OH, (preferably one of the radicals R 11 , R 12 and R 13 is OH), CN, alkenyl or alkynyl groups having 2 to 20 carbon atoms, preferably 2 to 6 carbon atoms and particularly preferably allyl or vinyl, oxiranyl, glycidyl, alkylene or alkenylene groups having 2 to 6 carbon atoms which are substituted with oxiranyl or glycidyl, aryl, heterocyclyl, aralkyl, aralkenyl (aryl.es alkenyl, where aryl is as previously defined and alkenyl is vinyl which is substituted by one or two Ci to C alkyl groups and / or halogen atoms, preferably substituted by chlorine), alkyl groups having 1 to 6 carbon atoms in which one to all of the hydrogen atoms, preferably one, are substituted by halogen , (preferably flu
• the particularly preferred initiators include benzyl halides, such as p-chloromethylstyrene, ⁇ -dichloroxylene, ⁇ , ⁇ -dichloroxylene, ⁇ , ⁇ -dibromoxylene and Hexakis ( ⁇ -bromomethyl) benzene, benzyl chloride, benzyl bromide, 1-bromo-1-phenylethane and 1-chloro-1-phenylethane;
• benzyl halides such as p-chloromethylstyrene, ⁇ -dichloroxylene, ⁇ , ⁇ -dichloroxylene, ⁇ , ⁇ -dibromoxylene and Hexakis ( ⁇ -bromomethyl) benzene, benzyl chloride, benzyl bromide, 1-bromo-1-phenylethane and 1-chloro-1-phenylethane;
• Carboxylic acid derivatives which are halogenated at the ⁇ -position such as, for example, propyl 2-bromopropionate, methyl 2-chloropropionate, ethyl 2-chloropropionate, methyl 2-bromopropionate, ethyl 2-bromoisobutyrate; Tosyl halides such as p-toluenesulfonyl chloride; Alkyl halides such as carbon tetrachloride, tribromo (meth) an, 1-vinylethyl chloride, 1-vinylethyl bromide; and halogen derivatives of phosphoric acid esters such as dimethyl phosphoric acid chloride.
• Tosyl halides such as p-toluenesulfonyl chloride
• Alkyl halides such as carbon tetrachloride, tribromo (meth) an, 1-vinylethyl chloride, 1-vinylethyl
• the initiator is generally used in a concentration in the range from 10 "4 mol / L to 3 mol / L, preferably in the range from 10 " 3 mol / L to 10 "1 mol / L and particularly preferably in the range from 5 * 10 " 2 mol / L to 5 * 10 "1 mol / L, without this being intended to be a limitation.
• the ratio of initiator to monomer gives the molecular weight of the polymer if the entire monomer is reacted. This ratio is preferably in the range of 10 "4 to 1 to 0.5 to 1, particularly preferably in the range from 5 * 10 " 3 to 1 to 5 * 10 "2 to 1.
• catalysts which comprise at least one transition metal.
• the transferable atomic group and the catalyst reversibly form a compound, the oxidation state of the transition metal being increased or decreased. It is assumed that free radicals are released or trapped, so that the radical concentration remains very low.
• transition metal compound to the transferable atomic group to insert ethylenically unsaturated monomers into the YX or Y (M) Z -X bond is made possible or facilitated, where Y and X have the meaning given above and M denotes the monomers, while z represents the degree of polymerization.
• Preferred transition metals are Cu, Fe, Cr, Co, Ne, Sm, Mn, Mo, Ag, Zn, Pd, Pt, Re, Rh, Ir, In, Yd, and / or Ru, which are used in suitable oxidation states. These metals can be used individually or as a mixture. It is believed that these metals catalyze the redox cycles of the polymerization, for example the redox pair Cu + / Cu 2+ or Fe 2+ / Fe 3+ is effective.
• the metal compounds as halides such as chloride or bromide, as alkoxide, hydroxide, oxide, sulfate, phosphate, or hexafluorophosphate, trifluoromethane sulfate are added to the reaction mixture.
• the preferred metallic compounds include Cu 2 0, CuBr, CuCI, Cul, CuN 3 , CuSCN, CuCN, CuN0 2 , CuN0 3 , CuBF 4 , Cu (CH 3 COO) Cu (CF 3 COO), FeBr 2 , RuBr 2 , CrCI 2 and NiBr 2 .
• the transition metals can be used as metal in the zero oxidation state, in particular in a mixture with the aforementioned compounds for catalysis, as is shown, for example, in WO 98/40415.
• the reaction rate of the reaction can be increased. It is believed that this increases the concentration is increased catalytically active transition metal compound by transition metals in a high oxidation state with metallic transition metal.
• the molar ratio of transition metal to initiator is generally in the range from 0.0001: 1 to 10: 1, preferably in the range from 0.001: 1 to 5: 1 and particularly preferably in the range from 0.01: 1 to 2: 1, without that this should result in a restriction.
• the polymerization takes place in the presence of ligands which can form a coordination compound with the metallic catalyst or catalysts.
• these ligands serve to increase the solubility of the transition metal compound.
• Another important function of the ligands is that the formation of stable organometallic compounds is avoided. This is particularly important since these stable compounds would not polymerize under the chosen reaction conditions.
• the ligands facilitate the abstraction of the transferable group of atoms.
• ligands are known per se and are described, for example, in WO 97/18247, WO 98/40415. These compounds generally have one or more nitrogen, oxygen, phosphorus and / or sulfur atoms via which the metal atom can be bonded. Many of these ligands can generally be represented by the formula R 16 -Z- (R 18 -Z) m -R 17 , in which R 16 and R 17 independently denote H, d to C 20 alkyl, aryl, heterocyclyl, which may can be substituted. These substituents include alkoxy radicals and the alkylamino radicals. R 16 and R 17 can optionally form a saturated, unsaturated or heterocyclic ring.
• Z means O, S, NH, NR 19 or PR 19 , where R 19 has the same meaning as R 16 .
• R 8 independently denotes a divalent group with 1 to 40 C atoms, preferably 2 to 4 C atoms, which are linear, can be branched or cyclic, such as a methylene, ethylene, propylene or butylene group. The importance of alkyl and aryl has been explained previously.
• Heterocyclyl radicals are cyclic radicals with 4 to 12 carbon atoms, in which one or more of the CH 2 groups of the ring are replaced by hetero atom groups, such as O, S, NH, and / or NR, where the radical R, which has the same meaning, like R 16 has.
• R 1 , R 2 , R 3 and R 4 independently denote H, d to C 20 alkyl, aryl, heterocyclyl and / or heteroaryl, the radicals R 1 and R 2 or R 3 and R 4 can together form a saturated or unsaturated ring.
• Preferred ligands here are chelate ligands which contain N atoms.
• the preferred ligands include triphenylphosphine, 2,2-bipyridine, alkyl-2,2-bipyridine, such as 4,4-di- (5-nonyl) -2,2-bipyridine, 4,4-di- (5 heptyl) - 2,2 bipyridine, tris (2-aminoethyl) amine (TREN), N, N, N, N ', N "-pentamethyldiethylenetriamine, 1.1, 4,7,10,10- Hexamethyltriethlyentetramin and / or tetramethylethylene diamine
• TREN (2-aminoethyl) amine
• N, N, N, N ', N "-pentamethyldiethylenetriamine 1.1, 4,7,10,10- Hexamethyltriethlyentetramin and / or tetramethylethylene diamine
• TREN (2-aminoethyl) amine
• TREN 2,7,10,10- He
• the ratio of ligand to transition metal depends on the denticity of the ligand and the coordination number of the transition metal.
• the molar ratio is in the range 100: 1 to 0.1: 1, preferably 6: 1 to 0.1: 1 and particularly preferably 3: 1 to 0.5: 1, without any intention that this should impose a restriction.
• the monomers, the transition metal catalysts, the ligands and the initiators are selected depending on the desired polymer solution. It is believed that a high rate constant of the reaction between the transition metal-ligand complex and the transferable atomic group is essential for a narrow molecular weight distribution. If the rate constant of this reaction is too low, the concentration of radicals becomes too high, so that the typical termination reactions occur, which are responsible for a broad molecular weight distribution.
• the exchange rate depends, for example, on the transferable atom group, the transition metal, the ligands and the anion of the transition metal compound. Those skilled in the art will find valuable information on the selection of these components, for example, in WO 98/40415.
• the block copolymers according to the invention can also be obtained, for example, by means of RAFT methods ("Reversible Addition Fragmentation Chain Transfer").
• RAFT methods Reversible Addition Fragmentation Chain Transfer
• This method is described in detail in WO 98/01478, for example, to which express reference is made for the purposes of the disclosure.
• the monomer compositions are carried out in the presence of chain transfer agents so that "living" radical polymerization takes place.
• Dithiocarboxylic acid esters are used in particular, polymeric dithiocarboxylic acid esters also being known.
• the preferred chain transfer agents include, in particular, dithiocarboxylic acid esters of the formula
• radical R 1 represents hydrogen, halogen or a group having 1 to 20 carbon atoms and the radical Z represents a group having 1 to 20 carbon atoms.
• the radicals R 1 and / or Z preferably have a radical-stabilizing group.
• radical stabilizing group has been explained in relation to the ATRP process.
• the preferred dithiocarboxylic acid esters include cumyl dithioformate (2-phenylprop-2-yl dithioformate), cumyl dithiobenzoate (2-phenylprop-2-yl dithiobenzoate), benzyl dithiobenzoate and benzyl dithioacetate.
• RAFT polymerization is generally started with classic radical formers.
• classic radical formers include, among others, the azo initiators well known in the art, such as AIBN and 1, 1-azobiscyclohexane carbonitrile, and also peroxy compounds, such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert.-butyl per-2-ethylhexanoate, ketone peroxide, tert-butyl peroctoate, methyl peronutoxate, methyl peroxide, Dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, 2,5-bis (2-ethylhexanoyl-peroxy) -2,5-dimethylhexane, tert-butyl peroxy-2- ethylhexanoate, tert-butyl per
• the polymerization can be carried out under normal pressure, negative pressure or positive pressure.
• the polymerization temperature is also not critical. In general, however, it is in the range from -20 ° to 200 ° C, preferably 0 ° to 130 ° C and particularly preferably 60 ° to 120 ° C.
• the polymerization can be carried out with or without a solvent.
• solvent is to be understood broadly here.
• the polymerization is preferably carried out in a non-polar solvent.
• a non-polar solvent include hydrocarbon solvents, such as, for example, aromatic solvents, such as toluene, benzene and xylene, saturated hydrocarbons, such as, for example, cyclohexane, heptane, octane, nonane, decane, dodecane, which can also be branched.
• hydrocarbon solvents such as, for example, aromatic solvents, such as toluene, benzene and xylene
• saturated hydrocarbons such as, for example, cyclohexane, heptane, octane, nonane, decane, dodecane, which can also be branched.
• solvents can be used individually or as a mixture.
• Particularly preferred solvents are mineral oils and synthetic oils and mixtures thereof. Of these, mineral oils are particularly preferred.
• Mineral oils are known per se and are commercially available. They are generally obtained from crude oil or crude oil by distillation and / or refining and, if appropriate, further purification and upgrading processes, the term mineral oil in particular denoting the higher-boiling fractions of Crude or petroleum fall. In general, the boiling point of mineral oil is higher than 200 ° C, preferably higher than 300 ° C, at 50 mbar. It is also possible to produce by smoldering shale oil, coking hard coal, distilling with the exclusion of air from brown coal and hydrogenating hard coal or brown coal. To a small extent, mineral oils are also made from raw materials of vegetable (e.g. jojoba, rapeseed) or animal (e.g. claw oil) origin. Accordingly, mineral oils have different proportions of aromatic, cyclic, branched and linear hydrocarbons depending on their origin.
• vegetable e.g. jojoba, rapeseed
• animal e.g. claw oil
• paraffin-based, naphthenic and aromatic components in crude oils or mineral oils, the terms paraffin-based component standing for longer-chain or strongly branched iso-alkanes and naphthenic component for cycloalkanes.
• mineral oils have different proportions of n-alkanes, iso-alkanes with a low degree of branching, so-called monomethyl-branched paraffins, and compounds with heteroatoms, in particular O, N and / or S, which are said to have polar properties.
• the proportion of n-alkanes in preferred mineral oils is less than 3% by weight, the proportion of O, N and / or S-containing compounds is less than 6% by weight.
• mineral oil mainly comprises naphthenic and paraffin-based alkanes, which generally have more than 13, preferably more than 18 and most preferably more than 20 carbon atoms.
• the proportion of these compounds is generally> 60% by weight, preferably> 80% by weight, without any intention that this should impose a restriction.
• Liquid chromatography on silica gel shows the following components, the percentages relating to the total weight of the mineral oil used in each case: n-alkanes with about 18 to 31 carbon atoms:
• Aromatics with 14 to 32 carbon atoms :
• Synthetic oils include organic esters, organic ethers, such as silicone oils, and synthetic hydrocarbons, especially polyolefins. They are usually somewhat more expensive than mineral oils, but have advantages in terms of their performance.
• synthetic oils can particularly preferably be used as solvents.
• solvents can, inter alia, be present in an amount of from 1 to 99% by weight, preferably from 5 to 95% by weight, particularly preferably from 5 to 60% by weight and very particularly preferably from 10 to 50% by weight to the total weight of the mixture, are used without any limitation.
• the block copolymers produced in this way generally have a molecular weight in the range from 1,000 to 1,000,000 g / mol, preferably in the range from 10 * 10 3 to 500 * 10 3 g / mol and particularly preferably in the range from 20 * 10 3 to 300 * 10 3 g / mol, without any limitation. These values relate to the weight average molecular weight of the polydisperse polymers in the composition.
• the particular advantage of ATRP or RAFT compared to the conventional radical polymerization process is that polymers with a narrow molecular weight distribution can be produced.
• the polymers according to the invention have a polydispersity, which is given by M w / M n , in the range from 1 to 12, preferably 1 to 4.5, particularly preferably 1 to 3 and very particularly preferably 1, 05 to 2.
• the weight average molecular weight M w and the number average molecular weight M n can be determined by known methods, for example by gel permeation chromatography (GPC).
• the lubricant compositions according to the invention comprise base oil.
• base oil any compound that provides a sufficient lubricating film that does not crack even at elevated temperatures is suitable as the base oil.
• the viscosities can be used, such as those specified for engine oils in the SAE specifications. Suitable compounds include natural oils, mineral oils and synthetic oils as well as mixtures thereof.
• Natural oils are animal or vegetable oils, such as claw oils or jojoba oils. Mineral oils have previously been described in detail as solvents. They are particularly advantageous in terms of their low price. Synthetic oils include organic esters, synthetic hydrocarbons, especially polyolefins, which meet the aforementioned requirements. They are usually somewhat more expensive than mineral oils, but have advantages in terms of their performance.
• the lubricants according to the invention are particularly suitable as greases and lubricating oils, which include motor oils, gear oils, turbine oils, hydraulic fluids, pump oils, heat transmission oils, insulating oils, cutting oils and cylinder oils.
• the lubricant compositions according to the invention can have one or more additives which are widely known in the art.
• additives include viscosity index improvers, antioxidants, anti-aging agents, corrosion inhibitors, detergents, Dispersants, EP additives, defoamers, friction reducers, pour point depressants, dyes, odorants and / or demulsifiers.
• the additives cause a favorable flow behavior at low and high temperatures (improvement in the viscosity index), they suspend solids (detergent-dispersant behavior), neutralize acidic reaction products and the like. form a protective film on the cylinder surface (EP additive, for "extreme pressure”).
• EP additive for "extreme pressure”
• the amounts in which these additives are used depend on the area of application of the lubricant. In general, however, the proportion of the base oil is between 25 to 90% by weight, preferably 50 to 75% by weight.
• the proportion of friction-reducing block copolymer in the lubricants according to the invention is preferably in the range from 0.01 to 50% by weight, particularly preferably in the range from 0.01 to 25% by weight.
• the proportion of friction-reducing block copolymer in the lubricants according to the invention can also be from 0.01 to 100% by weight. be.
• the RAFT polymerization experiments were carried out in a round-bottom flask equipped with saber stirrer, patio heater, nitrogen transfer, intensive cooler and dropping funnel.
• 608.0 g of the LI A mixture (LIMA: mixture of long-chain methacrylates, which was obtained from the reaction of methyl methacrylate with ®LIAL 125 from Sasol; C ⁇ 2 to C 15 fatty alcohol) together with 2.90 g of cumyldithiobenzoate, 1 , 22 g of tBPO (tert-butyl peroctoate) and 160 g of mineral oil are placed in the reaction flask and rendered inert by adding dry ice and passing nitrogen. The mixture was then heated to 85 ° C. with stirring.
• the structure of the VI improvers was investigated using chromatographic analysis methods such as size exclusion chromatography (SEC), gradient high-pressure liquid chromatography (gradient HPLC) and two-dimensional liquid chromatography. The results obtained are shown in Table 1.
• the structure of the VI improvers was investigated using chromatographic analysis methods such as size exclusion chromatography (SEC), gradient high-pressure liquid chromatography (gradient HPLC) and two-dimensional liquid chromatography. The results obtained are shown in Table 1.
• DMAPMAM N- (3-dimethylaminopropyl) methacrylamide
• Ethoxylated methacrylate methacrylate available by transesterification of
• DMAEMA dimethylaminoethyl methacrylate Examples 5 to 8 and Comparative Examples 5 to 8, 10 and 11
• Figure 1 shows the friction behavior of the paraffin-based base oil mixture according to Comparative Example 10 as a function of the average speed of the two surfaces moving against each other.
• the data obtained are shown as a solid line.
• the friction curve of the lubricating oil with the non-dispersing VI improver according to Comparative Example 11 shows absolutely a slightly reduced coefficient of friction, but no improvement in terms of the friction behavior towards low speeds.
• the data obtained are shown as filled circles (•).
• the curvature of the curve is almost identical within the scope of the measurement accuracy, which means that mixed and limit friction areas can be reached at an unchanged high speed.
• the absolute lowering The course of friction in the case of the polymer-containing formulation can be attributed here to the replacement of base oil components by a proportion of VI improver (comparative example 9) in the lubricant composition.
• Figure 2 shows the Stribeck curves of the lubricant mixture according to Example 5, Comparative Example 5 and Comparative Example 11.
• the data of the lubricant mixture according to Example 5 are open squares (D)
• the data of the lubricant mixtures according to Comparative Example 5 and Comparative Example 11 are filled squares ( ⁇ ) or as filled circles (•).
• Figure 2 shows that the lubricant that contains the VI improver according to Example 1 has a significantly reduced coefficient of friction from a speed of 0.4 m / s.
• the friction curve of the Stribeck curve is so far shifted to low speeds that within the scope of the measurement possibilities of the mini traction machine up to 0.0056 m / s, no significant increase in the friction coefficient can be observed.
• the speed range between 0.4 and 0.04 m / s there is even a slight reduction in the coefficient of friction as the speed decreases.
• Figure 3 shows the Stribeck curves of the lubricant mixture according to Example 6, Comparative Example 6 and Comparative Example 11.
• the data of the lubricant mixture according to Example 6 are open squares (D)
• the data of the lubricant mixtures according to Comparative Example 6 and Comparative Example 11 are filled squares ( ⁇ ) or as filled circles (•).
• Figure 4 shows the Stribeck curves of the lubricant mixture according to Example 7, Comparative Example 7 and Comparative Example 11.
• the data of Lubricant mixture according to Example 7 are shown as open squares (D)
• the data of the lubricant mixtures according to Comparative Example 7 and Comparative Example 11 are shown as filled squares ( ⁇ ) or as filled circles (•).
• Figure 5 shows the Stribeck curves of the lubricant mixture according to Example 8, Comparative Example 8 and Comparative Example 11.
• the data of the lubricant mixture according to Example 8 are open squares (D)
• the data of the lubricant mixtures according to Comparative Example 8 and Comparative Example 11 are filled squares ( ⁇ ) or as filled circles (•).

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