EP1558715B1 - Verwendung Schmieröls zur Reduzierung des Kraftstoffverbrauchs - Google Patents

Verwendung Schmieröls zur Reduzierung des Kraftstoffverbrauchs Download PDF

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EP1558715B1
EP1558715B1 EP03750716A EP03750716A EP1558715B1 EP 1558715 B1 EP1558715 B1 EP 1558715B1 EP 03750716 A EP03750716 A EP 03750716A EP 03750716 A EP03750716 A EP 03750716A EP 1558715 B1 EP1558715 B1 EP 1558715B1
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use according
general formula
additives
ranging
lubricating
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French (fr)
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EP1558715A1 (de
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Silvano Fattori
Mauro Anzani
Antonio Vettor
Giuseppe Tripaldi
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Eni SpA
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Eni SpA
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    • 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/045—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and non-macromolecular compounds
    • 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
    • C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/0206—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbased sulfonic acid salts
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal salts
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089—Overbased salts
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
    • 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
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines

Definitions

  • the present invention relates to lubricating compositions capable of guaranteeing an improvement in the fuel economy performances of internal combustion engines, also without resorting to specific additives conventionally known as friction modifiers or reducers.
  • the above compositions envisage the presence of particular deterging additives selected from the group of sulfophenates, preferably superbasic, and particular anti-wear additives having the general formula ZnP 2 S 4 O 4 R 4 .
  • lubricants serve to protect metallic surfaces from direct contact, and this role, at hydrodynamic or elasto-hydrodynamic lubrication regimes (hereinafter indicated as H regimes), is effected thanks to a fundamental characteristic of the oil, i.e. its viscosity.
  • H regimes hydrodynamic or elasto-hydrodynamic lubrication regimes
  • the higher the viscosity the more the presence of thick lubricating layers on the metallic surface, for its protection, is guaranteed.
  • high viscosity values which is a representative parameter of intermolecular friction leads to a more difficult flow of the lubricating layers and to the generation of passive friction which dissipates useful mechanical energy.
  • the greater fluidity of the oils at H regimes is obtained by improving the characteristics of the base oils and polymeric additives, particularly viscosity modifier and/or viscosity index enhancer additives.
  • Measurement of the friction coefficient variations at the various lubrication regimes is a useful method for identifying new and advantageous solutions for the formulation of f.e. products.
  • These measurements can be conveniently effected by means of a ball-on-disk tribometer which operates under mixed movement conditions of the rolling/sliding type.
  • a ball-on-disk tribometer which operates under mixed movement conditions of the rolling/sliding type.
  • SLC Stribeck-Like Curves
  • the definitive validation of the above tribological measurements is obtained by means of engine tests required by specifications on the part of European, American and Japanese organisms and manufacturers.
  • organometallic additives with Molybdenum for example dithiophosphates, dithiocarbamates, dithioamides
  • organometallic additives with Molybdenum for example dithiophosphates, dithiocarbamates, dithioamides
  • tribo-reactions chemical reactions in the solid-solid contact area
  • EP-A-0913455 discloses a lubricant composition comprising sulfurized phenates and ZnDTP which are P esters, used to improve fuel economy.
  • Molybdenum increases the content of ashes, metals, sulfur and (at times) phosphorous of the mixture, and these variations are not coherent with the necessity of improving the compatibility of the oils with post-treatment systems of the exhaust gases of vehicles.
  • polar ester products can generally create a negative competition with respect to the solid to defend, obstructing the action of the anti-wear additive.
  • Lubricating compositions for engine oils have now been found, which are capable of improving the f.e. performance of an internal combustion engine lubricated with the above lubricating compositions, which overcome the drawbacks indicated above.
  • the present invention relates to lubricating compositions for internal combustion engines capable of reducing the fuel consumption of engines lubricated by the compositions themselves, the above lubricating compositions comprising:
  • the sulfophenates (I) salified with calcium can be neutral or superbasic, preferably superbasic.
  • superbasic means that the above sulfophenates are treated with a quantity of base which is higher than the stoichiometric value. The above excess normally ranges from about 125% to about 220% molar.
  • the detergent additives comprise (i) from 60 to 100% by weight of sulfophenates having general formula (I) and may comprise (ii) from 0 to 40% by weight of other detergents selected from calcium sulfonates, calcium alkylbenzene sulfonates, calcium salicylate.
  • the anti-wear additives used have a general formula of the type ZnP 2 SgO 4 R 4 , wherein R 4 is an alkyl radical having the formula -CH 2 R 5 , wherein R 5 is a linear and/or branched saturated alkyl radical, having from 2 to 15, preferably from 2 to 7, carbon atoms.
  • R 5 is preferably selected from -(CH 2 ) 3 CH 3 , -CH(CH 3 )CH 3 , -C(CH 3 ) 3 , and relative mixtures.
  • compositions used in the present invention can also be obtained using compositions which contain, in addition to components (a)-(c), friction modifying or reducing additives, provided they are compatible with the same components (a) - (c).
  • the base oils (a) are selected from one or more of mineral or synthetic oils (among synthetic oils, poly ⁇ -olefins (PAO) and ester bases can be mentioned), typically used in lubricating oils for internal combustion engines fed by both gasoline and gas oil.
  • the base oils can come from various processings, for example from hydro-refining or conversion processes of heavy waxes. Mixtures of mineral or synthetic oils can obviously be used.
  • the viscosity of the above base oils can fall within a range of 2.0 to 10.0 mm 2 /s, preferably from 2.5 to 8.0 mm 2 /s, measured at 100°C.
  • These bases, also possibly mixed with each other, are contained in a predominant quantity, reaching, in relation to the remaining group of additives necessary, up to 95-98% w; their concentration is typically equal to about 85% w.
  • An object of the invention also relates to the fuel economy upgrading of secondary synergic properties of the above detergent and anti-wear additives, as these additives are typically used in the formulation of lubricating oils for internal combustion engines, to guarantee compliance with various specifications.
  • a further object of the invention relates to a method which allows convenient and economical f.e. products to be formulated, without resorting to potentially critical variations to the already complex lubricating mixture.
  • Another important object of the invention relates to the possibility of ensuring a high duration of the f.e. performances, due to the fact that said performances are guaranteed by additives traditionally used for long durations, as a much greater duration range of the oil must be guaranteed with respect to the range required by the f.e. engine test.
  • the invention is the use of anti-wear additives of the zinc alkyl dithiophosphate type and detergents of the sulfophenate type which, when mixed in suitable ratios in a typical formulation for engine oils, give the mixture an evident fuel economy advantage.
  • the f.e. performance can be obtained within a range of concentrations which, for anti-wear, varies from 0.3 to 5.0 %w, preferably from 0.8 to 3.0 %w; for the sulfophenate detergent from 0.5 to 5.0%w, preferably from 1.0 to 4.0%w.
  • said mixture significantly reduces the friction coefficient at regimes closest to boundary conditions, and in particular, also the friction coefficient at regimes closest to M and H conditions.
  • the lubricating composition used in the present invention can contain one or more components normally used in formulations for engines oils, for example viscosity index enhancers and/or viscosity modifiers, dispersing agents, antioxidants, anti-rust agents, anti-foam agents, demulsifiers, pour point depressants.
  • viscosity index enhancers and/or viscosity modifiers for example viscosity index enhancers and/or viscosity modifiers, dispersing agents, antioxidants, anti-rust agents, anti-foam agents, demulsifiers, pour point depressants.
  • Ashless nitrogenated dispersing agents typically used normally comprise oil-soluble polymeric structures functionalized with nitrogenated substituents capable of aggregating with polar particles or substances to be dispersed.
  • the dispersing agents typically contain one or more nitrogenated parts bound to the polymeric skeleton, often by means of a bridge, and can be selected from all the known oil-soluble derivates, such as salts, amides, imides, amino-esters, oxyazolinic derivatives of mono or dicarboxylic acids with a long hydrocarbon chain and relative hydrocarbon anhydrides; long-chain thiocarboxylates of hydrocarbons to which a polyamine is directly bound; Mannich condensation products formed by condensation between long-chain substituted phenols with formaldehyde and polyalkylene polyamines. Numerous examples of dispersing agents are indicated in patent literature, for example in US-A-5,962,381 .
  • Non-nitrogenated dispersing agents also exist, for example esters prepared by reaction between functionalized oil-soluble polymeric hydrocarbons and hydroxyl compounds, such as mono or polycarboxylic alcohols, or with aromatic compounds such as phenols and naphthols. Ester dispersing agents can also be prepared starting from unsaturated alcohols such as allyl alcohol, or starting from ether-alcohols.
  • Convenient viscosity modifiers which can be added to the lubricating composition of the present invention comprise oil-soluble polymers having an weight average molecular weight ranging from about 10,000 to about 1,000,000, preferably from about 20,000 to about 500,000, as determined by gel permeation chromatography or light scattering methods.
  • Typical examples of these polymers comprise polyisobutene, ethylene/propylene/alphaolefin copolymers, (co)polymethacrylates, copolymers of styrene and acrylic esters, copolymers of vinyl compounds and unsaturated carboxylic acids; partially hydrogenated copolymers of styrene and isoprene, styrene and butadiene, isoprene and butadiene; partially hydrogenated homopolymers of butadiene and isoprene.
  • Viscosity modifying compounds also exist, which act as dispersing agents - viscosity modifiers, see for example US-A-4,089,794 ; US-A-4,160,739 and US-A-4,137,185 .
  • Other dispersing agents - viscosity modifiers are ethylene or propylene copolymers grafted with nitrogenated compounds, see for example US-A-4,068,056 , US-A-4,146,489 and US-A-4,149,984 .
  • the f.e. lubricating composition of the present invention can also contain antioxidants, which reduce the tendency of mineral oils to degrade by thermo-oxidation during their use.
  • antioxidants are hindered phenols, variously substituted aromatic amines, salts of alkaline-earth metals of alkylphenol thioesters having C 5 to C 12 side chains, calcium nonylphenol sulfide, oil-soluble phenates, sulfurized phenates.
  • Typical anti-rust compounds which can be used in the lubricating composition of the present invention are polyoxyalkylene polyols and relative esters, and polyoxyalkylene phenols.
  • demulsifying agents can be obtained by the reaction between an alkylene oxide and an adduct obtained by reacting a bis-epoxide with a polyhydroxyl alcohol (see EP-A-330,522 ).
  • Anti-foam agents which can be used are compounds of the polysiloxane type, for example silicon oil or polydimethyl siloxanes.
  • additives are pour point depressants which lower the minimum temperature at which the fluid flows and can be poured.
  • Typical examples of these additives which improve the fluidity at low temperatures of the lubricating composition are the well-known dialkyl fumarate/vinyl acetate copolymers and polyalkyl methacrylates.
  • the lubricating composition of the present invention is prepared by the conventional mixing of the various components, both essential and complementary.
  • the lubricating composition of the present invention is characterized by a more favourable SLC with respect to the corresponding formulation without these specific detergent and anti-wear additives. This advantage can be observed along the whole measurement rate range, thus being indifferently apparent in one or more of the "hydrodynamic”, elasto-hydrodynamic", “mixed” and “boundary” conditions.
  • a preparative operating sequence of the instrument was prepared, gradual heating from a low to high temperature (from 40 to 135°C), friction coefficient measurements by curves at various S/R values, and the construction of the SLC.
  • an SLC curve of this type obtained in the final phase at 135°C), useful for evaluating potential energy dissipations, is indicated in Figure 1 .
  • each curve is constructed with average data of at least two tests and the standard deviation is always lower than 10%.
  • the friction coefficient values are extracted from these curves at the inlet rates of 0.01 - 0.1 - 1.0 m/sec ( figure 1 ); these values were considered, for the sake of comparison, as being representative of the boundary, mixed and hydrodynamic (or elasto-hydrodynamic) lubrication regimes (B, M, H) respectively.
  • the relative comparison between the terns of friction coefficient values thus obtained on the various mixtures, rather than their absolute value, allows a conclusion to be reached as to their fuel economy potentiality.
  • the formulations relating to this example (F1-C, F2, F3-C), together with the common complementary components, all envisage the use of an anti-wear additive zinc dithiophosphate of primary alcohols (DTP1-A), as per Table 1.
  • DTP1-A zinc dithiophosphate of primary alcohols
  • F1-C a sulfonate detergent (SF) however was used, for F2, a sulfophenate (SFF1), and for F3-C a salicylate (SL), all superbasic.
  • the formulations of this example all contain a primary zinc alkyl dithiophosphate anti-wear additive, but with a different organic structure from the previous one (DTP1-B, see the Note to Table 1).
  • the formulation F7-C contains the detergent SF, F8 the detergent SFF1, F9-C the detergent SL.
  • Both of the formulations F10-C and F11 were prepared with PAO bases and with superbasic sulfophenate detergent SFF2, having a different structure with respect to that used in the other examples (see the Note to Table 1). Furthermore:
  • the friction coefficient data confirm the synergic action of the sulfophenate/primary dithiophosphate pair, with respect to the analogous sulfophenate/secondary dithiophosphate pair.
  • the sulfophenate/primary dithiophosphate pair shows unexpected antifriction performances, it is important to verify that said performances are compatible and coherent with respect to additives specifically commercialized as antifriction agents, particularly with respect to Molybdenum additives and ashless additives of an ester nature (see the state of the art).
  • 4 formulations were prepared, all containing an anti-wear agent zinc dithiophosphate of primary alcohols DTP1-A.
  • the first two (F12, F13) also contain the other component which serves for the antifriction synergy claimed (a sulfophenate, SFF1).
  • the first (F12) also contains a Molybdenum anti-wear additive (MoDTC)
  • the second (F13) contains an ashless ester antifriction additive (GMO).
  • the further formulations F14-C and F15-C, both containing the antifriction additive GMO, contain a sulfonate (SF) and salicylate (SL) detergent, respectively.
  • the addition of the two antifriction additives described allows some of the friction coefficient values to be improved, demonstrating a good compatibility, from this point of view, of the synergic pair towards additives of both species.
  • the results obtained from the further comparative formulations F14-C and F15-C show, on the other hand, that the specific addition of the anti-friction additive GMO, in formulations without the pair of synergic additives claimed, does not provide better results with respect to the F2, object of the invention.
  • the formulations F16-C and F17 are based on XHVI.
  • the formulation F16-C is characterized by a detergent addition to the superbasic sulfonate (SF), anti-wear agent dithiophosphate of secondary alcohols DPT2-A, but with the addition of Molybdenum antifriction agent to try and recuperate a low friction performance on a formulation which does not contain the synergic pair, object of the invention.
  • the formulation F17 of the present invention contains the synergic pair (SFF2/DTP1-B) but without antifriction agent.
  • compositions with significant SLC friction curves were subjected to engine fuel economy evaluation, according to methods prescribed by performance specifications of engine oils.
  • phase II the fuel economy measurement takes place in two distinct phases, one which precedes the aging of the oil (phase I) and the other which follows it (phase II), so that the fuel economy retention can also be evaluated; in the case of the test with an M111 engine, on the other hand, the measurements only refer to the non-aged oil.
  • the formulation which in the group of additives contains the superbasic sulfophenate/primary zinc dithiophosphate pair (F8), object of the present invention, with the Mercedes M111 test, has an FEI value which exceeds the limit of the ACEA A1-B1 specifications (2.5%).
  • compositions tested in this context containing combinations of detergents/anti-wear agents of a different type (F7-C) from those of the present invention, even with the addition of a molybdenum friction modifying additive (F16-C), provide insufficient results with the Sequence VIB test.
  • MoTA Mothioamide

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Claims (16)

  1. Verwendung einer Additivzusammensetzung als reibungsverringerndes Additiv für Schmiermittelzusammensetzungen für Verbrennungsmotoren, umfassend ein Basisöl mit einer Viskosität, die zum Schmieren geeignet ist, wobei die Additivzusammensetzung umfasst:
    (i) Detergensadditive, wobei mindestens 60 Gew.-% der Detergensadditive ausgewählt sind aus Sulphenaten mit der allgemeinen Struktur (I) RΦ(OH)-Sn-(OH) ΦR', wobei R und R' gleich oder unterschiedlich Alkylreste mit von 1 bis 16 Kohlenstoffatomen sind, n von 1 bis 5 reicht; und wobei beide Hydroxyle mit einem oder mehreren Erdalkalimetallen versalzt sind;
    (ii) Abriebfeste Additive ausgewählt aus Zinkdithiophosphaten mit der allgemeinen Formel (II) ZnP2S4O4R4, wobei R ein Alkylrest mit der Formel -CH2R5 ist, wobei R5 ein lineares und/oder verzweigtes gesättigtes Alkylrest ist, mit 2 bis 15 Kohlenstoffatomen;
    wobei die Additivzusammensetzung zu der Schmiermittelzusammensetzung in einer Menge so hinzugefügt wird, dass eine Menge an Detergensadditiven (i) die von 0,5 Gew.-% bis 5,0 Gew.-% bezogen auf das Gesamtgewicht der Schmiermittelzusammensetzung reicht; eine Menge an Abriebfesten Additiven (ii) die von 0,3 Gew.-% bis 5,0 Gew.-% bezogen auf das Gesamtgewicht der Schmiermittelzusammensetzung reicht, zu erhalten.
  2. Verwendung nach Anspruch 1, wobei die Additivzusammensetzung zu der Schmiermittelzusammensetzung in so einer Menge hinzugefügt wird, um eine Menge an Detergensadditiven (i) von 1,0 bis 4%, bezogen auf das Gesamtgewicht der Schmiermittelzusammensetzung zu erhalten.
  3. Verwendung nach Anspruch 1, wobei die Additivzusammensetzung zu der Schmiermittelzusammensetzung in so einer Menge hinzugefügt wird, um eine Menge von abriebfesten Additiven (ii) reichend von 0,8 bis 3,0% bezogen auf das Gesamtgewicht der Schmiermittelzusammensetzung zu erhalten.
  4. Verwendung nach Anspruch 1, wobei mindestens 70 Gew.-% der Detergensadditive (i) ausgewählt ist aus Sulphophenaten mit der allgemeinen Formel (I).
  5. Verwendung nach Anspruch 1, wobei bezogen auf die Verbindung mit der allgemeinen Formel (I) n von 1 bis 4 reicht.
  6. Verwendung nach Anspruch 1, wobei bezogen auf die Verbindung mit der allgemeinen Formel (I) beide Hydroxyle in der Paraposition bezogen auf R und R' sind.
  7. Verwendung nach Anspruch 1, wobei bezogen auf die Verbindung mit der allgemeinen Formel (I) beide Hydroxyle mit Calcium versalzt sind.
  8. Verwendung nach Anspruch 7, wobei das mit Calcium versalzte Detergensadditiv mit der allgemeinen Formel (I) eine Gesamtbasenzahl (total base number, TBN) die von 50 bis 400 reicht, aufweist.
  9. Verwendung nach Anspruch 8, wobei das mit Calcium versalzte Detergensadditiv mit der allgemeinen Formel (I) eine Gesamtbasenzahl (total base number, TBN) die von 100 bis 300 reicht, aufweist.
  10. Verwendung nach Anspruch 1, wobei die Detergensadditive (i) von 0 Gew.-% bis 40 Gew.-% an Detergentien, die sich von den Verbindungen mit der allgemeinen Formel (I) unterscheiden, ausgewählt aus Calciumsulphonaten, Calciumalkylbenzolsulphonaten, Calciumsalicylat umfassen.
  11. Verwendung nach Anspruch 1, wobei in der Verbindung mit der allgemeinen Formel (II), R ein Alkylrest mit der Formel -CH2R5 ist, wobei R5 ein lineares und/oder verzweigtes, gesättigtes Alkylrest mit 2 bis 7 Kohlenstoffatomen ist.
  12. Verwendung nach Anspruch 11, wobei R5 ausgewählt ist aus: -(CH2)3CH3, - CH(CH3)CH3, -C(CH3)3, und relativen Mischungen.
  13. Verwendung nach Anspruch 1, wobei die Basisöle (a) eine bei 100°C gemessene Viskosität im Bereich von 2,0 bis 10 mm2/s aufweisen.
  14. Verwendung nach Anspruch 13, wobei das Basisöl eine bei 100°C gemessene Viskosität im Bereich von 2,5 bis 8 mm2/s aufweist.
  15. Verwendung nach Anspruch 1, wobei das Basisöl ausgewählt ist aus einem oder mehreren von Mineralölen oder synthetischen Ölen.
  16. Verwendung nach Anspruch 1, wobei R und R' gleich oder unterschiedlich Alkylreste mit von 9 bis 12 Kohlenstoffatomen sind.
EP03750716A 2002-10-31 2003-10-15 Verwendung Schmieröls zur Reduzierung des Kraftstoffverbrauchs Expired - Lifetime EP1558715B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
IT002322A ITMI20022322A1 (it) 2002-10-31 2002-10-31 Olio lubrificante per motori atto a ridurre il consumo di carburante
ITMI20022322 2002-10-31
PCT/EP2003/011419 WO2004039928A1 (en) 2002-10-31 2003-10-15 Lubricating oil for engines suitable for reducing fuel consumption

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EP1558715A1 EP1558715A1 (de) 2005-08-03
EP1558715B1 true EP1558715B1 (de) 2012-12-26

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US5490945A (en) * 1991-04-19 1996-02-13 The Lubrizol Corporation Lubricating compositions and concentrates
US5328620A (en) * 1992-12-21 1994-07-12 The Lubrizol Corporation Oil additive package useful in diesel engine and transmission lubricants
US5744430A (en) * 1995-04-28 1998-04-28 Nippon Oil Co., Ltd. Engine oil composition
CA2251418C (en) * 1997-10-30 2007-08-14 The Lubrizol Corporation A method to improve cu corrosion performance of mo-dtc and active sulfur by adding sunflower oil

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AU2003268940A1 (en) 2004-05-25

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