EP1788068B1 - Verwendung eines Magnesium Detergenz in einer Schmierölzusammensetzung - Google Patents

Verwendung eines Magnesium Detergenz in einer Schmierölzusammensetzung Download PDF

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Publication number
EP1788068B1
EP1788068B1 EP06124257.4A EP06124257A EP1788068B1 EP 1788068 B1 EP1788068 B1 EP 1788068B1 EP 06124257 A EP06124257 A EP 06124257A EP 1788068 B1 EP1788068 B1 EP 1788068B1
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Prior art keywords
lubricating oil
those
features
oil composition
detergents
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English (en)
French (fr)
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EP1788068A1 (de
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Peter Busse
Helmut Leonhardt
Peter Sant
Malcom J Willars
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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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
    • 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
    • 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
    • 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
    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic 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
    • C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, 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
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen 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
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • 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
    • 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
    • C10N2030/08—Resistance to extreme temperature
    • 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
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • 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
    • C10N2030/18—Anti-foaming 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
    • C10N2030/36—Seal compatibility, e.g. with rubber
    • 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
    • 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
    • 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
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel engines

Definitions

  • the present invention relates to a lubricating oil composition, in particular to a lubricating oil composition which is suitable for lubricating internal combustion engines.
  • lubricating oil compositions having reduced sulphated ash, sulphur and/or phosphorus concentrations therein (i.e. so-called low-SAPS lubricating oil compositions).
  • DPF diesel particulate filters
  • Phosphorus concentrations may be generally reduced by reducing the amount of zinc dithiophosphates which are present as anti-wear additives in lubricating oil compositions.
  • Sulphur levels in lubricating oil compositions may be reduced by employing low sulphur level base oils and reducing the amount of sulphur-containing additives employed therein.
  • Sulphated ash is the total weight percent of residue remaining after a lubricating oil composition has been carbonised, and the residue subsequently treated with sulphuric acid and heated to constant weight.
  • the sulphated ash content in a lubricating oil composition is related to the total metal content therein. Sulphated ash may be conveniently measured according to ASTM D874.
  • the major sources of sulphated ash in a lubricating oil composition are generally any metal detergent additives and zinc dithiophosphate anti-wear additives that are employed therein.
  • Sulphated ash deposits can clog the diesel particulate filter (DPF) of vehicles, thereby reducing filter life, raising back pressure in the vehicle engine and causing increased fuel consumption.
  • DPF diesel particulate filter
  • VW Volkswagen
  • DPF diesel particulate filter
  • Total Base Number is a measure of how well a lubricating oil composition can neutralise acidic by-products of combustion/oxidation and is defined as the quantity of acid, expressed in terms of the equivalent number of milligrams of potassium hydroxide, that is required to neutralize all basic constituents present in 1 gram of a sample of the lubricating oil composition (test methods include, for example, ISO 3771, ASTM D-2896 and ASTM D-4739).
  • TBN TBN
  • TBN basicity
  • metal detergents are the primary source of TBN in crankcase lubricating oil compositions.
  • the starting TBN i.e. of fresh unused lubricating oil compositions
  • low-SAPS lubricating oil compositions tends to be lower than in lubricating oil compositions having higher sulphated ash, sulphur and/or phosphorus concentrations therein.
  • EP-A-1362905 describes fuel oil and lubricating oil compositions for diesel engines having a diesel particulate filter. Said compositions comprise a small amount of a molybdenum compound to improve the combustion property of particulate matter trapped in a diesel particulate filter.
  • compositions may comprise additional known additives for their conventional purposes, it should be noted that EP-A-1362905 is in no way concerned with using specific additives to try to reduce clogging in a diesel particulate filter from the outset.
  • EP-A-1362905 of the degree of clogging of a real diesel particulate filter from a lubricating oil composition comprising a calcium or magnesium based detergent.
  • US-A-6114288 discloses lubricating oil compositions for internal combustion engines having a sulphated ash content in the range of from 0.8 to 1.8 mass % according to JIS K2272, which compositions comprise base oil, specific zinc dialkyl dithiophosphates and metallic detergent chosen from i) calcium alkylsalicylate and ii) a mixture of calcium alkylsalicylate and magnesium alkylsalicylate.
  • US-A-6114288 Whilst the Examples in US-A-6114288 test the wear performance of lubricating oil compositions comprising various alkaline earth metal detergents such as calcium sulphonate, magnesium sulphonate, calcium salicylate and magnesium salicylate, it is of note that US-A-6114288 is in no way concerned with the performance of said lubricating oil compositions in diesel particulate filter tests, and in particular in the VW diesel particulate filter test.
  • US 2002/0019320 A1 describes lubricating oil compositions having a low sulphated ash content, a low phosphorus content, and a low sulphur content. Said lubricating oil compositions are said to have good detergency at high temperatures.
  • Detergents used in the lubricating oil compositions of US 2002/0019320 A1 are those containing an organic acid metal salt which is selected from the group consisting of a non-sulphurised alkali metal or alkaline earth metal salt of an alkylsalicylic acid having a TBN of 10 to 350 mg.KOH/g and a non-sulphurised alkali metal or alkaline earth metal salt of an alkylphenol derivative having a Mannich base structure, in an amount of 0.1 to 1 wt. % in terms of sulphated ash.
  • an organic acid metal salt which is selected from the group consisting of a non-sulphurised alkali metal or alkaline earth metal salt of an alkylsalicylic acid having a TBN of 10 to 350 mg.KOH/g and a non-sulphurised alkali metal or alkaline earth metal salt of an alkylphenol derivative having a Mannich base structure, in an amount of 0.1 to 1 wt. % in
  • US 2004/0127371 A1 seeks means to reduce the amount of metal-containing compounds in lubricating oil compositions in order that said compositions are more suitable for use in engines provided with particulate filters.
  • US 2004/0127371 A1 indicates that the amount of detergent needed to neutralise mineral acids generated during the combustion and ameliorate engine corrosion can be reduced in engines operated by low sulphur fuels.
  • US 2004/0127371 A1 describes a lubricating oil composition for use in a compression ignited (diesel) internal combustion engine operated with diesel fuel having a sulphur content of less than 50 ppm, said lubricating oil composition comprising a major amount of oil of lubricating viscosity, and at least one metal-containing detergent, wherein said lubricating oil composition has a total ash content of less than 1.0 wt. %, based on the total weight of the lubricating oil composition.
  • US 2004/0127371 A1 does not provide any teaching on how to reduce the adverse clogging effect of sulphated ash on the diesel particulate filter units without having to compromise on the basicity of the lubricating oil composition.
  • US 2004/0176260 A1 discusses accumulation of ash in exhaust gas after-treatment devices from metal detergents and zinc dialkyl dithiophosphate additives and the resulting deterioration in detergency and anti-wear properties if this problem is addressed by reducing the content of said additives in a lubricating oil composition.
  • US 2004/0176260 A1 discloses means to compensate for this deterioration by blending specific ashless dispersants and phosphorus-containing ashless anti-wear additives, alternatively with a fatty acid amide in specific amounts whilst decreasing the amounts of zinc dialkyl dithiophosphate and metallic detergents.
  • the present invention provides the use, in a lubricating oil composition comprising base oil, of one or more magnesium detergents, for the reduction of clogging in a diesel particulate filter, as compared to the use of calcium detergents.
  • Clogging of the diesel particulate filter is preferably measured using the VW diesel particulate filter test.
  • the one or more magnesium detergents used in the present invention are preferably selected from magnesium salicylate detergents, magnesium phenate detergents and magnesium sulphonate detergents. Magnesium salicylate and magnesium phenate detergents are particularly preferred.
  • said one or more magnesium detergents are preferably used in a total amount of not greater than 0.2 wt. % in terms of magnesium content, more preferably in a total amount of not greater than 0.17 wt. % in terms of magnesium content and most preferably in a total amount of not greater than 0.15 wt. % in terms of magnesium content, based on the total weight of the lubricating oil composition.
  • the magnesium detergents used in the present invention can be either neutral or overbased.
  • the expression “overbased” is equivalent to “basic”, “superbased”, “hyperbased” and “high-metal containing salts”. These magnesium detergents contain an excess metal content compared to the amount of metal which would be present according to the stoichiometry of the metal and the acidic organic compound reacted with the metal. Processes for making such neutral and basic metal salts are well known in the art.
  • Neutral salts can be made by heating a mineral oil solution of an acidic organic compound with a stoichiometric equivalent amount of a metal neutralizing agent such as the metal oxide, hydroxide, carbonate, bicarbonate, or sulfide at a temperature above 50 °C and filtering the resulting mass.
  • Basic salts are made similarly with the exception that a stoichiometric excess of the metal is used.
  • overbased magnesium detergents are used.
  • Detergents can be characterized by their total base number (TBN).
  • TBN total base number
  • the total base numbers of the one or more magnesium detergents are each, independently, in the range of from 30 to 600 mg.KOH/g, more preferably in the range of from 30 to 450 mg.KOH/g and most preferably in the range of from 30 to 350 mg.KOH/g, as measured by ISO 3771.
  • Magnesium salicylates that may be conveniently used may be either substituted or unsubstituted. Suitable substituents include aliphatic groups containing from 1 to 40 carbon atoms and optionally containing one or more oxygen and/or nitrogen atoms, and hydroxy groups. Preferred substituents are alkyl groups containing in the range of from 6 to 30 carbon atoms, preferably in the range of from 12 to 20 carbon atoms. Preferably, the substituents are linear.
  • the magnesium salicylates may contain in the range of from 1 to 4 substituents, preferably in the range of from 1 to 3, most preferably 1 or 2 substituents. Most preferably, the magnesium salicylates may be substituted by 1 linear alkyl group containing in the range of from 14 to 18 carbon atoms.
  • mono-alkyl salicylic acids are prepared by alkylation of phenol and subsequent carboxylation. Therefore, a small amount (generally at most 20 %mol) of dialkyl salicylate and unsubstituted salicylate can be present in the mono-alkyl salicylate.
  • Magnesium salicylates which may be used in the present invention are commercially available.
  • a commercial magnesium salicylate is that available under the trade designation "Infineum C9012" from Infineum.
  • EP-A-1195427 describes magnesium phenates and methods of making such detergents.
  • EP-A-1195427 , WO-A-97/14774 and US-A-5534168 describe magnesium sulphonate and methods of making overbased magnesium sulphonates.
  • Magnesium phenates and magnesium sulphonates which may be used in the present invention are commercially available.
  • a commercial magnesium sulphonate is that available under the trade designation "Infineum C9340" from Infineum.
  • the starting TBN value of the lubricating oil composition used in the present invention is preferably in the range of from 4.0 to 12.0 mg.KOH/g, more preferably in the range of from 6.0 to 11.0 mg.KOH/g, even more preferably in the range of from 6.0 to 10.0 mg.KOH/g and most preferably in the range of 6.0 to 9.5 mg.KOH/g, as measured by ISO 3771.
  • the lubricating oil composition preferably has a sulphated ash content of not greater than 1.0 wt. %, more preferably not greater than 0.9 wt. % and most preferably not greater than 0.8 wt. %, based on the total weight of the lubricating oil composition.
  • the lubricating oil composition preferably has a sulphur content of not greater than 1.2 wt. %, more preferably not greater than 0.8 wt. % and most preferably not greater than 0.3 wt. %, based on the total weight of the lubricating oil composition.
  • preferred lubricating oil compositions have one or more of the following features:
  • particularly preferred lubricating oil compositions have one or more of the following features:
  • the amount of base oil incorporated in the lubricating oil composition is preferably present in an amount in the range of from 60 to 92 wt. %, more preferably in an amount in the range of from 75 to 90 wt. % and most preferably in an amount in the range of from 75 to 88 wt. %, with respect to the total weight of the lubricating oil composition.
  • base oil used in the present invention there are no particular limitations regarding the base oil used in the present invention, and various conventional known mineral oils and synthetic lubricating oils may be conveniently used.
  • Mineral oils include liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oil of the paraffinic, naphthenic, or mixed paraffinic/naphthenic type which may be further refined by hydrofinishing processes and/or dewaxing.
  • Naphthenic base oils have low viscosity index (VI) (generally 40-80) and a low pour point.
  • Such base oils are produced from feedstocks rich in naphthenes and low in wax content and are used mainly for lubricants in which colour and colour stability are important, and VI and oxidation stability are of secondary importance.
  • Paraffinic base oils have higher VI (generally >95) and a high pour point. Said base oils are produced from feedstocks rich in paraffins, and are used for lubricants in which VI and oxidation stability are important.
  • Fischer-Tropsch derived base oils may be conveniently used as the base oil in the lubricating oil composition of the present invention, for example, the Fischer-Tropsch derived base oils disclosed in EP-A-776959 , EP-A-668342 , WO-A-97/21788 , WO-00/15736 , WO-00/14188 , WO-00/14187 , WO-00/14183 , WO-00/14179 , WO-00/08115 , WO-99/41332 , EP-1029029 , WO-01/18156 and WO-01/57166 .
  • the Fischer-Tropsch derived base oils disclosed in EP-A-776959 , EP-A-668342 , WO-A-97/21788 , WO-00/15736 , WO-00/14188 , WO-00/14187 , WO-00/14183 , WO-00/14179 , WO-00/08115 ,
  • Synthetic processes enable molecules to be built from simpler substances or to have their structures modified to give the precise properties required.
  • Synthetic base oils include hydrocarbon oils such as olefin oligomers (PAOs), dibasic acids esters, polyol esters, and dewaxed waxy raffinate. Synthetic hydrocarbon base oils sold by the Shell group under the designation "XHVI” (trade mark) may be conveniently used.
  • PAOs olefin oligomers
  • XHVI XHVI
  • the base oil is constituted from mineral oils and/or synthetic base oils which contain more than 80% wt of saturates, preferably more than 90 % wt., as measured according to ASTM D2007.
  • the base oil contains less than 1.0 wt. %, preferably less than 0.1 wt. % of sulphur, calculated as elemental sulphur and measured according to ASTM D2622, ASTM D4294, ASTM D4927 or ASTM D3120.
  • the viscosity index of the base oil is more than 80, more preferably more than 120, as measured according to ASTM D2270.
  • the lubricating oil composition has a kinematic viscosity in the range of from 2 to 80 mm 2 /s at 100 °C, more preferably of from 3 to 70 mm 2 /s, most preferably of from 4 to 50 mm 2 /s.
  • the lubricating oil composition may optionally further comprise one or more additional additives such as anti-oxidants, anti-wear additives, supplementary detergents, dispersants, friction modifiers, viscosity index improvers, pour point depressants, corrosion inhibitors, defoaming agents and seal fix or seal compatibility agents.
  • additional additives such as anti-oxidants, anti-wear additives, supplementary detergents, dispersants, friction modifiers, viscosity index improvers, pour point depressants, corrosion inhibitors, defoaming agents and seal fix or seal compatibility agents.
  • the lubricating oil composition may comprise one or more aminic and/or phenolic antioxidants.
  • aminic antioxidants which may be conveniently used include alkylated diphenylamines, phenyl- ⁇ -naphthylamines, phenyl- ⁇ -naphthylamines and alkylated ⁇ -naphthylamines.
  • Preferred aminic antioxidants include dialkyldiphenylamines such as p,p'-dioctyl-diphenylamine, p,p'-di- ⁇ -methylbenzyl-diphenylamine and N-p-butylphenyl-N-p'-octylphenylamine, monoalkyldiphenylamines such as mono-t-butyldiphenylamine and mono-octyldiphenylamine, bis(dialkylphenyl)amines such as di-(2,4-diethylphenyl)amine and di(2-ethyl-4-nonylphenyl)amine, alkylphenyl-1-naphthylamines such as octylphenyl-1-naphthylamine and n-t-dodecylphenyl-1-naphthylamine, 1-naphthylamine, arylnaph
  • Preferred aminic antioxidants include those available under the following trade designations: "Sonoflex OD-3" (ex. Seiko Kagaku Co.), “Irganox L-57” (ex. Ciba Specialty Chemicals Co.) and phenothiazine (ex. Hodogaya Kagaku Co.).
  • phenolic antioxidants which may be conveniently used include C7-C9 branched alkyl esters of 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-benzenepropanoic acid, 2-t-butylphenol, 2-t-butyl-4-methylphenol, 2-t-butyl-5-methylphenol, 2,4-di-t-butylphenol, 2,4-dimethyl-6-t-butylphenol, 2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-4-alkylphenols such as 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methylphenol and 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-alkoxyphenols such as 2,6-di-t-butyl
  • Preferred phenolic antioxidants include those available under the following trade designations: "Irganox L-135" (ex. Ciba Specialty Chemicals Co.), “Anteeji DBH” (ex. Kawaguchi Kagaku Co.,), “Yoshinox SS” (ex. Yoshitomi Seiyaku Co.), “Antage W-400” (ex. Kawaguchi Kagaku Co.), “Antage W-500” (ex. Kawaguchi Kagaku Co.), “Antage W-300” (ex. Kawaguchi Kagaku Co.), “Ionox 220AH” (ex. Shell Japan Co.), bisphenol A, produced by the Shell Japan Co., "Irganox L109" (ex.
  • Ciba Specialty Chemicals Co. Ciba Specialty Chemicals Co.
  • Tominox 917 Ex. Yoshitomi Seiyaku Co.
  • Irganox L115 Ex. Ciba Specialty Chemicals Co.
  • Sumilizer GA80 Ex. Sumitomo Kagaku
  • Antage RC ex. Kawaguchi Kagaku Co.
  • Irganox L101 Ex. Ciba Speciality Chemicals Co.
  • Yoshinox 930 Ex. Yoshitomi Seiyaku Co.
  • Ionox 330 Ex. Shell Japan Co.
  • the lubricating oil composition may comprise mixtures of one or more phenolic antioxidants with one or more aminic antioxidants.
  • the lubricating oil composition may comprise one or more anti-wear additives.
  • Anti-wear additives that may be conveniently used include molybdenum-containing compounds, boron-containing compounds and zinc-containing compounds.
  • molybdenum-containing compounds may conveniently include molybdenum dithiocarbamates, trinuclear molybdenum compounds, for example as described in WO-A-98/26030 , sulphides of molybdenum and molybdenum dithiophosphate.
  • Said molybdenum-containing anti-wear additives may be conveniently added to the lubricating oil composition in an amount in the range of from 0.1 to 3.0 wt. %, based on the total weight of lubricating oil composition.
  • Boron-containing compounds that may be conveniently used include borate esters, borated fatty amines, borated epoxides, alkali metal (or mixed alkali metal or alkaline earth metal) borates and borated overbased metal salts.
  • Said boron-containing anti-wear additives may be conveniently added to the lubricating oil composition in an amount in the range of from 0.1 to 3.0 wt. %, based on the total weight of lubricating oil composition.
  • Preferred zinc-containing anti-wear additives are one or more zinc dithiophosphates selected from zinc dialkyl-, diaryl- or alkylaryl-dithiophosphates.
  • Zinc dithiophosphate is a well known additive in the art and may be conveniently represented by general formula II; wherein R 2 to R 5 may be the same or different and are each a primary alkyl group containing from 1 to 20 carbon atoms preferably from 3 to 12 carbon atoms, a secondary alkyl group containing from 3 to 20 carbon atoms, preferably from 3 to 12 carbon atoms, an aryl group or an aryl group substituted with an alkyl group, said alkyl substituent containing from 1 to 20 carbon atoms preferably 3 to 18 carbon atoms.
  • Zinc dithiophosphate compounds in which R 2 to R 5 are all different from each other can be used alone or in admixture with zinc dithiophosphate compounds in which R 2 to R 5 are all the same.
  • the or each zinc dithiophosphate used in the present invention is a zinc dialkyl dithiophosphate.
  • suitable zinc dithiophosphates which are commercially available include those available ex. Lubrizol Corporation under the trade designations “Lz 1097” and “Lz 1395", those available ex. Chevron Oronite under the trade designations “OLOA 267” and “OLOA 269R”, and that available ex. Ethyl under the trade designation “HITEC 7197”; zinc dithiophosphates such as those available ex. Lubrizol Corporation under the trade designations “Lz 677A”, “Lz 1095” and “Lz 1371", that available ex. Chevron Oronite under the trade designation “OLOA 262” and that available ex. Ethyl under the trade designation "HITEC 7169”; and zinc dithiophosphates such as those available ex. Lubrizol Corporation under the trade designations “Lz 1370” and “Lz 1373” and that available ex. Chevron Oronite under the trade designation "OLOA 260".
  • the lubricating oil composition may preferably comprise in the range of from 0.4 to 1.0 wt. % of zinc dithiophosphate, more preferably in the range of from 0.4 to 0.9 wt. % and most preferably in the range of from 0.45 to 0.8 wt. %, based on total weight of the lubricating oil composition.
  • the total amount of phosphorus in the lubricating oil composition is preferably in the range of from 0.04 to 0.1 wt. %, more preferably in the range of from 0.04 to 0.09 wt. % and most preferably in the range of from 0.045 to 0.085 wt. %, based on total weight of the lubricating oil composition.
  • Supplementary detergents that may be conveniently used in the lubricating oil composition include one or more calcium detergents selected from calcium salicylates, calcium phenates and calcium sulphonates.
  • the calcium detergents can be either neutral or overbased.
  • the total base number of said calcium detergents is in the range of from 30 to 600 mg.KOH/g, more preferably in the range of from 30 to 450 mg.KOH/g, most preferably in the range of from 30 to 350 mg.KOH/g, as measured by ISO 3771.
  • Examples of commercial calcium detergents include the calcium salicylates which are available from Infineum under the trade designations "Infineum M7101", “Infineum M7102” and “Infineum M 7105”.
  • said one or more calcium detergents are used in a total amount of no greater than 0.12 wt. % in terms of calcium content, more preferably in a total amount of no greater than 0.08 wt. % in terms of calcium content and most preferably in a total amount of no greater than 0.05 wt. % in terms of calcium content, based on the total weight of the lubricating oil composition.
  • the lubricating oil composition may comprise an ash-free dispersant which is preferably admixed in an amount in the range of from 5 to 15 wt. %, based on the total weight of the lubricating oil composition.
  • dispersants examples include the polyalkenyl succinimides and polyalkenyl succininic acid esters disclosed in Japanese Patent Nos. 1367796 , 1667140 , 1302811 and 1743435 .
  • Preferred dispersants include borated succinimides.
  • Preferred friction modifiers that may be conveniently used include fatty acid esters and fatty acid amides.
  • the total amount of friction modifiers added to the lubricating oil composition in conveniently in the range of from 0.05 to 2.0 wt. %, based on the total weight of the lubricating oil composition.
  • viscosity index improvers which may conveniently used in the lubricating oil composition include the styrene-butadiene copolymers, styrene-isoprene stellate copolymers and the polymethacrylate-based and ethylene-propylene copolymers and the like disclosed in Japanese Patent Nos. 954077 , 1031507 , 1468752 , 1764494 and 1751082.
  • Such viscosity index improvers may be conveniently employed in an amount in the range of from 1 to 20 wt. %, based on the total weight of the lubricating oil composition.
  • dispersing-type viscosity index improvers comprising copolymerized polar monomer containing nitrogen atoms and oxygen atoms in the molecule may also be used therein.
  • Polymethacrylates such as those as disclosed in Japanese Patent Nos. 1195542 and 1264056 may be conveniently employed in the lubricating oil compositions of the present invention as effective pour point depressants.
  • compounds such as alkenyl succinic acid or ester moieties thereof, benzotriazole-based compounds and thiodiazole-based compounds may be conveniently used in the lubricating oil composition as corrosion inhibitors.
  • Compounds such as polysiloxanes, dimethyl polycyclohexane and polyacrylates may be conveniently used in the lubricating oil composition as defoaming agents.
  • seal fix or seal compatibility agents include, for example, commercially available aromatic esters.
  • the lubricating oil composition as herein before described may be conveniently prepared by admixing the one or more magnesium detergents, and, optionally, one or more additional additives, for example as herein before described, with base oil.
  • lubricating oil compositions comprising one or more magnesium detergents and base oil have been surprisingly found to give advantageous performance in diesel particulate filter tests, in particular in the VW diesel particulate filter test.
  • the use of said lubricating oil compositions gives a result of less than 50 % weight increase of a diesel particulate filter, as measured by the VW diesel particulate filter test.
  • a method of improving performance in a diesel particulate filter test comprising lubricating an internal combustion engine with a lubricating oil composition as hereinbefore described comprising one or more magnesium detergents and base oil.
  • Table 1 indicates the formulations that were tested.
  • the formulations in Table 1 comprised conventional antioxidants, anti-foams, dispersants, friction modifiers, seals fix additives, pour point depressants, viscosity index modifiers and zinc dithiophosphate additives.
  • the magnesium detergent used was that available under the trade designation "Infineum C9012" (TBN 345 mg.KOH/g) from Infineum.
  • the calcium detergents used were those available under the trade designations "Infineum M7101” (TBN 168 mg.KOH/g), “Infineum M7102” (TBN 64 mg.KOH/g) and “Infineum M7105” (TBN 280 mg.KOH/g) from Infineum.
  • the base oils used in said formulations were Group III base oils available from the Shell group under the trade designations "XHVI-5.2" and "XHVI-8.2".
  • the VW diesel particulate filter (DPF) test forms part of the VW factory fill specification 52195.
  • the VW diesel particulate filter test measures the percentage weight increase of a diesel particulate filter after a 450 hour engine test.
  • the publicly available test quotes results with respect to a percentage weight increase against the weight increase of the diesel particulate filter using a standard test reference oil.
  • the test limit for a VW pass is set at ⁇ 50 % weight increase against this reference oil.
  • Example 2 demonstrates that the use of magnesium detergent in combination with calcium detergent gives rise to a lubricating oil composition which is lower than the VW test limit.
  • TABLE 2 Results Ex. 1 Ex. 2 Comp. Ex. 1 Comp. Ex. 2 Soap (mmol/kg) 9.0 9.0 9.0 9.1 Starting Total Base Number (TBN) (mg.KOH/g) 9.50 6.40 7.70 6.70 Total Sulphated ash (wt. %)(ASTM D874) 0.80 0.61 0.80 0.70 Total Sulphur (wt. %)(ASTM D2622) ⁇ 0.3 0.21 ⁇ 0.3 ⁇ 0.3 Total Phosphorus (wt. %) (ICP-OES method) 0.049 0.083 0.047 0.059 Ca (wt.

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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 (10)

  1. Verwendung eines oder mehrerer Magnesium-Detergentien in einer Grundöl umfassenden Schmierölzusammensetzung zur Verringerung des Verstopfens in einem Dieselpartikelfilter im Vergleich zur Verwendung von Calcium-Detergentien.
  2. Verwendung nach Anspruch 1, wobei das Verstopfen durch den VW-Dieselpartikelfiltertest gemessen wird.
  3. Verwendung nach Anspruch 1 oder 2, wobei die Schmierölzusammensetzung einen Sulfataschegehalt von höchstens 1,0 Gew.-%, bezogen auf das Gesamtgewicht der Schmierölzusammensetzung, aufweist.
  4. Verwendung nach einem der Ansprüche 1 bis 3, wobei das eine bzw. die mehreren Magnesium-Detergentien aus Magnesiumsalicylat-Detergentien, Magnesiumphenat-Detergentien und Magnesiumsulfonat-Detergentien ausgewählt sind.
  5. Verwendung nach Anspruch 4, wobei das eine bzw. die mehreren Magnesium-Detergentien jeweils unabhängig voneinander einen gemäß ISO 3771 gemessenen TBN-Wert (TBN = Total Base Number, Gesamtbasenzahl) im Bereich von 30 bis 600 mg KOH/g aufweisen.
  6. Verwendung nach einem der Ansprüche 1 bis 5, wobei das Grundöl aus Mineralöl und/oder synthetischem Öl ausgewählt ist.
  7. Verwendung nach einem der Ansprüche 1 bis 6, wobei das eine bzw. die mehreren Magnesium-Detergentien in einer Gesamtmenge von höchstens 0,2 Gew.-% in Bezug auf den Magnesiumsgehalt, bezogen auf das Gesamtgewicht der Schmierölzusammensetzung, vorliegen.
  8. Verwendung nach einem der Ansprüche 1 bis 7, wobei die Schmierölzusammensetzung einen Phosphorgehalt im Bereich von 0,04 bis 0,1 Gew.-%, bezogen auf das Gesamtgewicht der Schmierölzusammensetzung, aufweist.
  9. Verwendung nach einem der Ansprüche 1 bis 8, wobei die Schmierölzusammensetzung ferner ein oder mehrere aus Antioxidantien, Verschleissschutzadditiven, zusätzlichen Detergentien, Dispergiermitteln, Reibungsmodifikatoren, Viskositätsindexverbesserern, Pourpoint-Erniedrigern, Korrosionsinhibitoren, Entschäumern und Dichtungsfixierungs- oder Dichtungsverträglichkeitsmitteln ausgewählte Additive umfasst.
  10. Verwendung einer Schmierölzusammensetzung gemäß einem der Ansprüche 1 bis 9 zum Erhalt eines Ergebnisses von weniger als 50% Gewichtszunahme eines Dieselpartikelfilters gemäß dem VW-Dieselpartikelfiltertest.
EP06124257.4A 2005-11-18 2006-11-16 Verwendung eines Magnesium Detergenz in einer Schmierölzusammensetzung Active EP1788068B1 (de)

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US8513169B2 (en) 2006-07-18 2013-08-20 Infineum International Limited Lubricating oil compositions
EP2457984B1 (de) 2010-11-30 2017-03-08 Infineum International Limited Schmierölzusammensetzung
ES2717752T3 (es) * 2013-12-05 2019-06-25 Infineum Int Ltd Una composición de aceite lubricante para motores de gas
US11034912B2 (en) * 2014-04-29 2021-06-15 Infineum International Limited Lubricating oil compositions
US20200277541A1 (en) * 2019-02-28 2020-09-03 Afton Chemical Corporation Lubricating compositions for diesel particulate filter performance

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US6569818B2 (en) * 2000-06-02 2003-05-27 Chevron Oronite Company, Llc Lubricating oil composition
US6962614B2 (en) * 2000-08-22 2005-11-08 Idemitsu Kosan Co., Ltd. Additive for diesel particulate filter

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