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EP1632553B1 - Composition d'huile lubrifiante - Google Patents

Composition d'huile lubrifiante Download PDF

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Publication number
EP1632553B1
EP1632553B1 EP05106999.5A EP05106999A EP1632553B1 EP 1632553 B1 EP1632553 B1 EP 1632553B1 EP 05106999 A EP05106999 A EP 05106999A EP 1632553 B1 EP1632553 B1 EP 1632553B1
Authority
EP
European Patent Office
Prior art keywords
composition
oil
lubricating oil
salicylate
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP05106999.5A
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German (de)
English (en)
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EP1632553A1 (fr
Inventor
Robert Shaw
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Infineum International Ltd
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Infineum International Ltd
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Filing date
Publication date
Priority claimed from EP04255398A external-priority patent/EP1632552A1/fr
Application filed by Infineum International Ltd filed Critical Infineum International Ltd
Priority to EP05106999.5A priority Critical patent/EP1632553B1/fr
Publication of EP1632553A1 publication Critical patent/EP1632553A1/fr
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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
    • 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
    • C10M2207/02—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
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • 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
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • 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

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.
  • 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.
  • European patent application 1 167 497 A2 discloses a low SAPS lubricating oil composition
  • Lubricating oils formulated in accordance with this patent application are stated to exhibit good high temperature detergency despite the lower sulfur, phosphorus and sulphated ash levels of the compositions.
  • 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 containing less than 5 millimoles of salicylate soap per kilogram of lubricating oil composition which comprises an admixture of :
  • the oil of lubricating viscosity may be selected from Group I, II, III or IV base stocks, synthetic ester base stocks or mixtures thereof.
  • 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.
  • the oil of lubricating viscosity does not comprise any Group I basestock oil.
  • 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 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 at least one overbased alkali metal or alkaline earth lubricating oil detergent having a relatively low soap content, i.e., between 20 and 25 wt.%.
  • these detergents surprisingly result in the oils having acceptable rating the XUD-IIBTE test for piston cleanliness while the same oil formulated with salicylates having a higher soap content show distinctly poorer results in the same test. Such a result is contrary to expectation, when conventionally the amount of soap is increased to provide improved piston cleanliness.
  • the overbased metal salicylate detergent may be C 8 -C 30 alkyl salicylates or mixtures thereof, with C 10 -C 20 alkyl salicylates being particularly preferred.
  • the detergent will be a calcium and/or magnesium salicylate and will have a Total Base Number at 100% active mass (TBN) between 10 and 700, more preferably between 50 and 650, and most preferably between 100 and 550.
  • TBN Total Base Number at 100% active mass
  • the most preferred detergent for use in this invention is an overbased calcium alkyl salicylate having a TBN between 100 and 550.
  • the amount of metal salicylate detergents used can vary broadly, but typically will be from about 0.2 to about 5 wt.%, preferably 0.3 to 1.5 wt.%, based on the total weight of the composition so as to provide less than 5 millimoles of salicylate soap per kilogram of the finished oil composition.
  • the amount of metal salicylate detergent used in the present invention provides the composition with at least 2 mmol soap per kilogram of the finished oil composition.
  • the metal salicylate is the sole metal lubricating oil detergent present in the lubricating oil compositions of the invention.
  • other metal-containing detergents such as metal sulfonates or phenates, may be present in the lubricating composition, but preferably only in very minor amounts.
  • the total amount of detergent present is limited to provide the finished oil composition with a sulfated ash content of 0.80 wt. % or lower.
  • An ashless dispersant generally comprises 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 of the present invention 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.
  • the ashless dispersant is suitably present in an amount of from 0.5 to 10.0 wt.%, preferably about 1 to 3 wt.%.
  • 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 GlissopalTM (from BASF) and UltravisTM (from BP-Amoco).
  • 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.
  • 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.
  • Preferred, but optional ingredients are oil soluble organomolybdenum compounds, friction modifiers, and viscosity modifiers.
  • any suitable oil soluble organo-molybdenum compound may be employed.
  • the molybdenum compound is thought to 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 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 should 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 may make 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 generally required when the base stock is a PAO or synthetic ester.
  • a 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, that is subsequently blended into base stock to make the finished lubricant.
  • the concentrate will typically be formulated to contain the additive(s) in proper amounts to provide the desired concentration in the final formulation when the concentrate is combined with a predetermined amount of a base lubricant.
  • the concentrate is preferably made in accordance with the method described in 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 was prepared and tested for piston merits according to the XUD-IIBTE fired engine test, a European passenger car diesel engine test (CEC L-56-T-98) which is part of the ACEA B specification, the same test was carried out on comparative formulations oils B and C.
  • the piston cleanliness results are given in Table 1. Oil A shows a distinct and surprising improvement notwithstanding the lower soap content.
  • Oil A a lubricating oil composition was prepared containing 0.51 wt.% calcium alkyl salicylate (TBN at 100% active matter 511, 23.6 mass % soap), organomolybdenum antiwear agent, friction modifier, dispersant, antioxidant, lubricating oil flow improver, viscosity modifier, antifoam agent, zinc dihydrocarbyl dithiophosphate and mineral oil base stocks.
  • This oil had 0.19 wt.% sulfur, 0.049 wt.% phosphorus and 0.5 wt.% sulfated ash and contained 3.6 millimoles of salicylate soap per kilogram of oil; the XUD-IIBTE piston merits value was 50.6
  • Oil B the formulation of Oil A above was duplicated except that all of the calcium alkyl salicylate of Oil A was replaced by 0.89 wt% of a calcium alkyl salicylate having a soap content of 35.6%, and the final oil had 13.2 millimoles of soap per kilogram of oil.
  • Oil C the formulation of Oil A above was duplicated except that the calcium alkyl salicylate of Oil A was replaced by 0.79 wt% of a calcium alkyl salicylate having a soap content of 37.1% and 0.30 wt% of a magnesium salicylate having a soap content of 30.3%, and the final oil had 9.5 millimoles of soap per kilogram of oil.

Landscapes

  • 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. Composition d'huile lubrifiante ayant une teneur en soufre allant jusqu'à 0,3 % en poids, une teneur en phosphore allant jusqu'à 0,08 % en poids, une teneur en cendres sulfatées allant jusqu'à 0,80 % en poids et contenant moins de 5 millimoles de savon de salicylate détergent par kilogramme de composition d'huile, qui comprend un mélange :
    (a) d'une quantité dominante d'une huile de viscosité propre à la lubrification ; et
    (b) d'un détergent pour huiles lubrifiantes à base d'alkylsalicylate de métal alcalin ou de métal alcalinoterreux surbasique ayant une teneur en savon de salicylate de 20 à 25 % en poids.
  2. Composition suivant la revendication 1, comprenant en outre un ou plusieurs membres du groupe consistant en des dispersants, des dispersants convenables sans cendres, un antioxydant, un dihydrocarbyldithiophosphate de zinc, des composés organiques de molybdène solubles dans l'huile, des modificateurs de frottement et des modificateurs de viscosité.
  3. Composition suivant la revendication 1 ou la revendication 2, dans laquelle l'ingrédient (b) est un salicylate de calcium ou de magnésium ayant un indice de basicité totale (TBN) à 100 % de masse active de 10 à 700.
  4. Composition suivant la revendication 2 ou 3, dans laquelle le dispersant est un polysisobuténylsuccinimide.
  5. Composition suivant la revendication 2, 3 ou 4, dans laquelle l'antioxydant est (i) une dialkyldiphénylamine dans laquelle le groupe alkyle est un groupe alkyle en C4 à C20, (ii) un phénol à encombrement stérique ou (iii) un de leurs mélanges.
  6. Composition suivant l'une quelconque des revendications 2 à 5, dans laquelle les groupes hydrocarbyle du dihydrocarbyldithiophosphate de zinc ont 2 à 8 atomes de carbone.
  7. Composition suivant l'une quelconque des revendications 2 à 6, dans laquelle le composé organique de molybdène est un dialkyldithiocarbamate.
  8. Composition suivant l'une quelconque des revendications précédentes, dans laquelle l'ingrédient (a) est une huile minérale.
  9. Composition suivant l'une quelconque des revendications précédentes, dans laquelle l'ingrédient (b) est le seul détergent métallique présent.
EP05106999.5A 2004-09-06 2005-07-28 Composition d'huile lubrifiante Active EP1632553B1 (fr)

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EP04255398A EP1632552A1 (fr) 2004-09-06 2004-09-06 Composition d'huile lubrifiante
EP05106999.5A EP1632553B1 (fr) 2004-09-06 2005-07-28 Composition d'huile lubrifiante

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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8680030B2 (en) 2005-11-18 2014-03-25 Exxonmobil Research And Engineering Company Enhanced deposit control for lubricating oils used under sustained high load conditions employing glycerine derivative with a grafted hindered phenolic and/or a hindered phenolic containing a thioether group
US20070117726A1 (en) * 2005-11-18 2007-05-24 Cartwright Stanley J Enhanced deposit control for lubricating oils used under sustained high load conditions

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2702604C2 (de) 1977-01-22 1984-08-30 Basf Ag, 6700 Ludwigshafen Polyisobutene
GB2056482A (en) 1979-08-13 1981-03-18 Exxon Research Engineering Co Lubricating oil compositions
US4938880A (en) 1987-05-26 1990-07-03 Exxon Chemical Patents Inc. Process for preparing stable oleaginous compositions
US6569818B2 (en) 2000-06-02 2003-05-27 Chevron Oronite Company, Llc Lubricating oil composition
US6784143B2 (en) * 2001-05-11 2004-08-31 Infineum International Ltd. Lubricating oil composition
US6583092B1 (en) * 2001-09-12 2003-06-24 The Lubrizol Corporation Lubricating oil composition
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
US6852679B2 (en) * 2002-02-20 2005-02-08 Infineum International Ltd. Lubricating oil composition

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