US20040224858A1 - Low sulfur, low ash, and low phosphorus lubricant additive package using overbased calcium phenate - Google Patents

Low sulfur, low ash, and low phosphorus lubricant additive package using overbased calcium phenate Download PDF

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Publication number
US20040224858A1
US20040224858A1 US10/430,057 US43005703A US2004224858A1 US 20040224858 A1 US20040224858 A1 US 20040224858A1 US 43005703 A US43005703 A US 43005703A US 2004224858 A1 US2004224858 A1 US 2004224858A1
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Prior art keywords
additive package
oil soluble
lubricant additive
soluble lubricant
oil
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Abandoned
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US10/430,057
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English (en)
Inventor
Carl Esche
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Afton Chemical Intangibles LLC
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Ethyl Corp
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Assigned to ETHYL CORPORATION reassignment ETHYL CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ESCHE, CARL K.
Priority to US10/430,057 priority Critical patent/US20040224858A1/en
Application filed by Ethyl Corp filed Critical Ethyl Corp
Priority to CA002463799A priority patent/CA2463799A1/en
Priority to AU2004201532A priority patent/AU2004201532B2/en
Priority to JP2004136704A priority patent/JP2004331974A/ja
Priority to CNA2004100430928A priority patent/CN1550542A/zh
Priority to SG200402384A priority patent/SG110092A1/en
Priority to EP04252645A priority patent/EP1475430A2/en
Assigned to SUNTRUST BANK, AS ADMINISTRATIVE AGENT reassignment SUNTRUST BANK, AS ADMINISTRATIVE AGENT SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ETHYL CORPORATION
Assigned to AFTON CHEMICAL INTANGIBLES LLC reassignment AFTON CHEMICAL INTANGIBLES LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ETHYL CORPORATION
Publication of US20040224858A1 publication Critical patent/US20040224858A1/en
Abandoned legal-status Critical Current

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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
    • C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/24—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
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral 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
    • 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—Overbased sulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • 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
    • C10M2219/089—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
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/42—Phosphor free or low phosphor content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/43—Sulfur free or low sulfur content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/45—Ash-less or low ash content
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/52—Base number [TBN]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • 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
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
    • 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
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/044—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions
    • 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
    • C10N2040/135—Steam engines or turbines
    • 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

Definitions

  • the present invention relates to lubricating oil compositions, their method of preparation, and use. More specifically, this invention relates to oil soluble lubricating additive package to achieve low sulfur, low ash, and low phosphorus levels in fully formulated oil.
  • the oil soluble lubricating package compositions herein are particularly useful in crankcase lubricants.
  • An embodiment of the present invention provides an oil soluble lubricating additive package that can be used to formulate a low sulfur, low ash, and low phosphorus content oil for use in either gasoline or diesel engines. Further, a second embodiment provides lubricating oils that contain minimal sulfur, ash, and phosphorus levels.
  • Another embodiment provided herein is a method for lubricating the moving parts of a machine.
  • an oil soluble lubricant additive package comprising at least one overbased metal phenate having a total base number of from about 120 to about 360 and at least one detergent, wherein the weight ratio of the overbased metal phenate to the detergent is from about 1:1 to about 3:1.
  • At least one of the detergent(s) is selected from the group consisting of calcium sulfonate, magnesium sulfonate, sodium sulfonate, non-sulfurized phenates, sulfurized phenates, salicylates, overbased saligenin, and combinations thereof.
  • a method for lubricating an engine crankcase that comprises the step of: at least partially filling the crankcase with the oil soluble lubricant additive package disclosed herein.
  • Also provided is a method for lubricating the moving parts of a machine that comprises the step of contacting at least one moving part with the oil soluble lubricant additive package disclosed herein.
  • an oil soluble lubricant additive that comprises: an overbased metal phenate having a total base number of from about 120 to about 360; and at least one dispersant, wherein the weight ratio of the overbased metal phenate to the dispersant is from about 1:4 to about 1:12.
  • the oil soluble lubricant additive package herein can in one embodiment utilize dispersants having a molecular weight of at least 500. However, dispersants may also be used that have a molecular weight of from about 1000 to about 6000.
  • At least one dispersant is a maleic anhydride functionalized polyisobutylene polymer that has been reacted with a polyamine.
  • the at least one dispersant is the product of a Mannich reaction, and/or the at least one dispersant is an ethylene-propylene type dispersant.
  • Oil soluble lubricant additive package formulations herein may additionally comprise at least one component selected from the group consisting of: viscosity index improvers and pour point depressants.
  • Also provided is a method for lubricating an engine crankcase comprising the step of at least partially filling the crankcase with the oil soluble lubricant additive package disclosed herein.
  • Also provided is a method for lubricating moving parts of a machine comprising the step of contacting at least one moving part with the oil soluble lubricant additive package disclosed herein.
  • an oil soluble lubricating additive package comprising: an overbased metal phenate having a total base number of from about 120 to about 360; and at least one antioxidant, wherein the weight ratio of overbased metal phenate to antioxidant is from about 10:1 to about 1:3.
  • At least one of the antioxidants is selected from the group consisting of: zinc dithiophosphates, alkylated diphenylamines, sulfurized olefins, phenols, hindered phenols, and sulfurized phenols.
  • machines lubricated by the inventive lubricating oils disclosed herein are machines lubricated by the inventive lubricating oils disclosed herein. While the machine may be any machine that uses a lubricating oil to maintain the operability of its moving parts, it is preferred that the machine is selected from the group consisting of: gas engines, diesel engines, turbine engines, automatic transmissions, manual transmissions, hypoid axles, and gear boxes.
  • Also provided is a method for lubricating an engine crankcase comprising the step of at least partially filling the crankcase with the oil soluble lubricant additive package disclosed herein.
  • Also provided is a method for lubricating moving parts of a machine comprising the step of contacting at least one moving part with the oil soluble lubricant additive package disclosed herein.
  • an oil soluble lubricant additive package comprising: an overbased calcium phenate having a total base number of at least 120; and at least one component selected from the group consisting of: detergents, dispersants, antioxidants, friction modifiers, viscosity index improvers, and pour point depressants.
  • the oil soluble lubricant additive package herein has at least one property selected from the group consisting of: a sulfur content less than about 3 wt % and a phosphorus content less than about 1.2 wt %.
  • oil soluble lubricant additive package herein is essentially free of non-sulfurized Mannich phenates.
  • Also provided is a method for lubricating an engine crankcase comprising the step of at least partially filling the crankcase with the oil soluble lubricant additive package disclosed herein.
  • Also provided is a method for lubricating moving parts of a machine comprising the step of contacting at least one moving part with the oil soluble lubricant additive package disclosed herein.
  • One method of achieving a low sulfur, low ash, and low phosphate oil formulation of the present invention can comprise the steps of: providing an oil soluble lubricant additive package comprising an overbased metal phenate having a total base number of from about 120 to about 360; and admixing the oil soluble lubricant additive package with at least a base oil so as to form a lubricating oil having a total base number of less than about 10, and at least one property selected from the group consisting of: a sulfur content less than about 0.3 wt %, a phosphorus content of less than about 0.11 wt %, and an ash content less than about 1.2 wt %.
  • the overbased metal phenate can in an embodiment be selected from the group consisting of: overbased calcium phenate and overbased magnesium phenate.
  • oil soluble lubricant additive package herein can comprise at least one additive selected from the group consisting of: detergents, dispersants, antioxidants, friction modifiers, viscosity index improvers, and pour point depressants.
  • each oil soluble lubricant additive package it is also effective herein for each oil soluble lubricant additive package to have a sulfur content and a phosphorus content sufficient to yield a lubricating oil having a sulfur content less than about 0.3 wt % and a phosphorus content of less than about 0.11 wt % when the lubricating oil comprises less than 20 wt % of the oil soluble lubricant additive package.
  • each of the above disclosed formulations includes at least one of the metal phenates as an overbased metal phenate.
  • the overbased metal phenate is selected from the group consisting of: overbased calcium phenate and overbased magnesium phenate.
  • the invention described herein also includes lubricating oils comprising the oil soluble lubricant additive packages disclosed herein. It is preferred that the lubricating oil has a total base number of less than about 10, and at least one property selected from the group consisting of: a sulfur content less than about 0.3 wt %, a phosphorus content of less than about 0.11 wt %, and an ash content less than about 1.2 wt %.
  • machines lubricated by the inventive lubricating oils disclosed herein are machines lubricated by the inventive lubricating oils disclosed herein. While the machine may be any machine that uses a lubricating oil to maintain the operability of its moving parts, in one embodiment the machine is selected from the group consisting of: gas engines, diesel engines, turbine engines, automatic transmissions, manual transmissions, hypoid axles, and gear boxes.
  • the present invention also includes vehicles comprising at least one of the oil soluble lubricant additive packages disclosed herein.
  • any of the inventive methods and articles disclosed herein may be practiced on or with a wide variety of machines, it is preferred that the machine is selected from the group consisting of: gas engines, diesel engines, turbine engines, automatic transmissions, manual transmissions, hypoid axles, and gear boxes.
  • the base oils useful herein include natural lubricating oils, synthetic lubricating oils and mixtures thereof. Suitable lubricating oils also include basestocks obtained by isomerization of synthetic wax and slack wax, as well as basestocks produced by hydrocracking the aromatic and polar components of the crude. In general, both the natural and synthetic lubricating oils will each have a kinematic viscosity ranging from about 1 to about 40 mm 2 /s (cSt) at 100° C., although typical applications will require each of the base oils to have a viscosity ranging from about 1 to about 12, preferably 2 to 8, mm 2 /s (cSt) at 100° C.
  • Natural lubricating oils include animal oils, vegetable oils (e.g., castor oil and lard oil), petroleum oils, mineral oils, and oils derived from coal or shale.
  • the preferred natural lubricating oil is mineral oil.
  • the mineral oils useful in this invention can include but are not limited to all common mineral oil base stocks. This would include oils that are naphthenic or paraffinic in chemical structure. Oils that are refined by conventional methodology using acid, alkali, and clay or other agents such as aluminum chloride, or be extracted oils produced, for example, by solvent extraction with solvents such as phenol, sulfur dioxide, furfural, dichlorodiethyl ether, etc. They may be hydrotreated or hydrorefined, dewaxed by chilling or catalytic dewaxing processes, or hydrocracked. The mineral oil may be produced from natural crude sources or be composed of isomerized wax materials or residues of other refining processes.
  • the oil of lubricating viscosity is a hydrotreated, hydrocracked and/or iso-dewaxed mineral oil having a Viscosity Index (VI) of greater than 80, preferably greater than 90; greater than 90 volume % saturates and less than 0.03 wt. % sulfur.
  • VI Viscosity Index
  • Group II and Group III basestocks are also particularly suitable for use in the present invention, and are typically prepared from conventional feedstocks using a severe hydrogenation step to reduce the aromatic, sulfur and nitrogen content, followed by dewaxing, hydrofinishing, extraction and/or distillation steps to produce the finished base oil.
  • Group II and III basestocks differ from conventional solvent refined Group I basestocks in that their sulfur, nitrogen and aromatic contents are very low. As a result, these base oils are compositionally very different from conventional solvent refined basestocks.
  • the American Petroleum Institute has categorized these different basestock types as follows: Group I, >0.03 wt. % sulfur, and/or ⁇ 90 vol % saturates, viscosity index between 80 and 120; Group II, ⁇ 0.03 wt.
  • the base oil comprises a mineral oil having a VI of at least 110.
  • the lubricating oils may be derived from refined, re-refined oils, or mixtures thereof.
  • Unrefined oils are obtained directly from a natural source or synthetic source (e.g., coal, shale, or tar sands bitumen) without further purification or treatment.
  • Examples of unrefined oils include shale oil obtained directly from a retorting operation, petroleum oil obtained directly from distillation, or an ester oil obtained directly from an esterification process, each of which is then used without further treatment.
  • Refined oils are similar to the unrefined oils except that refined oils have been treated in one or more purification steps to improve one or more properties.
  • Suitable purification techniques include distillation, hydrotreating, dewaxing, solvent extraction, acid or base extraction, filtration, and percolation, all of which are known to those skilled in the art.
  • Re-refined oils are obtained by treating used oils in processes similar to those used to obtain the refined oils. These re-refined oils are also known as reclaimed or reprocessed oils and are often additionally processed by techniques for removal of spent additives and oil breakdown products.
  • Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as oligomerized, polymerized, and interpolymerized olefins; alkylbenzenes; polyphenyls; and alkylated diphenyl ethers, alkylated diphenyl sulfides, as well as their derivatives, analogs, and homologs thereof, and the like.
  • Preferred synthetic oils are oligomers of ⁇ -olefins, particularly oligomers of 1-decene, having a viscosity ranging from about 1 to about 12, preferably 2 to 8, mm 2 /s (cSt) at 100° C. These oligomers are known as poly- ⁇ -olefins or PAOs.
  • Synthetic lubricating oils also include alkylene oxide polymers, interpolymers, copolymers, and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc.
  • This class of synthetic oils is exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide; the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polypropylene glycol having a molecular weight of 100-1500); and mono- and poly-carboxylic esters thereof (e.g., the acetic acid esters, mixed C 3 -C 8 fatty acid esters, and C 12 oxo acid diester of tetraethylene glycol).
  • Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, subric acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids, etc.) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoethers, propylene glycol, etc.).
  • dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, subric acid, sebasic acid, fumaric acid, adipic acid,
  • esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl isothalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebasic acid with two moles of tetraethylene glycol and two moles of 2-ethyl-hexanoic acid, and the like.
  • a preferred type of oil from this class of synthetic oils is adipates of C 4 to C 12 alcohols.
  • Esters useful as synthetic lubricating oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane pentaeythritol, dipentaerythritol, tripentaerythritol, and the like.
  • Silicon-based oils (such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils) comprise another useful class of synthetic lubricating oils. These oils include tetra-ethyl silicate, tetra-isopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) silicate, tetra-(p-tert-butylphenyl) silicate, hexa-(4-methyl-2-pentoxy)-disiloxane, poly(methyl)-siloxanes and poly (methylphenyl) siloxanes, and the like.
  • oils include tetra-ethyl silicate, tetra-isopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-
  • Other synthetic lubricating oils include liquid esters of phosphorus containing acids (e.g., tricresyl phosphate, trioctylphosphate, and diethyl ester of decylphosphonic acid), polymeric tetra-hydrofurans, poly-alpha-olefins, and the like.
  • liquid esters of phosphorus containing acids e.g., tricresyl phosphate, trioctylphosphate, and diethyl ester of decylphosphonic acid
  • polymeric tetra-hydrofurans e.g., polymeric tetra-hydrofurans, poly-alpha-olefins, and the like.
  • the oil soluble lubricating additive package of one example of the present invention contains at least one metal salt of an acidic organic compound. These salts are generally referred to as overbased materials or overbased metal salts. Overbased materials are single phase, homogeneous Newtonian systems characterized by a metal content in excess of that which would be present according to the stoichiometry of the metal and the particular acidic organic compound reacted with the metal.
  • metal ratio is the ratio of the total equivalents of the metal to the equivalents of the acidic organic compound.
  • a neutral metal salt has a metal ratio of one.
  • a salt having 4.5 times as much metal as present in a normal salt will have metal excess of 3.5 equivalents, or a ratio of 4.5.
  • the overbased metal salts used herein are prepared by reacting an acidic material (typically an inorganic acid or lower carboxylic acid, preferably carbon dioxide) with a mixture comprising an acidic organic compound, a reaction medium comprising at least one inert, organic solvent (mineral oil, naphtha, toluene, xylene, etc.) for the acidic organic compound, a stoichiometric excess of a metal base, and a promoter.
  • an acidic material typically an inorganic acid or lower carboxylic acid, preferably carbon dioxide
  • a reaction medium comprising at least one inert, organic solvent (mineral oil, naphtha, toluene, xylene, etc.) for the acidic organic compound, a stoichiometric excess of a metal base, and a promoter.
  • the metals useful in making the overbased compositions of the present invention can include magnesium and calcium, as well as any other suitable or desirable metal.
  • An example of a comparative conventional commercially available sulfurized overbased calcium phenate is Oloa 218E having a sulfur content of 3% and commercially available from Oronite, a division of Chevron-Texaco.
  • a detergent is an additive that reduces the formation of piston deposits, for example high-temperature varnish and lacquer deposits, in engines.
  • Detergents typically possess acid-neutralizing properties and are capable of keeping finely divided solids in suspension.
  • Metal detergents are used preferably for improving the acid-neutralizing properties, high-temperature detergency, and anti-wear properties of the resulting lubricating oil composition.
  • Detergents used herein may be any detergent used in lubricating oil formulations, and may be of the ash-producing or ashless variety.
  • Detergents suitable for use in the present invention include all of the detergents customarily used in lubricating oils, including metal detergents.
  • metal detergents are those selected from alkali metal or alkaline earth metal sulfonates, alkali metal or alkaline earth metal phenates, and alkali metal or alkaline earth metal salicylates.
  • Dispersants used in the present invention may be ash-producing or ashless. Suitable dispersants for use herein can typically comprise amine, alcohol, amide, or ester polar moieties attached to the polymer backbone via a bridging group.
  • the dispersant may be, for example, selected from oil-soluble salts, esters, amino-esters, amides, imides, and oxazolines of long chain hydrocarbon substituted mono- and dicarboxylic acids or their anhydrides; thiocarboxylate derivatives of chain hydrocarbons; long chain aliphatic hydrocarbons having a polyamine attached directly thereto; and Mannich condensation products formed by condensing a long chain substituted phenol with formaldehyde and polyalkylene polyamine, and Koch reaction products.
  • the long chain aliphatic hydrocarbons can be polymers such as polyalkylenes, including, for example, polyisobutylene, polyethylene, polypropylene, and copolymers thereof and/or copolymers with other alpha-olefins.
  • Typical PIB molecular weights useful herein can range from about 950 to 6000.
  • Useful antioxidant materials include oil soluble phenolic compounds, oil soluble sulfurized organic compounds, oil soluble amine antioxidants, oil soluble organo borates, oil soluble organo phosphites, oil soluble organo phosphates, oil soluble organo dithiophosphates and mixtures thereof.
  • Such antioxidants can be metal free (that is, free of metals which are capable of generating sulfated ash), and therefore are most preferably ashless (having a sulfated ash value not greater than 1 wt. % SASH, as determined by ASTM D874).
  • the oil soluble organo dithiophosphates can include zinc dialkyldithiophosphates.
  • zinc dithiophosphates are well known antioxidants.
  • preferred zinc dithiophosphates are zinc dipropyldithiophosphate, zinc dibutyldithiophosphate, zinc dipentyldithiophosphate, zinc dihexyidithiophosphate, zinc diheptyldithiophosphate, and zinc dioctyldithiophosphate, of which alkyl groups may be straight-chain or branched, and mixtures thereof.
  • zinc dialkyldithiophosphates having alkyl groups having different carbon number (3 to 8 carbon atoms) or structure in one molecule are also eligible.
  • Friction modifiers serve to impart the proper friction characteristics to lubricating oil compositions.
  • Friction modifiers include such compounds as aliphatic amines or ethoxylated aliphatic amines, aliphatic fatty acid amines, aliphatic carboxylic acids, aliphatic carboxylic esters of polyols such as glycerol esters of fatty acid as exemplified by glycerol phenate, aliphatic carboxylic ester-amides, aliphatic phosphonates, aliphatic phosphates, aliphatic thiophosphonates, aliphatic thiophosphates, etc., wherein the aliphatic group usually contains above about eight carbon atoms so as to render the compound suitably oil soluble.
  • aliphatic substituted succinimides formed by reacting one or more aliphatic succinic acids or anhydrides with ammonia.
  • friction modifiers containing molybdenum are friction modifiers containing molybdenum.
  • molybdenum-containing friction modifiers include those found in U.S. Pat. Nos. 5,650,381; RE37,363E; 5,628,802; 4,889,647; 5,412,130; 4,786,423; 4,812,246; 5,137,647; 5,364,545; 5,840,672; 5,925,600; 5,962,377; 5,994,277; 6,017,858; 6,150,309; 6,174,842; 6,187,723; 6,268,316; European Patent Nos.
  • suitable friction modifiers are found in U.S. Pat. Nos. 3,933,659; 4,105,571; 3,779,928; 3,778,375; 3,852,205; 3,879,306; 3,932,290; 3,932,290; 4,028,258; 4,344,853; 5,102,566; 6,103,674; 6,174,842; 6,500,786; 6,500,786; and 6,509,303. Additional representative examples of suitable friction modifiers are found in U.S. Patent Application Publication No. 2002/0137636 A1. The disclosures of the above references are incorporated herein by reference.
  • Viscosity index improvers impart high and low temperature operability to the lubricating oil and permit it to remain relatively viscous at elevated temperatures and also exhibit acceptable viscosity or fluidity at low temperatures.
  • Viscosity index improvers are generally high molecular weight hydrocarbon polymers including polyesters. The viscosity index improvers may also be derivatized to include other properties or functions, such as the addition of dispersancy properties.
  • These oil soluble viscosity modifying polymers will generally have number average molecular weights of from 10 3 to 10 6 , preferably 10 4 to 10 6 , as determined by gel permeation chromatography or osmometry.
  • the viscosity index improvers useful herein can include polymethacrylate-based ones, olefin copolymer-based ones, (e.g., isobutylene-based and ethylene-propylene copolymer based ones), polyalkyl styrene-based ones, hydrogenated styrene-butadiene copolymer-based ones, and styrene-maleic anhydride ester copolymer-based ones.
  • polymethacrylate-based ones e.g., isobutylene-based and ethylene-propylene copolymer based ones
  • polyalkyl styrene-based ones e.g., hydrogenated styrene-butadiene copolymer-based ones
  • styrene-maleic anhydride ester copolymer-based ones styrene-maleic anhydride ester copolymer-based ones.
  • pour point depressants are used to improve low temperature properties of oil-based compositions. See, for example, page 8 of “Lubricant Additives” by C. V. Smalheer and R. Kennedy Smith (Lezius Hiles Co. publishers, Cleveland, Ohio, 1967).
  • Examples of useful pour point depressants are polymethacrylates; polyacrylates; polyacrylamides; condensation products of haloparaffin waxes and aromatic compounds; vinyl carboxylate polymers; and ter-polymers of dialkylfumarates, vinyl esters of fatty acids and alkyl vinyl ethers. Pour point depressants are described in U.S. Pat. Nos.
  • the CAT 1N engine test is a commonly used test for evaluating the acceptability of heavy-duty diesel engine oils for Caterpillar engines.
  • the test employs a single cylinder aluminum piston diesel engine.
  • the acceptability of an oil formulation is based upon the following parameters: average oil consumption, piston deposits, % top groove fill, % top land heavy carbon. Further, in order to pass the CAT 1N diesel test, no stuck pistons, piston rings or liner distress is permitted.
  • a control formulation comprising a non-sulfurized phenate prepared by a Mannich reaction between an alkylphenol and a polyamine was compared to a formulation wherein the sulfur-free Mannich phenate was replaced with a low sulfur overbased calcium phenate of the present invention.
  • the following table compares the control formulation's performance against the inventive formulation.
  • the column marked “Test #1” provides the pass/fail limits for the CAT 1N test for a single trial. If a given oil formulation does not provide satisfactory results with a single trial, multiple trials may be averaged together and this average compared against the corresponding pass/fail limits for the number of tests being averaged. That is to say, if two trials of the inventive formulation were averaged together, the averaged results would be compared against the pass/fail limits provided in the “Test #2” column.
  • inventive formulation performed well in the CAT 1N test.
  • inventive formulation did not require additional trials, as single trial performance was satisfactory.
  • inventive formulation exhibited a marked reduction in top groove fill percentage.
  • inventive formulation exhibited a significant reduction in deposit weight.
  • inventive formulation also outperformed the control formulation in both oil consumption and oil consumption at the end of the test.

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AU2004201532A AU2004201532B2 (en) 2003-05-06 2004-04-13 Low sulfur, low ash, and low phosphorus lubricant additive package using overbased calcium phenate
JP2004136704A JP2004331974A (ja) 2003-05-06 2004-04-30 過塩基化されたカルシウムフェネートを使用した低硫黄分、低灰分、低燐分の潤滑剤添加物パッケージ
CNA2004100430928A CN1550542A (zh) 2003-05-06 2004-04-30 高碱性苯酚钙制备的低硫、低灰、低磷润滑添加剂包
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