EP0765931B1 - Huiles lubrifiantes comprenant des sels métalliques carbonatés alcoylphénols sulfurés et des sels métalliques carbonatés d'acides alcoylarylsulfoniques - Google Patents

Huiles lubrifiantes comprenant des sels métalliques carbonatés alcoylphénols sulfurés et des sels métalliques carbonatés d'acides alcoylarylsulfoniques Download PDF

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Publication number
EP0765931B1
EP0765931B1 EP95306745A EP95306745A EP0765931B1 EP 0765931 B1 EP0765931 B1 EP 0765931B1 EP 95306745 A EP95306745 A EP 95306745A EP 95306745 A EP95306745 A EP 95306745A EP 0765931 B1 EP0765931 B1 EP 0765931B1
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Prior art keywords
phenate
alkyl
carbonated
ratio
sulfonate
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EP0765931A1 (fr
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Terry V. Friesen
James J. Harrison
William R. Ruhe
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Chevron Oronite Co LLC
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Chevron Chemical Co LLC
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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
    • 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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
    • C10M133/56—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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
    • C10M135/10—Sulfonic acids or derivatives 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
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
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    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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    • C10M2215/26—Amines
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
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    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
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    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/088—Neutral salts
    • C—CHEMISTRY; METALLURGY
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
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    • C10M2219/089—Overbased salts
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    • 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
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    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
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    • 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
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    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/28—Rotary engines

Definitions

  • the present invention relates to phenate-containing lubricating oils having good soot dispersancy and good rust inhibition.
  • Viscosity increase due to soot accumulation in the oil can cause severe damage to diesel engines as a result of slow drainage of oil back to the sump, gelation of the oil in the sump, or filter plugging, all of which can result in reduced oil flow to critical bearings and oil-cooled parts, such as pistons.
  • Rust inhibition is also a key performance parameter for lubricating oils. Poor rust inhibiting properties can result in stuck valve lifters, impairing the operation of the engine.
  • Sulfurized, carbonated, calcium alkylphenates are well known detergents for lubricating oils, including heavy duty diesel crankcase applications. They provide certain advantages over other types of metallic detergents, specifically sulfonates, in that they impart oxidation protection to the lubricating oil.
  • formulations based solely on sulfurized, carbonated, calcium alkylphenates as the overbased detergent are deficient in rust inhibition, and are usually formulated with special rust inhibitors. These inhibitors add cost to the formulation and can sometimes cause compatibility problems with the other additives in the lubricating oil formulation.
  • U.S. Patent 3,236,770 teaches a diesel lubricating oil with basic sulfonates or basic phenates, in combination with a dialkylthiophosphate. Sulfonates and phenates are used as alternatives, not mixtures.
  • U.S. Patent 4,328,111 teaches a diesel lubricating oil with the reaction product of a basic compound (overbased metal sulfonate, phenate, or mixture thereof) with a phosphorus-containing material.
  • a basic compound overbased metal sulfonate, phenate, or mixture thereof
  • a phosphorus-containing material The mixture of phenate and sulfonate is not discussed in the specification and is not found in the examples.
  • U.S. Patent 4,938,881 teaches a diesel lubricating oil with a carboxylic dispersant, a salt of sulfonic or carboxylic acid, a dithiophosphoric acid, and a carboxylic ester derivative. It can also contain a salt of a sulfur acid, phosphorus acid, carboxylic acid, phenol, or mixtures thereof.
  • the preferred salt is of an alkylated benzene sulfonic acid.
  • U.S. Patent 5,071,576 teaches a mixture of overbased phenate and overbased alkyl aryl sulfonate.
  • the sulfonate has at least one long chain alkyl group (greater than 40 carbon atoms). Up to 85% of the base can be contributed by the phenate.
  • U.S. Patent 5,202,036, which is similar to U.S. Patent 4,938,881, teaches a diesel lubricating oil with a carboxylic dispersant and a salt of acidic organic compound.
  • the salt can be of sulfur acid, phosphorus acid, carboxylic acid, phenol, or mixtures thereof.
  • the preferred salt is of an alkylated benzene sulfonic acid.
  • EP Patent Application 552892-A1 teaches a diesel lubricating oil with zinc dithiophosphate, an antioxidant, an overbased metal sulfurized phenate, and a metal alkyl aromatic sulfonate.
  • the phenate constitutes from 50 wt. % to 80 wt. % of the phenate/sulfonate, but the sulfonate is not overbased.
  • US-A-3562159 (equivalent to FR-A-20/4251) discloses synthetic lubricants containing a carboxylic acid ester of lubricating viscosity as the basic liquid and, as additives, an acylated alkylene polyamine, a basic alkaline earth metal sulfonate, a metal phosphorodithioate, and (optionally) a basic alakaline earth metal salt of a phosulfurized hydrocarbon, an ester of a hydrocarbon-substituted succinic acid, and a basic alkaline earth metal salt of an alkylphenol sulfide.
  • the lubricants must contain no more than about 15% (by weight) mineral oil.
  • the present invention provides a lubricating oil composition having a major amount of an oil of lubricating viscosity, a minor amount of a carbonated sulfurized metal alkyl phenate, and a minor amount of a carbonated metal alkyl aryl sulfonate.
  • the lubricating oil also contains a unique class of modified polyamino alkenyl or alkyl succinimide compounds prepared from the succinimide reaction product of (1) an alkenyl- or alkyl-substituted succinic anhydride derived from a polyolefin having a number average molecular weight (Mn) of about 2000 to about 2700 and a weight average molecular weight (Mw) to Mn ratio of about 1 to about 5; and (2) a polyalkylene polyamine having greater than 4 nitrogen atoms per mole.
  • the modified succinimides of the present invention are obtained by post-treating the succinimide reaction product with a cyclic carbonate.
  • the soot dispersancy of the composition is superior when the total base equivalents donated by the phenate is more than 85% of the total base equivalents donated by the phenate and sulfonate.
  • the total base equivalents donated by the phenate is at least 90% of the total base equivalents donated by the phenate and sulfonate.
  • the carbonated sulfurized metal alkyl phenate is highly basic, with a total base number (TBN) of from 175 to 300, and a base ratio of metal to alkyl phenate of from 1.1:1 to 4:1.
  • TBN total base number
  • the molar ratio of carbonate to total metallic base is at least 0.4:1, preferably 0.5:1 to 0.75:1.
  • the alkyl phenate portion of the molecule is derived from a monoalkylphenol, the alkyl group containing from about 9 to 28 carbon atoms.
  • the carbonated metal alkyl aryl sulfonate is a carbonated magnesium sulfonate with a total base number of at least 175, most preferably 300 to 400, with a base ratio of metal to sulfonate of at least 8:1 and most preferably 11:1 to 35:1.
  • the carbonated sulfurized metal alkyl phenate, carbonated metal alkyl aryl sulfonate, and succinimide dispersant can be used in combination with a noncarbonated metal sulfonate, an oxidation inhibitor, a viscosity index improver; and a zinc dithiophosphate.
  • the Figure is a graph of test data that shows the criticality on soot dispersion of the percentage of total base equivalents donated by the phenate relative to the total base equivalents donated by the phenate and sulfonate.
  • the present invention involves a lubricating oil composition as defined in claim 1.
  • the total base equivalents donated by the phenate is more than 85% of the total base equivalents donated by the phenate and sulfonate.
  • the total base equivalents donated by the phenate is at least 90% of the total base equivalents donated by the phenate and sulfonate.
  • the base oil used with the additive compositions of this invention may be mineral oil or synthetic oils of lubricating viscosity and preferably suitable for use in the crankcase of an internal combustion engine.
  • the lubricating oils may be derived from synthetic or natural sources.
  • Mineral oil for use as the base oil in this invention includes paraffinic, naphthenic and other oils that are ordinarily used in lubricating oil compositions.
  • Synthetic oils include both hydrocarbon synthetic oils and synthetic esters.
  • Useful synthetic hydrocarbon oils include liquid polymers of alpha olefins having the proper viscosity. Especially useful are the hydrogenated liquid oligomers of C 6 to C 12 alpha olefins such as 1-decene trimer.
  • alkyl aryls of proper viscosity such as didodecyl benzene can be used.
  • Useful synthetic esters include the esters of both monocarboxylic acids and polycarboxylic acids as well as monohydroxy alkanols and polyols. Typical examples are didodecyl adipate, pentaerythritol tetracaproate, di-2-ethylhexyl adipate, dilaurylsebacate and the like.
  • Complex esters prepared from mixtures of mono and dicarboxylic acids and mono and dihydroxy alkanols can also be used.
  • Blends of hydrocarbon oils with synthetic oils are also useful. For example, blends of 10 to 25 weight percent hydrogenated 1-decene trimer with 75 to 90 weight percent 150 SUS (38°C(100°F)) mineral oil gives an excellent lubricating oil base.
  • the carbonated sulfurized metal alkyl phenate is highly basic, with a total base number of at least 175, most preferably 175 to 300, and a base ratio of metal to alkyl phenate of at least 1.1:1, most preferably 1.5:1 to 4:1.
  • the molar ratio of carbonate to total metallic base is at least 0.4:1, preferably 0.5:1 to 0.75:1.
  • the alkyl phenate portion of the molecule is derived from a monoalkyl phenol, the alkyl group containing from about 9 to 28 carbon atoms.
  • the preferred metal is calcium.
  • the alkyl group can be branched, linear, or mixtures thereof.
  • Such a carbonated sulfurized metal alkyl phenate is disclosed by Walter W. Hanneman in U.S. Patent No. 3,178,368, entitled "Process for Basic Sulfurized Metal Phenates," which is hereby incorporated by reference for all purposes.
  • the carbonated metal alkyl aryl sulfonate is also highly basic, with a total base number of at least 175, most preferably 300 to 400, with a base ratio of metal to sulfonate of at least 8:1 and most preferably 11:1 to 35:1.
  • These slulfonates can be derived by sulfonating naturally occuring aromatics present in heavy base oils or by sulfonating alkylated aromatics.
  • Such a carbonated metal alkyl aryl sulfonate is disclosed by T.C. Jao in U.S. Patent No. 5,132,033, entitled "Methods for Preparing Overbased Calcium Sulfonates," which is hereby incorporated by reference for all purposes.
  • the metal is preferably magnesium because magnesium sulfonate gives superior performance in the Sequence IID rust test, and gives a higher total base number per wt. % of sulfated ash.
  • Modified polyamino alkenyl or alkyl succinimides useful in this invention are prepared by post-treating a polyamino alkenyl or alkyl succinimide with a cyclic carbonate.
  • the polyamino alkenyl or alkyl succinimides are typically prepared by reaction of an alkenyl or alkyl succinic anhydride with a polyamine.
  • succinimide Alkenyl or alkyl succinimides are disclosed in numerous references and are well known in the art. Certain fundamental types of succinimides and related materials encompassed by the term of art "succinimide” are taught in U.S. Patent Nos. 2,992,708; 3,018,291; 3,024,237; 3,100,673; 3,219,666; 3,172,892; and 3,272,746, the disclosures of which are hereby incorporated by reference. The term “succinimide” is understood in the art to include many of the amide, imide and amidine species that are also formed by this reaction. The predominant product, however, is succinimide and this term has been generally accepted as meaning the product of a reaction of an alkenyl- or alkyl-substituted succinic acid or anhydride with a polyamine.
  • a thermal process for the preparation of alkenyl- or alkyl-substituted succinic anhydride involving the reaction of a polyolefin and maleic anhydride has been described in the art. This thermal process is characterized by the thermal reaction of a polyolefin with maleic anhydride.
  • the alkenyl- or alkyl-substituted succinic anhydride may be prepared as described in U.S. Patents Nos. 4,388,471 and 4,450,281, which are incorporated herein by reference.
  • Other examples of the preparation of alkenyl- or alkyl-substituted succinic anhydrides are taught in U.S. Patents Nos. 3,018,250 and 3,024,195, which are incorporated herein by reference.
  • the alkenyl or alkyl succinic anhydride reactant is derived from a polyolefin having an Mn from about 2000 to about 2700 and a Mw/Mn ratio of about 1 to about 5.
  • the alkenyl or alkyl group of the succinimide has an Mn value from about 2100 to about 2400.
  • Suitable polyolefin polymers for reaction with maleic anhydride include polymers comprising a major amount of C 2 to C 5 monoolefin, e.g., ethylene, propylene, butylene, iso-butylene and pentene.
  • the polymers can be homopolymers such as polyisobutylene as well as copolymers of two or more such olefins such as copolymers of: ethylene and propylene, butylene, and isobutylene, etc.
  • copolymers include those in which a minor amount of the copolymer monomers, e.g., 1 to 20 mole percent, is a C 4 to C 8 diolefin, e.g., a copolymer of isobutylene and butadiene or a copolymer of ethylene, propylene and 1,4-hexadiene, etc.
  • a particularly preferred class of olefin polymers for reaction with maleic anhydride comprises the polybutenes, which are prepared by polymerization of one or more of 1-butene, 2-butene and isobutene. Especially desirable are polybutenes containing a substantial proportion of units derived from isobutene. The polybutene may contain minor amounts of butadiene, which may or may not be incorporated in the polymer. These polybutenes are readily available commercial materials well known to those skilled in the art. Disclosures thereof will be found, for example, in U.S. Patents Nos. 3,215,707; 3,231,587; 3,515,669; 3,579,450; and 3,912,764, as well as U.S. Patent Nos. 4,152,499 and 4,605,808. The above are incorporated by reference for their disclosures of suitable polybutenes.
  • Suitable succinic anhydride reactants also include copolymers having alternating polyalkylene and succinic groups, such as those taught in U.S. Patent No. 5,112,507, which is hereby incorporated by reference.
  • the polyamine to be reacted with the alkenyl or alkyl succinic anhydride to produce the polyamino alkenyl or alkyl succinimide employed in this invention is generally a polyalkylene polyamine.
  • the polyalkylene polyamine has an average nitrogen atom to molecule ratio of greater than 4.0, up to a maximum of about 12.
  • Most preferred are polyamines having an average nitrogen atom to molecule ratio of from about 5 to about 7.
  • Preferred polyalkylene polyamines also contain from about 4 to about 40 carbon atoms, there being preferably from 2 to 3 carbon atoms per alkylene unit.
  • the polyamine preferably has a carbon-to-nitrogen ratio of from about 1:1 to about 10:1.
  • a suitable molar charge of polyamine to alkenyl or alkyl succinic anhydride for making the compounds of this invention is from about 0.35:1 to about 0.6:1; although preferably from about 0.4:1 to about 0.5:1.
  • the phrase "molar charge of polyamine to alkenyl or alkyl succinic anhydride" means the ratio of the number of moles of polyamine to the number of moles of succinic groups in the succinic anhydride reactant.
  • the polyamino alkenyl or alkyl succinimides formed as described above are then reacted with a cyclic carbonate.
  • the resulting modified polyamino alkenyl succinimide has one or more nitrogens of the polyamino moiety substituted with a hydroxy hydrocarbyl oxycarbonyl, a hydroxy poly(oxyalkylene) oxycarbonyl, a hydroxyalkylene, hydroxyalkylenepoly(oxyalkylene), or mixture thereof.
  • reaction of a polyamino alkenyl or alkyl succinimide with a cyclic carbonate is conducted at a temperature sufficient to cause reaction of the cyclic carbonate with the polyamino alkenyl or alkyl succinimide.
  • reaction temperatures of from about 20° C to about 250° C are preferred with temperatures of from about 100° C to 200° C being more preferred and temperatures of from 150° C to 180° C are most preferred.
  • the reaction may be conducted neat, wherein both the alkenyl or alkyl succinimide and the cyclic carbonate are combined in the proper ratio, either alone or in the presence of a catalyst (such as an acidic, basic or Lewis acid catalyst), and then stirred at the reaction temperature.
  • a catalyst such as an acidic, basic or Lewis acid catalyst
  • suitable catalysts include, for instance, phosphoric acid, boron trifluoride, alkyl or aryl sulfonic acid, alkali or alkaline carbonate.
  • the reaction may be conducted in a diluent.
  • the reactants may be combined in a solvent such as toluene, xylene, oil or the like, and then stirred at the reaction temperature. After reaction completion, volatile components may be stripped off.
  • a diluent it is preferably inert to the reactants and products formed and is generally used in an amount sufficient to insure efficient stirring.
  • Examples of metal compounds that may be reacted with the dithiophosphoric acid to produce zinc dithiophosphate include zinc oxide, zinc hydroxide, zinc carbonate, and zinc propylate.
  • the total amount of the zinc dithiophosphate present is in the range of 3 to 30, preferably 10 to 20, millimoles of zinc per kilogram of finished product.
  • the reason for this range is that less than 10 mm/kg could easily result in failing valve train wear performance, while greater than 20 mm/kg leads to the concern of phosphorus poisoning of the catalytic converters.
  • a heavy duty diesel lubricating oil composition was blended as a 7 TBN oil as described below.
  • a conventional commercial oil might contain from 0.25 to 0.75 wt. % of rust inhibitor, the examples below were formulated without rust inhibitor to illustrate the advantages of the present invention.
  • Component wt. % Base Equivalents sulfurized carbonated metal phenate (250 TBN, 1.9:1 base ratio) 2.1 50 polyamino alkenyl or alkyl succinimide 5.5 low overbased calcium sulfonate 1.6 zinc dithiophosphate 1.4 molybdenum inhibitor 0.2 viscosity index improver 7.0 Base oil Balance
  • a second lubricating oil composition was blended as a 7 TBN oil as in Example 1 with the exception that a portion of the sulfurized carbonate metal phenate was replaced with carbonated magnesium alkylsulfonate such that the magnesium sulfonate accounted for 10% of the total base equivalents supplied by the carbonated detergent as described below:
  • Component wt. % Base Equivalents sulfurized carbonated metal phenate 1.9 45 carbonated magnesium alkylsulfonate (400 TBN, 15:1 base ratio) 0.13 5
  • the formulations in Examples 1 through 7 were evaluated in a dispersancy bench test.
  • the test provides a rapid means for determining an oil's ability to control viscosity increase due to soot loading.
  • carbon black is added to the finished oil.
  • the mixture is well mixed and degassed in a vacuum oven.
  • the viscosity of the oil is measured at 100° C before and after the addition of the carbon black. Oils with poor dispersancy will exhibit a higher viscosity increase due to the agglomeration of the carbon black in the oil.
  • the Figure is a graph of this test data. Note that there is a substantial improvement in soot dispersancy when the phenate constitutes more than 85% of the metal base.
  • the formulations in examples 1 through 4 were evaluated in a modified D665 rust bench test.
  • This test is designed to evaluate an oil's ability to inhibit rust formation in crankcase internal combustion engines.
  • the oil is placed in a stirred beaker heated to 80 C.
  • a previously cleaned metal coupon is suspended in the oil, and a sufficient amount of dilute (0.2N) aqueous hydrochloric acid is added to neutralize all of the base present in the oil.
  • the oil-dilute acid mixture is then stirred for 7 hours at 80 C, at which point the stirrer is stopped and the metal coupon removed.
  • Example % metal from phenate Rust rating (10 clean) 1 100 8.26 3 95 8.76 2 90 8.6 4 85 8.8

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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 (8)

  1. Composition d'huile lubrifiante comprenant :
    (a) une quantité dominante d'une huile de viscosité propre à la lubrification ;
    (b) une petite quantité d'un alkylphénate métallique sulfuré carbonaté ;
    (c) une petite quantité d'un alkylarylsulfonate métallique carbonaté ; dans laquelle les équivalents totaux de base cédés par le phénate sont supérieurs à 85 % des équivalents totaux de base cédés par le phénate et le sulfonate ; et
    (d) une petite quantité d'un polyamino-alcényl- ou -alkyl-succinimide dans lequel le succinimide comprend le produit de réaction :
    (a) d'un anhydride succinique à substituant alcényle ou alkyle dérivé d'une polyoléfine ayant une valeur de Mn de 2000 à 2700 et un rapport Mw/Mn de 1 à 5 ; et
    (b) d'une polyalkylène-polyamine ayant un taux moyen d'atomes d'azote par molécule supérieur à 4,0 ; le produit de réaction étant soumis à un post-traitement avec un carbonate cyclique.
  2. Composition d'huile lubrifiante suivant la revendication 1, dans laquelle les équivalents totaux de base cédés par le phénate sont au moins égaux à 90 % des équivalents totaux de base cédés par le phénate et le sulfonate.
  3. Composition d'huile lubrifiante suivant la revendication 1 ou 2, dans laquelle l'alkylphénate métallique sulfuré carbonaté est un alkylphénate de calcium sulfuré carbonaté qui a un indice de basicité total de 175 à 300, qui a un rapport de base du métal à l'alkylphénate compris dans l'intervalle de 1,1:1 à 4:1 ; et qui a un rapport molaire du carbonate à la base métallique totale compris dans l'intervalle de 0,5:1 à 0,75:1, le groupe alkyle contenant environ 9 à 28 atomes de carbone.
  4. Composition d'huile lubrifiante suivant la revendication 1, 2 ou 3, dans laquelle l'alkylarylsulfonate métallique carbonaté consiste en un alkylarylsulfonate de magnésium carbonaté ayant un indice de basicité total de 300 à 400, avec un rapport de base du métal au sulfonate compris dans l'intervalle de 11:1 à 35:1.
  5. Composition d'huile lubrifiante suivant la revendication 1, dans laquelle le rapport molaire de charge de la polyamine à l'anhydride succinique est compris dans l'intervalle de 0,35:1 à 0,6:1 ; et le rapport molaire de charge du carbonate cyclique à l'azote d'amine basique dans le produit de réaction est compris dans l'intervalle de 1,5:1 à 4:1.
  6. Composition d'huile lubrifiante suivant l'une quelconque des revendications précédentes, dans laquelle la polyoléfine a une valeur de Mn de 2100 à 2400.
  7. Composition d'huile lubrifiante suivant l'une quelconque des revendications précédentes, dans laquelle la polyalkylène-polyamine a un taux moyen d'atomes d'azote par molécule de 5 à 7.
  8. Composition d'huile lubrifiante suivant la revendication 1, comprenant :
    (a) une quantité dominante d'une huile de viscosité propre à la lubrification ;
    (b) une petite quantité d'un alkylphénate de calcium sulfuré carbonaté ;
    (c) une petite quantité d'un alkylarylsulfonate de magnésium carbonaté, les équivalents totaux de base cédés par le phénate étant égaux à plus de 85 % des équivalents totaux de base cédés par le phénate et le sulfonate ;
    (d) une petite quantité d'un alkylarylsulfonate métallique non carbonaté ;
    (e) une petite quantité d'un polyamino-alcényl- ou -alkyl-succinimide,
    la quantité du succinimide étant inférieure à environ 3 % en poids sur la base du polymère sec, et le succinimide comprenant le produit de réaction :
    (i) d'un anhydride succinique à substituant alcényle ou alkyle dérivé d'un polyisobutène ayant une valeur de Mn de 2100 à 2400 et un rapport Mw/Mn de 1 à 5 ; et
    (ii) d'une polyalkylène-polyamine ayant un taux moyen d'atomes d'azote par molécule supérieur à 4 ; le rapport molaire de charge de la polyamine à l'anhydride succinique étant compris dans l'intervalle de 0,4:1 à 0,5:1 ;
    le produit de réaction étant soumis à un post-traitement avec du carbonate d'éthylène en un rapport molaire de charge du carbonate d'éthylène à l'azote d'amine basique dans le produit de réaction du type succinimide compris dans l'intervalle de 2:1 à 3:1 ;
    (f) une petite quantité d'un inhibiteur d'oxydation ;
    (g) une petite quantité d'un agent améliorant l'indice de viscosité ;
    (h) une petite quantité d'un dithiophosphate de zinc.
EP95306745A 1995-09-25 1995-09-25 Huiles lubrifiantes comprenant des sels métalliques carbonatés alcoylphénols sulfurés et des sels métalliques carbonatés d'acides alcoylarylsulfoniques Expired - Lifetime EP0765931B1 (fr)

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US6715473B2 (en) * 2002-07-30 2004-04-06 Infineum International Ltd. EGR equipped diesel engines and lubricating oil compositions
US6869919B2 (en) 2002-09-10 2005-03-22 Infineum International Ltd. Lubricating oil compositions
US7678746B2 (en) 2003-10-30 2010-03-16 The Lubrizol Corporation Lubricating compositions containing sulphonates and phenates
EP1680491B1 (fr) * 2003-10-30 2012-12-26 The Lubrizol Corporation Compositions lubrifiantes contenant des sulfonates et des phenates
WO2009085800A1 (fr) 2007-12-27 2009-07-09 The Lubrizol Corporation Composition lubrifiante contenant un détergent
CN113186015B (zh) * 2021-02-02 2024-02-06 安徽澳润新材料有限公司 一种高碱值磺酸镁清净剂及其制备方法

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US3562159A (en) * 1968-06-26 1971-02-09 Lubrizol Corp Synthetic lubricants
US4123369A (en) * 1976-12-01 1978-10-31 Continental Oil Company Lubricating oil composition
US4131551A (en) * 1977-08-15 1978-12-26 Standard Oil Company Railway lubricating oil
GB8723909D0 (en) * 1987-10-12 1987-11-18 Exxon Chemical Patents Inc Lubricant oil additive
US4927551A (en) * 1987-12-30 1990-05-22 Chevron Research Company Lubricating oil compositions containing a combination of a modified succinimide and a Group II metal overbased sulfurized alkylphenol
US5370805A (en) * 1993-11-18 1994-12-06 Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. Chlorine-free diesel engine lubricating composition
GB9400417D0 (en) * 1994-01-11 1994-03-09 Bp Chemicals Additives Lubricating oil composition

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