EP1724329B1 - Combinaison de détergents métalliques dans des compositions d'huiles lubrifiantes - Google Patents

Combinaison de détergents métalliques dans des compositions d'huiles lubrifiantes Download PDF

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Publication number
EP1724329B1
EP1724329B1 EP06112912A EP06112912A EP1724329B1 EP 1724329 B1 EP1724329 B1 EP 1724329B1 EP 06112912 A EP06112912 A EP 06112912A EP 06112912 A EP06112912 A EP 06112912A EP 1724329 B1 EP1724329 B1 EP 1724329B1
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EP
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Prior art keywords
mass
oil composition
salicylate
calcium
magnesium
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EP06112912A
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German (de)
English (en)
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EP1724329A1 (fr
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Robert William Shaw
Ian Alexander Weston Bell
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Infineum International Ltd
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Infineum International Ltd
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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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
    • 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
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/42—Phosphor free or low phosphor content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/45—Ash-less or low ash content
    • 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
    • C10N2030/52—Base number [TBN]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines

Definitions

  • This invention relates to internal combustion engine crankcase lubricating oil compositions (or lubricants), more especially to composition suitable for use in piston engine, especially gasoline (spark-ignited) and diesel (compression-ignited), lubrication; and to use of additives in such compositions for reducing wear.
  • crankcase lubricant is an oil used for general lubrication in an internal combustion engine where an oil sump is situated generally below the crankshaft of the engine and to which circulated oil returns. It is well-known to include additives in crankcase lubricants for several purposes.
  • EP-A-1 338 643 ('643) describes crankcase lubricants that contain overbased calcium or magnesium salicylate and that have less than 50 ppm of phosphorus. '643 describes tests on an example of such a lubricant, containing calcium salicylate and having no phosphorus, to measure the average cam wear, which is reported to be within ILSAC GF-3 engine test limits.
  • a problem in the disclosure of '643 is that it concerns itself with cam wear alone, not with cam and lifter wear combined, in low phosphorus-content crankcase lubricants that contain a salicylate-based detergent system.
  • Cam ⁇ plus ⁇ lifter wear is one of the parameters of the sequence IIIG test, which is an API Category SM, ILSAC Category GF-4 test carried out during high temperature conditions and which simulates high-speed service during relatively high ambient temperature conditions.
  • WO 96/37582 A describes use of such combinations but describes them only for providing friction-reducing properties.
  • the present invention provides the magnesium salicylate and calcium salicylate in a defined ratio, in lubricants containing no greater than 0.08 mass % of phosphorus.
  • EP 953629A claims and describes a lubricating oil composition for internal combustion engines which has a high temperature high shear viscosity according to ASTM D 4684 in the range of from 2.1 to less than 2.9 mPas, which composition comprises lubricating base oil and: (1) zinc dialkyldithiophosphate so that the phosphorus content in the oil is from 0.04 to 0.12 mass %, where the relationship between the primary and secondary alcohol in the zinc dialkyldithiophosphate alcohol residue satisfies the following expression in terms of the amount (mass %) of elemental phosphorus in the oil: 0.04 ⁇ (Pri) + (Sec) ⁇ 0.12, and 0 ⁇ (Pri) ⁇ 0.03, where (Pri) is the mass% of primary alcohol residue and (Sec) is the mass% of secondary alcohol residue, and: (2) metallic detergent chosen from (i) calcium alkylsalicylate and (ii) a mixture of calcium alkylsalicylate and magnesium alkylsalicylate
  • the lubricating oil composition is intended to provide good antiwear properties with respect to moving valve parts in four stroke engines. This document teaches that when a mixture of calcium alkylsalicylate and magnesium alkysalicylate is used, the amount of metallic magnesium content in the lubricating oil should not exceed the amount of metallic calcium in the oil.
  • EP 1310549A claims and discloses a crankcase lubricating oil composition
  • a crankcase lubricating oil composition comprising, or made by admixing, an oil of lubricating viscosity in a major amount, and, in respective amounts, a boron-containing additive and one or more co-additives, wherein the lubricating oil composition has greater than 200 ppm by mass of boron, less than 600 ppm by mass of phosphorus and less than 4000 ppm by mass of sulfur, based on the mass of the oil composition.
  • the oil composition may comprise salicylate detergents and where calcium salicylate and magnesium salicylate are used, the calcium salicylate should be present in a greater amount than the magnesium salicylate, based on the mass of the respective metals.
  • EP 1329496A describes and claims a crankcase lubricating oil composition
  • a crankcase lubricating oil composition comprising, or made by admixing, an oil of lubricating viscosity in a major amount, and, in respective minor amounts, a boron-containing additive and one or more co-additives, wherein the lubricating oil composition has greater than 200 ppm by mass of boron, less than 900 ppm by mass of phosphorus and less than 6000 ppm by mass of sulfur, based on the mass of the oil composition.
  • the oil composition may comprise salicylate detergents such as calcium salicylate and magnesium salicylate. This document teaches that the amount of calcium in the oil composition from calcium salicylate should be greater than the amount of magnesium in the oil composition from magnesium salicylate.
  • the present invention provides an internal combustion engine crankcase lubricating oil composition as claimed in claim 1 of the set of claims following the present description of the invention.
  • Preferred and optional features of the lubricating oil composition are defined in the other claims of the said set of claims.
  • the invention provides a method of lubricating a compression-ignited or spark ignited internal combustion engine, which method comprises supplying to the engine a lubricating oil composition according to the said first aspect of the invention.
  • the invention provides the use of a metal detergent system consisting essentially of a calcium salicylate and a magnesium salicylate, as defined in one or more of the aforesaid claims or the said first aspect of the invention, to improve the cam and lifter wear as measured in the Sequence III G test in the crankcase lubrication of an internal combustion engine by a lubricating oil composition having a phosphorus concentration, expressed as atoms of the phosphorus, of not greater than 0.08 mass % based on the mass of the lubricating oil composition.
  • a lubricating oil composition according to the present invention may have a phosphorus content of at least 0.005, preferably at least 0.01 mass %, based on the mass of the oil composition.
  • a lubricating oil composition according to the present invention may have a total base number (TBN) of between 2 and 9, preferably between 4 and 8.
  • base oil or base stock is the primary liquid constituent of the composition into which additives and possibly other oils are blended.
  • a base oil may be selected from natural (vegetable, animal or mineral) and synthetic lubricating oils and mixtures thereof. It may range in viscosity from light distillate mineral oils to heavy lubricating oils such as gas engine oil, mineral lubricating oil, motor vehicle oil and heavy duty diesel oil. Generally the viscosity of the oil ranges from 2 to 30, especially 5 to 20, mm 2 s -1 at 100°C.
  • Natural oils include animal and vegetable oils (e.g. castor and lard oil), liquid petroleum oils and hydrorefined, solvent-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.
  • Synthetic lubricating oils include hydrocarbon oils such as polymerized and interpolymerized olefins (e.g. polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly (1-hexenes), poly (1-octenes), poly (1-decenes)); alkylbenzenes (e.g. dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di (2-ethylhexyl)benzenes); polyphenols (e.g. biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides and derivatives, analogues and homologues thereof.
  • hydrocarbon oils such as polymerized and interpolymerized olefins (e.g. polybutylenes,
  • Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g. phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety of alcohols (e.g. butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol).
  • dicarboxylic acids e.g. phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dim
  • esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.
  • Esters useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols, and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
  • Unrefined, refined and re-refined oils can be used in the compositions of the present invention.
  • Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment.
  • a shale oil obtained directly from retorting operations a petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further treatment would be unrefined oil.
  • Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration and percolation are known to those skilled in the art.
  • Re-refined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. Such re-refined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for approval of spent additive and oil breakdown products.
  • base oil examples include gas-to-liquid (“GTL”) base oils, i.e. the base oil may be an oil derived from Fischer-Tropsch-synthesised hydrocarbons made from synthesis gas containing hydrogen and carbon monoxide using a Fischer-Tropsch catalyst. These hydrocarbons typically require further processing in order to be useful as a base oil. For example, they may, by methods known in the art, be hydroisomerized; hydrocracked and hydroisomerized; dewaxed; or hydroisomerized and dewaxed.
  • GTL gas-to-liquid
  • Base oil may be categorised in Groups 1 to V according to the API EOLCS 1509 definition.
  • the oil of lubricating viscosity is provided in a major amount, in combination with a minor amount of the additive (B) and, if necessary, one or more co-additives such as described hereinafter, constituting the composition.
  • This preparation may be accomplished by adding the additive directly to the oil or by adding it in the form of a concentrate thereof to disperse or dissolve the additive.
  • Additives may be added to the oil by any method known to those skilled in the art, either prior to, contemporaneously with, or subsequent to, addition of other additives.
  • oil-soluble or “oil-dispersible”, or cognate terms, used herein do not necessarily indicate that the compounds or additives are soluble, dissolvable, miscible, or are capable or being suspended in the oil in all proportions. They do mean, however, that they are, for instance, soluble or stably dispersible in oil to an extent sufficient to exert their intended effect in the environment in which the oil is employed. Moreover, the additional incorporation of other additives may also permit incorporation of higher levels of a particular additive, if desired.
  • Metal detergents are additives that reduce formation of piston deposits in engines and that may have acid-neutralising properties, and the term 'detergent' is used herein to define a material capable of providing either or both of these functions within the lubricating oil composition. They are based on metal "soaps", that is metal salts of acidic organic compounds, sometimes referred to as surfactants, and that generally comprise a polar head with a long hydrophobic tail.
  • the metal detergent system comprises magnesium salicylate and calcium salicylate.
  • each salicylate is alkyl-substituted for example with independent alkyl groups having from 8 to 30 carbon atoms and which may be linear, branched or cyclic.
  • alkyl groups there may be mentioned the following: octyl, nonyl, decyl, dodecyl, pentadecyl, octadecyl, eicosyl, docosyl, tricosyl, hexacosyl, triacontyl, dimethylcyclohexyl, ethylcyclohexyl, methylcyclohexylmethyl and cyclohexylethyl.
  • substantially all of the metal detergent system is the magnesium salicylate and the calcium salicylate in the sense that it contains, at most, minor or adventitious amounts of metal detergents other than the magnesium salicylate and the calcium salicylate. More preferred is a metal detergent system from which metal phenates and metal sulfonates are absent.
  • the mass ratio of magnesium to calcium atoms is 5:4 or greater, such as 6:4, 8:5, 10:6 or greater.
  • the mass ratio of magnesium atoms to calcium is up to 5:1, and preferably up to 5:2.
  • the magnesium salicylate and the calcium salicylate provide from 50 to 4,000 preferably from 100 to 3,000, ppm by mass of atoms of magnesium and of calcium, based on the mass of the lubricating oil composition.
  • additives such as the following, may also be present in the lubricating oil compositions of the present invention.
  • Ashless dispersants comprise an oil-soluble polymeric hydrocarbon backbone having functional groups that are capable of associating with particles to be dispersed.
  • the dispersants comprise amine, alcohol, amide, or ester polar moieties attached to the polymer backbone often via a bridging group.
  • the ashless dispersants may be, for example, selected from oil-soluble salts, esters, amino-esters, amides, imides, and oxazolines of long chain hydrocarbon substituted mono and dicarboxylic acids or their anhydrides; thiocarboxylate derivatives of long chain hydrocarbons; long chain aliphatic hydrocarbons having a polyamine attached directly thereto; and Mannich condensation products formed by condensing a long chain substituted phenol with formaldehyde and a polyalkylene polyamine.
  • Anti-wear agents may comprise dihydrocarbyl dithiophosphate metal salts wherein the metal may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel, copper, or preferably, zinc.
  • Dihydrocarbyl dithiophosphate metal salts may be prepared in accordance with known techniques by first forming a dihydrocarbyl dithiophosphoric acid (DDPA), usually by reaction of one or more alcohols or a phenol with P 2 S 5 and then neutralizing the formed DDPA with a metal compound.
  • DDPA dihydrocarbyl dithiophosphoric acid
  • a dithiophosphoric acid may be made by reacting mixtures of primary and secondary alcohols.
  • multiple dithiophosphoric acids can be prepared where the hydrocarbyl groups on one are entirely secondary in character and the hydrocarbyl groups on the others are entirely primary in character.
  • any basic or neutral metal compound could be used but the oxides, hydroxides and carbonates are most generally employed. Commercial additives frequently contain an excess of metal due to the use of an excess of the basic metal compound in the neutralization reaction.
  • ZDDP zinc dihydrocarbyl dithiophosphates
  • R and R' may be the same or different hydrocarbyl radicals containing from 1 to 18, preferably 2 to 12, carbon atoms and including radicals such as alkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic radicals.
  • Particularly preferred as R and R' groups are alkyl groups of 2 to 8 carbon atoms.
  • the radicals may, for example, be ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl.
  • the total number of carbon atoms (i.e. R and R') in the dithiophosphoric acid will generally be about 5 or greater.
  • the zinc dihydrocarbyl dithiophosphate can therefore comprise zinc dialkyl dithiophosphates.
  • the ZDDP should preferably be added to the lubricating oil compositions in amounts no greater than from about 1.1 to 1.3 mass %, based upon the total mass of the lubricating oil composition.
  • Viscosity modifiers function to impart high and low temperature operability to a lubricating oil.
  • the VM used may have that sole function, or may be multifunctional.
  • Multifunctional viscosity modifiers that also function as dispersants are also known.
  • Suitable viscosity modifiers are polyisobutylene, copolymers of ethylene and propylene and higher alpha-olefins, polymethacrylates, polyalkylmethacrylates, methacrylate copolymers, copolymers of an unsaturated dicarboxylic acid and a vinyl compound, inter polymers of styrene and acrylic esters, and partially hydrogenated copolymers of styrene/ isoprene, styrene/butadiene, and isoprene/butadiene, as well as the partially hydrogenated homopolymers of butadiene and isoprene and isoprene/divinylbenzene.
  • Oxidation inhibitors or antioxidants reduce the tendency of base stocks to deteriorate in service which deterioration can be evidenced by the products of oxidation such as sludge and varnish-like deposits on the metal surfaces and by viscosity growth.
  • oxidation inhibitors include hindered phenols, aromatic amines, alkaline earth metal salts of alkylphenolthioesters having preferably C 5 to C 12 alkyl side chains, calcium nonylphenol sulfides, ashless oil soluble phenates and sulfurized phenates, phosphosulfurized or sulfurized hydrocarbons, phosphorus esters, metal thiocarbamates and oil-soluble copper compounds as described in U.S. Patent 4,867,890 .
  • Friction Modifiers which include boundary lubricant additives that lower friction coefficient and hence improve fuel economy may be used.
  • Examples include ester-based organic friction modifiers such as partial fatty acid esters of polyhydric alcohols, for example, glycerol monooleate; and amine-based organic frication modifiers.
  • Further examples are additives that deposit molybdenum disulphide such as organo-molybdenum compounds where the molybdenum is, for example, in dinuclear or trinuclear form.
  • Rust inhibitors selected from the group consisting of nonionic polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols, and anionic alkyl sulfonic acids may be used.
  • Copper and lead bearing corrosion inhibitors may be used, but are typically not required with the formulation of the present invention.
  • such compounds are the thiadiazole polysulfides containing from 5 to 50 carbon atoms, their derivatives and polymers thereof.
  • Derivatives of 1,3,4 thiadiazoles such as those described in U.S. Patent Nos. 2,719,125 ; 2,719,126 ; and 3,087,932 ; are typical.
  • Other similar materials are described in U.S. Patent Nos. 3,821,236 ; 3,904,537 ; 4,097,387 ; 4,107,059 ; 4,136,043 ; 4,188,299 ; and 4,193,882 .
  • additives are the thio and polythio sulfenamides of thiadiazoles such as those described in GB Patent Specification No. 1,560,830 .
  • Benzotriazoles derivatives also fall within this class of additives. When these compounds are included in the lubricating composition, they are preferably present in an amount not exceeding 0.2 mass % active ingredient.
  • a small amount of a demulsifying component may be used.
  • a preferred demulsifying component is described in EP 330,522 . It is obtained by reacting an alkylene oxide with an adduct obtained by reacting a bis-epoxide with a polyhydric alcohol.
  • the demulsifier should be used at a level not exceeding 0.1 mass % active ingredient. A treat rate of 0.001 to 0.05 mass % active ingredient is convenient.
  • Pour point depressants otherwise known as lube oil flow improvers, lower the minimum temperature at which the fluid will flow or can be poured.
  • Such additives are well known. Typical of those additives which improve the low temperature fluidity of the fluid are C 8 to C 18 dialkyl fumarate/vinyl acetate copolymers, polyalkylmethacrylates and the like.
  • Foam control can be provided by many compounds including an antifoamant of the polysiloxane type, for example, silicone oil or polydimethyl siloxane.
  • each of the components can be added directly to the base stock or base oil blend by dispersing or dissolving it in the base stock or base oil blend at the desired level of concentration. Such blending may occur at ambient temperature or at an elevated temperature.
  • all the additives except for the viscosity modifier and the pour point depressant are blended into a concentrate or additive package described herein as the additive package, that is subsequently blended into base stock to make the finished lubricant.
  • the concentrate will typically be formulated to contain the additive(s) in proper amounts to provide the desired concentration in the final formulation when the concentrate is combined with a predetermined amount of a base lubricant.
  • the concentrate is preferably made in accordance with the method described in US 4,938,880 .
  • the final crankcase lubricating oil composition may employ from 2 to 20, preferably 4 to 18, and most preferably 5 to 17, mass % of the concentrate or additive package with the remainder being base stock.
  • it has a sulphated ash concentration of not greater than 1.0 mass % and/or a sulphur concentration, expressed as atoms of sulphur, of not greater than 0.3, preferably not greater than 0.2, mass %.
  • the invention is applicable to a range of internal combustion engines such as compression-ignited and spark-ignited two-or four-stroke reciprocating engines.
  • internal combustion engines such as compression-ignited and spark-ignited two-or four-stroke reciprocating engines.
  • Examples include engines for power-generation, locomotive and marine equipment and heavy duty on-highway trucks; heavy duty off-highway engines such as may be used for agriculture, construction and mining and engines for light duty commercial and passenger car applications.
  • Each lubricant had a phosphorus content of 0.08 mass %, and a salicylate anion content of 17 mmol l -1 .
  • the Sequence III G Test utilizes a 1996 General Motors 3800 cc Series II, water-cooled, 4 cycle, V-6 gasoline engine as the test apparatus.
  • the Sequence III G test engine is an overhead valve design (OHV) and uses a single camshaft operating both intake and exhaust valves via pushrods and hydraulic valve lifters in a sliding-follower arrangement. Using unleaded gasoline, the engine runs a 10-minute initial oil-levelling procedure followed by a 15-minute slow ramp up to speed and load conditions. The engine then operates at 125 bhp, 3,600 rpm and 150° C oil temperature for 100 hours, interrupted at 20-hour intervals for oil level checks.
  • OCV overhead valve design

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

Claims (7)

  1. Composition d'huile lubrifiante de carter de moteur à combustion interne, ayant une concentration en phosphore, exprimée en atomes de phosphore, non supérieure à 0,08 % en masse, sur la base de la masse de la composition d'huile, composition qui comprend ou qui est préparée en mélangeant :
    A. une huile de viscosité propre à la lubrification, en une quantité dominante ; et
    B. un système détergent métallique, comme additif en une petite quantité, consistant essentiellement en un salicylate de calcium et un salicylate de magnésium et ayant un rapport en masse des atomes de magnésium aux atomes de calcium allant de 5:4 ou plus à 5:1, le salicylate de calcium et le salicylate de magnésium fournissant 50 à 4000 ppm en masse d'atomes de calcium et de magnésium, sur la base de la masse de la composition d'huile.
  2. Composition d'huile suivant la revendication 1, ayant une concentration en cendres sulfatées non supérieure à 1,0 % en masse.
  3. Composition d'huile suivant la revendication 1 ou la revendication 2, ayant une concentration en soufre, exprimée en atomes de soufre, non supérieure à 0,3, de préférence non supérieure à 0,2, % en masse.
  4. Composition d'huile suivant l'une quelconque des revendications 1 à 3, dans laquelle le salicylate de calcium et le salicylate de magnésium fournissent 100 à 3000 ppm en masse d'atomes de calcium et de magnésium, sur la base de la masse de la composition d'huile.
  5. Composition d'huile suivant l'une quelconque des revendications 1 à 4, comprenant un ou plusieurs additifs, autres que le salicylate de calcium et le salicylate de magnésium, choisis entre des dispersants, des détergents, des antioxydants, des agents anti-usure, des modificateurs de frottement, des inhibiteurs de corrosion, des agents abaissant le point d'écoulement, des désémulsionnants et des agents antimousse.
  6. Procédé de lubrification d'un moteur à combustion interne à allumage par compression ou à allumage par étincelle, qui comprend l'alimentation du moteur avec une composition d'huile lubrifiante suivant l'une quelconque des revendications 1 à 5.
  7. Utilisation d'un système détergent métallique consistant essentiellement en un salicylate de calcium et un salicylate de magnésium, tel que défini dans la revendication 1, pour améliorer l'usure des cames et des poussoirs de la manière mesurée dans l'essai Sequence II G dans la lubrification du carter d'un moteur à combustion interne avec une composition d'huile lubrifiante ayant une concentration en phosphore, exprimée en atomes de phosphore, non supérieure à 0,08 % en masse sur la base de la masse de la composition d'huile lubrifiante.
EP06112912A 2005-05-20 2006-04-21 Combinaison de détergents métalliques dans des compositions d'huiles lubrifiantes Active EP1724329B1 (fr)

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EP2690165B1 (fr) 2012-07-25 2015-07-08 Infineum International Limited Utilisation d'un détergent de salicylate de magnésium dans une composition d'huile lubrifiante

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2719125A (en) 1952-12-30 1955-09-27 Standard Oil Co Oleaginous compositions non-corrosive to silver
US2719126A (en) 1952-12-30 1955-09-27 Standard Oil Co Corrosion inhibitors and compositions containing same
US3087932A (en) 1959-07-09 1963-04-30 Standard Oil Co Process for preparing 2, 5-bis(hydrocarbondithio)-1, 3, 4-thiadiazole
US3821236A (en) 1972-05-03 1974-06-28 Lubrizol Corp Certain 2-halo-1,2,4-thiadiazole disulfides
US3904537A (en) 1972-05-03 1975-09-09 Lubrizol Corp Novel disulfides derived from 1,2,4-thiadiazole
US4193882A (en) 1973-07-06 1980-03-18 Mobil Oil Corporation Corrosion inhibited lubricant composition
US4136043A (en) 1973-07-19 1979-01-23 The Lubrizol Corporation Homogeneous compositions prepared from dimercaptothiadiazoles
GB1560830A (en) 1975-08-08 1980-02-13 Exxon Research Engineering Co Sulphenamides
US4097387A (en) 1976-09-03 1978-06-27 Standard Oil Company (Indiana) Olefin-dimercapto-thiadiazole compositions and process
US4107059A (en) 1977-06-27 1978-08-15 Pennwalt Corporation Polymer of 1,2,4-thiadiazole and lubricants containing it as an additive
US4188299A (en) 1978-05-17 1980-02-12 Standard Oil Company (Indiana) Oil soluble dithiophosphoric acid derivatives of mercaptothiadiazoles
GB2056482A (en) 1979-08-13 1981-03-18 Exxon Research Engineering Co Lubricating oil compositions
US4938880A (en) 1987-05-26 1990-07-03 Exxon Chemical Patents Inc. Process for preparing stable oleaginous compositions
IL89210A (en) 1988-02-26 1992-06-21 Exxon Chemical Patents Inc Lubricating oil compositions containing demulsifiers
JPH07316577A (ja) 1994-05-20 1995-12-05 Tonen Corp 潤滑油組成物
JP5057603B2 (ja) 1998-05-01 2012-10-24 昭和シェル石油株式会社 内燃機関用潤滑油組成物
EP1310549B1 (fr) 2001-11-09 2006-05-31 Infineum International Limited Composition d'huile lubrifiante contenant du bore et une faible concentration de soufre et de phosphore
EP1329496A1 (fr) 2002-01-14 2003-07-23 Infineum International Limited Composition d'huile lubrifiante contenant du bore et une faible concentration de soufre et de phosphore
US6852679B2 (en) 2002-02-20 2005-02-08 Infineum International Ltd. Lubricating oil composition

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