EP1340804B1 - Schmierölzusammensetzung - Google Patents

Schmierölzusammensetzung Download PDF

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Publication number
EP1340804B1
EP1340804B1 EP03250829.3A EP03250829A EP1340804B1 EP 1340804 B1 EP1340804 B1 EP 1340804B1 EP 03250829 A EP03250829 A EP 03250829A EP 1340804 B1 EP1340804 B1 EP 1340804B1
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EP
European Patent Office
Prior art keywords
mass
oil
lubricating
composition
viscosity
Prior art date
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EP03250829.3A
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English (en)
French (fr)
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EP1340804A1 (de
Inventor
Robin Scott
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Infineum International Ltd
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Infineum International Ltd
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Priority claimed from EP02251357A external-priority patent/EP1340803A1/de
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Publication of EP1340804A1 publication Critical patent/EP1340804A1/de
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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
    • 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
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic 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
    • 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
    • C10M2207/2805—Esters 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
    • 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—Overbasedsulfonic 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
    • 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
    • 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
    • C10N2030/04—Detergent property or dispersant property
    • 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
    • C10N2030/43—Sulfur free or low sulfur 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
    • 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • the present invention concerns lubricating oil compositions for lubricating the crankcase of engines, particularly compression-ignited engines, such as heavy duty diesel engines, for example, engines found in road trucks.
  • Lubrication of the crankcase of internal combustion engines is necessary to maintain the performance and expected life-time of the engine, for example by keeping the engine as clean as possible.
  • the heavy duty trucking market employs the diesel engine as its preferred power source due to its excellent longevity, and specialised lubricants have been developed to meet the more stringent performance requirements of such heavy duty diesel engines than passenger car engines.
  • EP 1 167 497 A2 describes diesel motor lubricating oil compositions having low contents of sulfated ash, phosphorus and sulfur. Good detergency at high temperatures is reported for compositions which contain metal-containing detergents with a certain amount of soap content in oils based on mixtures of Group II and Group III base stocks.
  • viscous lubricating oil compositions tend to provide better engine cleanliness than less viscous lubricating oil compositions: this is particularly evident in the OM441 LA engine test, where piston cleanliness is assessed on two grooves on the piston.
  • a potential means of improving the cleanliness effect of oil compositions is to include detergent additives, such as calcium or magnesium sulfonate and phenate, which are believed to improve engine cleanliness.
  • detergent additives such as calcium or magnesium sulfonate and phenate
  • regulations aimed at reducing environmental pollution caused by exhaust gas components, such as particulates and nitrogen oxides (NO x ) are driving lubricating oil compositions to lower sulfated ash, and therefore, to a reduced amount of detergents.
  • metal-containing additives such as metal detergents, zinc compounds and molybdenum compounds, contribute to the amount of sulfated ash.
  • the present invention provides a heavy duty diesel engine lubricating oil composition comprising, or made by admixing:
  • the present invention provides a method of lubricating a heavy duty diesel engine, which engine has a total displacement of at least 6.5 litres and a displacement per cylinder of at least 1.0 litre per cylinder, which method comprises supplying to the engine a lubricating oil composition as defined in the first aspect.
  • the present invention provides the use of in excess of 50 mass% of an oil of lubricating viscosity in a lubricating oil composition comprising a detergent composition and one or more other additives, for improving the piston cleanliness of a heavy duty diesel engine, said oil of lubricating viscosity consisting of a mixture of a Group I base stock and a Group III base stock, the oil of lubricating viscosity comprising at least 35 mass % of a Group III basestock, based on the mass of the oil of lubricating viscosity, that contains at most 0.03 mass % of sulfur, based on the mass of said basestock, and that has a viscosity index of 120 or greater and has greater than or equal to 90 mass % saturates, based on the mass of said basestock, said lubricating oil composition passing either the API CG-4 or the ACEA E2-96 engine test.
  • the present invention provides a method of improving the piston cleanliness of a heavy duty diesel engine, particularly in the OM441 LA test, by adding to the engine a lubricating oil composition as defined in the first aspect.
  • TBN Total Base Number as measured by ASTM D2896.
  • Oil-soluble or oil-dispersible does not necessarily indicate that the additives are soluble, dissolvable, miscible or capable of being suspended in the oil of lubricating viscosity, in all proportions. They do mean, however, that they are, for example, soluble or stably dispersible in the 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.
  • ppm means parts per million, expressed by mass based on the mass of the lubricating oil composition.
  • the lubricating oil compositions of this invention comprise defined individual, i.e. separate, components that may or may not remain the same chemically before and after mixing.
  • various components of the composition essential as well as optional and customary, may react under the conditions of formulation, storage or use, and that the invention also provides the product obtainable or obtained as a result of any such reaction.
  • Heavy duty diesel engines according to the present invention are preferably used in land-based vehicles, more preferably large road vehicles, such as large trucks.
  • the road vehicles typically have a weight greater than 12 tonnes.
  • the engines used in such vehicles tend to have a total displacement of at least 6.5, preferably at least 8, more preferably at least 10, such as at least 15, litres; engines having a total displacement of 12 to 20 litres are preferred.
  • engines having a total displacement greater than 24 litres are not considered land-based vehicles.
  • the engines according to the present invention also have a displacement per cylinder of at least 1.0 or at least 1.5, such as at least 1.75, preferably at least 2, litres per cylinder.
  • heavy duty diesel engines in road vehicles have a displacement per cylinder of at most 3.5, such as at most 3.0; preferably at most 2.5, litres per cylinder.
  • the term "heavy duty” in relation to internal combustion engines is known in the art: see ASTM D4485 at ⁇ 3.17 where heavy duty engine operation is characterised by average speeds, power outputs and internal temperatures that are generally close to potential maximums; therefore, a heavy duty diesel engine is considered to operate generally under such conditions.
  • the terms 'total displacement' and 'displacement per cylinder' are known to those skilled in the art of internal combustion engines (see “ Diesel Engine Reference Book", edited by B. Challen and R. Baranescu, second edition, 1999, published by SAE International ). Briefly, the term “displacement' corresponds to the volume of the cylinder in the engine as determined by the piston movement and consequently the “total displacement” is the total volume dependent on the number of cylinders; and the term 'displacement per cylinder' is the ratio of the total displacement to the number of cylinders in the engine.
  • the present invention particularly concerns multigrade lubricating oil compositions (also known as multigrade lubricants) that tend to be less viscous.
  • the SAE J300 classification defines the lubricants according to their viscometric properties, such as their maximum low temperature cranking and pumping viscosities and maximum and minimum kinematic viscosities at 100 oC.
  • the lubricating oil compositions in each aspect of the present invention, have a low temperature cranking viscosity or cold cranking simulated viscosity, independently of the amount of sulfated ash, as measured by ASTM D2602, of less than 6000 mPa.s at -30 oC, more preferably less than 6200 mPa.s at -35 oC.
  • the lubricating oil compositions in each aspect of the present invention, have a sulfated ash, independently of the cold cranking simulated viscosity, as measured by ASTM D874, of less than 1.25 or 1.15, more preferably less than any of 1.05, 1.00, and 0.95, such as less than 0.90, especially less than 0.85, advantageously less than 0.75, mass %, based on the mass of the oil composition.
  • the sulfated ash can be in the range from 0 to 0.5 mass %.
  • the amount of sulfated ash is derived from metal-containing additives only, more preferably the sulfated ash is derived from metal detergents only, such as a calcium detergent and/or a magnesium detergent.
  • the lubricating oil compositions in each aspect of the present invention, have a TBN of less than 11.2 or 10.5 or 9.8, preferably less than any one of 9.2, 8.8 and 8.5, especially less than 7.8, advantageously less than 7. 1.
  • the TBN can be in the range from 2.1 to 5.5.
  • the lubricating oil compositions in each aspect of the present invention, have a metal content, whether transition metal or alkaline earth metal or alkali metal, of less than 4800 or 4400 or 4000, more preferably less than any of 3700, 3500 and 3300, especially less than 3000, advantageously less than 2600, ppm.
  • the metal content can be in the in the range from 0 to 1800 ppm.
  • Test methods for measuring metal content are well known to those skilled in the art.
  • lubricating oil compositions of the present invention have a maximum kinematic viscosity at 100 oC, independently of the cold cranking simulated viscosity and the amount of sulfated ash, of less than 21.9 mm 2 s; preferably less than 16.3 mm 2 s; such as less than 12.5 mm 2 s; especially less than 9.3 mm 2 s.
  • the kinematic viscosity at 100 oC can be, for example, in the range of 16.3 to less than 21.9; preferably in the range of 12.5 to less than 16.3; more preferably in the range of 9.3 to less than 12.5; such as in the range of 5.6 to less than 9.3.
  • the lubricating oil compositions of the present invention are multigrade oil compositions having a viscosmetric grade of an SAE 10W-X or an SAE 5W-X or 0W-X, where X represents any one of 20, 30, 40 and 50, preferably X is 20 or 30 or 40, more preferably X represents 40.
  • API American Petroleum Institute
  • API Association des Constructeur Europeén d'Autombile
  • JASO Japanese Standards Organisation
  • a heavy duty lubricating oil composition of the present invention preferably satisfies at least the performance requirements of heavy duty diesel engine lubricants, such as at least the API CG-4; preferably at least the API CH-4; especially at least the API Cl-4.
  • the lubricating oil composition of the invention independently of meeting the API performance requirements, preferably satisfies, in particular relating to piston cleanliness, at least the ACEA E2-96; more preferably at least the ACEA E3-96; advantageously at least the ACEA E5-99; and especially at least ACEA E4-99.
  • the lubricating oil composition of the invention, independently of meeting the API and ACEA performance requirements preferably satisfies the JASO DH-1 or Global DHD-1.
  • the oil of lubricating viscosity is the major liquid constituent of a lubricating oil composition.
  • the oil of lubricating viscosity includes (a) oil added to a concentrate or additive package, and (b) any oil present in a concentrate or additive package.
  • Basestocks may be made using a variety of different processes including but not limited to distillation, solvent refining, hydrogen processing, oligomerization, esterification, and rerefining.
  • API 1509 "Engine Oil Licensing and Certification System” Fourteenth Edition, December 1996 states that all basestocks are divided into five general categories:
  • test methods used in defining the above groups are ASTM D2007 for saturates; ASTM D2270 for viscosity index; and one of ASTM D2622, 4294, 4927 and 3120 for sulfur.
  • the oil of lubricating viscosity of the first and third aspects comprises at least 35 mass % of a Group III basestock, based on the mass of the oil of lubricating viscosity, that contains at most 0.03 mass % of sulfur, based on the mass of said basestock, and that has a viscosity index of 120 or greater and has greater than or equal to 90 mass % saturates, based on the mass of said basestock.
  • the oil of lubricating viscosity comprises said basestock in an amount of at least 45, such as at least 50, especially in the range of 55 to 95, advantageously from 65 to 90, for example 70 to 80 or 85, mass %, based on the mass of the oil of lubricating viscosity.
  • the oil of lubricating viscosity includes the basestock that arise from the provision of additive components in the oil composition.
  • the defined proportion of said basestock is that added to the concentrate or additive package.
  • an additive composition comprises a detergent composition and one or more other additives, which may include other metal-containing additives, such as zinc dithiophosphates.
  • a detergent composition contains a detergent.
  • a detergent is an additive that reduces formation of piston deposits, for example high-temperature varnish and lacquer deposits, in engines; it has acid-neutralising properties and is capable of keeping finely divided solids in suspension. It is based on metal "soaps", that is metal salts of organic acids, also known as surfactants herein.
  • a detergent comprises a polar head, e.g. the metal salt of the organic acid, with a long hydrophobic tail for oil solubility. Therefore, the organic acids typically have one or more functional groups, such as OH or COOH or SO 3 H; and a hydrocarbyl substituent.
  • organic acids examples include sulfonic acids; phenols, salicylic acids and sulfurised derivatives thereof; and carboxylic acids.
  • the detergents of the present invention can comprise metal salts of an organic acid and particles of basic inorganic salts (e.g. calcium carbonate particles).
  • each or the metal detergent in the detergent composition may be neutral or overbased, such terms are understood by those skilled in the art.
  • a detergent composition comprising one or more metal salts of organic acids may be present, for example, a mixture of metal sulfonate and metal phenate.
  • the detergents of the present invention may be salts of one type of organic acid or salts of more than one type of organic acids, for example hybrid complex detergents. Preferably, they are salts of one type of organic acid.
  • a hybrid complex detergent is where the basic material within the detergent is stabilised by more than one type of organic acid. It will be appreciated by one skilled in the art that a single type of organic acid may contain a mixture of organic acids of the same type. For example, a sulfonic acid may contain a mixture of sulfonic acids of varying molecular weights. Such an organic acid composition is considered as one type. Thus, complex detergents are distinguished from mixtures of two or more separate overbased detergents, an example of such a mixture being one of an overbased calcium salicylate detergent with an overbased calcium phenate detergent.
  • overbased complex detergents examples include calcium phenate-salicylate-sulfonate detergent, calcium phenate-sulfonate detergent and calcium phenate-salicylate detergent.
  • EP-A-0 750 659 describes a calcium salicylate phenate complex made by carboxylating a calcium phenate and then sulfurising and overbasing the mixture of calcium salicylate and calcium phenate. Such complexes may be referred to as "phenalates"
  • Preferred complex detergents are salicylate-based detergents, for example, a calcium phenate-salicylate-sulfonate detergent and "phenalates".
  • a detergent whether a complex or not, can have a Total Base Number (TBN) in the range of 15 or 60 to 600, preferably 100 to 450, more preferably 160 to 400.
  • TBN Total Base Number
  • the detergent composition may also comprise ashless detergents, i.e. non-metal containing detergents.
  • the detergent composition comprises at least one overbased metal detergent.
  • Group 1 and Group 2 metals are preferred as metals in the detergents; more preferably calcium and magnesium, especially preferred is calcium.
  • the amount of alkaline earth metal in the lubricating oil composition, in each aspect of the invention is less than 3200, or 3000 or 2800, more preferably less than any of 2500, 2400 and 2300, especially less than 2000, advantageously less than 1800, ppm.
  • the alkaline earth metal content can be in the range from 0 to 1200 ppm.
  • the detergent composition is present in the oil composition, in each aspect of the invention, in an amount, based on surfactant content, of at most 50, preferably at most 30, especially at most 20, millimoles of surfactant per kilogram of the oil composition (mmol/kg).
  • the amount of detergent composition, based on surfactant content, in the oil composition is 10 to 15 mmol/kg.
  • Means for determining the amount of surfactant are known to those skilled in the art. For example, a skilled person can calculate the amounts in the final lubricating oil composition from information concerning the amount of raw materials (e.g., organic acids) used to make the detergent(s) and from information concerning the amount of detergent(s) used in the final oil composition. Analytical methods (e.g., dialysis, metal analysis, CO2 analyis, potentiometric titration and chromatography) can also be used to determine the amounts of surfactant.
  • raw materials e.g., organic acids
  • Analytical methods e.g., dialysis, metal analysis, CO2 analyis, potentiometric titration and chromatography
  • additives may also be present in the oil composition of the present invention.
  • Co-additives suitable in the present invention include viscosity index improvers, corrosion inhibitors, oxidation inhibitors or antioxidants, dispersants, rust inhibitors or rust prevention agents, anti-wear agents, pour point depressants, demulsifiers, and anti-foaming agents.
  • Viscosity index improvers impart high and low temperature operability to a lubricating oil and permit it to remain shear stable at elevated temperatures and also exhibit acceptable viscosity or fluidity at low temperatures.
  • Suitable compounds for use as viscosity modifiers are generally high molecular weight hydrocarbon polymers, including polyesters, such as polymethacrylates; poly(ethylene-co-propylene) polymers and closely related modifications (so called olefin copolymers); hydrogenated poly(styrene-co-butadiene or -isoprene) polymers and modifications; and esterified poly(styrene-co-maleic anhydride) polymers .
  • Oil-soluble viscosity modifying polymers generally have number average molecular weights of at least 15,000 to 1,000,000, preferably 20,000 to 600,000, as determined by gel permeation chromatography or light scattering methods.
  • number average molecular weights of at least 15,000 to 1,000,000, preferably 20,000 to 600,000, as determined by gel permeation chromatography or light scattering methods.
  • Corrosion inhibitors reduce the degradation of metallic parts contacted by the lubricating oil composition.
  • Thiadiazoles for example those disclosed in US-A-2 719 125 , 2 719 126 and 3 087 932 are examples of corrosion inhibitors for lubricating oils.
  • Oxidation inhibitors reduce the tendency of mineral oils to deteriorate in service, evidence of such deterioration being, for example, the production of varnish-like deposits on metal surfaces and of sludge, and viscosity increase.
  • Suitable oxidation inhibitors include sulfurized alkyl phenols and alkali or alkaline earth metal salts thereof; hindered phenols; diphenylamines; phenyl-naphthylamines; and phosphosulfurized or sulfurized hydrocarbons.
  • oxidation inhibitors or antioxidants which may be used in lubricating oil compositions include oil-soluble copper compounds.
  • the copper may be blended into the oil as any suitable oil-soluble copper compound.
  • oil-soluble it is meant that the compound is oil-soluble under normal blending conditions in the oil or additive package.
  • the copper may, for example, be in the form of a copper dihydrocarbyl thio- or dithio-phosphate.
  • the copper may be added as the copper salt of a synthetic or natural carboxylic acid, for example, a C 8 to C 18 fatty acid, an unsaturated acid, or a branched carboxylic acid.
  • oil-soluble copper dithiocarbamates are oil-soluble copper dithiocarbamates, sulfonates, phenates, and acetylacetonates.
  • particularly useful copper compounds are basic, neutral or acidic copper Cu I and/or Cu II salts derived from alkenyl succinic acids or anhydrides.
  • Copper antioxidants will generally be employed in an amount of from about 5 to 500 ppm by weight of the copper, in the final lubricating composition.
  • Dispersants maintain oil-insoluble substances, resulting from oxidation during use, in suspension in the fluid, thus preventing sludge flocculation and precipitation or deposition on metal parts.
  • So-called ashless dispersants are organic materials which form substantially no ash on combustion, in contrast to metal-containing (and thus ash-forming) detergents.
  • Borated metal-free dispersants are also regarded herein as ashless dispersants.
  • Suitable dispersants include, for example, derivatives of long chain hydrocarbyl-substituted carboxylic acids, in which the hydrocarbyl group has a number average molecular weight tends of less than 15,000, such as less than 5000; examples of such derivatives being derivatives of high molecular weight hydrocarbyl-substituted succinic acid.
  • Such hydrocarbyl-substituted carboxylic acids may be reacted with, for example, a nitrogen-containing compound, advantageously a polyalkylene polyamine, or with an alcohol.
  • Particularly preferred dispersants are the reaction products of polyalkylene amines with alkenyl succinic anhydrides.
  • Examples of specifications disclosing dispersants of the last-mentioned type are US-A-3 202 678 , 3 154 560 , 3 172 892 , 3 024 195 , 3 024 237 , 3 219 666 , 3 216 936 and BE-A-662 875 .
  • Heavy duty diesel engine lubricating oil compositions tend to have a higher amount of nitrogen, preferably derived from a dispersant, than passenger car engine oil compositions because more oil-insoluble substances, such as soot, are formed in heavy duty diesel engines.
  • the nitrogen content is preferably at least 0.06, more preferably at least 0.08, such as at least 0.10, especially at least 0.12, mass %, based on the mass of the oil composition.
  • the amount of nitrogen, preferably derived from the dispersant tends not to be more than 0.2 mass %. The amount of nitrogen is measured according to ASTM D4629.
  • dispersancy may be provided by polymeric compounds capable of providing viscosity index improving properties and dispersancy, such compounds are known as a multifunctional viscosity index improvers.
  • polymeric compounds capable of providing viscosity index improving properties and dispersancy, such compounds are known as a multifunctional viscosity index improvers.
  • Such polymers differ from conventional viscosity index improvers in that they provide performance properties, such as dispersancy and/or antioxidancy, in addition to viscosity index improvement.
  • Multifunctional viscosity index improvers are prepared by chemically attaching various functional moieties, for example amines, alcohols and amides, onto polymers, which polymers preferably tend to have a number average molecular weight of at least 15,000, such in the range from 20,000 to 600,000, as determined by gel permeation chromatography or light scattering methods.
  • the polymers used may be those described above with respect to viscosity modifiers. Therefore, amine molecules may be incorporated to impart dispersancy and/or antioxidancy characteristics, whereas phenolic molecules may be incorporated to improve antioxidant properties.
  • a specific example therefore, is an inter-polymer of ethylene-propylene post grafted with an active monomer such as maleic anhydride and then derivatized with, for example, an alcohol or amine.
  • EP-A-24146 and EP-A-0 854 904 describe examples of dispersants and dispersant viscosity index improvers, which are accordingly incorporated herein.
  • Rust inhibitors selected from the group consisting of nonionic polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols, and anionic alkyl sulfonic acids may be used.
  • Zinc dihydrocarbyl dithiophosphates are very widely used as antiwear agents.
  • ZDDPs for use in oil-based compositions are those of the formula Zn[SP(S)(OR 1 )(OR 2 )] 2 wherein R 1 and R 2 contain from 1 to 18, and preferably 2 to 12, carbon atoms.
  • Sulfur- and molybdenum-containing compounds are also examples of anti-wear additives. Also suitable are ashless phosphorus- and sulfur-containing compounds.
  • Foam control may be provided by an antifoamant of the polysiloxane type, for example, silicone oil or polydimethyl siloxane.
  • a small amount of a demulsifying component may be used.
  • a preferred demulsifying component is described in EP-A-0 330 522 . It is obtained by reacting an alkylene oxide with an adduct obtained by reacting a bis-epoxide with polyhydric alcohol.
  • additives may provide a multiplicity of effects; thus for example, a single additive may act as a dispersant-oxidation inhibitor. This approach is well known and need not be further elaborated herein.
  • an anti-wear additive such as a metal dihydrocarbyldithiophosphate, for example, zinc dihydrocarbyldithiophosphate, is present in the lubricating oil compositions of the present invention.
  • each additive is typically blended into the base oil in an amount which enables the additive to provide its desired function.
  • Representative effective amounts of such additives, when used in lubricants, are as follows: Additive Mass % a .
  • the additives may be incorporated into an oil of lubricating viscosity (also known as a base oil) in any convenient way.
  • each additive can be added directly to the oil by dispersing or dissolving it in the oil at the desired level of concentration. Such blending may occur at ambient temperature or at an elevated temperature.
  • an additive is available as an admixture with a base oil so that the handling thereof is easier.
  • additives When a plurality of additives are employed it may be desirable, although not essential, to prepare one or more additive packages (also known as additive compositions or concentrates) comprising additives and a diluent, which can be a base oil, whereby the additives, with the exception of viscosity modifiers, multifuntional viscosity modifiers and pour point depressants, can be added simultaneously to the base oil to form the lubricating oil composition. Dissolution of the additive package(s) into the oil of lubricating viscosity may be facilitated by diluent or solvents and by mixing accompanied with mild heating, but this is not essential.
  • additive packages also known as additive compositions or concentrates
  • a diluent which can be a base oil
  • dissolution of the additive package(s) into the oil of lubricating viscosity may be facilitated by diluent or solvents and by mixing accompanied with mild heating, but this is not essential.
  • the additive package(s) will typically be formulated to contain the additive(s) in proper amounts to provide the desired concentration in the final formulation when the additive package(s) is/are combined with a predetermined amount of oil of lubricating viscosity.
  • one or more detergents may be added to small amounts of base oil or other compatible solvents (such as a carrier oil or diluent oil) together with other desirable additives to form additive packages containing from 2.5 to 90, preferably from 5 to 75, most preferably from 8 to 60, mass %, based on the mass of the additive package, of additives on an active ingredient basis in the appropriate proportions.
  • the final formulations may typically contain 5 to 40 mass % of the additive package(s), the remainder being oil of lubricating viscosity.
  • the amount of additives in the final lubricating oil composition is generally dependent on the type of the oil composition, for example, a heavy duty diesel engine lubricating oil composition has 2 to 20, preferably 5 to 18, more preferably 7 to 16, such as 8 to 14, mass % of additives, based on the mass of the oil composition.
  • a method of preparing the oil composition according to the present invention can involve admixing an oil of lubricating viscosity and one or more additives or an additive package that comprises one or more of the additives.
  • a means of increasing the power output of an engine, particularly a compression-ignited engine, is to include a turbocharger in its assembly.
  • the turbo-charger enables more fuel to be burnt per given cylinder size by pressurising the intake air so that more air is charged to the cylinder.
  • Turbo-chargers are typically powered by the gas expelled through the exhaust, and this can lead to a loss of efficiency of the turbo-charger during the life-time of the engine because species contained in the exhaust gas deposit within the turbo-charger. It has been also discovered that lubricating oil compositions of the present invention can minimise the loss of efficiency of a turbo-charger.
  • a method of determining the loss of efficiency is, for example, the OM441 LA test, where a boost pressure loss, as a percent, is given: the higher the boost pressure loss the greater the loss of efficiency.
  • Lubricating oil compositions identified herein as Examples A to D and Examples 1 to 4, were blended by methods known in the art at comparable TBN from oils of lubricating viscosity and additive concentrates.
  • Examples A to D are comparative and Examples 1 to 4 are of the invention.
  • Table 1 shows details of the oil of lubricating viscosity used and the physical properties of the resulting oil compositions. Comparative Example A was blended to a SAE 15W40 viscometric grade, whereas comparative Examples B to D and Examples 1 to 4 were blended to an SAE 10W40 viscometric grade.
  • Comparative Examples A to D and Examples 1 to 4 were tested for piston cleanliness and boost pressure loss in the OM441 LA test, according to the CEC-L-52-T-97 procedure. The results are also given in Table 1.
  • Example A a SAE 15W40 lubricating oil composition, provided better piston cleanliness and boost pressure loss than Example B, an oil composition containing the same additives as those in Example A but blended to a SAE 10W40 viscometric grade.
  • ACEA E5-99 performance specification sets a passing limit of at least 25 merits points for piston cleanliness and at most 4 % for boost pressure loss. Accordingly, at least about 35 mass % of a Group III basestock in an oil of lubricating viscosity may be required to meet the limits set by ACEA E5-99 in respect of the piston cleanliness and boost pressure loss.

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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 (6)

  1. Schmierölzusammensetzung für einen Hochleistungsdieselmotor, die umfasst oder hergestellt wird durch Mischen von:
    (A) mehr als 50 Masse-% der Zusammensetzung Öl mit Schmierviskosität, bestehend aus einer Mischung aus Gruppe I-Basisöl und Gruppe III-Basisöl, welches Öl mit Schmierviskosität mindestens 35 Masse-%, bezogen auf die Masse des Öls mit Schmierviskosität, Gruppe III-Basisöl umfasst, das höchstens 0,03 Masse-% Schwefel enthält, bezogen auf die Masse des Basisöls, und das einen Viskositätsindex von 120 oder mehr aufweist und mehr als oder gleich 90 Masse-% gesättigte Verbindungen aufweist, bezogen auf die Masse des Basisöls, und
    (B) weniger als 50 Masse-% der Zusammensetzung einer Additivzusammensetzung, die
    (i) eine Detergenszusammensetzung, und
    (ii) ein oder mehrere andere Additive umfasst,
    wobei die Ölzusammensetzung eine simulierte Kaltstartviskosität von kleiner als 7000 mPa.s bei -25°C aufweist, wie gemäß ASTM D2602 gemessen, und weniger als 1,35 Masse-% Sulfatasche, wie gemäß ASTM D874 gemessen, bezogen auf die Masse der Ölzusammensetzung.
  2. Ölzusammensetzung nach Anspruch 1, bei der die Detergenszusammensetzung ein Magnesiumdetergens-Additiv und/oder ein Calciumdetergens-Additiv umfasst.
  3. Ölzusammensetzung nach einem der Ansprüche 1 oder 2, die ferner ein Zinkdikohlenwasserstoffdithiophosphat-Additiv umfasst.
  4. Verfahren zur Schmierung eines Hochleistungsdieselmotors, welcher Motor einen Gesamthubraum von mindestens 6,5 Litern und einen Hubraum pro Zylinder von mindestens 1,0 Liter pro Zylinder aufweist, bei welchem Verfahren dem Motor eine Schmierölzusammensetzung gemäß einem der Ansprüche 1 bis 3 zugeführt wird.
  5. Verwendung von mehr als 50 Masse-% Öl mit Schmierviskosität in einer Schmierölzusammensetzung, die eine Detergenszusammensetzung und ein oder mehrere andere Additive umfasst, zur Verbesserung der Kolbensauberkeit eines Hochleistungsdieselmotors, welches Öl mit Schmierviskosität aus einer Mischung aus Gruppe I-Basisöl und Gruppe III-Basisöl besteht, und welches Öl mit Schmierviskosität mindestens 35 Masse-%, bezogen auf die Masse des Öls mit Schmierviskosität, Gruppe III-Basisöl umfasst das höchstens 0,03 Masse-% Schwefel enthält, bezogen auf die Masse des Basisöls, und das einen Viskositätsindex von 120 oder mehr aufweist und mehr als oder gleich 90 Masse-% gesättigte Verbindungen aufweist, bezogen auf die Masse des Basisöls, wobei die Schmierölzusammensetzung entweder den API CG-4 oder den ACEA E2-96 Motortest besteht.
  6. Verfahren zur Verbesserung der Kolbensauberkeit eines Hochleistungsdieselmotors, indem eine Schmierölzusammensetzung gemäß einem der Ansprüche 1 bis 4 in den Motor eingebracht wird.
EP03250829.3A 2002-02-27 2003-02-11 Schmierölzusammensetzung Expired - Lifetime EP1340804B1 (de)

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EP02251357A EP1340803A1 (de) 2002-02-27 2002-02-27 Schmierölzusammensetzungen
EP02251357 2002-02-27
EP03250829.3A EP1340804B1 (de) 2002-02-27 2003-02-11 Schmierölzusammensetzung

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Publication number Priority date Publication date Assignee Title
GB0326808D0 (en) * 2003-11-18 2003-12-24 Infineum Int Ltd Lubricating oil composition
EP1824950A1 (de) * 2004-10-25 2007-08-29 The Lubrizol Corporation Korrosionsinhibierung
US20080236538A1 (en) * 2007-03-26 2008-10-02 Lam William Y Lubricating oil composition for improved oxidation, viscosity increase, oil consumption, and piston deposit control

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US4956122A (en) * 1982-03-10 1990-09-11 Uniroyal Chemical Company, Inc. Lubricating composition
US4420647A (en) * 1982-04-26 1983-12-13 Texaco Inc. Semi-synthetic lubricating oil composition
CA2013545C (en) * 1989-04-03 1999-01-26 Glen Paul Fetterman Jr. Improved ashless lubricant compositions for internal combustion engines
GB2292747B (en) * 1994-08-26 1998-09-16 Exxon Research Engineering Co Lubricant composition containing copolymer to improve seal compatability
US5942475A (en) * 1996-09-06 1999-08-24 Exxon Chemical Patents Inc. Engine oil lubricants formed from complex alcohol esters
US6300291B1 (en) * 1999-05-19 2001-10-09 Infineum Usa L.P. Lubricating oil composition
EP1087008B2 (de) * 1999-09-21 2008-08-06 Infineum International Limited Multigrad Schmiermittelzusammensetzungen für Motorgehäuse
US6569818B2 (en) * 2000-06-02 2003-05-27 Chevron Oronite Company, Llc Lubricating oil composition
EP1266954A1 (de) * 2001-06-15 2002-12-18 Infineum International Limited Spezifische Basisölgemische für Dieselmotorenschmierzusammensetzungen

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