EP0277729B1 - Veschleissschutz-Schmiermittelzusammensetzungen mit geringem Phosphorgehalt - Google Patents

Veschleissschutz-Schmiermittelzusammensetzungen mit geringem Phosphorgehalt Download PDF

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Publication number
EP0277729B1
EP0277729B1 EP88300500A EP88300500A EP0277729B1 EP 0277729 B1 EP0277729 B1 EP 0277729B1 EP 88300500 A EP88300500 A EP 88300500A EP 88300500 A EP88300500 A EP 88300500A EP 0277729 B1 EP0277729 B1 EP 0277729B1
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EP
European Patent Office
Prior art keywords
additive composition
lubricating oil
additive
present
range
Prior art date
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Expired - Lifetime
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EP88300500A
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English (en)
French (fr)
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EP0277729A1 (de
Inventor
Anthony Joseph Rollin
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Ethyl Corp
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Ethyl Corp
BP Corp North America Inc
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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
    • 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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/16—Reaction products obtained by Mannich reactions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
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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
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/086—Imides
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • 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
    • C10M2215/26—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
    • 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
    • C10M2217/042—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds between the nitrogen-containing monomer and an aldehyde or ketone
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2217/043—Mannich bases
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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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
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10M2219/08—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
    • 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
    • C10M2219/08—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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    • 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
    • C10M2219/08—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
    • C10M2219/089—Overbased 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
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/061—Esters derived from boron
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • 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
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    • 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
    • C10N2040/251—Alcohol fueled engines
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10N2040/255—Gasoline 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
    • C10N2040/255—Gasoline engines
    • C10N2040/28—Rotary engines

Definitions

  • the present invention is directed to a novel composition that is useful as a lubricant additive.
  • the present invention relates to a lubricant additive composition that is characterized by antiwear and friction retention properties while providing reduced phosphorus levels.
  • the invention relates to formulation of a so-called universal or mixed fleet lubricant oil additive composition (i.e. one that will result in a lubricant meeting the requirements of both heavy duty and passenger car engine tests) which has reduced phosphorus and which comprises zinc dialkyldithiophosphate having both primary and secondary character in combination with a succinimide dispersant.
  • Lubricating oils particularly mineral oils, deteriorate under heavy loads and as a result of oxidation during their use in internal combustion engines to form products, some of which are corrosive and some of which agglomerate to form sludge-like deposits and varnish-like deposits.
  • Such sludge-like material occurs when the crankcase lubricant is subjected to alternate hot and cold environments, which are present in ordinary stop-and-go driving.
  • Sludge is a complex mixture of fuel combustion products, unburned fuel, carbon, lead anti-knock residues, and water and, if not maintained in fine suspension in the lubricating oil, will deposit on engine parts. Such deposits are deleterious to engine performance.
  • additives and additive formulations have been added to lubricating oils to minimize deterioration and to enhance performance.
  • Such materials as neutral and over-based metal long chain alkyl substituted sulfonates, phenates, salicylates, and phosphonates and thiophosphonates have been added as detergents and/or detergent-dispersants.
  • Materials such as polymers and/or copolymers containing a carboxylate ester function and one or more polar functions, N-substituted long chain alkenyl succinimides, high-molecular weight amides and polyamides, high-molecular weight esters and polyesters, and amine salts of high-molecular weight organic acids, have been added as ashless dispersants to disperse the cold sludge formed under stop-and-go driving conditions.
  • Materials such as metal dithiophosphates, metal dithiocarbamates, sulfurized terpenes, and phosphosulfurized terpenes, have been added as corrosion inhibitors.
  • one or more additives are incorporated often into the lubricant composition to furnish or to enhance antiwear and friction retention properties of that composition. Examples of art describing such lubricating oil compositions are discussed hereinbelow.
  • Rowe discloses lubricating oil compositions that contain a small amount of a mixture of a metal salt of an O,O-diorgano-phosphorodithioate and a boroaryl compound in synergistic proportions.
  • An example of such mixture is a mixture of zinc, O,O-diisopropylphosphorodithioate and 9-hydroxy-9,10 boroxarophenanthrene. The amount of the mixture is sufficient to improve antiwear properties of the compositions.
  • Braid discloses lubricant compositions containing esters of O,O-diorgano-S-(2-hydroxyalkyl) phosphorodithioates, which are antioxidants and corrosion inhibitors.
  • Clark discloses a friction-reducing additive for use in lubricating oils.
  • the additive comprises a hydrocarbon oil of lubricating viscosity, an extreme pressure antiwear agent, an alkaline material, such as an overbased calcium sulfonate, a viscosity index improving agent, and optionally an antifoam agent and an antioxidant agent.
  • the antiwear agent comprises a mixture of an oil dispersion of solid, inorganic film-forming potassium borate, antimony dialkylphosphorodithioate, and a liquid chlorinated paraffin.
  • Salentine discloses a lubricating oil composition having improved wear properties, which composition comprises an oil of lubricating viscosity having dispersed therein a hydrated alkali-metal borate extreme-pressure agent and an effective amount of a mixture of a non-sulfur-containing phosphate, a monothiophosphate, and a dithiophosphate, the mixture of phosphate, monothiophosphate, and dithiophosphate being in the ratio of 0.90-10:0.90-1.10:0.47-0.67.
  • a lubricating oil composition comprising an oil of lubricating viscosity and a minor amount of a multifunctional additive consisting of the metal salt of a partially borated, partially phosphosulfurized hydroxyl-containing ester derived from a polyol, e.g., a zinc salt of borated, partially phosphosulfurized glycerol monooleate.
  • the additive is an effective friction-reducing, antioxidant, and copper strip passivating additive in lubricants.
  • Patent 4,483,775 Yamaguchi discusses this problem and suggests that the detrimental effect of the overbased calcium hydrocarbyl sulfonates on the wear of metal parts in the internal combustion engine can be overcome by adding to the lubricating oil containing these materials an effective amount of a complex prepared by reacting an insoluble metal salt of a diisopropyl dithiophosphoric acid with an oil-soluble alkenyl or alkyl mono- or bis-succinimide in specific amounts.
  • Yamaguchi also points out that there is another problem that is associated with the use of phosphorus-containing additives in lubricating oils.
  • the phosphorus can have a deleterious effect upon the catalysts that are employed in the emissions control systems of internal combustion engines of automobiles.
  • the overbased metal hydrocarbyl sulfonates tend to offset the effectiveness of the metal dihydrocarbyldithiophosphates, additional amounts of the metal dihydrocarbyldithiophosphates must be employed and such increased amounts of these additives will introduce additional amounts of phosphorus into the lubricating oil.
  • EP-A-020674 discloses a lubricating oil composition comprising
  • an additive composition which is suitable for use in so-called universal or mixed fleet oils.
  • Such an oil by definition, is one which is capable of passing a rigorous battery of engine tests which measure the performance of the oil for both passenger car and heavy duty (i.e. diesel) applications.
  • pasenger car catalytic converters of phosphorus which is typically introduced into the oil via the anti-wear agent zinc dialkyldithiophosphate
  • it would be particularly advantageous if an additive composition suitable for a universal oil could be formulated with reduced levels of phosphorus.
  • a general object of the invention is to provide an additive composition which affords passing wear protection for a universal oil at reduced phosphorus levels.
  • an additive composition for addition to an oil of lubricating viscosity suitable for passenger car and heavy duty use comprising: (a) zinc dialkyldithiophosphate having both primary and secondary character such that the primary to secondary ratio is 1:1 to 5:1, said mixed primary/secondary zinc dialkyldithiophosphate being present in the additive composition in amount such that a lubricating oil containing an effective amount of said additive composition has a phosphorus content of not greater than 0.1 wt %; (b) a succinimide dispersant in such amount that a lubricating oil containing 9 to 12 percent of said additive composition will comprise at least about 0.5 wt % succinimide; (c) a boron content such that a lubricating oil containing said additive composition contains at least 100 ppm boron; and (d) an effective amount of basic salts comprising high base magnesium sulfonates and high base calcium sulfonates such that a lubricating oil
  • the molar ratio of primary to secondary alkyl groups in the zinc dialkyldithiophosphate (hereafter occasionaly referred to as "ZDDP") is within the range of about 1.7:1 to about 3.5:1 and preferably about 1.7:1 to about 4.5:1.
  • the preferred amount of succinimide dispersant in the additive composition is such that will provide at least .5 wt. % of the succinimide in the finished oil and most preferably about .5 to about 3.5 wt. %.
  • the preferred phosphorus level in the additive composition is such as will provide a phosphorus level of about .06 wt.% to about .09 wt.%.
  • the preferred TBN of the additive is such as will provide a TBN in the finished oil within the range of about 8-12 and preferably about 9-11. It should be noted that all dispersant amounts are expressed in terms of active dispersant absent any diluent, except, however, in the examples where dispersant amounts are expressed in terms of a 40% active material containing added diluent.
  • the additive composition of the present invention has a boron content sufficient to provide a boron level in the finished oil of within the range of about 100 ppm(wt) to about 600 ppm and preferably in the range of 150 ppm to 450 ppm.
  • the advantages of the invention is the ability to reduce the level of phosphorus required in an additive composition for a mixed fleet oil despite the requirement of high TBN in such oils, which is necessary for passing heavy duty engine cleanliness tests, while at the same time obtaining passing wear peformance. Reducing the phosphorus in the oil composition benefits the catalytic converter in passenger cars.
  • the succinimide dispersant required in the present invention is critical in accomplishing the reduction in phosphorus for the following reasons:
  • increasing the secondary character of the ZDDP makes it possible to reduce the overall amount of ZDDP (and thus the total phosphorus required in the additive and resulting oil) without giving up passing wear performance.
  • the additive composition of the present invention must comprise (a) zinc dialkyldithiophosphate having both primary and secondary character such that the primary to secondary ratio (expressed in moles) is within the range of from about 1:1 to about 5:1, and (b) succinimide dispersant.
  • the total amount of phosphorus in the additive as provided by the ZDDP, must be such that the amount of phosphorus present in a lubricating oil containing an effective amount of the additive is not greater than about .1% by weight of the lubricating oil, and the TBN of the additive composition must be such that a lubricating oil containing an effective amount of the additive composition will have a TBN of at least 8.
  • An effective amount of the additive composition of the present invention means a treat level in the lubricant which will allow the oil to pass both heavy duty and passenger car tests.
  • additive composition optionally may be present in the additive composition.
  • rust inhibitors such as normal or overbased sulfurized metal phenates or metal sulfonates.
  • oxidation inhibitors such as normal or overbased sulfurized metal phenates or metal sulfonates.
  • detergents such as normal or overbased sulfurized metal phenates or metal sulfonates.
  • zinc dialkyldithiophosphate having both primary and secondary character for use in the present invention functions as a corrosion and wear inhibitor.
  • zinc dialkyldithiophosphate is prepared by forming a dithiophosphoric acid via a reaction of a phenol or an alcohol with phosphorus pentasulfide and subsequently neutralizing the dithiophosphoric acid with a zinc compound, such as zinc oxide.
  • a zinc compound such as zinc oxide.
  • Such preparation is well known in the art and is presented, for example, in U.S. Patent 2,261,047 and U.S. Patent 4,483,775.
  • This type of dialkyldithiophosphate can be identified by the alcohol that is employed in its preparation.
  • a primary alcohol is employed, the product is referred to as a primary zinc dialkyldithiophosphate.
  • the zinc dialkyldithiophosphate is identified as a secondary zinc dialkyldithiophosphate.
  • Suitable primary alcohols for use in the preparation of the primary zinc dialkyldithiophosphate are n-butyl alcohol, n-octyl alcohol, isoamyl alcohol, isooctyl alcohol, and isobutyl alcohol.
  • Suitable secondary alcohols are isopropyl alcohol, methyl isobutyl carbinol, 2-amyl alcohol, and 2-butyl alcohol.
  • the resulting ZDDP is a hydrid having both primary and secondary character.
  • the term "zinc dialkyldithiophosphate having both primary and secondary character” includes any of the following: (a) a zinc dialkyldithiophosphate preparation obtained by mixing a desired amount of primary zinc dialkyldithiophosphate with a desired amount of secondary zinc dialkyldithiophosphate; (b) a zinc dialkyldithiophosphate which results from employing a mixture of primary and secondary alcohols in the preparation of the zinc dialkyldithiophosphate; and (c) a zinc dialkyldithiophosphate obtained by mixing a primary or a secondary zinc dialkyldithiophosphate with a zinc dialkyldithiophosphate meeting the definition of (b).
  • ratio of primary to secondary or “primary to secondary ratio” means the molar ratio of primary alkyl groups to
  • the primary to secondary ratio in the zinc dialkyldithiophosphate is within the range of about 1:1 to about 5:1, preferably, within the range of about 1.7:1 to about 3.5:1, and more preferably, within the range of about 1.7:1 to about 2.5:1.
  • the total amount of the mixed primary/secondary dialkyldithiophosphates should be an amount that will provide a phosphorus content in the lubricating oil composition not greater than 0.1 wt%, based upon the weight of the lubricating oil composition.
  • the zinc dialkyldithiophosphate should be present in a total amount that will provide a phosphorus content in the lubricating oil composition that falls within the range of about 0.06 wt% to about 0.09 wt%, and most preferably within the range of about 0.06 wt% to about 0.08 wt%, based upon the weight of the lubricating oil composition.
  • the prescribed 1°:2° molar ratio in the ZDDP used in the present invention is important when one considers the object of maintaining the phosphorus content in the additive composition at such a level that a finished oil containing an effective amount of the composition has a phosphorus content of not greater than about .1 wt % of the finished oil. If the total phosphorus is decreased, then in accordance with the present invention, passing wear can be maintained by increasing the 2° character of the ZDDP. Such an adjustment appears practicable where the phosphorus (in terms of the finished oil) is between about .06 and about 0.1 wt percent.
  • the prescribed ratios of 1° to 2°character are based upon this fact, and the desirability of using the minimum amount of 2° character in the ZDDP to maintain wear protection (given the deleterious effect of the the 2° ZDDP on friction performance).
  • the ratio will increase as the total phosphorus (in terms of the oil) approaches about .1 wt%, and will decrease as the phosphorus level approaches about .06 wt.%.
  • a second required component of the additive composition of the present invention is a succinimide dispersant.
  • Such succinimide is an N-substituted long chain-alkenyl succinimide.
  • the alkenyl radical is derived from liquid polyisobutenes containing from 50 to 200 carbon atoms.
  • Such a succinimide is an oil-soluble nitrogen containing composition.
  • the preparation of succinimide dispersants is known in the art. Among such art are U.S. Patents 3,172,892; 3,272,746; and 3,219,666. The disclosures of these patents are incorporated herein by reference.
  • an acylated nitrogen intermediate compound is formed by reacting a substantially aliphatic olefin polymer-substituted succinic-acid producing compount having at least about 50 aliphatic carbon atoms in the polymer substituent with at least about one half equivalent of an amine for each equivalent of acid-producing compound used, said reaction being carried out at a temperature within the range of about 80°C to about 250°C.
  • the amine is selected from a group consisting of alkylene amines, hydroxysubstituted alkylene amines, and polyalkylene polyamines.
  • the polymer substituent of the succinic acid-producing compound is derived conveniently from a polymer of isobutene.
  • the polyisobutene has an average molecular weight that is within the range of about 700 to about 5,000.
  • Suitable amines are alkylene amines, alkylene diamines having the structure NH2-R-NH2, wherein R is an alkylene group having from 2 to 24 carbon atoms, and the so-called polyalkyleneamines, sometimes referred to as alkylene polyamines or polyalkylene polyamines, which generally have the structure H2N--(R--NH) n H, where R is an aliphatic hydrocarbon group containing about 2 to about 4 carbon atoms and n is an integer from 1 to 10.
  • Representative amines include methylene amines, ethylene amines, butylene amines, propylene amines, pentalene amines, ethylene diamine, triethylene tetraamine, propylene diamine, decamethylene diamine, octamethylene diamine, di(heptamethylene)triamine, tripropylene tetramine, tetraethylene pentamene, trimethylene diamine, pentaethylene hexamine, di(trimethylene)triamine, etc.
  • a preferred polyalkylene polyamine is tetraethylene pentamine (TEPA).
  • the succinimide dispersant is present in the additive composition of the present invention in an amount sufficient to provide a lubricating oil containing an effective amount of the additive composition at least about .5 wt, % by weight of the lubricating oil. While a preferred range is about .5 to about 3.5 the maximum amount of succinimide is an economic consideration and is not critical in the present invention. However the requirement of at least .5 wt% is critical insofar as lesser amounts fail to provide the desired advantage of passing frictional tests, in particular the Allison C-3, when phosphorus levels of less than .1 by weight of the lube oil, in combination with the 1°/2° ratios discussed above, are employed.
  • the additive composition of the present invention comprises sufficient TBN such that a universal oil comprising an effective treat level of said additive composition is provided with a TBN of at least 8, preferably, within the range of about 9 to about 11, and more preferably, about 10.
  • Examples of components that are suitable for providing the required TBN in the additive composition of the present invention are overbased metal sulfonates and over based phenates.
  • the sulfonates are normal or basic metal salts of petroleum ("mahogany") sulfonic acids and long chain alkyl substitued benzene sulfonic acids.
  • the phenates are normal or basic salts of alkylphenols, alkylphenol sulfisides, and alkylphenol-aldehyde condensation products.
  • a normal metal salt of an acid is a salt which contains the stoichiometric amount of metal required for the neutralization of the acidic group or groups present in the acid.
  • a basic salt or overbased salt is a salt which contains more metal than is required to stoichiometrically neutralize the acidic group or groups present. While both normal and overbased sulfonates and phenates provide detergent properties for lubricating oil compositions, the overbased or superbasic or hyperbasic salts provide unusually high detergent power and, consequently, have a much greater capacity to neutralize acidic contaminants than do the normal sulfonates and phenates.
  • an overbased sulfonate is prepared by mixing a promoter, catalyst or solvent with a normal sulfonate and a larger excess of metallic base, followed by heating, carbonation and filtration.
  • Carbonation of the reaction mass is accomplished conveniently with carbon dioxide and is employed to increase the amount of metal base colloidally dispersed as metal carbonate in the filtered product.
  • Phenols, trioacids, of phosphorus, alcoholates, alcohols, ketones, and alkanolamines can be used as promoters for catalysts.
  • Typical metallic bases are basic compounds of alkaline earth metals, such as calcium, barium, or magnesium. Overbased metal sulfonates are discussed thoroughly in the prior art. Examples of such art are: United Kingdom Patent Application GB 2,082,619A and U.S. Patents 2,865,956; 2,956,018; 2,671,430; 3,779,920; 3,907,691; 4,137,184; 4,261,840; and 4,326,972.
  • overbased metal phenates are presented in the prior art.
  • Typical examples of the prior art are U.S. Patents 2,680,096; 3,036,917; 3,178,368; 3,194,761; 3,437,595; 3,464,910; 3,779,920; and 4,518,807.
  • the reduced-phosphorus additive composition further comprises boron sufficient to provide within the range of from about 100 to about 600 ppm(wt.) boron in the finished oil containing the additive composition of the invention.
  • the additive composition may contain an additional dispersant comprising at least on member of the group consisting of Mannich and succinate ester-amide (SEA) dispersant in an amount sufficient to provide preferably up to about 5 wt% of the second dispersant in the finished oil.
  • SEA Mannich and succinate ester-amide
  • the succinate ester-amide dispersant can be prepared in accordance with techniques which have been disclosed in the art (See for example U.S. Patent No. 4,426,305) by reacting an aliphatic hydrocarbon substituted succinic acid anhydride with an oxyalkylated amine.
  • the long chain aliphatic hydrocarbon-substituted succinic acid compound that is used in the preparation of the second dispersant can be obtained by reacting an ethylenically unsaturated dicarboxylic acid compound (acid or anhydride), such as maleic acid, maleic anhydride, or fumeric acid, with a suitable olefin or halogenated olefin at a temperature within the range of about 100°C to 300°C. An alkenyl or alkyl substituted succinic acid or anhydride is produced.
  • the unsaturated groups in the alkenyl group can be removed by standard hydrogenated techniques.
  • the olefins or halosubstitued olefins contain from about 8 to about 500 carbon atoms, or more, and can include homopolymers and copolymers of monoolefins, such as ethylene, propylene, l-butene, isobutene, and the like. However, any of the techniques known in the art can be employed to produce this long chain succinic acid compound.
  • the oxyalkylated amine suitable for reaction with the above described long chain aliphatic hydrocarbon succinic acid compound can be prepared in accordance with known methods by reacting an alkylene oxide with an amine having primary or secondary amine groups.
  • Suitable amines are alkylene diamines having the structure NH2-R-NH2, wherein R is an alkylene group having from 2 to 24 carbon atoms, such as ethylene, 1, 2-propylene, trimethylene, hexamethylene, dodecamethylene, tetracosene, etc.
  • polyalkyleneamines sometimes referred to as alkylene polyamines or polyalkylene polyamines.
  • R is an aliphatic hydrocarbon group containing about 2 to about 4 carbon atoms and n is an integer from 1 to 6.
  • Representative examples include ethylenediamine, 1,2-propylenediamine, 1,2-butylenediamine, 1,3-propanediamine, diethylenetriamine, triethylenetetramine, tetraethylene pentamine (TEPA), etc.
  • Suitable hydroxyalkylating reactants include halohydrins and vicinal epoxies (olefin oxides) having from 2 to 4 carbon atoms in the alkylating agent, such as ethylene oxide, 1, 2-propylene oxide, 1, 2-butylene oxide, 2-chloro-l, ethanol, 2-chloro-l-propanol, 3-bromo-l-prophanol, and 4-chloro-butanol.
  • the hydroxyalkylating agents can be used in a concentration of about 2.0 to 6 moles per mole of amine, and hydroxyalkylation can be carried out under conventional conditions, i.e., by reaction at 50°C to 300°C for a period of time within the range of 1 to 10 hours.
  • the long chain aliphatic succinic acid compound is reacted with the N-substituted hydroxy alkyl diamine under conditions that are normally employed in the art and at a temperature within the range of about 0°C to about 250°C.
  • a solvent such as benzene, toluene, naphtha, lube oil, xylene, and normal hexane, can be used to facilitate the control reaction.
  • the optional second dispersant may also be a Mannich dispersant.
  • Mannich dispersants made from hydrocarbon substituted phenols, formaldehyde and amines are well known in the patent literature. See U.S. Patent Nos. 3,413,347; 3,725,277; 3,368,972; 3,798,165; 3,697,574, and 4,426,305. These patents are incorporated by reference.
  • the optional second dispersant can be present in the lubricating oil composition in an amount within the range of about 0 wt % to about 5 wt%, preferably, within the range of about 0 wt% to about 3 wt%.
  • the additive composition of the present invention preferably contains boron in an amount such that a lubricating oil containing an effective amount of the additive composition, will have a boron content within the range of about 100 ppm(wt) to about 600 ppm(wt) boron.
  • the preferred boron level is about 150 to about 450 ppm(wt) in the finished oil.
  • the presence of boron is preferred for the protection of fluorinated elastomer hydrocarbon seals, and also enhances the anti-wear properties of the additive composition, especially where TBN is supplied by high-based calcium sulfonate. The latter is known to deleteriously effect the wear protection afforded by zinc dialkyldithiophosphate.
  • boron is preferably present in an amount sufficient to provide about 150 ppm(wt) to about 450 ppm(wt) in the finished oil.
  • Boron may be introduced into the additive composition in accordance with conventional techniques.
  • a boron compound such as boron oxide, boron dihalides (boron trifluoride, boron tribromide, boron tricholoride), boron acids, such as tetraboric acid and metaboric acid, and simple esters of the boron acids, can be reacted with the succinimide, SEA or Mannich dispersants discussed above at a temperature within the range of about 50°C to about 250°C, preferably from about 100°C to about 170°C, with a sufficient concentration of boron compound to yield a boronated dispersant product containing at least 0.15% by weight boron (excluding lube oil).
  • the boron compound can be reacted in a ratio within the range of about 0.1 to 10 moles of boron compound for equivalent of dispersant compound.
  • the reaction can be carried out in the presence of diluent or solvent.
  • a portion of the succinimide, Mannich or SEA dispersant intended for the additive composition of the invention may be segregated and heated with a boronating agent to introduce a higher level of boron than would be desired in the final dispersant. This overboronated product can then be blended back into the unboronated dispersant to achieve the desired level of boron.
  • the additive composition of the present invention may contain other additive components, such as viscosity index improvers, pour point depressants, and antioxidants.
  • the additive composition of the present invention comprises a mixture of several additive components, some of which are mandatory and some of which are optional.
  • This blend or mixture is prepared easily by introducing one or more of the components into another component. It is not critical that a particular component be added to another particular component, i.e., there is no particular sequence which must be used when adding the various components in preparing the blend.
  • the blend is a composition that will provide antiwear and friction retention properties to the lubricating oil to which it is added while minimizing the phosphorus level in that particular lubricating oil composition.
  • the additive composition of the present invention can be added to a petroleum oil or synethetic oil of lubricating viscosity to provide antiwear and friction retention properties while minimizing the amount of phosphorus in the resulting lubricating oil composition.
  • the additive composition of the present invention is quite suitable for addition to a lubricant that is being employed in heavy duty vehicles, such as those used in military operations.
  • Lubricating oil compositions containing the additive composition of the present invention provide suitable anti-wear and friction retention properties. In addition, they contain only a limited amount of phosphorus and, consequently, minimize the phosphorus content in the engine and thus extend the life of the catalyst in the catalytic converter of the automobile.
  • the additive composition of the present invention will be present in the lubricating oil composition in an amount that is within the range of about 9 wt% to about 12 wt%, based upon the weight of the lubricating oil composition. More particularly, the additive composition is present in the lubricating oil composition in an amount that is within the range of about 10% to about 11 wt%, based upon the weight of the lubricating oil composition.
  • the scope of the present invention includes concentrates of the additive composition.
  • concentrates are made up of about 90 wt% to about 10 wt% of an oil having lubricating viscosity.
  • the concentrates contain the additive composition plus a suitable diluent.
  • Typical diluents are inert diluents, preferably an oil of lubricating viscosity, so that the concentrate may be mixed conveniently with the lubricating oil that will make up the desired lubricating oil composition.
  • Lubricating oils that are suitable as diluents typically will have viscosities that are within the range of about 35 Saybolt Universal Seconds (SUS) at 100°F (38°C) to about 1,000 SUS at 100°F (38°C).
  • oil of lubricating viscosity can be used as the diluent for the concentrate of the present invention
  • the oil of lubricating viscosity in the lubricating oil composition can be employed as the diluent in the concentrate.
  • Lubricating oils that are suitable for use in the lubricating oil compositions and concentrates of the present invention are oils of lubricating viscosity and are either petroleum oils or synthetic oils.
  • the petroleum oils can be paraffinic, naphthenic, or even halogen-substituted hydrocarbons.
  • Typical synthetic oils are those comprising syntheticesters, diester, ethers, polyolefins, or combinations thereof.
  • oils of lubricating viscosity will have viscosities that fall in the range of about 50 SUS to about 5,000 SUS at 100°F (38°C), preferably viscosities in the range of about 50 SUS to about 2,000 SUS at 100°F (38°C), and more preferably, viscosities in the range of about 80 SUS to about 1,000 SUS at 100°F (38°C).
  • a lubricating oil composition which lubricating oil composition comprises a major portion of an oil having lubricating viscosity in combination with a minor portion of an additive composition as described above.
  • a preferred embodiment of the lubricating oil additive composition of the present invention was prepared. This embodiment had the composition presented hereinbelow in Table I. This additive was then introduced into a Mid-East base stock. The resulting lubricating oil composition had an SAE grade of 15W-40. The additive composition made up 10.3 wt% of the lubricating oil composition, which had a TBN of about 10. The lubricating oil composition also contained 4.1 wt% Viscoplex 2-50 viscosity index improver obtained from Rohm-Darmstadt. The concentration of each of the components of the additive composition in the lubricating oil composition is also provided in Table I. The additive composition contained 1,700 ppm(wt) boron, while the SAE 15W-40 oil, identified hereinafter as Sample No. 1, contained 180 ppm(wt) boron. Furthermore, Sample No. 1 contained 784 ppm(wt) phosphorus. The molar ratio of primary to secondary in the zinc dialkyldithiophosphate was 4.4
  • SAE 15W-40 Oil Sample No. 1 which contained a preferred embodiment of the additive composition of the present invention, met all performance criteria of the tests. It is particularly noteworthy that acceptable wear protection was provided in the Sequence IIID and V-D Tests while acceptable performance was provided in the Caterpillar TO-2 and Allison C-3 Tests. Sample No. 1 is a preferred embodiment of the lubricating oil composition of the present invention.
  • Sample No. 1 was the formulation presented in Table I hereinabove.
  • Sample No. 4 had a similar composition, but the alkyl diarylamine oxidation inhibitor was replaced by a sulfurized oxidation inhibitor.
  • Sample No. 5 a North Sea base stock (less stable than the Mid-East stock) was employed. The results are presented hereinbelow in Table IV.
  • the mixture of primary zinc dialkyldithiophosphate and secondary zinc dialkyldithiophosphate provided acceptable wear protection.
  • the preferred embodiments of the lubricating oil composition of the present invention were compared for diesel cleanliness to Sample No. 9, a similar additive composition but with a different detergent, and Sample No. 4, a similar additive composition but with a different oxidation inhibitor.
  • the different detergent was a low base calcium sulfonate.
  • the different oxidation inhibitor was a sulfurized oxidation inhibitor.
  • the test method employed was the Caterpillar 1G2 Test. The results are presented hereinbelow in Table VI.
  • Samples Nos. 1 and 6 embodiments of the lubricating oil composition of the present invention passed the specification for top groove fill; however, Sample No. 6 did not provide an acceptable value for weighted total demerits. On the other hand, the latter sample provided a small top groove fill. Each of the other two samples furnished acceptable diesel engine cleanliness response.
  • Sample No. 10 employed an SAE 30 weight lubricating oil derived from the Mid-East base stock obtained from the British Petroleum Company.
  • An Acryloid 150 pour point depressant obtained from Rohm & Haas was also a component of Sample No. 10. This sample was subjected to a Sequence V-D Test. The results are presented hereinbelow in Table VII. Also shown in Table VII are the results obtained with Sample No. 1, which is a multigrade oil containing a preferred embodiment of the additive composition of the present invention.
  • Sample No. 11 Another embodiment of a lubricating oil composition of the present invention, Sample No. 11, was prepared and subjected to a Sequence V-D Test and a Caterpiller 1G2 Test. Results of these tests are presented hereinbelow in Table VIII.
  • Sample No. 11 contained 795 ppm(wt) phosphorus and 190 ppm(wt) boron. The results obtained with Sample No. 1 are also provided in Table VIII.
  • Each of these samples was a 15W-40 lubricating oil composition and each contained an embodiment of the additive composition of the present invention.
  • Sample No. 1 contained Viscoplex 2-50, obtained from Rohm Darmstadt. Viscoplex 1-50 is a dispersant polymethacrylate viscosity index improver.
  • Sample No. 11 contained ECA 6911, obtained from Paramins, a division of Exxon Corporation, as a viscosity index improver.
  • Two additive compositions were prepared and were added to a Mid-East base stock to provide 15W-40 grade lubricating oil compositions.
  • One additive composition was an embodiment of the present invention and, when added to the base oil, resulted in lubricating oil Sample No. 12.
  • the other was a prior art additive composition and resulted in lubricating oil Sample No. 13.
  • the primary to secondary molar ratio in the zinc dialkyldithiophosphate for Sample No. 12 was 1.7.
  • Samples 13, 14 and 15 contained only primary zinc dialkyldithiophosphate.
  • the SEA dispersant was prepared from propoxylated hexamethylenediamine and Indopol H-1500 polybutenes obtained from Amoco Chemicals Corporation.
  • the succinimide dispersant was also prepared using Indopol H-1500 polybutenes.
  • Samples Nos. 14, 15 and 17 contained the additive composition of the present invention. Of these, only Sample No. 17 provided unacceptable friction performance.
  • Additional lubricating oil formulations containing embodiments of the additive composition of the present invention were prepared and tested for wear performance in the Sequence IIID and Sequence V-D Tests and for friction performance in the Detroit Diesel Allison C-3 Friction Test. The results of these tests are presented hereinbelow in Table XI.
  • the molar ratio of 1°:2° in the zinc dialkyldithiophosphate to phosphorus from secondary zinc dialkyldithiophosphate is about 3.9.
  • the results of the above examples indicate that the additive compositions of the present invention are effective in wear control while simultaneously accommodating friction response.
  • the lubricating oils containing them i.e., the lubricating oils of the present invention, provide acceptable wear performance and friction performance while minimizing the amount of phosphorus in the engine emission system.

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Claims (11)

1. Additivzusammensetzung zur Zugabe zu einem Öl mit Schmierviskosität, geeignet für Personenwagen und zur Verwendung im Hochleistungsbereich, umfassend: (a) Zinkdialkyldithiophosphat, das sowohl primäre als auch sekundäre Gruppen aufweist, wobei das Verhältnis von primär zu sekundar 1:1 bis 5:1 ist, wobei das gemischt primäre/sekundäre Zinkdialkyldithiophosphat in der Additivzusammensetzung in einer solchen Menge vorhanden ist, daß ein Schmieröl, das eine wirksame Menge der Additivzusammensetzung enthält, einen Phosphorgehalt von nicht mehr als 0,1 Gewichtsprozent hat; (b) ein Succinimiddispersionsmittel in solcher Menge, daß ein Schmieröl, das eine wirksame Menge der Additivzusammensetzung enthält, mindestens etwa 0,5 Gewichtsprozent Succinimid umfaßt; (c) einen solchen Borgehalt, daß ein Schmieröl, das diese Additivzusammensetzung enthält, mindestens 100 ppm (Gew.) Bor enthält; und (d) eine wirksame Menge basischer Salze, die hochbasische Magnesiumsulfonate und hochbasische Calciumsulfonate umfassen, so daß ein Schmieröl, das 9 bis 12 Gewichtsprozent der Additivzusammensetzung enthält, eine TBN im Bereich von 8 bis 12 hat.
2. Additivzusammensetzung nach Anspruch 1, wobei das gemischt primäre/sekundäre Zinkdialkyldithiophosphat in der Additivzusammensetzung in einer solchen Menge vorhanden ist, daß ein Schmieröl, das 9 bis 12 Gewichtsprozent der Additivzusammensetzung enthält, einen Phosphorgehalt im Bereich von 0,06 bis 0,09 % hat.
3. Additivzusammensetzung nach Anspruch 2, wobei das gemischt primäre/sekundäre Zinkdialkyldithiophosphat in der Additivzusammensetzung in einer solchen Menge vorhanden ist, daß ein Schmieröl, das 9 bis 12 Gewichtsprozent der Additivzusammensetzung enthält, einen Phosphorgehalt im Bereich von 0,07 bis 0,08 % hat.
4. Additivzusammensetzung nach einem der vorhergehenden Ansprüche, die einen solchen Borgehalt hat, daß ein Schmieröl, das 9 bis 12 Gewichtsprozent der Additivzusammensetzung enthält, einen Borgehalt im Bereich von 100 bis 600 ppm, bezogen auf das Gewicht des Öls, aufweist.
5. Additivzusammensetzung nach Anspruch 4, wobei der Borgehalt im Bereich von 150 bis 350 ppm liegt.
6. Additivzusammensetzung nach einem der vorhergehenden Ansprüche, weiter umfassend ein Dispersionsmittel, das mindestens ein Glied, ausgewählt aus Succinatesteramiddispersionsmitteln und Mannich-Dispersionsmitteln, umfaßt.
7. Additivzusammensetzung nach einem der vorhergehenden Ansprüche, mit einer solchen TBN, daß ein Schmieröl, das 9 bis 12 % der Additivzusammensetzung enthält, eine TBN im Bereich von 9 bis 11 hat.
8. Additivzusammensetzung nach einem der vorhergehenden Ansprüche, wobei das Succinimid das Reaktionsprodukt eines Polyalkylenpolyamins und einer mit einer langkettigen Alkylgruppe substituierten Bernsteinsäure oder eines Bernsteinsäureanhydrids ist.
9. Additivzusammensetzung nach Anspruch 8, worin das Polyalkylenpolyamin TEPA ist.
10. Additivzusammensetzung nach Anspruch 1, mit einer solchen TBN und einem solchen Phosphor- und Borgehalt, daß ein Schmieröl, das 9 bis 12 Gewichtsprozent der Additivzusammensetzung enthält, eine TBN von 9 bis 11, einen Phosphorgehalt von 0,06 bis 0,09 Gewichtsprozent und einen Borgehalt von 150 bis 450 ppm (Gew.) hat, wobei das Additiv weiterhin ein Succinatesteraiddispersionsmittel umfaßt.
11. Schmierölzusammensetzung, die als Hauptanteil ein Grundöl mit Schmierviskosität in kombination mit einem geringeren Anteil an Additivzusammensetzung nach einem der Ansprüche 1 bis 10 umfaßt.
EP88300500A 1987-01-21 1988-01-21 Veschleissschutz-Schmiermittelzusammensetzungen mit geringem Phosphorgehalt Expired - Lifetime EP0277729B1 (de)

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CN101798545A (zh) * 2009-02-11 2010-08-11 中国石油天然气股份有限公司 一种润滑油组合物
CN101798545B (zh) * 2009-02-11 2013-07-31 中国石油天然气股份有限公司 一种润滑油组合物
EP4306624A1 (de) * 2022-07-14 2024-01-17 Afton Chemical Corporation Molybdän enthaltende getriebeschmiermittel

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