EP1640441B1 - Schmierölzusammenstzungen mit niedrigen Phosphor-, Schwefel- und sulfatierten Asche-Gehalten - Google Patents

Schmierölzusammenstzungen mit niedrigen Phosphor-, Schwefel- und sulfatierten Asche-Gehalten Download PDF

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EP1640441B1
EP1640441B1 EP05107526A EP05107526A EP1640441B1 EP 1640441 B1 EP1640441 B1 EP 1640441B1 EP 05107526 A EP05107526 A EP 05107526A EP 05107526 A EP05107526 A EP 05107526A EP 1640441 B1 EP1640441 B1 EP 1640441B1
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Prior art keywords
oil
group
lubricating oil
composition according
lubricating
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English (en)
French (fr)
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EP1640441A1 (de
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Robert Shaw
Michele Thornhill
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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
    • 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
    • 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
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • 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
    • C10N2030/40—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
    • 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 lubricating oil compositions. More particularly, the present invention relates to lubricating oil compositions, which have low levels of phosphorus, sulfur and sulfated ash.
  • Such exhaust gas after-treatment devices may include catalytic converters, which can contain one or more oxidation catalysts, NO x storage catalysts, and/or NH 3 reduction catalysts; and/or a particulate trap.
  • Oxidation catalysts can become poisoned and rendered less effective by exposure to certain elements/compounds present in engine exhaust gasses, particularly by exposure to phosphorus and phosphorus compounds introduced into the exhaust gas by the degradation of phosphorus-containing lubricating oil additives.
  • Reduction catalysts are sensitive to sulfur and sulfur compounds in the engine exhaust gas introduced by the degradation of both the base oil used to blend the lubricant, and sulfur-containing lubricating oil additives.
  • Particulate traps can become blocked by metallic ash, which is a product of degraded metal-containing lubricating oil additives.
  • dihydrocarbyl dithiophosphate metal salts The metal may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper.
  • ZDDP zinc salts of dihydrocarbyl dithiophosphate
  • lubricating oil additives that exert a minimum negative impact on such after-treatment devices must be identified, and OEM specifications for "new service fill” and “first fill lubricants are expected to require maximum sulfur levels of 0.30 wt. %; maximum phosphorus levels of 0.08 wt. %, and sulfated ash contents below 0.80 wt. %.
  • Such lubricating oil compositions can be referred to as "low SAPS (low sulfated ash, phosphorus, sulfur) lubricating oil compositions.
  • EP 1167497 discloses a low SAPS lubricating oil composition comprising a metal detergent having a certain soap content, which is stated to exhibit acceptable high temperature stability.
  • EP 1361263 discloses a low SAPS lubricating oil composition can exhibit acceptable high temperature stability by use of a metal-containing detergent having enough soap content with a specific ashless dispersant, zinc dialkyldithiophosphate, zinc dialkylaryldithiophosphate and a specific oxidation inhibitor.
  • US 2003/014889 discloses a low SAPS formulation that demonstrates improved wear performance, which comprises a boron-containing additive providing greater than 200 ppm boron.
  • the selected lubricating oil composition must provide adequate lubricant performance, including adequate wear protection and detergency.
  • the performance of lubricating oil compositions used in light duty spark and compression-ignited vehicular internal combustion engines, specifically antiwear and engine cleaning performance, must be maintained at the high level dictated by the "new service", and "first fill" specifications of the OEM's.
  • the present invention is based on the discovery that a lubricating oil can be formulated which complies with the low SAPS requirements yet exhibits a passing value for piston cleanliness and viscosity control in the fired engine XUD-IIBTE test and satisfies the requirements of the Mercedes-Benz Seals test surprisingly through use of a magnesium detergent and a relatively high ashless dispersant content.
  • a lubricating oil composition having a sulfur content of up to 0.3 wt.%, a phosphorus content of up to 0.08 wt.%, a sulfated ash content of up to 0.80 wt.% and a total base number ( TBN) of about 8 to 9 which comprises an admixture of:
  • the oil of lubricating viscosity may be selected from Group I, II, III, IV or V base stocks or synthetic ester base stocks.
  • the base stock groups are defined in the American Petroleum Institute (API) publication "Engine Oil Licensing and Certification System", Industry Services Department, Fourteenth Edition, December 1996, Addendum 1, December 1998 .
  • the base stock will have a viscosity preferably of 3-12, more preferably 4-10, most preferably 4.5-8 mm 2 /s (cSt.) at 100°C.
  • Esters useful as synthetic base stock oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.
  • Table A - Analytical Methods for Testing Base Stocks Property Test Method Saturates ASTM D2007 Viscosity Index ASTM D2270 Sulfur ASTM D2622, D4294, D4927, or D3120
  • the oil of lubricating viscosity comprises substantially no Group I base stock oil.
  • the oil of lubricating viscosity used in this invention should have a viscosity index of at least 95, preferably at least 100.
  • Preferred oils are (a) base oil blends of Group III base stocks with Group II base stocks, where the combination has a viscosity index of at least 110; or (b) Group III base stocks or blends of more than one Group III base stock. Mineral oils are preferred.
  • the present invention requires the presence of an overbased magnesium salicylate lubricating oil detergent having a TBN of 200 to 500, preferably 300 to 500, in such amount so as to provide to the lubricating oil composition a TBN of 5.3 to 7.3 of the total required TBN of 8 to 9. There will be employed 0.4 to 1.0 wt.% of the magnesium detergent.
  • Lubricating oil compositions according to the present invention surprisingly exhibit a "pass rating in certain aspects of the XUD-IIBTE test and in the Mercedes-Benz Seals test, while the same oil formulated without a magnesium salicylate detergent will show distinctly poorer results in the same test.
  • Other types of metal detergents may be present so long as the sulfated ash content of the oil remains at 0.80 wt. % or less.
  • Metal-containing or ash-forming detergents function both as detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life.
  • Detergents generally comprise a polar head with long hydrophobic tail, with the polar head comprising a metal salt of an acid organic compound.
  • the salts may contain a substantially stoichiometric amount of the metal in which they are usually described as normal or neutral salts, and would typically have a total base number (TBN), as may be measured by ASTM D-2896 of from 0 to 80. It is possible to include large amounts of a metal base by reacting an excess of a metal compound, such as an oxide or hydroxide, with an acid gas such as carbon dioxide.
  • the resulting overbased detergent comprises neutralized detergent as the outer layer of a metal base (e.g., carbonate) micelle.
  • a metal base e.g., carbonate
  • Such overbased detergents may have a TBN of 150 or greater, and overbased detergents typically used have a TBN from 200 to 500, or more.
  • Detergents that are conventionally employed include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and naphthenates and other oil-soluble carboxylates of a metal, particularly the alkali or alkaline earth metals, e.g., barium, sodium, potassium, lithium, calcium, and magnesium.
  • a metal particularly the alkali or alkaline earth metals, e.g., barium, sodium, potassium, lithium, calcium, and magnesium.
  • the most commonly used metals are calcium and magnesium, which may both be present in detergents used in a lubricant, and mixtures of calcium and/or magnesium with sodium.
  • Particularly convenient metal detergents are neutral and overbased metal detergents having TBN of from 20 to 450. Combinations of detergents, whether overbased or neutral or both, may be used.
  • Sulfonates may be prepared from sulfonic acids, which are typically obtained by the sulfonation of alkyl substituted aromatic hydrocarbons such as those obtained from the fractionation of petroleum or by the alkylation of aromatic hydrocarbons.
  • the alkaryl sulfonates usually contain from about 9 to about 80 or more carbon atoms, preferably from about 16 to about 60 carbon atoms per alkyl substituted aromatic moiety.
  • Metal salts of phenols and sulfurized phenols are prepared by reaction with an appropriate metal compound such as an oxide or hydroxide and neutral or overbased products may be obtained by methods well known in the art.
  • Sulfurized phenols may be prepared by reacting a phenol with sulfur or a sulfur containing compound such as hydrogen sulfide, sulfur monohalide or sulfur dihalide, to form products which are generally mixtures of compounds in which 2 or more phenols are bridged by sulfur containing bridges.
  • Carboxylate detergents e.g., salicylates
  • an aromatic carboxylic acid can contain an appropriate metal compound such as an oxide or hydroxide and neutral or overbased products may be obtained by methods well known in the art.
  • the aromatic moiety of the aromatic carboxylic acid can contain heteroatoms, such as nitrogen and oxygen. Preferably, the moiety contains only carbon atoms; more preferably the moiety contains six or more carbon atoms; for example benzene is a preferred moiety.
  • the aromatic carboxylic acid may contain one or more aromatic moieties, such as one or more benzene rings, either fused or connected via alkylene bridges.
  • Preferred substituents in oil-soluble salicylic acids are alkyl substituents.
  • the alkyl groups advantageously contain 5 to 100, preferably 9 to 30, especially 14 to 20, carbon atoms. Where there is more than one alkyl group, the average number of carbon atoms in all of the alkyl groups is preferably at least 9 to ensure adequate oil solubility.
  • Ashless dispersants generally 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 dispersant 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 polyalkylene polyamine.
  • Dispersants of the present invention are nitrogen containing and are present in amounts of from 2.5 to 4.0 wt%.
  • the nitrogen content of the lubricant composition provided by the dispersant should be in the range of 0.05 to 0.1 wt. % N.
  • Preferred are borated or non-borated polyisobutenyl succinimide dispersants wherein the polyisobutenyl has an Mn of about 500 to 3,000, preferably about 900 to 2,500.
  • a preferred embodiment utilizes polyisobutenyl succinimide dispersants prepared using polyisobutylene prepared from a pure isobutylene stream or a Raffinate I stream to prepare reactive isobutylene polymers with terminal vinylidene olefins.
  • these polymers referred to as highly reactive polyisobutylene (HR-PIB)
  • HR-PIB highly reactive polyisobutylene
  • these polymers have a terminal vinylidene content of at least 65%, e.g., 70%, more preferably at least 80%, most preferably at least 85%.
  • the preparation of such polymers is described, for example, in U.S. Patent No. 4,152,499 .
  • HR-PIB is known and HR-PIB is commercially available under the tradenames Glissopal TM (from BASF) and Ultravis TM (from BP-Amoco).
  • Preferred, but optional ingredients are antioxidants, zinc dihydrocarbyldithiophosphates, oil soluble organomolybdenum compounds, friction modifiers, and viscosity modifiers.
  • 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. They are suitably present in amount of from 0.1 to 5.0 wt.%, preferably 0.25 to 1.0 wt.%.
  • Suitable oxidation inhibitors include hindered phenols, alkaline earth metal salts of alkylphenolthioesters having preferably C 5 to C 12 alkyl side chains, calcium nonylphenol sulfide, ashless oil soluble phenates and sulfurized phenates, phosphosulfurized or sulfurized hydrocarbons, alkyl substituted diphenylamine, alkyl substituted phenyl and napthylamines, phosphorous esters, metal thiocarbamates, ashless thiocarbamates and oil soluble copper compounds as described in U.S. 4,867,890 .
  • dialkyl substituted diphenylamines wherein the alkyl is C 4 -C 20 , such as dinonyl diphenylamine and the hindered phenols, such as isooctyl-3,5-di-tert-butyl-4-hydroxycinnamate and mixtures of same.
  • the zinc dihydrocarbyl dithiophosphates are oil soluble salts of dihydrocarbyl dithiophosphoric acids and may be represented by the following formula: wherein 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.
  • ZDDP is the most commonly used antioxidant/antiwear agent in lubricating oil compositions for internal combustion engines, and in conventional passenger car diesel engines formulated to meet present European ACEA specifications.
  • the lubricating oil compositions of the present invention suitably contain an amount of ZDDP (or other dihydrocarbyl dithiophosphate metal salt) that introduces about 0.02 to 0.08 wt.%, preferably 0.02 to 0.06 wt.% of phosphorus into the lubricating oil composition.
  • the phosphorus content of the lubricating oil compositions is determined in accordance with the procedures of ASTM D5185.
  • any suitable oil soluble organo-molybdenum compound may be employed.
  • the molybdenum compound will function both as an antiwear and antioxidant additive.
  • dimeric and trimeric molybdenum compounds are used.
  • oil soluble organo-molybdenum compounds are the dialkyldithiocarbamates, dialkyldithiophosphates, dialkyldithiophosphinates, xanthates, thioxanthates, carboxylates and the like, and mixtures thereof.
  • Particularly preferred are molybdenum dialkylthiocarbamates.
  • the molybdenum dialkyldithiocarbamate dimer to be used as an additive in the present invention is a compound expressed by the following formula: R 1 through R 4 independently denote a straight chain, branched chain or aromatic hydrocarbyl group; and X1 through X4 independently denote an oxygen atom or a sulfur atom.
  • the four hydrocarbyl groups, R 1 through R 4 may be identical or different from one another.
  • organo-molybdenum compounds useful in the lubricating compositions of this invention are trinuclear (trimeric) molybdenum compounds, especially those of the formula Mo 3 S k L n Q z and mixtures thereof wherein the L are independently selected ligands having organo groups with a sufficient number of carbon atoms to render the compound soluble in the oil, n is from 1 to 4, k varies from 4 to 7, Q is selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. At least 21 total carbon atoms should be present among all the ligands' organo groups, such as at least 25, at least 30, or at least 35 carbon atoms.
  • the ligands are selected from the group consisting of -X-R 1, and and mixtures thereof, wherein X, X 1 , X 2 , and Y are independently selected from the group of oxygen and sulfur, and wherein R 1 , R 2 , and R are independently selected from hydrogen and organo groups that may be the same or different.
  • the organo groups are hydrocarbyl groups such as alkyl (e.g., in which the carbon atom attached to the remainder of the ligand is primary or secondary), aryl, substituted aryl and ether groups. More preferably, each ligand has the same hydrocarbyl group.
  • hydrocarbyl denotes a substituent having carbon atoms directly attached to the remainder of the ligand and is predominantly hydrocarbyl in character within the context of this invention.
  • substituents include the following:
  • the organo groups of the ligands have a sufficient number of carbon atoms to render the compound soluble in the oil.
  • the number of carbon atoms in each group will generally range between about 1 to about 100, preferably from about 1 to about 30, and more preferably between about 4 to about 20.
  • Preferred ligands include dialkyldithiophosphate, alkylxanthate, carboxylates, dialkyldithiocarbamate, and mixtures thereof. Most preferred are the dialkyldithiocarbamates. Those skilled in the art will realize that formation of the compounds requires selection of ligands having the appropriate charge to balance the core's charge (as discussed below).
  • Oil-soluble trinuclear molybdenum compounds are preferred and can be prepared by reacting in the appropriate liquid(s)/solvent(s) a molybdenum source such as (NH 4 ) 2 Mo 3 S 13 ⁇ n(H 2 O), where n varies between 0 and 2 and includes non-stoichiometric values, with a suitable ligand source such as a tetralkylthiuram disulfide.
  • a molybdenum source such as (NH 4 ) 2 Mo 3 S 13 ⁇ n(H 2 O), where n varies between 0 and 2 and includes non-stoichiometric values
  • oil-soluble trinuclear molybdenum compounds can be formed during a reaction in the appropriate solvent(s) of a molybdenum source such as (NH 4 ) 2 Mo 3 S 13 ⁇ n(H 2 O), a ligand source such as tetralkylthiuram disulfide, dialkyldithiocarbamate, or dialkyldithiophosphate, and a sulfur abstracting agent such cyanide ions, sulfite ions, or substituted phosphines.
  • a molybdenum source such as (NH 4 ) 2 Mo 3 S 13 ⁇ n(H 2 O)
  • a ligand source such as tetralkylthiuram disulfide, dialkyldithiocarbamate, or dialkyldithiophosphate
  • a sulfur abstracting agent such cyanide ions, sulfite ions, or substituted phosphines.
  • a trinuclear molybdenum-sulfur halide salt such as [M'] 2 [Mo 3 S 7 A 6 ], where M' is a counter ion, and A is a halogen such as Cl, Br, or I, may be reacted with a ligand source such as a dialkyldithiocarbamate or dialkyldithiophosphate in the appropriate liquid(s)/solvent(s) to form an oil-soluble trinuclear molybdenum compound.
  • the appropriate liquid/solvent may be, for example, aqueous or organic.
  • the ligand chosen must have a sufficient number of carbon atoms to render the compound soluble in the lubricating composition.
  • oil-soluble does not necessarily indicate that the compounds or additives are soluble in the oil in all proportions. It does mean that they are soluble in use, transportation, and storage.
  • a basic nitrogen compound selected from the group consisting of succinimide, a carboxylic acid amide, a hydrocarbyl monoamine, a phosphoramide, a thiophosphoramide, a Mannich base, a dispersant viscosity index improver, or a mixture thereof
  • the sulfurized molybdenum containing compositions may be generally characterized as a molybdenum/sulfur complex of a basic nitrogen compound.
  • the precise molecular formula of these molybdenum compositions is not known with certainty. However, they are believed to be compounds in which molybdenum, whose valences are satisfied with atoms of oxygen or sulfur, is either complexed by, or the salt of one or more nitrogen atoms of the basic nitrogen containing compound used in the preparation of these compositions.
  • the lubricating compositions of the present invention may contain a minor amount of an oil soluble molybdenum compound.
  • An amount of at least 10 ppm up to about 2,000 ppm of molybdenum from a molybdenum compound may be present in the lubricating oil composition.
  • Preferably, about 500 ppm to 1,000 ppm of molybdenum from a molybdenum compound is used. These values are based upon the weight of the lubricating composition.
  • At least one organic oil soluble friction modifier may preferably be incorporated in the lubricating oil composition.
  • the friction modifier makes up about 0.02 to 2.0 wt.% of the lubricating oil composition.
  • Friction modifiers include such compounds as aliphatic amines or ethoxylated aliphatic amines, aliphatic fatty acid amides, aliphatic carboxylic acids, aliphatic carboxylic esters of polyols such as glycerol esters of fatty acids as exemplified by glycerol oleate, which is preferred, aliphatic carboxylic ester-amides, aliphatic phosphonates, aliphatic thiophosphates, etc., wherein the aliphatic group usually contains above about eight carbon atoms so as to render the compound suitably oil soluble.
  • aliphatic substituted succinimides formed by reacting one or more aliphatic succinic acids or anhydrides with ammonia.
  • 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. These may be used in amounts of from 0.01 to 5.0 wt.%, preferably about 0.1 to 3.0 wt.%. They are preferably used when mineral oil base stocks are employed but are not required when the base stock is a PAO or synthetic ester.
  • the viscosity modifier functions to impart high and low temperature operability to a lubricating oil.
  • the VM used may have that sole function, or may be multifunctional. It may be present in amounts of from 0.01 to 20.0 wt. %, preferably about 1.0 to 10.0 wt.%. These are preferably employed when the base stock is a mineral oil.
  • 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.
  • Foam control can be provided by many compounds including an antifoamant of the polysiloxane type, for example, silicone oil or polydimethyl siloxane.
  • additives can provide a multiplicity of effects; thus for example, a single additive may act as a dispersant-oxidation inhibitor. This approach is well known and does not require further elaboration.
  • 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.
  • the invention comprising the product results from the admixture of the additive components to form a lubricating oil composition.
  • 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, which 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 U.S. 4,938,880 . That patent describes making a pre-mix of ashless dispersant and metal detergents that is pre-blended at a temperature of at least about 100°C. Thereafter, the pre-mix is cooled to at least 85°C and the additional components are added.
  • the final crankcase lubricating oil formulation may employ from 2 to 20 mass %, preferably 4 to 18 mass %, and most preferably about 5 to 17 mass % of the concentrate or additive package, with the remainder being base stock.
  • inventive Oil A and comparative Oils B and C were prepared and tested for piston merits and viscosity increase according to the XUD-IIBTE fired engine test, a European passenger car diesel engine test (CEC L-56-T-98) that is part of the ACEA B specification. Oils A and C were also testes in the Mercedes-Benz Seals test. The results are given in Table 1. Inventive Oil A shows a distinct and surprising improvement.
  • Oil A a lubricating oil composition was prepared containing 0.54 wt.% magnesium alkyl salicylate detergent (TBN 340), 1.32 wt.% calcium alkyl salicylate detergent, organomolybdenum antiwear agent, friction modifier, 3.23 wt. % polyisobutenyl succinimide dispersant, antioxidant, lubricating oil flow improver, viscosity modifier, antifoam agent, zinc dihydrocarbyl dithiophosphate and mineral oil base stocks.
  • the dispersant provided 0.07 wt% nitrogen to the lubricant composition.
  • This oil had 0.2 wt.% sulfur, 0.08 wt.% phosphorus and 0.78 wt.% sulfated ash and had a TBN of 8.7.
  • Oil B the formulation of Oil A above was duplicated except that the magnesium detergent was replaced with 1.60 wt.% of a calcium salicylate detergent.
  • the dispersant provided 0.07 wt% nitrogen to the lubricating oil composition.
  • Oil B had 0.2 wt% sulfur, 0.08 wt% phosphorus, 0.78 wt % sulfated ash and a TBN of 7.7.
  • Oil C the formulation of Oil B above was duplicated except that there was present 3.93 wt.% of the same dispersant.
  • the dispersant provided 0.08 wt% nitrogen to the lubricating oil composition.
  • Oil C had 0.2 wt% sulfur, 0.08 wt% phosphorus, 0.8 wt% sulfated ash and a TBN of 8.2.

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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 (9)

  1. Schmierölzusammensetzung, die einen Schwefelgehalt von bis zu 0,3 Ges.-%, einen Phosphorgehalt von bis zu 0,08 Gew.-%, einen Gehalt an Sulfatasche von bis zu 0,80 Gew.-% und eine Gesamtbasenzahl von 8 bis 9 aufweist, und die eine Mischung von:
    (a) einer größeren Menge an Öl mit Schmierviskosität, das ausgewählt ist aus einem oder mehreren aus der Gruppe bestehend aus Gruppe I, Gruppe II, Gruppe III, Gruppe IV, Gruppe V und synthetischen Esterbasismaterialölen,
    (b) überbasischem Magnesiumsalicylat-Schmieröldetergens, das eine Gesamtbasenzahl (TBN) von 200 bis 500 aufweist und in einer Menge von 0,4 bis 1,0 Ges.-% der Schmierölzusammensetzung vorliegt, und
    (c) aschefreiem Dispergiermittel, das in einer Menge von mindestens 2,5 bis 4 Gew.-% vorliegt und der Schmierölzusammensetzung einen Stickstoffgehalt von 0,05 bis 0,1 Gew.-% verleiht, umfasst.
  2. Zusammensetzung nach Anspruch 1, die ferner eines oder mehrere der Mitglieder aus der Gruppe bestehend aus Antioxidantien, Zinkdikohlenwasserstoff-Dithiophosphaten, öllöslichen Organomolybdänverbindungen, Reibungsmodifizierungsmitteln und Viskositätsmodifizierungsmitteln umfasst.
  3. Zusammensetzung nach Anspruch 1 oder Anspruch 2, wobei das Dispergiermittel ein Polyisobutenylsuccinimid ist.
  4. Zusammensetzung nach Anspruch 2 oder Anspruch 3, wobei das Antioxidans ein (i) Dialkyldiphenylamin ist, wobei das Alkyl C4 bis C20-Alkyl ist oder (ii) ein sterisch gehindertes Phenol ist.
  5. Zusammensetzung nach einem der Ansprüche 2 bis 4, wobei die Kohlenwasserstoffgruppen des Zinkdikohlenwasserstoff-Dithiophospats 2 bis 8 Kohlenstoffatome aufweisen.
  6. Zusammensetzung nach einem der Ansprüche 2 bis 5, wobei die Organomolybdänverbindung ein Dialkyldithiocarbamat ist.
  7. Zuammensetzung nach einem der vorhergehenden Ansprüche, wobei das Öl mit Schmierviskosität ein Mineralöl ist.
  8. Verwendung einer Schmierölzusammensetzung gemäß einem der Ansprüche 1 bis 7 in einem Verbrennungsmotor, um verbesserte Kolbensauberkeit und/oder Viskositätskontrolle zur Verfügung zu stellen.
  9. Verfahren zum Verbessern der Kolbensauberkeit, bei dem einnem Motor eine Schmierölzusammensetzung gemäß einem der Ansprüche 1 bis 7 zugeführt wird.
EP05107526A 2004-09-27 2005-08-16 Schmierölzusammenstzungen mit niedrigen Phosphor-, Schwefel- und sulfatierten Asche-Gehalten Active EP1640441B1 (de)

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EP1884558B1 (de) * 2006-07-19 2019-04-10 Infineum International Limited Schmierölzusammensetzung
EP2194114A3 (de) * 2010-03-19 2010-10-27 Shell Internationale Research Maatschappij B.V. Composition de lubrification
DK2767578T3 (en) 2013-02-19 2016-05-09 Lukoil Marine Lubricants Germany Gmbh A method and apparatus for producing a cylinder oil

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US6569818B2 (en) * 2000-06-02 2003-05-27 Chevron Oronite Company, Llc Lubricating oil composition
US7026273B2 (en) * 2001-11-09 2006-04-11 Infineum International Limited Lubricating oil compositions
US6730638B2 (en) * 2002-01-31 2004-05-04 Exxonmobil Research And Engineering Company Low ash, low phosphorus and low sulfur engine oils for internal combustion engines
JP4011967B2 (ja) * 2002-05-07 2007-11-21 シェブロンジャパン株式会社 潤滑油組成物

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