Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
  • C10M2203/102—Aliphatic fractions
  • C10M2203/1025—Aliphatic fractions used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/28—Amides; Imides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/04—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
  • 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
  • C10M2227/09—Complexes with metals
• • 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
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/12—Groups 6 or 16
• • 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
  • C10N2020/02—Viscosity; Viscosity index
• • 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
  • C10N2030/02—Pour-point; Viscosity index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/04—Detergent property or dispersant property
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
• • 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
  • C10N2030/74—Noack Volatility
• • 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
• • 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
• • 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
  • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
  • C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

Definitions

• the disclosure relates to lubricant compositions having improved resistance to the formation of engine deposits, including turbocharger deposits, when used in a boosted internal combustion engine.
• Turbocharged or supercharged engines i.e. boosted or forced induction internal combustion engines
• the lubricants used in these engines are exposed to extreme conditions when the engine is stopped, and the lubricant sits in a hot turbocharger as it cools.
• a lubricant in this environment is prone to the formation of hard deposits in the turbocharger. This phenomenon causes a significant deterioration of turbocharger efficiency and has the potential to cause poor performance and/or severe damage to the engine.
• turbocharger use engine design, engine coatings, piston shape, fuel choice, and/or engine oil additives may contribute to the formation of these deposits in turbocharged engines. Accordingly, there is a need for engine oil additive components and/or combinations that are effective to reduce or prevent the formation of deposits in turbocharged gasoline engines.
• TCO Temperature Increase refers to the percent increase in the TCO Temperature from the 100 cycle TCO Temperature to the 1800 cycle TCO temperature as defined by the formula: 1800 cycle TCO Temperature ⁇ 100 cycle TCO temperature 100 cycle TCO Temperature .
• the present disclosure relates to a first lubricating oil composition and method of operating a boosted internal combustion engine with the first lubricating oil composition, hereinafter referred to as Invention A, and a second lubricating oil composition and method of operating a boosted internal combustion engine with the second lubricating oil composition, hereinafter referred to as Invention B.
• the lubricating oil composition includes greater than 50 wt.% of a base oil of lubricating viscosity.
• the lubricating oil composition has a ratio of total metal from the one or more metal-containing detergent(s) in ppm in the lubricating oil composition to the total nitrogen in ppm in the lubricating oil composition of less than 1.9; a ratio of total metal from the one or more metal-containing detergent(s) in ppm in the lubricating oil composition to the total boron in ppm in the lubricating oil composition is less than 7.5; and a ratio of total metal from the one or more metal-containing detergent(s) in ppm in the lubricating oil composition to the total molybdenum in ppm in the lubricating oil composition is less than 23.8.
• the lubricating oil composition has a NOACK volatility as measured by the method of ASTM D-5800 at 250 °C of less than 11.0 wt.%, and the lubricating oil composition is effective to ensure a TCO Temperature Increase of less than 9.0% as measured using the 2015 version of the General Motors dexos1® Turbocharger Coking Test (TC Test).
• TC Test General Motors dexos1® Turbocharger Coking Test
• the disclosure provides a method for reducing or preventing the formation of deposits in a boosted internal combustion engine.
• the method includes a step of lubricating a boosted internal combustion engine with a lubricating oil composition comprising greater than 50 wt.% of a base oil of lubricating viscosity.
• the lubricating oil composition has a ratio of total metal from the one or more metal-containing detergent(s) in ppm in the lubricating oil composition to the total nitrogen in ppm in the lubricating oil composition of less than 1.9; a ratio of total metal from the one or more metal-containing detergent(s) in ppm in the lubricating oil composition to the total boron in ppm in the lubricating oil composition is less than 7.5; and a ratio of total metal from the one or more metal-containing detergent(s) in ppm in the lubricating oil composition to the total molybdenum in ppm in the lubricating oil composition is less than 23.8.
• the lubricating oil composition has a NOACK volatility as measured by the method of ASTM D-5800 at 250 °C of less than 11.0 wt.%.
• NOACK volatility as measured by the method of ASTM D-5800 at 250 °C of less than 11.0 wt.%.
• the ratio of total metal from the one or more metal-containing detergent(s) in ppm in the lubricating oil composition to the total nitrogen in ppm in the lubricating oil composition may be less than 1.8 or may be from 0.1 to less than 1.9, or from 0.1 to less than 1.8, or from 0.1 to 1.7.
• the ratio of total metal from the one or more metal-containing detergent(s) in ppm in the lubricating oil composition to the total boron in ppm in the lubricating oil composition may be less than 7.3 or from 0.1 to less than 7.5, or from 0.1 to less than 7.3, or from 0.1 to 7.0.
• the ratio of total metal from the one or more metal-containing detergent(s) in ppm in the lubricating oil composition to the total molybdenum in ppm in the lubricating oil composition may be less than 20.0, or less than 15.0, or 0.1 to less than 23.8, or from 0.1 to less than 20.0, or from 0.1 to less than 15.0, or from 0.1 to 13.0, or from 1.0 to 13.0.
• the lubricating oil composition may have a NOACK volatility as measured by the method of ASTM D-5800 at 250 °C of 2.0 wt.% to less than 11.0 wt.%, or from 2.0 wt.% to 10.9 wt.%, or 5.0 wt.% to 10.9 wt.%.
• the lubricating oil composition may be effective to ensure a TCO Temperature Increase of less than 8.0% as measured using the 2015 version of the General Motors dexos1® Turbocharger Coking Test, or less than 7.0%, or 0.01% to less than 9.0%, or 0.01% to less than 7.0%, or 0.1% to less than 7.0%, or 1.0% to less than 6.0%.
• the lubricating oil composition includes greater than 50 wt.% of a base oil of lubricating viscosity and one or more borated compound(s).
• the lubricating oil composition also includes one or more molybdenum-containing compound(s) in an amount sufficient to provide greater than about 40 ppm by weight molybdenum to the lubricating oil composition, based on a total weight of the lubricating composition.
• the lubricating oil composition includes one or more magnesium-containing detergent(s).
• the lubricating oil composition comprises one or more overbased calcium-containing detergent(s) in an amount sufficient to provide less than about 1800 ppm by weight calcium to the lubricating oil composition, based on the total weight of the lubricating composition.
• the disclosure provides a method for reducing or preventing the formation of deposits in a boosted internal combustion engine.
• the method includes a step of lubricating a boosted internal combustion engine with a lubricating oil composition comprising greater than 50 wt.% of a base oil of lubricating viscosity and one or more borated compound(s).
• the lubricating oil composition includes one or more molybdenum-containing compound(s) in an amount sufficient to provide greater than about 40 ppm by weight molybdenum to the lubricating oil composition, based on a total weight of the lubricating composition.
• the lubricating oil composition includes one or more magnesium-containing detergent(s).
• the lubricating oil composition comprises one or more overbased calcium-containing detergent(s) in an amount sufficient to provide less than about 1800 ppm by weight calcium to the lubricating oil composition, based on the total weight of the lubricating composition.
• the one or more molybdenum containing compound(s) may be present in an amount sufficient to provide at least about 50 ppm by weight molybdenum to the lubricating oil composition, or at least about 80 ppm by weight, or greater than 40 ppm by weight to 1200 ppm by weight, or greater than 40 ppm by weight to 900 ppm by weight, or at least about 80 ppm by weight to 800 ppm by weight molybdenum to the lubricating oil composition based on the total weight of the lubricating composition.
• the one or more calcium-containing overbased detergent(s) may be selected from an overbased calcium sulfonate detergent, an overbased calcium phenate detergent, and an overbased calcium salicylate detergent. In each of the foregoing embodiments, the one or more overbased calcium-containing detergent(s) may provide from about 1000 to about 1750 ppm, or from 1100 to 1700 ppm by weight calcium to the lubricating oil composition based on a total weight of the lubricating oil composition.
• the one or more magnesium-containing detergent(s) may be overbased, and wherein the one or more overbased calcium-containing detergent(s) and the one or more overbased magnesium-containing detergent(s) may each have a total base number (TBN) of greater than 225 mg KOH/g, measured by the method of ASTM D-2896, or a TBN of about 250 mg KOH/gram or greater, or a TBN of about 300 mg KOH/gram or greater, or a TBN of about 350 mg KOH/gram or greater, or a TBN of about 375 mg KOH/gram or greater, or a TBN of about 400 mg KOH/gram or greater; or a TBN of greater than 225 mg KOH/g to 425 mg KOH/gram, or a TBN of about 250 mg KOH/gram to 425 mg KOH/gram, or a TBN of about 300 mg KOH/gram to 425 mg KOH/gram, or a TBN of about 350 mg KOH/gram to 4
• TBN total base number
• the one or more overbased magnesium containing detergent(s) may be an overbased magnesium sulfonate.
• the one or more magnesium-containing detergent(s) may be present in an amount sufficient to provide 20 ppm by weight to 1800 ppm by weight magnesium to the lubricating oil composition, based on the total weight of the lubricating composition, or 100 ppm by weight to 1200 ppm by weight magnesium, or greater than about 140 ppm by weight to about 550 ppm by weight magnesium, based on the total weight of the lubricating composition.
• the ratio of total boron in ppm by weight to total nitrogen in ppm by weight may be less than about 0.29, or from 0.01 to 0.28 or from 0.05 to 0.28.
• the ratio of total calcium in ppm by weight to total boron in ppm by weight may be greater than about 4.9 to less than about 9.7 or from 5.0 to 9.0, or from 5.0 to 7.5.
• the percent calcium from the one or more overbased calcium-containing detergent(s) based on the total calcium and magnesium from the one or more overbased calcium-containing detergent(s) and the one or more overbased magnesium-containing detergent(s), respectively may be greater than 50%, or greater than 50% to 99%, or from 60% to 99% or from 65% to 95%.
• the one or more borated compound(s) may be included in the lubricating oil composition in an amount sufficient to provide greater than 50 ppm boron to the lubricating oil composition, or greater than 100 ppm boron, or from greater than 50 ppm to 1000 ppm boron, or greater than 100 ppm to 800 ppm boron, or 110 ppm to 600 ppm boron, or 120 ppm to 500 ppm boron to the lubricating oil composition.
• the lubricating oil composition may be effective to ensure a TCO Temperature Increase of less than 8.5% as measured using the 2015 version of the General Motors dexos1® Turbocharger Coking Test, or less than 8.0% or less than 7.5%; or 0.01% to less than 9.0%, or 0.05% to less than 8.5%, or 0.1% to less than 7.5%.
• the lubricating oil compositions may optionally also contain one or more low-based/neutral detergents, wherein the low-based/neutral detergent has a TBN of up to 175 mg KOH/g, or up to 150 mg KOH/g, measured by the method of ASTM D-2896.
• the low-based/neutral detergent may include a calcium-containing detergent.
• the low-based/neutral calcium-containing detergent may be selected from a calcium sulfonate detergent, a calcium phenate detergent, a calcium salicylate detergent or a mixture thereof.
• the low-based/neutral detergent may be a calcium sulfonate detergent or a calcium phenate detergent.
• “overbased” may be abbreviated “OB” and in some instances, “low-based/neutral” may be abbreviated “LB/N.”
• the low-based/neutral detergent may comprise at least 0.1 wt.% of the lubricating oil composition. In some embodiments, the low-based/neutral detergent may comprise at least 0.25 wt.%, or 0.1 wt.% to 5.0 wt, or 0.15wt.% to 3.0 wt.%, or 0.15 wt.% to 1.0 wt.% of the lubricating oil composition.
• the one or more low-based/neutral calcium-containing detergents may provide from about 10 to about 1000 ppm calcium by weight to the lubricating oil composition based on a total weight of the lubricating oil composition. In each of the foregoing embodiments, the one or more low-based/neutral calcium-containing detergents may provide from 25 to less than 800 ppm, or from 50 to 600 ppm, or from 100 to 500 ppm by weight calcium to the lubricating oil composition based on a total weight of the lubricating oil composition.
• the one of the one or more overbased calcium-containing detergent(s) may be an overbased calcium sulfonate detergent.
• the total TBN of the lubricating oil composition may be at least 6.0 mg KOH/g of the lubricating oil composition. as measured by the method of ASTM D-2896, or 6.4 to 12.0 mg KOH/g of the lubricating oil composition, or 6.5 to 12.0 mg KOH/g of the lubricating oil composition, as measured by the method of ASTM D-2896.
• the lubricating oil composition may comprise a dispersant.
• the dispersant may be a boron-containing dispersant.
• the boron-containing dispersant may be present in an amount of 1.0-10 wt.%, based on the total weight of the lubricating oil composition.
• the boron-containing dispersant may be present in an amount of 1.0-8.5 wt.%, based on the total weight of the lubricating oil composition.
• the lubricating oil composition may have nitrogen present in an amount of about 500 ppm to about 2500 ppm, or in an amount of about 700 ppm to about 2000 ppm, or about 900 ppm to about 1600 ppm, all based on a total weight of the lubricating oil composition.
• the total metal from the one or more metal-containing detergent(s) may be present in an amount to provide from about 100 ppm to about 3500 ppm metal to the lubricating oil composition, or from about 1100 to about 3000 ppm of metal, or about 1150 to about 2500 ppm of metal, or about 1200 to about 2400 ppm of metal, or less than 1800 ppm of metal to the lubricating oil composition.
• the lubricating oil may further comprise one or more components selected from the group consisting of friction modifiers, antiwear agents, dispersants, antioxidants, and viscosity index improvers.
• the lubricating oil may include greater than 50% base oil, wherein the base oil may be selected from the group consisting of Group II, Group III, Group IV, Group V base oils, and any combination of two or more of the foregoing, and wherein the greater than 50 wt.% of base oil may be other than diluent oils that arise from provision of additive components or viscosity index improvers in the composition.
• the lubricating oil composition may comprise greater than 50 wt.% of a Group II base oil, a Group III base oil or a combination thereof, or greater than 70 wt.%, or greater than 75 wt.%, or greater than 80 wt.%, or greater than 85 wt.%, or greater than 90 wt.% of a Group II base oil, a Group III base oil or a combination thereof, or greater than 97 wt.% of a combination of a Group II base oil and a Group III base oil.
• the lubricating step lubricates turbocharger or supercharger components and a combustion chamber or cylinder walls of a spark-ignited direct injection engine or spark-ignited port fuel injected internal combustion engine provided with a turbocharger or a supercharger, including passages, bushings and other components found in a turbocharger or supercharger.
• the overbased calcium-containing detergent may optionally exclude overbased calcium salicylate detergents.
• the lubricating oil composition may not contain any Group IV base oils.
• the lubricating oil composition may not contain any Group V base oils.
• oil composition lubrication composition
• lubricating oil composition lubricating oil
• lubricant composition lubricating composition
• lubricating composition lubricating composition
• fully formulated lubricant composition lubricant
• lubricant crankcase oil
• crankcase lubricant engine oil
• engine lubricant motor oil
• motor lubricant are considered synonymous, fully interchangeable terminology referring to the finished lubrication product comprising greater than 50 wt.% of a base oil plus a minor amount of an additive composition.
• additive package As used herein, the terms "additive package,” “additive concentrate,” “additive composition,” “engine oil additive package,” “engine oil additive concentrate,” “crankcase additive package,” “crankcase additive concentrate,” “motor oil additive package,” “motor oil concentrate,” are considered synonymous, fully interchangeable terminology referring the portion of the lubricating oil composition excluding the greater than 50 wt.% of base oil stock mixture.
• the additive package may or may not include the viscosity index improver or pour point depressant.
• overbased relates to metal salts, such as metal salts of sulfonates, carboxylates, salicylates, and/or phenates, wherein the amount of metal present exceeds the stoichiometric amount.
• metal salts may have a conversion level in excess of 100% (i.e., they may comprise more than 100% of the theoretical amount of metal needed to convert the acid to its "normal,” “neutral” salt).
• metal ratio often abbreviated as MR, is used to designate the ratio of total chemical equivalents of metal in the overbased salt to chemical equivalents of the metal in a neutral salt according to known chemical reactivity and stoichiometry.
• the metal ratio is one and in an overbased salt, MR, is greater than one.
• They are commonly referred to as overbased, hyperbased, or superbased salts and may be salts of organic sulfur acids, carboxylic acids, salicylates, and/or phenols.
• the lubricating oil composition may contain one or more overbased metal salts.
• the one or more overbased metal salt(s) can include an overbased detergent having a TBN of greater than 225 mg KOH/g.
• the overbased detergent may be a combination of two or more overbased detergents each having a TBN of greater than 225 mg KOH/g.
• the one or more overbased detergent(s) can include one or more overbased calcium-containing detergents having a TBN of greater than 225 mg KOH/g measured by the method of ASTM D-2896.
• hydrocarbyl substituent or “hydrocarbyl group” or “alkyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
• hydrocarbyl groups include:
• percent by weight means the percentage the recited component represents to the weight of the entire composition.
• ppm ppm by weight of the total weight of the lubricating oil composition unless expressly stated otherwise.
• soluble oil-soluble
• dispenser dispensers
• soluble dissolvable, miscible, or capable of being suspended in the oil in all proportions.
• the foregoing terms do mean, however, that they are, for instance, soluble, suspendable, dissolvable, or stably dispersible in oil to an extent sufficient to exert their intended effect in the environment in which the oil is employed.
• additional incorporation of other additives may also permit incorporation of higher levels of a particular additive, if desired.
• the transitional phrase "consisting essentially of” as used herein limits the scope of an embodiment of the invention to the specified materials or steps and those that do not materially affect the basic and novel characteristic(s) of the invention.
• the basic and novel characteristics of the invention may be one or more of NOACK volatility, and TC Test performance.
• TBN Total Base Number in mg KOH/g composition as measured by the method of ASTM D-2896.
• alkyl refers to straight, branched, cyclic, and/or substituted saturated chain moieties of from about 1 to about 100 carbon atoms.
• alkenyl refers to straight, branched, cyclic, and/or substituted unsaturated chain moieties of from about 3 to about 10 carbon atoms.
• aryl refers to single and multi-ring aromatic compounds that may include alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy, halo substituents, and/or heteroatoms including, but not limited to, nitrogen, oxygen, and sulfur.
• Lubricants, combinations of components, or individual components of the present description may be suitable for use in various types of internal combustion engines. Suitable engine types may include, but are not limited to heavy duty diesel, passenger car, light duty diesel, medium speed diesel, marine engines, or motorcycle engines.
• An internal combustion engine may be a diesel fueled engine, a gasoline fueled engine, a natural gas fueled engine, a bio-fueled engine, a mixed diesel/biofuel fueled engine, a mixed gasoline/biofuel fueled engine, an alcohol fueled engine, a mixed gasoline/alcohol fueled engine, a compressed natural gas (CNG) fueled engine, or mixtures thereof.
• a diesel engine may be a compression ignited engine.
• a diesel engine may be a compression ignited engine with a spark-ignition assist.
• a gasoline engine may be a spark-ignited engine.
• An internal combustion engine may also be used in combination with an electrical or battery source of power.
• An engine so configured is commonly known as a hybrid engine.
• the internal combustion engine may be a 2-stroke, 4-stroke, or rotary engine.
• Suitable internal combustion engines include marine diesel engines (such as inland marine), aviation piston engines, low-load diesel engines, and motorcycle, automobile, locomotive, and truck engines.
• the internal combustion engine may contain components of one or more of an aluminum-alloy, lead, tin, copper, cast iron, magnesium, ceramics, stainless steel, composites, and/or mixtures thereof.
• the components may be coated, for example, with a diamond-like carbon coating, a lubricated coating, a phosphorus-containing coating, molybdenum-containing coating, a graphite coating, a nano-particle-containing coating, and/or mixtures thereof.
• the aluminum-alloy may include aluminum silicates, aluminum oxides, or other ceramic materials. In one embodiment the aluminum-alloy is an aluminum-silicate surface.
• aluminum alloy is intended to be synonymous with “aluminum composite” and to describe a component or surface comprising aluminum and another component intermixed or reacted on a microscopic or nearly microscopic level, regardless of the detailed structure thereof. This would include any conventional alloys with metals other than aluminum as well as composite or alloy-like structures with non-metallic elements or compounds such with ceramic-like materials.
• the lubricating oil composition for an internal combustion engine may be suitable for any engine irrespective of the sulfur, phosphorus, or sulfated ash (ASTM D-874) content.
• the sulfur content of the engine oil lubricant may be about 1 wt.% or less, or about 0.8 wt.% or less, or about 0.5 wt.% or less, or about 0.3 wt.% or less, or about 0.2 wt.% or less. In one embodiment the sulfur content may be in the range of about 0.001 wt.% to about 0.5 wt.%, or about 0.01 wt.% to about 0.3 wt.%.
• the phosphorus content may be about 0.2 wt.% or less, or about 0.1 wt% or less, or about 0.085 wt.% or less, or about 0.08 wt.% or less, or even about 0.06 wt.% or less, about 0.055 wt.% or less, or about 0.05 wt.% or less. In one embodiment the phosphorus content may be about 50 ppm to about 1000 ppm, or about 325 ppm to about 850 ppm.
• the total sulfated ash content may be about 2 wt.% or less, or about 1.5 wt.% or less, or about 1.1 wt.% or less, or about 1 wt.% or less, or about 0.8 wt.% or less, or about 0.5 wt.% or less. In one embodiment the sulfated ash content may be about 0.05 wt.% to about 0.9 wt.%, or about 0.1 wt.% or about 0.2 wt.% to about 0.45 wt.%.
• the sulfur content may be about 0.4 wt.% or less, the phosphorus content may be about 0.08 wt.% or less, and the sulfated ash is about 1 wt.% or less. In yet another embodiment the sulfur content may be about 0.3 wt.% or less, the phosphorus content is about 0.05 wt.% or less, and the sulfated ash may be about 0.8 wt.% or less.
• ASTM D4951 is a test method which covers eight elements and can provide elemental composition data. ASTM D5185 can be used to determine 22 elements in used and unused lubricating oils and base oils, and can provide screening of used oils for indications of wear.
• the total TBN of the lubricating oil composition may be at least 6.0 mg KOH/g. as measured by the method of ASTM D-2896, or 6.4 to 12.0 mg KOH/g, or 6.5 to 12.0 mg KOH/g, as measured by the method of ASTM D-2896.
• the lubricating oil composition is an engine oil, wherein the lubricating oil composition may have (i) a sulfur content of about 0.5 wt.% or less, (ii) a phosphorus content of about 0.1 wt.% or less, and (iii) a sulfated ash content of about 1.5 wt.% or less.
• the lubricating oil composition is suitable for use with engines powered by low sulfur fuels, such as fuels containing about 1 to about 5% sulfur. Highway vehicle fuels contain about 15 ppm sulfur (or about 0.0015% sulfur).
• the lubricating oil composition is suitable for use with boosted internal combustion engines including turbocharged or supercharged internal combustion engines.
• lubricants of the present description may be suitable to meet one or more industry specification requirements such as ILSAC GF-3, GF-4, GF-5, GF-6, PC-11, CI-4, CJ-4, CK-4, FA-4, ACEA A1/B1, A2/B2, A3/B3, A3/B4, A5/B5, C1, C2, C3, C4, C5, E4/E6/E7/E9, Euro 5/6, Jaso DL-1, Low SAPS, Mid SAPS, or original equipment manufacturer specifications such as DexosTM 1, DexosTM 2, MB-Approval 229.51/229.31, 229.71, 229.3/229.5, VW 502.00, 503.00/503.01, 504.00, 505.00, 506.00/506.01, 507.00, 508.00, 509.00, BMW Longlife-04, Porsche C30, Peugeot Citro ⁇ n Automobiles B71 2290, B71 2296, B71 2297, B71 2300, B71 2302, B71 2312, B71 2007,
• a “functional fluid” is a term which encompasses a variety of fluids including but not limited to tractor hydraulic fluids, power transmission fluids including automatic transmission fluids, continuously variable transmission fluids and manual transmission fluids, hydraulic fluids, including tractor hydraulic fluids, some gear oils, power steering fluids, fluids used in wind turbines, compressors, some industrial fluids, and fluids related to power train components. It should be noted that within each of these fluids such as, for example, automatic transmission fluids, there are a variety of different types of fluids due to the various transmissions having different designs which have led to the need for fluids of markedly different functional characteristics. This is contrasted by the term “lubricating fluid" which is not used to generate or transfer power.
• tractor hydraulic fluids are all-purpose products used for all lubricant applications in a tractor except for lubricating the engine.
• These lubricating applications may include lubrication of gearboxes, power take-off and clutch(es), rear axles, reduction gears, wet brakes, and hydraulic accessories.
• a functional fluid is an automatic transmission fluid
• the automatic transmission fluids must have enough friction for the clutch plates to transfer power.
• the friction coefficient of fluids has a tendency to decline due to the temperature effects as the fluid heats up during operation. It is important that the tractor hydraulic fluid or automatic transmission fluid maintain its high friction coefficient at elevated temperatures, otherwise brake systems or automatic transmissions may fail. This is not a function of an engine oil.
• Tractor fluids may combine the performance of engine oils with transmissions, differentials, final-drive planetary gears, wet-brakes, and hydraulic performance. While many of the additives used to formulate a UTTO or a STUO fluid are similar in functionality, they may have deleterious effect if not incorporated properly. For example, some anti-wear and extreme pressure additives used in engine oils can be extremely corrosive to the copper components in hydraulic pumps. Detergents and dispersants used for gasoline or diesel engine performance may be detrimental to wet brake performance. Friction modifiers specific to quiet wet brake noise, may lack the thermal stability required for engine oil performance. Each of these fluids, whether functional, tractor, or lubricating, are designed to meet specific and stringent manufacturer requirements.
• Embodiments of the present disclosure may provide lubricating oils suitable for crankcase applications and having improvements in the following characteristics: air entrainment, alcohol fuel compatibility, antioxidancy, antiwear performance, biofuel compatibility, foam reducing properties, friction reduction, fuel economy, pre-ignition prevention, rust inhibition, sludge and/or soot dispersability, piston cleanliness, turbocharger deposit formation and water tolerance.
• Engine oils of the present disclosure may be formulated by the addition of one or more additives, as described in detail below, to an appropriate base oil formulation.
• the additives may be combined with a base oil in the form of an additive package (or concentrate) or, alternatively, may be combined individually with a base oil (or a mixture of both).
• the fully formulated engine oil may exhibit improved performance properties, based on the additives added and their respective proportions.
• boosted internal combustion engines of the present disclosure include turbocharged and supercharged internal combustion engines.
• the boosted internal combustion engines include spark-ignited, direct injection and/or spark-ignited, port fuel injection engines.
• the spark-ignited internal combustion engines may be gasoline engines.
• the composition of the invention includes a lubricating oil composition containing a base oil of lubricating viscosity and a particular additive composition.
• the methods of the present disclosure employ the lubricating oil composition containing the additive composition.
• the lubricating oil composition may be surprisingly effective for use in reducing or preventing the formation of carbonaceous deposits in a boosted internal combustion engine, including carbonaceous deposits in the components of the turbocharger or supercharger, lubricated with the lubricating oil composition. Since the deposits act as insulators, the amount of deposits can be measured indirectly by measuring the temperature increase in one of the turbocharger coolant passages.
• the lubricating oil composition of the present invention is effective to ensure a TCO Temperature Increase of less than 9.0% as measured using the 2015 version of the General Motors dexos1® Turbocharger Coking Test.
• the disclosure provides a method for reducing or preventing the formation of deposits in a boosted internal combustion engine.
• the method includes a step of lubricating the boosted internal combustion engine with a lubricating oil composition including greater than 50 wt.% of a base oil of lubricating viscosity; wherein a ratio of total metal from the one or more metal-containing detergent(s) in ppm in the lubricating oil composition to the total nitrogen in ppm in the lubricating oil composition is less than 1.9; a ratio of total metal from the one or more metal-containing detergent(s) in ppm in the lubricating oil composition to the total boron in ppm in the lubricating oil composition is less than 7.5; and a ratio of total metal from the one or more metal-containing detergent(s) in ppm in the lubricating oil composition to the total molybdenum in ppm in the lubricating oil composition is less than 23.8; the lubricating oil composition
• lubricating a boosted internal combustion engine with this lubricating oil composition there will be improved resistance to deposit formation in the boosted internal combustion engine, including in the components of the turbocharger or supercharger, as shown by its ability to ensure a TCO Temperature Increase of less than 9.0% as measured using the 2015 version of the General Motors dexosl® Turbocharger Coking Test.
• the boosted internal combustion engine is operated and lubricated with the lubricating oil composition whereby the amount of deposits in the engine, including in the components of the turbocharger or supercharger, lubricated with the lubricating oil composition may be reduced or prevented.
• the disclosure provides a method for reducing or preventing the formation of deposits in a boosted internal combustion engine.
• the method includes a step of lubricating the boosted internal combustion engine with a lubricating oil composition including greater than 50 wt.% of a base oil of lubricating viscosity; one or more borated compound(s); one or more molybdenum-containing compound(s) in an amount sufficient to provide greater than about 40 ppm by weight molybdenum to the lubricating oil composition, based on a total weight of the lubricating composition; one or more magnesium-containing detergent(s); one or more overbased calcium-containing detergent(s) in an amount sufficient to provide less than about 1800 ppm by weight calcium to the lubricating oil composition, based on the total weight of the lubricating composition.
• lubricating a boosted internal combustion engine with this lubricating oil composition there will be improved resistance to deposit formation in the boosted internal combustion engine, as shown by its ability to ensure a TCO Temperature Increase of less than 9.0% as measured using the 2015 version of the General Motors dexos1® Turbocharger Coking Test.
• the boosted internal combustion engine is operated and lubricated with the lubricating oil composition whereby the amount of deposits in the engine, including in the components of the turbocharger or supercharger, lubricated with the lubricating oil composition may be reduced or prevented.
• the combustion chamber or cylinder walls of a spark-ignited direct injection engine or spark-ignited port fuel injected internal combustion engine provided with a turbocharger or a supercharger, as well as the passages, bushings and other components of the turbocharger or supercharger are lubricated with the lubricating oil composition and the lubricated spark-ignited direct injection engine is operated whereby the deposits in the turbocharger of the engine lubricated with the lubricating oil composition may be reduced or prevented.
• the calcium in the lubricating oil composition may be provided by various sources including detergents.
• the lubricating oil composition may comprise at least one detergent selected from one or more overbased calcium-containing detergents having a TBN of greater than 225 mg KOH/g, measured by the method of ASTM D-2896, and optionally one or more low-based/neutral calcium-containing detergents having a TBN of up to 175 mg KOH/g, measured by the method of ASTM D-2896.
• the lubricating oil composition contains both boron and nitrogen.
• One source for providing boron and/or nitrogen to the lubricating oil composition is boron-containing dispersants.
• the lubricating oil composition may comprise a dispersant which can be a boron-containing dispersant.
• the boron-containing dispersant may be present in an amount of 1.0-10 wt.%, based on the total weight of the lubricating oil composition, and even more preferably the boron-containing dispersant may be in an amount of 1.0-8.5 wt.%, based on the total weight of the lubricating oil composition.
• the nitrogen may be present in the lubricating oil composition in an amount of about 500 ppm to about 2500 ppm, or about 700 ppm to about 2000 ppm, or about 900 ppm to about 1600 ppm.
• the nitrogen present in the lubricant composition can be added as part of one or more of the dispersants, antioxidants and friction modifiers.
• the base oil used in the lubricating oil compositions herein may be selected from any of the base oils in Groups I-V as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines.
• the five base oil groups are as follows: Table 1 Base oil Category Sulfur (%) Saturates (%) Viscosity Index Group I > 0.03 and/or ⁇ 90 80 to 120 Group II ⁇ 0.03 And ⁇ 90 80 to 120 Group III ⁇ 0.03 And ⁇ 90 ⁇ 120 Group IV All polyalphaolefins (PAOs) Group V All others not included in Groups I, II, III, or IV
• Groups I, II, and III are mineral oil process stocks.
• Group IV base oils contain true synthetic molecular species, which are produced by polymerization of olefinically unsaturated hydrocarbons.
• Many Group V base oils are also true synthetic products and may include diesters, polyol esters, polyalkylene glycols, alkylated aromatics, polyphosphate esters, polyvinyl ethers, and/or polyphenyl ethers, and the like, but may also be naturally occurring oils, such as vegetable oils.
• Group III base oils are derived from mineral oil, the rigorous processing that these fluids undergo causes their physical properties to be very similar to some true synthetics, such as PAOs. Therefore, oils derived from Group III base oils may be referred to as synthetic fluids in the industry.
• the base oil used in the disclosed lubricating oil composition may be a mineral oil, animal oil, vegetable oil, synthetic oil, or mixtures thereof.
• Suitable oils may be derived from hydrocracking, hydrogenation, hydrofinishing, unrefined, refined, and re-refined oils, and mixtures thereof.
• Unrefined oils are those derived from a natural, mineral, or synthetic source without or with little further purification treatment. Refined oils are similar to the unrefined oils except that they have been treated in one or more purification steps, which may result in the improvement of one or more properties. Examples of suitable purification techniques are solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, and the like. Oils refined to the quality of an edible may or may not be useful. Edible oils may also be called white oils. In some embodiments, lubricating oil compositions are free of edible or white oils.
• Re-refined oils are also known as reclaimed or reprocessed oils. These oils are obtained similarly to refined oils using the same or similar processes. Often these oils are additionally processed by techniques directed to removal of spent additives and oil breakdown products.
• Mineral oils may include oils obtained by drilling or from plants and animals or any mixtures thereof.
• oils may include, but are not limited to, castor oil, lard oil, olive oil, peanut oil, corn oil, soybean oil, and linseed oil, as well as mineral lubricating oils, such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types.
• Such oils may be partially or fully hydrogenated, if desired. Oils derived from coal or shale may also be useful.
• Useful synthetic lubricating oils may include hydrocarbon oils such as polymerized, oligomerized, or interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene/isobutylene copolymers); poly(1-hexenes), poly(1-octenes), trimers or oligomers of 1-decene, e.g., poly(1-decenes), such materials being often referred to as ⁇ -olefins, and mixtures thereof; alkyl-benzenes (e.g.
• dodecylbenzenes dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls); diphenyl alkanes, alkylated diphenyl alkanes, alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof or mixtures thereof.
• Polyalphaolefins are typically hydrogenated materials.
• oils include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and the diethyl ester of decane phosphonic acid), or polymeric tetrahydrofurans.
• Synthetic oils may be produced by Fischer-Tropsch reactions and typically may be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure as well as other gas-to-liquid oils.
• the greater than 50 wt.% of base oil included in a lubricating composition may be selected from the group consisting of Group I, Group II, a Group III, a Group IV, a Group V, and a combination of two or more of the foregoing, and wherein the greater than 50 wt.% of base oil is other than base oils that arise from provision of additive components or viscosity index improvers in the composition.
• the greater than 50 wt.% of base oil included in a lubricating composition may be selected from the group consisting of Group II, a Group III, a Group IV, a Group V, and a combination of two or more of the foregoing, and wherein the greater than 50 wt.% of base oil is other than diluent oils that arise from provision of additive components or viscosity index improvers in the composition.
• the amount of the oil of lubricating viscosity present may be the balance remaining after subtracting from 100 wt.% the sum of the amount of the performance additives inclusive of viscosity index improver(s) and/or pour point depressant(s) and/or other top treat additives.
• the oil of lubricating viscosity that may be present in a finished fluid may be a major amount, such as greater than about 50 wt.%, greater than about 60 wt.%, greater than about 70 wt.%, greater than about 80 wt.%, greater than about 85 wt.%, or greater than about 90 wt.%, all based on the total weight of the lubricating oil composition.
• the lubricating oil composition may comprise not more than 10 wt.% of a Group IV base oil, a Group V base oil, or a combination thereof. In each of the foregoing embodiments, the lubricating oil compositions may comprise less than 5 wt.% of a Group V base oil. In some embodiments, the lubricating oil composition does not contain any Group IV base oils and/or the lubricating oil composition does not contain any Group V base oils.
• the lubricating oil composition may comprise one or more detergents.
• the lubricating oil composition may comprise one or more overbased calcium-containing detergents and optionally other detergents.
• Suitable detergent substrates include phenates, sulfur containing phenates, sulfonates, calixarates, salixarates, salicylates, carboxylic acids, phosphorus acids, mono- and/or di-thiophosphoric acids, alkyl phenols, sulfur coupled alkyl phenol compounds, or methylene bridged phenols.
• Suitable detergents and their methods of preparation are described in greater detail in numerous patent publications, including US 7,732,390 and references cited therein.
• the detergent substrate may be salted with an alkali or alkaline earth metal such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof.
• the detergent is free of barium.
• a suitable detergent may include alkali or alkaline earth metal salts of petroleum sulfonic acids and long chain mono- or di-alkylarylsulfonic acids with the aryl group being benzyl, tolyl, and xylyl.
• suitable additional detergents include, but are not limited to, calcium phenates, calcium sulfur containing phenates, calcium sulfonates, calcium calixarates, calcium salixarates, calcium salicylates, calcium carboxylic acids, calcium phosphorus acids, calcium mono- and/or di-thiophosphoric acids, calcium alkyl phenols, calcium sulfur coupled alkyl phenol compounds, calcium methylene bridged phenols, magnesium phenates, magnesium sulfur containing phenates, magnesium sulfonates, magnesium calixarates, magnesium salixarates, magnesium salicylates, magnesium carboxylic acids, magnesium phosphorus acids, magnesium mono- and/or di-thiophosphoric acids, magnesium alkyl phenols, magnesium sulfur coupled alkyl phenol compounds, magnesium methylene bridged phenols, sodium phenates, sodium sulfur containing phenates, sodium sulfonates, sodium calixarates, sodium salixarates, sodium salicylates, sodium carboxylic acids, sodium phosphorus
• Overbased detergents are well known in the art and may be alkali or alkaline earth metal overbased detergents. Such detergents may be prepared by reacting a metal oxide or metal hydroxide with a substrate and carbon dioxide gas.
• the substrate is typically an acid, for example, an acid such as an aliphatic substituted sulfonic acid, an aliphatic substituted carboxylic acid, or an aliphatic substituted phenol.
• overbased relates to metal salts, such as metal salts of sulfonates, carboxylates, and phenates, wherein the amount of metal present exceeds the stoichiometric amount.
• Such salts may have a conversion level in excess of 100% (i.e., they may comprise more than 100% of the theoretical amount of metal needed to convert the acid to its "normal,” “neutral” salt).
• metal ratio often abbreviated as MR, is used to designate the ratio of total chemical equivalents of metal in the overbased salt to chemical equivalents of the metal in a neutral salt according to known chemical reactivity and stoichiometry. In a normal or neutral salt, the metal ratio is 1 and in an overbased salt, MR, is greater than 1. They are commonly referred to as overbased, hyperbased, or superbased salts and may be salts of organic sulfur acids, carboxylic acids, or phenols.
• An overbased detergent may have a TBN of greater 225 mg KOH/gram, or as further examples, an overbased detergent may have a TBN of about 250 mg KOH/gram or greater, or a TBN of about 300 mg KOH/gram or greater, or a TBN of about 350 mg KOH/gram or greater, or a TBN of about 375 mg KOH/gram or greater, or a TBN of about 400 mg KOH/gram or greater, as measured by the method of ASTM D-2896.
• overbased detergents include, but are not limited to, overbased calcium phenates, overbased calcium sulfur containing phenates, overbased calcium sulfonates, overbased calcium calixarates, overbased calcium salixarates, overbased calcium salicylates, overbased calcium carboxylic acids, overbased calcium phosphorus acids, overbased calcium mono- and/or di-thiophosphoric acids, overbased calcium alkyl phenols, overbased calcium sulfur coupled alkyl phenol compounds, overbased calcium methylene bridged phenols, overbased magnesium phenates, overbased magnesium sulfur containing phenates, overbased magnesium sulfonates, overbased magnesium calixarates, overbased magnesium salixarates, overbased magnesium salicylates, overbased magnesium carboxylic acids, overbased magnesium phosphorus acids, overbased magnesium mono- and/or dithiophosphoric acids, overbased magnesium alkyl phenols, overbased magnesium sulfur coupled alkyl phenol compounds, or overbased magnesium methylene bridged phenols.
• the overbased detergent may have a metal to substrate ratio of from 1.1:1, or from 2:1, or from 4:1, or from 5:1, or from 7:1, or from 10:1.
• a detergent is effective at reducing or preventing rust in an engine.
• the total detergent may be present at up to 10 wt.%, or about up to 8 wt.%, or up to about 4 wt.%, or greater than about 1 wt.% to about 8 wt.%, or greater than about 1 wt.% to about 4 wt.%, based on a total weight of the lubricating oil composition.
• the total metal from the one or more metal-containing detergent(s) may be present in an amount to provide from about 100 ppm to about 3500 ppm metal to the finished fluid.
• the metal-containing detergent may provide from about 1100 to about 3000 ppm of metal, or about 1150 to about 2500 ppm of metal, or about 1200 to about 2400 ppm of metal, or less than 1800 ppm of metal to the finished fluid.
• the overbased detergent may be an overbased magnesium-containing detergent.
• the overbased magnesium-containing detergent may be selected from an overbased magnesium sulfonate detergent, an overbased magnesium phenate detergent, and an overbased magnesium salicylate detergent.
• the overbased magnesium-containing detergent comprises an overbased magnesium sulfonate detergent.
• the overbased detergent is one or more magnesium-containing detergents, preferably the overbased detergent is a magnesium sulfonate detergent.
• the total magnesium provided to the lubricating oil composition by the overbased magnesium detergent in each of the foregoing embodiments can be from 20 ppm by weight to 1500 ppm by weight magnesium to the lubricating oil composition, based on the total weight of the lubricating composition, or 100 ppm by weight to 800 ppm by weight magnesium, or greater than about 140 ppm by weight to about 550 ppm by weight magnesium, based on the total weight of the lubricating composition.
• the overbased magnesium detergent may have a TBN of greater 225 mg KOH/gram, or as further examples, the overbased magnesium detergent may have a TBN of about 250 mg KOH/gram or greater, or a TBN of about 300 mg KOH/gram or greater, or a TBN of about 350 mg KOH/gram or greater, or a TBN of about 400 mg KOH/gram or greater, or a TBN of about 425 mg KOH/gram or greater, as measured by the method of ASTM D-2896.
• the lubricating oil compositions of the present disclosure comprise at least one detergent selected from one or more overbased calcium-containing detergent(s) having a TBN of greater than 225 mg KOH/g, measured by the method of ASTM D-2896, and optionally one or more low-based/neutral calcium-containing detergent(s) having a TBN of up to 175 mg KOH/g, measured by the method of ASTM D-2896.
• the present disclosure also includes methods of using such lubricating oil compositions in a method or lubricating a boosted engine by lubricating the engine with the lubricating oil composition and operating the engine.
• the lubricating oil composition of the disclosure may have an overbased calcium-containing detergent selected from an overbased calcium sulfonate detergent, an overbased calcium phenate detergent, and an overbased calcium salicylate detergent.
• the overbased calcium-containing detergent comprises an overbased calcium sulfonate detergent.
• the overbased detergent is one or more calcium-containing detergents.
• the overbased detergent is a calcium sulfonate detergent.
• the one or more overbased calcium-containing detergent(s) may be in an amount sufficient to provide less than about 1800 ppm by weight calcium to the lubricating oil composition, based on the total weight of the lubricating composition, or from about 1000 to about 1750 ppm, or from 1100 to 1700 ppm by weight calcium to the lubricating oil composition based on a total weight of the lubricating oil composition.
• the lubricating oil compositions of the present invention may optionally also contain one or more low-based/neutral detergents.
• the low-based/neutral detergent has a TBN of up to 175 mg KOH/g, or up to 150 mg KOH/g.
• the low-based/neutral detergent may include a calcium-containing detergent.
• the low-based neutral calcium-containing detergent may be selected from a calcium sulfonate detergent, a calcium phenate detergent and a calcium salicylate detergent.
• the low-based/neutral detergent may be a calcium-containing detergent or a mixture of calcium-containing detergents.
• the low-based/neutral detergent may be a calcium sulfonate detergent or a calcium phenate detergent.
• the lubricating oil composition does not contain a low-based/neutral detergent.
• the low-based/neutral detergent when present, may comprise at least 0.1 wt.% of the lubricating oil composition. In some embodiments, the low-based/neutral detergent may comprise at least 0.25 wt.%, or 0 wt.% to 5.0 wt,% or 0.15 wt.% to 3.0 wt.%, or 0.15 wt.% to 1.0 wt.% of the lubricating oil composition.
• the low-based/neutral detergent may optionally include one or more low-based/neutral calcium-containing detergents.
• the one or more low-based/neutral calcium-containing detergents may provide from about 0 to about 1000 ppm calcium by weight to the lubricating oil composition based on a total weight of the lubricating oil composition. In some embodiments, the one or more low-based/neutral calcium-containing detergents may provide from 25 to less than 800 ppm, or from 50 to 600 ppm, or from 100 to 500 ppm by weight calcium to the lubricating oil composition based on a total weight of the lubricating oil composition.
• the ratio of the ppm of calcium, by weight, provided to the lubricating oil composition by the low-based/neutral detergent to the ppm of calcium, by weight, provided to the lubricating oil composition by the overbased calcium detergent may be from 0 to about 1, or from about 0.03 to about 0.7, or from about 0.05 to about 0.5, or from about 0.08 to about 0.4.
• the lubricating oil compositions herein contain molybdenum and this molybdenum may be provided to the lubricating oil composition in the form of one or more molybdenum-containing compounds.
• An oil-soluble molybdenum compound may have the functional performance of an antiwear agent, an antioxidant, a friction modifier, or mixtures thereof.
• An oil-soluble molybdenum compound may include molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum dithiophosphinates, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, a trinuclear organo-molybdenum compound, and/or mixtures thereof.
• the molybdenum sulfides include molybdenum disulfide.
• the molybdenum disulfide may be in the form of a stable dispersion.
• oil-soluble molybdenum compound may be selected from the group consisting of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment the oil-soluble molybdenum compound may be a molybdenum dithiocarbamate.
• Suitable examples of molybdenum compounds which may be used include commercial materials sold under the trade names such as Molyvan 822TM, MolyvanTM A, Molyvan 2000TM and Molyvan 855TM from R. T. Vanderbilt Co., Ltd., and Sakura-LubeTM S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710 available from Adeka Corporation, and mixtures thereof.
• Suitable molybdenum components are described in US 5,650,381 ; US RE 37,363 E1 ; US RE 38,929 E1 ; and US RE 40,595 E1 .
• the molybdenum compound may be an acidic molybdenum compound. Included are molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkaline metal molybdates and other molybdenum salts, e.g., hydrogen sodium molybdate, MoOCl 4 , MoO 2 Br 2 , Mo 2 O 3 Cl 6 , molybdenum trioxide or similar acidic molybdenum compounds.
• the compositions can be provided with molybdenum by molybdenum/sulfur complexes of basic nitrogen compounds as described, for example, in U.S. Pat. Nos.
• organo-molybdenum compounds are trinuclear molybdenum compounds, such as those of the formula Mo 3 S k L n Q z and mixtures thereof, wherein S represents sulfur, L represents independently selected ligands having organo groups with a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil, n is from 1 to 4, k varies from 4 through 7, Q is selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values.
• S sulfur
• L represents independently selected ligands having organo groups with a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil
• n is from 1 to 4
• k varies from 4 through 7
• Q is selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers
• At least 21 total carbon atoms may be present among all the ligands' organo groups, such as at least 25, at least 30, or at least 35 carbon atoms. Additional suitable molybdenum compounds are described in U.S. Pat. No. 6,723,685 .
• the one or more molybdenum containing compound(s) may be present in an amount sufficient to provide greater than about 40 ppm by weight of molybdenum to the lubricating composition, or at least about 50 ppm by weight molybdenum to the lubricating oil composition, or at least about 80 ppm by weight, or greater than 40 ppm by weight to 1200 ppm by weight, or greater than 40 ppm by weight to 900 ppm by weight, or at least about 80 ppm by weight to 800 ppm by weight molybdenum to the lubricating oil composition based on the total weight of the lubricating composition.
• the lubricating oil compositions herein contain boron which may be provided to the lubricating oil composition in the form of one or more boron-containing compound(s) (also referred to herein as one or more borated compound(s)) such as boron-containing dispersants as discussed above.
• boron-containing compound(s) also referred to herein as one or more borated compound(s)
• boron-containing dispersants such as discussed above.
• boron-containing compounds include borate esters, borated fatty amines, borated epoxides, borated detergents, and borated dispersants, such as borated succinimide dispersants, as disclosed in U.S. Patent No. 5,883,057 .
• the boron-containing compound(s) can be used in an amount sufficient to provide about 0.01 wt.% to about 10 wt.%, about 0.05 wt.% to about 8.5 wt.%, or about 0.1 wt.% to about 3 wt.% of the lubricating oil composition.
• the boron-containing compound(s) may be included in the lubricating oil composition in an amount sufficient to provide greater than 50 ppm boron to the lubricating oil composition, or greater than 100 ppm boron, or from greater than 50 ppm to 1000 ppm boron, or greater than 100 ppm to 800 ppm boron, or 110 ppm to 600 ppm boron, or 120 ppm to 500 ppm boron to the lubricating oil composition, based on the total weight of the lubricating composition.
• the lubricating oil composition may also include one or more optional components selected from the various additives set forth below.
• the lubricating oil compositions herein also may optionally contain one or more antioxidants.
• Antioxidant compounds are known and include for example, phenates, phenate sulfides, sulfurized olefins, phosphosulfurized terpenes, sulfurized esters, aromatic amines, alkylated diphenylamines (e.g., nonyl diphenylamine, di-nonyl diphenylamine, octyl diphenylamine, di-octyl diphenylamine), phenyl-alpha-naphthylamines, alkylated phenyl-alpha-naphthylamines, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, macromolecular antioxidants, or mixtures thereof. Antioxidant compounds may be used alone or in combination.
• the hindered phenol antioxidant may contain a secondary butyl and/or a tertiary butyl group as a sterically hindering group.
• the phenol group may be further substituted with a hydrocarbyl group and/or a bridging group linking to a second aromatic group.
• Suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol.
• the hindered phenol antioxidant may be an ester and may include, e.g., IRGANOXTM L-135 available from BASF or an addition product derived from 2,6-di-tert-butylphenol and an alkyl acrylate, wherein the alkyl group may contain about 1 to about 18, or about 2 to about 12, or about 2 to about 8, or about 2 to about 6, or about 4 carbon atoms.
• Another commercially available hindered phenol antioxidant may be an ester and may include ETHANOXTM 4716 available from Albemarle Corporation.
• Useful antioxidants may include diarylamines and high molecular weight phenols.
• the lubricating oil composition may contain a mixture of a diarylamine and a high molecular weight phenol, such that each antioxidant may be present in an amount sufficient to provide up to about 5%, by weight, based upon the total weight of the lubricating oil composition.
• the antioxidant may be a mixture of about 0.3 to about 1.5% diarylamine and about 0.4 to about 2.5% high molecular weight phenol, by weight, based upon the total weight of the lubricating oil composition.
• Suitable olefins that may be sulfurized to form a sulfurized olefin include propylene, butylene, isobutylene, polyisobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene or mixtures thereof.
• hexadecene, heptadecene, octadecene, nonadecene, eicosene or mixtures thereof and their dimers, trimers and tetramers are especially useful olefins.
• the olefin may be a Diels-Alder adduct of a diene such as 1,3-butadiene and an unsaturated ester, such as, butylacrylate.
• sulfurized olefin includes sulfurized fatty acids and their esters.
• the fatty acids are often obtained from vegetable oil or animal oil and typically contain about 4 to about 22 carbon atoms.
• suitable fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid or mixtures thereof.
• the fatty acids are obtained from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil or mixtures thereof.
• Fatty acids and/or ester may be mixed with olefins, such as ⁇ -olefins.
• the one or more antioxidant(s) may be present in ranges about 0 wt.% to about 5.0 wt.%, or about 0.1 wt.% to about 4.0 wt.%, or about 0.5 wt.% to about 3 wt.%, of the lubricating oil composition, based on the total weight of the lubricating composition.
• the lubricating oil compositions herein also may optionally contain one or more antiwear agents.
• suitable antiwear agents include, but are not limited to, a metal thiophosphate; a metal dialkyldithiophosphate; a phosphoric acid ester or salt thereof; a phosphate ester(s); a phosphite; a phosphorus-containing carboxylic ester, ether, or amide; a sulfurized olefin; thiocarbamate-containing compounds including, thiocarbamate esters, alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamyl)disulfides; and mixtures thereof.
• a suitable antiwear agent may be a molybdenum dithiocarbamate.
• the phosphorus containing antiwear agents are more fully described in European Patent 612 839 .
• the metal in the dialkyl dithiophosphate salts may be an alkali metal, alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc.
• a useful antiwear agent may be zinc dialkyldithiophosphate.
• suitable antiwear agents include titanium compounds, tartrates, tartrimides, oil soluble amine salts of phosphorus compounds, sulfurized olefins, phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate-containing compounds, such as thiocarbamate esters, thiocarbamate amides, thiocarbamic ethers, alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides.
• the tartrate or tartrimide may contain alkyl-ester groups, where the sum of carbon atoms on the alkyl groups may be at least 8.
• the antiwear agent may in one embodiment include a citrate.
• the antiwear agent may be present in ranges including about 0 wt.% to about 10 wt.%, or about 0.01 wt.% to about 8 wt.%, or about 0.05 wt.% to about 5 wt.%, or about 0.1 wt.% to about 3 wt.% or less than 2 wt.% of the lubricating oil composition, based on the total weight of the lubricating composition.
• An antiwear compound may be a zinc dihydrocarbyl dithiophosphate (ZDDP) having a P:Zn ratio of from about 1:0.8 to about 1:1.7.
• ZDDP zinc dihydrocarbyl dithiophosphate
• the lubricating oil composition may optionally further comprise one or more dispersants or mixtures thereof.
• Dispersants are often known as ashless-type dispersants because, prior to mixing in a lubricating oil composition, they do not contain ash-forming metals and they do not normally contribute any ash when added to a lubricant.
• Ashless type dispersants are characterized by a polar group attached to a relatively high molecular weight hydrocarbon chain.
• Typical ashless dispersants include N-substituted long chain alkenyl succinimides.
• N-substituted long chain alkenyl succinimides include polyisobutylene succinimide with number average molecular weight of the polyisobutylene substituent in the range about 350 to about 50,000, or to about 5,000, or to about 3,000.
• Succinimide dispersants and their preparation are disclosed, for instance in U.S. Pat. No. 7,897,696 or U.S. Pat. No. 4,234,435 .
• the polyolefin may be prepared from polymerizable monomers containing about 2 to about 16, or about 2 to about 8, or about 2 to about 6 carbon atoms.
• Succinimide dispersants are typically the imide formed from a polyamine, typically a poly(ethyleneamine).
• the present disclosure further comprises at least one polyisobutylene succinimide dispersant derived from polyisobutylene with number average molecular weight in the range about 350 to about 50,000, or to about 5000, or to about 3000.
• the polyisobutylene succinimide may be used alone or in combination with other dispersants.
• polyisobutylene when included, may have greater than 50 mol%, greater than 60 mol%, greater than 70 mol%, greater than 80 mol%, or greater than 90 mol% content of terminal double bonds.
• PIB is also referred to as highly reactive PIB ("HR-PIB").
• HR-PIB having a number average molecular weight ranging from about 800 to about 5000 is suitable for use in embodiments of the present disclosure.
• Conventional PIB typically has less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol% content of terminal double bonds.
• An HR-PIB having a number average molecular weight ranging from about 900 to about 3000 may be suitable.
• Such HR-PIB is commercially available, or can be synthesized by the polymerization of isobutene in the presence of a non-chlorinated catalyst such as boron trifluoride, as described in US Patent No. 4,152,499 to Boerzel, et al. and U.S. Patent No. 5,739,355 to Gateau, et al.
• HR-PIB may lead to higher conversion rates in the reaction, as well as lower amounts of sediment formation, due to increased reactivity.
• a suitable method is described in U.S. Patent No. 7,897,696 .
• the present disclosure further comprises at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA").
• PIBSA polyisobutylene succinic anhydride
• the PIBSA may have an average of between about 1.0 and about 2.0 succinic acid moieties per polymer.
• the % actives of the alkenyl or alkyl succinic anhydride can be determined using a chromatographic technique. This method is described in column 5 and 6 in U.S. Pat. No. 5,334,321 .
• the percent conversion of the polyolefin is calculated from the % actives using the equation in column 5 and 6 in U.S. Pat. No. 5,334,321 .
• the dispersant may be derived from a polyalphaolefin (PAO) succinic anhydride.
• PAO polyalphaolefin
• the dispersant may be derived from olefin maleic anhydride copolymer.
• the dispersant may be described as a poly-PIBSA.
• the dispersant may be derived from an anhydride which is grafted to an ethylene-propylene copolymer.
• Mannich bases are materials that are formed by the condensation of a higher molecular weight, alkyl substituted phenol, a polyalkylene polyamine, and an aldehyde such as formaldehyde. Mannich bases are described in more detail in U.S. Patent No. 3,634,515 .
• a suitable class of dispersants may be high molecular weight esters or half ester amides.
• a suitable dispersant may also be post-treated by conventional methods by a reaction with any of a variety of agents.
• agents include boron, urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenolic esters, and phosphorus compounds.
• US 7,645,726 ; US 7,214,649 ; and US 8,048,831 disclose suitable dispersants and post-treatments.
• both the compounds may be post-treated, or further post-treatment, with a variety of post-treatments designed to improve or impart different properties.
• post-treatments include those summarized in columns 27-29 of U.S. Pat. No. 5,241,003 .
• Such treatments include, treatment with:
• the TBN of a suitable dispersant may be from about 10 to about 65 on an oil-free basis, which is comparable to about 5 to about 30 TBN if measured on a dispersant sample containing about 50% diluent oil.
• the dispersant if present, can be used in an amount sufficient to provide up to about 10 wt.%, based upon the total weight of the lubricating oil composition.
• Another amount of the dispersant that can be used may be about 0.1 wt.% to about 10 wt.%, or about 1 wt.% to about 9 wt.%, or about 2 wt.% to about 8.5 wt.%, or about 2.75 wt.% to about 6.5 wt.%, based upon the total weight of the lubricating oil composition.
• the lubricating oil composition utilizes a mixed dispersant system. A single type or a mixture of two or more types of dispersants in any desired ratio may be used.
• the amount of dispersant used in the present lubricating oil compositions may be constrained by the ratio of total metal from the one or more metal-containing detergent(s) to the total nitrogen in the lubricating oil composition.
• the lubricating oil compositions herein also may optionally contain one or more friction modifiers.
• Suitable friction modifiers may comprise metal containing and metal-free friction modifiers and may include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated ether amines, amine oxides, amidoamines.
• nitriles betaines, quaternary amines, imines, amine salts, amino guanadine, alkanolamides, phosphonates, metal-containing compounds, glycerol esters, sulfurized fatty compounds and olefins, sunflower oil other naturally occurring plant or animal oils, dicarboxylic acid esters, esters or partial esters of a polyol and one or more aliphatic or aromatic carboxylic acids, and the like.
• Suitable friction modifiers may contain hydrocarbyl groups that are selected from straight chain, branched chain, or aromatic hydrocarbyl groups or mixtures thereof, and may be saturated or unsaturated.
• the hydrocarbyl groups may be composed of carbon and hydrogen or hetero atoms such as sulfur or oxygen.
• the hydrocarbyl groups may range from about 12 to about 25 carbon atoms.
• the friction modifier may be a long chain fatty acid ester.
• the long chain fatty acid ester may be a mono-ester, or a di-ester, or a (tri)glyceride.
• the friction modifier may be a long chain fatty amide, a long chain fatty ester, a long chain fatty epoxide derivatives, or a long chain imidazoline.
• suitable friction modifiers may include organic, ashless (metal-free), nitrogen-free organic friction modifiers.
• Such friction modifiers may include esters formed by reacting carboxylic acids and anhydrides with alkanols and generally include a polar terminal group (e.g. carboxyl or hydroxyl) covalently bonded to an oleophilic hydrocarbon chain.
• An example of an organic ashless nitrogen-free friction modifier is known generally as glycerol monooleate (GMO) which may contain mono-, di-, and tri-esters of oleic acid.
• GMO glycerol monooleate
• Other suitable friction modifiers are described in U.S. Pat. No. 6,723,685 .
• Aminic friction modifiers may include amines or polyamines. Such compounds can have hydrocarbyl groups that are linear, either saturated or unsaturated, or a mixture thereof and may contain from about 12 to about 25 carbon atoms. Further examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. Such compounds may have hydrocarbyl groups that are linear, either saturated, unsaturated, or a mixture thereof. They may contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.
• the amines and amides may be used as such or in the form of an adduct or reaction product with a boron compound such as a boric oxide, boron halide, metaborate, boric acid or a mono-, di- or tri-alkyl borate.
• a boron compound such as a boric oxide, boron halide, metaborate, boric acid or a mono-, di- or tri-alkyl borate.
• boron compound such as a boric oxide, boron halide, metaborate, boric acid or a mono-, di- or tri-alkyl borate.
• a friction modifier may optionally be present in ranges such as about 0 wt.% to about 10 wt.%, or about 0.01 wt.% to about 8 wt.%, or about 0.05 wt.% to about 4 wt.% or about 0.05 to about 2 wt.%, based on the total weight of the lubricating composition.
• the oil-soluble compound may be a transition metal containing compound or a metalloid.
• the transition metals may include, but are not limited to, titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, tungsten, and the like.
• Suitable metalloids include, but are not limited to, boron, silicon, antimony, tellurium, and the like.
• the oil-soluble compound that may be used in a weight ratio of Ca/M ranging from about 0.8:1 to about 70:1 is a titanium containing compound, wherein M is the total metal in the lubricant composition as described above.
• the titanium-containing compounds may function as antiwear agents, friction modifiers, antioxidants, deposit control additives, or more than one of these functions.
• titanium containing compounds that may be used in, or which may be used for preparation of the oils-soluble materials of, the disclosed technology are various Ti (IV) compounds such as titanium (IV) oxide; titanium (IV) sulfide; titanium (IV) nitrate; titanium (IV) alkoxides such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium 2-ethylhexoxide; and other titanium compounds or complexes including but not limited to titanium phenates; titanium carboxylates such as titanium (IV) 2-ethyl-1-3-hexanedioate or titanium citrate or titanium oleate; and titanium (IV) (triethanolaminato)isopropoxide.
• Ti (IV) compounds such as titanium (IV) oxide; titanium (IV) sulfide; titanium (IV) nitrate; titanium (IV) alkoxides such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium is
• the monohydric alkoxides may have 2 to 16, or 3 to 10 carbon atoms.
• the titanium compound may be the alkoxide of a 1,2-diol or polyol.
• the 1,2-diol comprises a fatty acid mono-ester of glycerol, such as oleic acid.
• the oil soluble titanium compound may be a titanium carboxylate.
• the titanium (IV) carboxylate may be titanium neodecanoate.
• titanium phosphates such as titanium dithiophosphates (e.g., dialkyldithiophosphates) and titanium sulfonates (e.g., alkylbenzenesulfonates), or, generally, the reaction product of titanium compounds with various acid materials to form salts, such as oil-soluble salts.
• Titanium compounds can thus be derived from, among others, organic acids, alcohols, and glycols.
• Ti compounds may also exist in dimeric or oligomeric form, containing Ti--O--Ti structures.
• Such titanium materials are commercially available or can be readily prepared by appropriate synthesis techniques which will be apparent to the person skilled in the art. They may exist at room temperature as a solid or a liquid, depending on the particular compound. They may also be provided in a solution form in an appropriate inert solvent.
• the titanium can be supplied as a Ti-modified dispersant, such as a succinimide dispersant.
• a Ti-modified dispersant such as a succinimide dispersant.
• Such materials may be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride, such as an alkenyl- (or alkyl) succinic anhydride.
• the resulting titanate-succinate intermediate may be used directly or it may be reacted with any of a number of materials, such as (a) a polyamine-based succinimide/amide dispersant having free, condensable --NH functionality; (b) the components of a polyamine-based succinimide/amide dispersant, i.e., an alkenyl- (or alkyl-) succinic anhydride and a polyamine, (c) a hydroxy-containing polyester dispersant prepared by the reaction of a substituted succinic anhydride with a polyol, aminoalcohol, polyamine, or mixtures thereof.
• a polyamine-based succinimide/amide dispersant having free, condensable --NH functionality
• the components of a polyamine-based succinimide/amide dispersant i.e., an alkenyl- (or alkyl-) succinic anhydride and a polyamine
• a hydroxy-containing polyester dispersant prepared by the
• the titanate-succinate intermediate may be reacted with other agents such as alcohols, aminoalcohols, ether alcohols, polyether alcohols or polyols, or fatty acids, and the product thereof either used directly to impart Ti to a lubricant, or else further reacted with the succinic dispersants as described above.
• succinic dispersants as described above.
• 1 part (by mole) of tetraisopropyl titanate may be reacted with about 2 parts (by mole) of a polyisobutene-substituted succinic anhydride at 140-150° C for 5 to 6 hours to provide a titanium modified dispersant or intermediate.
• the resulting material (30 g) may be further reacted with a succinimide dispersant from polyisobutene-substituted succinic anhydride and a polyethylenepolyamine mixture (127 grams + diluent oil) at 150° C for 1.5 hours, to produce a titanium-modified succinimide dispersant.
• a succinimide dispersant from polyisobutene-substituted succinic anhydride and a polyethylenepolyamine mixture (127 grams + diluent oil) at 150° C for 1.5 hours, to produce a titanium-modified succinimide dispersant.
• Another titanium containing compound may be a reaction product of titanium alkoxide and C 6 to C 25 carboxylic acid.
• Suitable carboxylic acids may include, but are not limited to caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, neodecanoic acid, and the like.
• the oil soluble titanium compound may be present in the lubricating oil composition in an amount to provide from 0 to 3000 ppm titanium or 25 to about 1500 ppm titanium or about 35 ppm to 500 ppm titanium or about 50 ppm to about 300 ppm titanium, based on the total weight of the lubricating composition.
• the lubricating oil compositions herein also may optionally contain one or more viscosity index improvers.
• Suitable viscosity index improvers may include polyolefins, olefin copolymers, ethylene/propylene copolymers, polyisobutenes, hydrogenated styreneisoprene polymers, styrene/maleic ester copolymers, hydrogenated styrene/butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkyl styrenes, hydrogenated alkenyl aryl conjugated diene copolymers, or mixtures thereof.
• Viscosity index improvers may include star polymers and suitable examples are described in US Patent No. 8,999,905 B2 .
• the lubricating oil compositions herein also may optionally contain one or more dispersant viscosity index improvers in addition to a viscosity index improver or in lieu of a viscosity index improver.
• Suitable viscosity index improvers may include functionalized polyolefins, for example, ethylene-propylene copolymers that have been functionalized with the reaction product of an acylating agent (such as maleic anhydride) and an amine; polymethacrylates functionalized with an amine, or esterified maleic anhydride-styrene copolymers reacted with an amine.
• the total amount of viscosity index improver and/or dispersant viscosity index improver may be about 0 wt.% to about 20 wt.%, about 0.1 wt.% to about 15 wt.%, about 0.1 wt.% to about 13 wt.%, or 0.25 wt.% to about 12 wt.%, or about 0.5 wt.% to about 11 wt.%, or about 3.0 wt.% to about 10.5 wt.%, of the lubricating oil composition.
• additives may be selected to perform one or more functions required of a lubricating fluid. Further, one or more of the mentioned additives may be multi-functional and provide functions in addition to or other than the function prescribed herein.
• a lubricating oil composition according to the present disclosure may optionally comprise other performance additives.
• the other performance additives may be in addition to specified additives of the present disclosure and/or may comprise one or more of metal deactivators, viscosity index improvers, ashless TBN boosters, friction modifiers, antiwear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, emulsifiers, pour point depressants, seal swelling agents and mixtures thereof.
• fully-formulated lubricating oil will contain one or more of these performance additives.
• Suitable metal deactivators may include derivatives of benzotriazoles (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles, or 2-alkyldithiobenzothiazoles; foam inhibitors including copolymers of ethyl acrylate and 2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylates, polyacrylates or polyacrylamides.
• benzotriazoles typically tolyltriazole
• dimercaptothiadiazole derivatives 1,2,4-triazoles
• benzimidazoles 2-alkyldithiobenzimidazoles
• Suitable foam inhibitors include silicon-based compounds, such as siloxane.
• Suitable pour point depressants may include a polymethylmethacrylates or mixtures thereof. Pour point depressants may be present in an amount sufficient to provide from about 0 wt.% to about 5 wt.%, about 0.01 wt.% to about 3 wt.%, or about 0.01 wt.% to about 1 wt.% based upon the total weight of the lubricating oil composition.
• Suitable rust inhibitors may be a single compound or a mixture of compounds having the property of inhibiting corrosion of ferrous metal surfaces.
• Non-limiting examples of rust inhibitors useful herein include oil-soluble high molecular weight organic acids, such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, and cerotic acid, as well as oil-soluble polycarboxylic acids including dimer and trimer acids, such as those produced from tall oil fatty acids, oleic acid, and linoleic acid.
• oil-soluble high molecular weight organic acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, and cerotic acid
• oil-soluble polycarboxylic acids including dimer and trim
• Suitable corrosion inhibitors include long-chain alpha, omega-dicarboxylic acids in the molecular weight range of about 600 to about 3000 and alkenylsuccinic acids in which the alkenyl group contains about 10 or more carbon atoms such as, tetrapropenylsuccinic acid, tetradecenylsuccinic acid, and hexadecenylsuccinic acid.
• alkenylsuccinic acids include the half esters of alkenyl succinic acids having about 8 to about 24 carbon atoms in the alkenyl group with alcohols such as the polyglycols. The corresponding half amides of such alkenyl succinic acids are also useful.
• a useful rust inhibitor is a high molecular weight organic acid.
• an engine oil is devoid of a rust inhibitor.
• the rust inhibitor if present, can be used in an amount sufficient to provide about 0 wt.% to about 5 wt.%, about 0.01 wt.% to about 3 wt.%, about 0.1 wt.% to about 2 wt.%, based upon the total weight of the lubricating oil composition.
• a suitable crankcase lubricant may include additive components in the ranges listed in the following table.
• Table 2 Component Wt. % (Broad) Wt. % (Typical) Dispersant(s) 0.0 - 10% 1.0 - 8.5% Antioxidant(s) 0.0 - 5.0 0.01 - 3.0 Metal Detergent(s) 0.1 - 15.0 0.2 - 8.0 Ashless TBN booster(s) 0.0 - 1.0 0.01 - 0.5 Corrosion Inhibitor(s) 0.0 - 5.0 0.0 - 2.0 Metal dihydrocarbyl dithiophosphate(s) 0.1 - 6.0 0.1 - 4.0 Ash-free amine phosphate salt(s) 0.0 - 3.0 0.0 - 1.5 Antifoaming agent(s) 0.0 - 5.0 0.001 - 0.15 Antiwear agent(s) 0.0 - 10.0 0.0 - 5.0 Pour point depressant(s) 0.0 - 5.0 0.01 - 1.5 Visco
• the percentages of each component above represent the weight percent of each component, based upon the total weight of the lubricating oil composition.
• the remainder of the lubricating oil composition consists of one or more base oils.
• Additives used in formulating the compositions described herein may be blended into the base oil individually or in various sub-combinations. However, it may be suitable to blend all of the components concurrently using an additive concentrate (i.e., additives plus a diluent, such as a hydrocarbon solvent). Additives used in formulating the compositions described herein may be blended into the base oil individually or in various sub-combinations. However, it may be suitable to blend all of the components concurrently using an additive concentrate (i.e., additives plus a diluent, such as a hydrocarbon solvent).
• an additive concentrate i.e., additives plus a diluent, such as a hydrocarbon solvent
• the present disclosure provides novel lubricating oil blends specifically formulated for use as automotive engine lubricants.
• Embodiments of the present disclosure may provide lubricating oils suitable for engine applications that provide improvements in one or more of the following characteristics: antioxidancy, antiwear performance, rust inhibition, fuel economy, water tolerance, air entrainment, seal protection, and turbocharger deposit reduction, i.e., resisting a TCO Temperature Increase.
• Fully formulated lubricants conventionally contain an additive package, referred to herein as a dispersant/inhibitor package or DI package, that will supply the characteristics that are required in the formulations.
• DI package a dispersant/inhibitor package
• Suitable DI packages are described for example in U.S. Patent Nos. 5,204,012 and 6,034,040 for example.
• additives included in the additive package may be dispersants, seal swell agents, antioxidants, foam inhibitors, lubricity agents, rust inhibitors, corrosion inhibitors, demulsifiers, viscosity index improvers, and the like.
• these components are well known to those skilled in the art and are generally used in conventional amounts with the additives and compositions described herein.
• Each of the lubricating oil compositions contained a major amount of a base oil, a DI package and one or more viscosity index improver(s), wherein the DI package (less the viscosity index improver) provided about 8 to about 16, percent by weight of the lubricating oil composition.
• the DI package contained conventional amounts of dispersant(s), antiwear additive(s), antifoam agent(s), and antioxidant(s) as set forth in Table 3 below.
• the DI package contained a succinimide dispersant, a borated succinimide dispersant, a molybdenum-containing compound, a friction modifier, one or more antioxidants, and one or more antiwear agents (unless specified otherwise).
• turbocharger coking tests were carried out using a 2012, 1.4L Chevy Cruze calibration engine with 3 liters of test oil charge and a qualified test fuel using the 2015 version of the General Motors dexos1® Turbocharger Coking Test (TC Test).
• the TCO Temperature is measured every 30 seconds.
• the "100 cycle TCO Temperature” is the average TCO temperature of cycle 1 to cycle 100 of the TC test.
• the “1800 cycle TCO Temperature” is the average TCO temperature from cycle 1701 to cycle 1800 of the TC Test. The test is considered a "pass” if the TCO Temperature Increase from the 100 cycle TCO Temperature to the 1800 cycle TCO Temperature is less than 9.0%.
• the impact of the total metal from the one or more metal-containing detergent(s) and the amounts of nitrogen, boron and molybdenum in varying ratios on the TCO temperature and the NOACK Volatility (ASTM D-5800 at 250 °C) was determined.
• the amounts of nitrogen, boron and molybdenum were determined by ICP analysis.
• Comparative examples C-1 and C-2 are not commercially available fluids but are designed to demonstrate technical problems experienced by one skilled in the art when the lubricant oil composition is modified to meet performance needs.
• formulations C-1, C-2, I-1 and 1-2 demonstrate the relationship between the total metal from the detergent:nitrogen weight ratio ("total metal:nitrogen ratio") and the TCO Temperature Increase.
• total metal:nitrogen ratio the total metal:nitrogen ratio
• the lubricating oil composition failed the TC Test, i.e., the TCO Temperature Increase was 9.0% or greater.
• each of the lubricating oil compositions of Inventive examples 1-1 and 1-2 having a total metal:nitrogen ratio which is inside the range of less than 1.9 passed the TC Test, i.e., the TCO Temperature Increase was less than 9.0%. Accordingly, Inventive examples I-1 and 1-2 showed an improved resistance to formation of turbocharger deposits in a boosted engine.
• formulations C-1, C-2, 1-1 and 1-2 demonstrate the relationship between the total metal from the detergent:boron weight ratio ("total metal:boron ratio") and the TCO Temperature Increase.
• total metal:boron ratio the total metal:boron ratio
• the lubricating oil composition failed the TC Test, i.e., the TCO Temperature Increase was 9.0% or greater.
• each of the lubricating oil compositions of Inventive examples I-1 and I-2 having a total metal:boron ratio which is inside the range of less than 7.5 passed the TC Test, i.e., the TCO Temperature Increase was less than 9.0%. Accordingly, Inventive examples 1-1 and 1-2 showed an improved resistance to formation of turbocharger deposits in a boosted engine.
• formulations C-1, C-2, I-1 and 1-2 demonstrate the relationship between the total metal from the detergent:molybdenum weight ratio ("total metal:molybdenum ratio”) and the TCO Temperature Increase.
• total metal:molybdenum ratio is outside the range of less than 23.8
• the lubricating oil composition failed the TC Test, i.e., the TCO Temperature Increase was 9.0% or greater.
• each of the lubricating oil compositions of Inventive examples I-1 and 1-2 having a total metal:molybdenum ratio which is inside the range of less than 23.8 passed the TC Test, i.e., the TCO Temperature Increase was less than 9.0%. Accordingly, Inventive examples I-1 and 1-2 showed an improved resistance to formation of turbocharger deposits in a boosted engine.
• formulations C-1, C-2, I-1 and 1-2 demonstrate the relationship between the type of base oil and the NOACK volatility.
• NOACK volatility is outside the range of less than 11.0 wt.%, as in Comparative examples C-1 and C-2.
• each of the lubricating oil compositions of Inventive examples I-1 and 1-2 having a combination of Group II and Group III base oils gave a NOACK volatility of less than 11.0 wt.%. Accordingly, Inventive examples 1-1 and I-2 showed NOACK volatility improvement.
• formulations C-3, 1-3, I-4, 1-5, I-6 and I-7 demonstrate the relationship between the amount of the organomolybdenum nitrogen complex and the TCO Temperature Increase.
• the one or more molybdenum-containing compound(s) are present in the lubricating oil composition in an amount sufficient to provide greater than about 40 ppm by weight molybdenum to the lubricating oil composition, based on a total weight of the lubricating composition.
• the amount is outside the range of greater than about 40 ppm by weight molybdenum, as in Comparative example C-3, the lubricating oil composition failed the TC Test, i.e., the TCO Temperature Increase was 9.0% or greater.
• each of the lubricating oil compositions of Inventive examples 1-3, I-4, 1-5, I-6 and 1-7 having molybdenum in the range of greater than about 40 ppm by weight from the molybdenum-containing compounds passed the TC Test, i.e., the TCO Temperature Increase was less than 9.0%. Accordingly, Inventive examples 1-3, 1-4, 1-5, I-6 and 1-7 showed an improved resistance to formation of turbocharger deposits in a boosted engine.
• formulations C-3, C-4, 1-3, I-4, I-5, 1-6 and 1-7 demonstrate the relationship between the presence of a magnesium-containing detergent in the lubricating oil composition and the TCO Temperature Increase.
• the lubricating oil composition has a magnesium-containing detergent.
• the lubricating oil composition failed the TC Test, i.e., the TCO Temperature Increase was 9.0% or greater.
• each of the lubricating oil compositions of Inventive examples 1-3, 1-4, I-5, I-6 and 1-7 have a magnesium-containing detergent, the lubricating oil composition passed the TC Test, i.e., the TCO Temperature Increase was less than 9.0%. Accordingly, Inventive examples 1-3, I-4, I-5, 1-6 and 1-7 showed an improved resistance to formation of turbocharger deposits in a boosted engine.
• formulations C-3, 1-3, 1-4, 1-5, 1-6 and 1-7 demonstrate the relationship between the amount of the one or more overbased calcium-containing detergent(s) and the TCO Temperature Increase.
• the one or more overbased calcium-containing detergent(s) is present in the lubricating oil composition in an amount sufficient to provide less than about 1800 ppm by weight calcium to the lubricating oil composition, based on a total weight of the lubricating composition.
• the amount is outside the range of less than about 1800 ppm by weight calcium, as in Comparative example C-3, the lubricating oil composition failed the TC Test, i.e., the TCO Temperature Increase was 9.0% or greater.
• each of the lubricating oil compositions of Inventive examples I-3, I-4, I-5, I-6 and I-7 formulated within the range of less than about 1800 ppm by weight calcium passed the TC Test, i.e., the TCO Temperature Increase was less than 9.0%. Accordingly, Inventive examples 1-3, 1-4, 1-5, 1-6 and 1-7 showed an improved resistance to formation of turbocharger deposits in a boosted engine.
• formulations C-3, C-4, C-5, I-3, 1-4, I-5, 1-6 and I-7 demonstrate the relationship between the ratio of total boron in ppm by weight to total nitrogen in the lubricating oil composition and the TCO Temperature Increase.
• the lubricating oil composition has a ratio of total boron in ppm by weight to total nitrogen in ppm by weight may be less than about 0.29.
• the lubricating oil composition has a ratio of total calcium in ppm by weight to total boron in ppm by weight may be greater than about 4.9 to less than about 9.7.
• the lubricating oil composition does not have a ratio of total calcium in ppm by weight to total boron in ppm by weight may be greater than about 4.9 to less than about 9.7, as in Comparative examples C-3, C-4 and C-5, the lubricating oil composition failed the TC Test, i.e., the TCO Temperature Increase was 9.0% or greater.
• each of the lubricating oil compositions of Inventive examples I-3, I-4, 1-5, 1-6 and 1-7 have a ratio of total calcium in ppm by weight to total boron in ppm by weight may be greater than about 4.9 to less than about 9.7, the lubricating oil composition passed the TC Test, i.e., the TCO Temperature Increase was less than 9.0%. Accordingly, Inventive examples I-3, I-4, 1-5, 1-6 and 1-7 showed an improved resistance to formation of turbocharger deposits in a boosted engine.
• each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. It is intended that the specification and examples be considered as exemplary only, with a true scope of the disclosure being indicated by the following claims.
• each amount/value or range of amounts/values for each component, compound, substituent or parameter disclosed herein is to be interpreted as also being disclosed in combination with each amount/value or range of amounts/values disclosed for any other component(s), compounds(s), substituent(s) or parameter(s) disclosed herein and that any combination of amounts/values or ranges of amounts/values for two or more component(s), compounds(s), substituent(s) or parameters disclosed herein are thus also disclosed in combination with each other for the purposes of this description.
• each lower limit of each range disclosed herein is to be interpreted as disclosed in combination with each upper limit of each range and each specific value within each range disclosed herein for the same component, compounds, substituent or parameter.
• this disclosure to be interpreted as a disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range or with each specific value within each range, or by combining each upper limit of each range with each specific value within each range.

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• Lubricants (AREA)

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• 2017
  • 2017-01-27 EP EP19203284.5A patent/EP3613831A1/de active Pending
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