WO2020161635A1 - Composition and method for preventing or reducing low speed pre-ignition in direct injected spark-ignited engines - Google Patents
Composition and method for preventing or reducing low speed pre-ignition in direct injected spark-ignited engines Download PDFInfo
- Publication number
- WO2020161635A1 WO2020161635A1 PCT/IB2020/050913 IB2020050913W WO2020161635A1 WO 2020161635 A1 WO2020161635 A1 WO 2020161635A1 IB 2020050913 W IB2020050913 W IB 2020050913W WO 2020161635 A1 WO2020161635 A1 WO 2020161635A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- saturated
- unsaturated
- hydrogen atom
- lubricating oil
- Prior art date
Links
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
- C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
- C10M139/04—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00 having a silicon-to-carbon bond, e.g. silanes
-
- 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
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/08—Metal carbides or hydrides
-
- 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
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/04—Metals; Alloys
-
- 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
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/22—Compounds containing sulfur, selenium or tellurium
-
- 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
- C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
- C10M139/06—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00 having a metal-to-carbon bond
-
- 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
- C10M155/00—Lubricating compositions characterised by the additive being a macromolecular compound containing atoms of elements not provided for in groups C10M143/00 - C10M153/00
- C10M155/02—Monomer containing silicon
-
- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/05—Metals; Alloys
-
- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/061—Carbides; Hydrides; Nitrides
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/028—Overbased salts thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/26—Overbased carboxylic acid salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/26—Overbased carboxylic acid salts
- C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/28—Amides; Imides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—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
- C10M2227/04—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 having a silicon-to-carbon bond, e.g. organo-silanes
-
- 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
- C10M2227/08—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 having metal-to-carbon bonds
-
- 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
- C10M2227/08—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 having metal-to-carbon bonds
- C10M2227/083—Sn compounds
-
- 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
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/04—Siloxanes with specific structure
- C10M2229/044—Siloxanes with specific structure containing silicon-to-hydrogen bonds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/02—Groups 1 or 11
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/08—Groups 4 or 14
-
- 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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/04—Detergent property or dispersant property
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/42—Phosphor free or low phosphor content compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- 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
Definitions
- This disclosure relates to a lubricant composition that contains at least one metal hydride compound.
- the disclosure also relates to a lubricant composition that contains at least one metal or metalloid hydrogen atom donor compound for a direct injected, boosted, spark ignited internal combustion engine.
- This disclosure also relates to a method for preventing or reducing low speed pre-ignition in an engine lubricated with a formulated oil.
- the formulated oil has a composition comprising at least one oil soluble or oil dispersible metal or metalloid hydrogen atom donor compound.
- LSPI low speed pre- ignition
- the present inventors have discovered a solution for addressing the problem of LSPI through the use of a metal hydride compound.
- a lubricating engine oil composition for use in down-sized boosted engines comprising a lubricating oil base stock as a major component, one or more silicon hydrides, germanium hydrides, and tin hydrides as minor component; wherein the downsized engine ranges from 0.5 liters to 3.8 liters.
- Also disclosed is a method for preventing or reducing low speed pre-ignition in a direct injected, boosted, spark ignited internal combustion engine comprising the step of lubricating the crankcase of the engine with a lubricating oil composition comprising from about 25 to about 3000 ppm of a metal or metalloid from the metal or metalloid hydrogen atom donor from one or more silicon hydrides, germanium hydrides, and fin hydrides, based on the total weight of the lubricating oil composition.
- silicon hydrides, germanium hydrides, and tin hydrides in a lubricating engine oil composition for preventing or reducing low speed pre-ignition in a direct injected, boosted, spark ignited interna! combustion engine.
- Boosting refers to running an engine at higher intake pressures than in naturally aspirated engines. A boosted condition can be reached by use of a turbocharger (driven by exhaust) or a supercharger (driven by the engine).“Boosting” allow engine manufacturers to use smaller engines, which provide higher power densities, to provide excellent performance while reducing frictional and pumping losses.
- oil soluble or dispersible is used.
- oil soluble or dispersible is meant that an amount needed to provide the desired level of activity or performance can be incorporated by being dissolved, dispersed or suspended in an oil of lubricating viscosity. Usually, this means that at least about 0.001 % by weight of the material can be incorporated in a lubricating oil composition.
- oil soluble and dispersible particularly "stably dispersible" see U.S. Pat. No. 4,320,019 which is expressly incorporated herein by reference for relevant teachings in this regard.
- Suifated ash refers to the non-combustible residue resulting from detergents and metallic additives in lubricating oil. Suifated ash may be determined using ASTM Test D874.
- Total Base Number refers to the amount of base equivalent to milligrams of KOH in one gram of sample. Thus, higher TBN numbers reflect more alkaline products, and therefore a greater alkalinity. TBN was determined using ASTM D 2896 test. Unless otherwise specified, all percentages are in weight percent.
- the level of sulfur in the lubricating oil compositions of the present invention is less than or equal to about 0.7 wt %, based on the total weight of the lubricating oil composition, e.g., a level of sulfur of about 0.01 wt. % to about 0.70 wt. %, 0.01 to 0.6 wt.%, 0 01 to 0.5 wt.%, 0 01 to 0.4 wt.%, 0 01 to 0.3 vvt.%, 0.01 to 0.2 wt.%, 0.01 wt. % to 0.10 wt. %.
- the level of sulfur in the lubricating oil compositions of the present invention is less than or equal to about 0.60 wt. %, less than or equal to about 0.50 wt. %, less than or equal to about 0.40 wt. %, less than or equal to about 0.30 wt %, less than or equal to about 0.20 wt. %, less than or equal to about 0.10 wt. % based on the total weight of the lubricating oil composition.
- the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.12 wt. %, based on the total weight of the lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. % to about 0.12 wt. %. In one embodiment, the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about
- the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.10 wt. %, based on the total weight of the lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. % to about 0.10 wt. %. In one embodiment, the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.09 wt.
- the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.08 wt. %, based on the total weight of the lubricating oil composition, e.g , a level of phosphorus of about 0.01 wt. % to about 0.08 wt. %. In one embodiment, the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.07 wt.
- the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.05 wt. %, based on the total weight of the lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. % to about 0.05 wt. %.
- the level of sulfated ash produced by the lubricating oil compositions of the present invention is less than or equal to about 1.60 wt. % as determined by ASTM D 874, e.g , a level of sulfated ash of from about 0.10 to about 1.60 wt. % as determined by ASTM D 874. In one embodiment, the level of sulfated ash produced by the lubricating oil compositions of the present invention is less than or equal to about 1.00 wt. % as determined by ASTM D 874, e.g., a level of sulfated ash of from about 0.10 to about 1.00 wt. % as determined by ASTM D 874.
- the level of sulfated ash produced by the lubricating oil compositions of the present invention is less than or equal to about 0.80 wt. % as determined by ASTM D 874, e.g., a level of sulfated ash of from about 0.10 to about 0.80 wt. % as determined by ASTM D 874. In one embodiment, the level of sulfated ash produced by the lubricating oil compositions of the present invention is less than or equal to about 0.60 wt. % as determined by ASTM D 874, e.g., a level of sulfated ash of from about 0.10 to about 0.60 wt. % as determined by ASTM D 874.
- the present lubricating oil composition may have a total base number (TBN) of 4 to 15 g KGH/g (e.g., 5 to 12 g KGH/g, 6 to 12 mg KOH/g, or 8 to 12 g KOH/g).
- TBN total base number
- BMEP break mean effective pressure
- the engine is operated at speeds between 500 rpm and 3000 rpm, or 800 rpm to 2800 rpm, or even 1000 rpm to 2800 rpm. Additionally, the engine may be operated with a break mean effective pressure of 10 bars to 30 bars, or 12 bars to 24 bars.
- the method of the invention is such that there are less than 150 LSPI events/million combustion cycles (can also be expressed as 15 LSPI events/100,000 combustion cycles) or less than 100 LSPI events/million combustion cycles or less than 70 LSPI events/million combustion cycles or less than 60 LSPi events/milllon combustion cycles or less than 50 LSPI events/million combustion cycles or less than 40 LSPI events/million combustion cycles, less than 30 LSPI events/million combustion cycles, less than 20 LSPI events/million combustion cycles, less than 10 LSPI events/million combustion cycles, or there may be 0 LSPI events/million combustion cycles.
- the present disclosure provides a method for preventing or reducing low speed pre-ignition in a direct injected, boosted, spark ignited internal combustion engine, said method comprising the step of lubricating the crankcase of the engine with a lubricating oil composition comprising at least one metal hydride compound.
- the amount of metal from the at least one metal hydride is from about 100 to about 3000 ppm, from about 200 to about 3000 ppm, from about 250 to about 2500 ppm, from about 300 to about 2500 ppm, from about 350 to about 2500 ppm, from about 400 ppm to about 2500 ppm, from about 500 to about 2500 ppm, from about 600 to about 2500 ppm, from about 700 to about 2500 ppm, from about 700 to about 2000 ppm, from about 700 to about 1500 ppm in the lubricating oil composition. In one embodiment, the amount of metal from the metal or metalloid hydrogen atom donor compounds is no more than about 2000 ppm or no more than 1500 ppm in the lubricating oil composition.
- the method of the invention provides a reduction in the number of LSPI events of at least 10 percent, or at least 20 percent, or at least 30 percent, or at least 50 percent, or at least 60 percent, or at least 70 percent, or at least 80 percent, or at least 90 percent, or at least 95 percent, compared to an oil that does not contain the at least one metal hydride compound.
- the present disclosure provides a method for reducing the severity of low speed pre-ignition events in a direct injected, boosted, spark ignited internal combustion engine, said method comprising the step of lubricating the crankcase of the engine with a lubricating oil composition comprising at least one metal hydride compound.
- LSPi events are determined by monitoring peak cylinder pressure (PP) and the crank angle of 2% mass fraction burn (MFB02) of the fuel charge in the cylinder. When both criteria are met, it can be said that an LSPi event has occurred.
- the threshold for peak cylinder pressure varies by test, but is typically 4-5 standard deviations above the average cylinder pressure.
- the MFB02 crank angle threshold is typically 4-5 standard deviations earlier than the average MFB02 crank angle.
- LSPI events can be reported as average events per test, events per 100,000 combustion cycles, events per cycle, and/or combustion cycles per event in one embodiment, the number of LSPI events, where both MFB02 and Peak Pressure (PP) Requirements that were greater than 90 bar of pressure, is less than 15 events, less than 14 events, less than 13 events, less than 12 events, less than 11 events, less than 10 events, less than 9 events, less than 8 events, less than 7 events, less than 6 events, is less than 5 events, less than 4 events, less than 3 events, less than 2 events, or less than 1 event per 100,000 combustion cycles in one embodiment, the number of LSPI events that were greater than 90 bar was zero events, or in other words completely suppressed LSPi events greater than 90 bar.
- PP Peak Pressure
- the number of LSPi events where both MFB02 and Peak Pressure (PP) Requirements that were greater than 100 bar of pressure is less than 15 events, less than 14 events, less than 13 events, less than 12 events, less than 11 events, less than 10 events, less than 9 events, less than 8 events, less than 7 events, less than 6 events, is less than 5 events, less than 4 events, less than 3 events, less than 2 events, or less than 1 event per 100,000 combustion cycles.
- the number of LSPi events that were greater than 100 bar was zero events, or in other words completely suppressed LSPI events greater than 100 bar.
- the number of LSPi events where both MFB02 and Peak Pressure (PP) Requirements that were greater than 110 bar of pressure is less than 15 events, less than 14 events, less than 13 events, less than 12 events, less than 11 events, less than 10 events, less than 9 events, less than 8 events, less than 7 events, less than 6 events, is less than 5 events, less than 4 events, less than 3 events, less than 2 events, or less than 1 event per 100,000 combustion cycles.
- the number of LSPI events that were greater than 110 bar was zero events, or in other words completely suppressed LSPI events greater than 110 bar.
- the number of LSPI events where both MFBQ2 and Peak Pressure (PP) Requirements that were greater than 120 bar of pressure is less than 15 events, less than 14 events, less than 13 events, less than 12 events, less than 11 events, less than 10 events, less than 9 events, less than 8 events, less than 7 events, less than 6 events, is less than 5 events, less than 4 events, less than 3 events, less than 2 events, or less than 1 event per 100,000 combustion cycles in one embodiment, the number of LSPI events that were greater than 120 bar was zero events, or in other words completely suppressed very severe LSPI events (i.e., events greater than 120 bar).
- the disclosure further provides the method described herein in which the engine is fueled with a liquid hydrocarbon fuel, a liquid nonhydrocarbon fuel, or mixtures thereof.
- Lubricating oil compositions suitable for use as passenger car motor oils conventionally comprise a major amount of oil of lubricating viscosity and minor amounts of performance enhancing additives, including ash-containing compounds.
- the metals as described herein are introduced into the lubricating oil compositions used in the practice of the present disclosure by one or more metal or metalloid hydrogen atom donor compounds.
- the oil of lubricating viscosity for use in the lubricating oil compositions of this disclosure is typically present in a major amount, e.g., an amount of greater than 50 wt. %, preferably greater than about 70 wt. %, more preferably from about 80 to about 99.5 wt. % and most preferably from about 85 to about 98 wt. %, based on the total weight of the composition.
- base oil as used herein shall be understood to mean a base stock or blend of base stocks which is a lubricant component that is produced by a single manufacturer to the same specifications (independent of feed source or manufacturer's location); that meets the same manufacturer's specification; and that is identified by a unique formula, product identification number, or both.
- the base oil for use herein can be any presently known or later-discovered oil of lubricating viscosity used in formulating lubricating oil compositions for any and all such applications, e.g., engine oils, marine cylinder oils, functional fluids such as hydraulic oils, gear oils, transmission fluids, etc.
- the base oils for use herein can optionally contain viscosity index improvers, e.g., polymeric aikyimethacrylates; olefinic copolymers, e.g., an ethylene-propylene copolymer or a styrene-diene copolymer; and the like and mixtures thereof.
- viscosity index improvers e.g., polymeric aikyimethacrylates
- olefinic copolymers e.g., an ethylene-propylene copolymer or a styrene-diene copolymer; and the like and mixtures thereof.
- the viscosity of the base oil is dependent upon the application. Accordingly, the viscosity of a base oil for use herein will ordinarily range from about 2 to about 2000 centistokes (cSt) at 100° Centigrade (C.). Generally, individually the base oils used as engine oils will have a kinematic viscosity range at 100° C.
- a lubricating oil composition having an SAE Viscosity Grade of 0W, OW-4, OW-8, OW-12, OW-16, 0W-20, QW-26, 0W-30, 0W- 40, 0W-50, 0W-60, 5W, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W, 10W-20, 10W- 30, 10W-40, 10W-50, 15W, 15W-20, 15W-30, 15W-40, 30, 40 and the like.
- Group I base oils generally refer to a petroleum derived lubricating base oil having a saturates content of less than 90 wt. % (as determined by ASTM D 2007) and/or a total sulfur content of greater than 300 ppm (as determined by ASTM D 2622, ASTM D 4294, ASTM D 4297 or ASTM D 3120) and has a viscosity index (VI) of greater than or equal to 80 and less than 120 (as determined by ASTM D 2270).
- Group li base oils generally refer to a petroleum derived lubricating base oil having a total sulfur content equal to or less than 300 parts per million (ppm) (as determined by ASTM D 2622, ASTM D 4294, ASTM D 4927 or ASTM D 3120), a saturates content equal to or greater than 90 weight percent (as determined by ASTM D 2007), and a viscosity index (VI) of between 80 and 120 (as determined by ASTM D 2270).
- ppm parts per million
- Group III base oils generally refer to a petroleum derived lubricating base oil having less than 300 ppm sulfur, a saturates content greater than 90 weight percent, and a VI of 120 or greater.
- Group IV base oils are poiyalphaolefins (PAOs).
- Group V base oils include all other base oils not included in Group I, II,
- the lubricating oil composition can contain minor amounts of other base oil components.
- the lubricating oil composition can contain a minor amount of a base oil derived from natural lubricating oils, synthetic lubricating oils or mixtures thereof.
- Suitable base oil includes base stocks obtained by isomerization of synthetic wax and slack wax, as well as hydrocracked base stocks produced by hydrocracking (rather than solvent extracting) the aromatic and polar components of the crude.
- Suitable natural oils include mineral lubricating oils such as, for example, liquid petroleum oils, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types, oils derived from coal or shale, animal oils, vegetable oils (e.g., rapeseed oils, castor oils and lard oil), and the like.
- mineral lubricating oils such as, for example, liquid petroleum oils, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types, oils derived from coal or shale, animal oils, vegetable oils (e.g., rapeseed oils, castor oils and lard oil), and the like.
- Suitable synthetic lubricating oils include, but are not limited to, hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins, e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1 -hexenes), poly(l-octenes), poly(1- decenes), and the like and mixtures thereof; aikyibenzenes such as dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethy!hexyi)-benzenes, and the like; polyphenyls such as biphenyls, terphenyls, alkylated polyphenyls, and the like; alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivative, analog
- oils include, but are not limited to, oils made by polymerizing olefins of less than 5 carbon atoms such as ethylene, propylene, butylenes, isobutene, pentene, and mixtures thereof. Methods of preparing such polymer oils are well known to those skilled in the art
- Additional synthetic hydrocarbon oils include liquid polymers of alpha olefins having the proper viscosity.
- Especially useful synthetic hydrocarbon oils are the hydrogenated liquid oligomers of C6 to C12 alpha olefins such as, for example, 1- decene trimer.
- Another class of synthetic lubricating oils include, but are not limited to, aikyiene oxide polymers, i.e., homopolymers, interpolymers, and derivatives thereof where the terminal hydroxyl groups have been modified by, for example, esterification or etherification.
- oils are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxide, the alkyl and phenyl ethers of these polyoxyaikyiene polymers (e.g., methyl poly propylene glycol ether having an average molecular weight of 1 ,000, diphenyl ether of polyethylene glycol having a molecular weight of 500-1000, diethyl ether of polypropylene glycol having a molecular weight of 1 ,000-1 ,500, etc.) or mono- and poiycarboxy!ic esters thereof such as, for example, the acetic esters, mixed Cs-Cs fatty acid esters, or the C13 oxo acid diester of tetraethylene glycol.
- the alkyl and phenyl ethers of these polyoxyaikyiene polymers e.g., methyl poly propylene glycol ether having an average molecular weight of 1 ,000, diphenyl ether of polyethylene
- Yet another class of synthetic lubricating oils include, but are not limited to, the esters of dicarboxyiic acids e.g., phthalic add, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, iinoieic acid dimer, maionic acids, alkyl malonic acids, alkenyl malonic acids, etc., with a variety of alcohols, e.g., butyl alcohol, hexyl alcohol, dodecyi alcohol, 2-ethyihexyl alcohol, ethylene glycol, diethyiene glycol monoether, propylene glycol, etc.
- dicarboxyiic acids e.g., phthalic add, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid
- esters include dibutyl adipate, di(2- ethyl hexyi)sebacate, di-n-hexyl fumarate, diocfyi sebacate, diisooctyl azeiate, diisodecyl azeiate, dioctyl phthaiate, didecyl phthalate, dieicosyl sebacate, the 2- ethylhexyi diester of Iinoieic acid dimer, the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2- ethylhexanoic acid and the like.
- Esters useful as synthetic oils also include, but are not limited to, those made from carboxylic acids having from about 5 to about 12 carbon atoms with alcohols, e.g., methanol, ethanol, etc., polyols and polyol ethers such as neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythrito!, and the like.
- Silicon-based oils such as, for example, polyalkyl-, po!yary!-, poiyalkoxy- or poiyaryioxy-siloxane oils and silicate oils, comprise another useful class of synthetic lubricating oils. Specific examples of these include, but are not limited to, tetraethyl silicate, tetra-isopropyl silicate, tetra-(2-ethylhexyi) silicate, tetra ⁇ (4 ⁇ methy! ⁇ hexyl)silicate, tetra-(p-tert-butyiphenyi)silicate, hexyl-(4-metby!-2-pentoxy)disiloxane, poly(methyl)siloxanes, poly(methylphenyi)siloxanes, and the like.
- Still yet other useful synthetic lubricating oils include, but are not limited to, liquid esters of phosphorous containing acids, e.g., tricresyi phosphate, trioctyl phosphate, diethyl ester of decane phosphionic acid, etc., polymeric tetrahydrofurans and the like.
- the lubricating oil may be derived from unrefined, refined and rerefined oils, either natural, synthetic or mixtures of two or more of any of these of the type disclosed hereinabove.
- Unrefined oils are those obtained directly from a natural or synthetic source (e.g., coal, shale, or tar sands bitumen) without further purification or treatment.
- Examples of unrefined oils include, but are not limited to, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from distillation or an ester oil obtained directly from an esterification process, each of which is then used without further treatment.
- Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties.
- These purification techniques are known to those of skill in the art and include, for example, solvent extractions, secondary distillation, acid or base extraction, filtration, percolation, hydrotreating, dewaxing, etc.
- Rerefined oils are obtained by treating used oils in processes similar to those used to obtain refined oils.
- Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products.
- Lubricating oil base stocks derived from the hydroisomerization of wax may also be used, either alone or in combination with the aforesaid natural and/or synthetic base stocks.
- Such wax isomerate oil is produced by the hydroisomerization of natural or synthetic waxes or mixtures thereof over a hydroisomerization catalyst.
- Natural waxes are typically the slack waxes recovered by the solvent dewaxing of mineral oils; synthetic waxes are typically the wax produced by the Fischer-Tropsch process.
- lubricating viscosity examples include non-conventionai or unconventional base stocks that have been processed, preferably cataiyticaily, or synthesized to provide high performance lubrication characteristics.
- Metal or Metalloid Hydrogen Atom Donor Compounds The lubrication oil compositions herein can contain one or more metal or metalloid hydrogen atom donor compounds selected from the group consisting of silicon hydrides, germanium hydrides, and tin hydrides.
- the one or more metal or metalloid hydrogen atom donor compounds have the following formula: (Formula 2),
- R is a C6-C14 aryl group, saturated or unsaturated C1-C30 alkyl group, or a C3-C10 cydoalkyl group
- Re is H, a C6-C14 aryl group, saturated or unsaturated C1-C30 alkyl group, or a C3-C10 cydoalkyl group
- R7 is a C8-C14 aryl group, saturated or unsaturated C1-C30 alkyl group, or
- R is a C6-C14 aryl group, saturated or unsaturated C1-C30 alkyl group, or a C3-C10 cydoalkyl group,
- Rs is H, a C6-C14 aryl group, saturated or unsaturated C1-C30 alkyl group, or a C3-C10 cydoalkyl group
- Re is H, a C8-C14 aryl group, saturated or unsaturated C1-C30 aikyi group, or a C3-C10 cy
- the one or more metal or metalloid hydrogen atom donor compounds have the following formula:
- R4 is a C6-C14 aryl group, saturated or unsaturated C1-C30 alkyl group, or a C3-C10 cydoalkyl group
- Rs is H, a C6-G14 aryl group, saturated or unsaturated C1-C30 alkyl group, or a C3-C10 cydoalkyl group
- R7 is a C6-C14 aryl group
- the one or more metal or metalloid hydrogen atom donor compounds have the following formula:
- R4 is a C6-C14 aryl group, saturated or unsaturated C1-C30 alkyl group, or a C3-C10 cycloaikyi group
- Rs is H, a C6-G14 aryl group, saturated or unsaturated C1-C30 alkyl group, or a C3-C10 cycloalkyl group
- Re is H, a C6-C14 aryl group, saturated or unsaturated C1-C3G alkyl group, or a C3-C10 cycloalky
- the one or more metal or metalloid hydrogen atom donor compounds have the following formula:
- Rs is a C8-C14 aryl group, saturated or unsaturated C1-C30 alkyl group, or a C3-C1Q cycloalkyl group; and n is 0 or an integer from 1 to 400.
- the one or more metal or metalloid hydrogen atom donor compounds have the following formula:
- the one or more metal or metalloid hydrogen atom donor compounds have the following formula:
- Rg is a C8-C14 aryl group, saturated or unsaturated C1-C30 alkyl group; and m is an integer from 1 to 20.
- the metal or metalloid hydrogen atom donor compound is one in which the hydride is directly bonded to the metal atom.
- the metal hydride is not a silazane.
- the amount of the metal or metalloid hydrogen atom donor compound can be from about 0.001 wt. % to about 25 wt. %, from about 0.05 wt. % to about 20 wt. %, or from about 0.1 wt. % to about 15 wt. %, or from about 0.1 wt. % to about 5 wt %, from about, 0.1 wt. % to about 4.0 wt %, based on the total weight of the lubricating oil composition.
- the present disclosure provides a lubricating engine oil composition for a direct injected, boosted, spark ignited internal combustion engine comprising at least one metal hydride compound.
- the amount of metal from the at least one metal or metalloid hydrogen atom donor compound is from about 25 to about 3000 ppm, from about 100 to about 3000 ppm, from about 200 to about 3000 ppm, or from about 250 to about 2500 ppm, from about 300 to about 2500 ppm, from about 350 to about 2500 ppm, from about 400 ppm to about 2500 ppm, from about 500 to about 2500 ppm, from about 600 to about 2500 ppm, from about 700 to about 2500 ppm, from about 700 to about 2000 ppm, from about 700 to about 1500 ppm.
- the amount of metal from the metal or metalloid hydrogen atom donor compound is no more than about 2000 ppm or no more than about 1500 ppm.
- the metals in each of these embodiments being selected from silicon, germanium, tin or a combination thereof.
- the metal or metalloid hydrogen atom donor compounds can be combined with conventional lubricating oil detergent additives which contain magnesium and/or calcium.
- the calcium detergent(s) can be added in an amount sufficient to provide the lubricating oil composition from 0 to about 2400 ppm of calcium metal, from 0 to about 2200 ppm of calcium metal, from 100 to about 2000 ppm of calcium metal, from 200 to about 1800 ppm of calcium metal, or from about 100 to about 1800 ppm, or from about 200 to about 1500 ppm, or from about 300 to about 1400 ppm, or from about 400 to about 1400 ppm, of calcium metal in the lubricating oil composition.
- the magnesium detergent(s) can be added in an amount sufficient to provide the lubricating oil composition from about 100 to about 1000 ppm of magnesium metal, or from about 100 to about 600 ppm, or from about 100 to about 500 ppm, or from about 200 to about 500 ppm of magnesium metal in the lubricating oil composition.
- the metal or metalloid hydrogen atom donor compounds can be combined with conventional lubricating oil detergent additives which contain lithium.
- the lithium detergent(s) can be added in an amount sufficient to provide the lubricating oil composition from 0 to about 2400 ppm of lithium metal, from 0 to about 2200 ppm of lithium metal, from 100 to about 2000 ppm of lithium metal, from 200 to about 1800 ppm of lithium metal, or from about 100 to about 1800 ppm, or from about 200 to about 1500 ppm, or from about 300 to about 1400 ppm, or from about 400 to about 1400 ppm, of lithium metal in the lubricating oil composition.
- the metal or metalloid hydrogen atom donor compounds can be combined with conventional lubricating oil detergent additives which contain sodium.
- the sodium detergenf(s) can be added in an amount sufficient to provide the lubricating oil composition from 0 to about 2400 ppm of sodium metal, from 0 to about 2200 ppm of sodium metal, from 100 to about 2000 ppm of sodium metal, from 200 to about 1800 ppm of sodium metal, or from about 100 to about 1800 ppm, or from about 200 to about 1500 ppm, or from about 300 to about 1400 ppm, or from about 400 to about 1400 ppm, of sodium metai in the lubricating oil composition.
- the metai or metalloid hydrogen atom donor compound can be combined with conventional lubricating oil detergent additives which contain potassium in one embodiment the potassium detergent(s) can be added in an amount sufficient to provide the lubricating oil composition from 0 to about 2400 ppm of potassium metal, from 0 to about 2200 ppm of potassium metai, from 100 to about 2000 ppm of potassium metal, from 200 to about 1800 ppm of potassium metai, or from about 100 to about 1800 ppm, or from about 200 to about 1500 ppm, or from about 300 to about 1400 ppm, or from about 400 to about 1400 ppm, of potassium metal in the lubricating oil composition.
- the disclosure provides a lubricating engine oil composition
- a lubricating engine oil composition comprising a lubricating oil base stock as a major component; and at least one metai hydride compound, as a minor component; and wherein the engine exhibits greater than 50% reduced low speed pre-ignition, based on normalized low speed pre ignition (LSPI) counts per 100,000 engine cycles, engine operation at between 500 and 3,000 revolutions per minute and brake mean effective pressure (BMEP) between 10 and 30 bar, as compared to low speed pre-ignition performance achieved in an engine using a lubricating oil that does not comprise of at least one metai hydride compound.
- LSPI normalized low speed pre ignition
- BMEP brake mean effective pressure
- the disclosure provides a lubricating engine oil composition for use in a down-sized boosted engine comprising a lubricating oil base stock as a major component; and at least one metal hydride compound, as a minor component; where the downsized engine ranges from about 0.5 to about 3.6 liters, from about 0.5 to about 3.0 liters, from about 0.8 to about 3.0 liters, from about 0.5 to about 2.0 liters, or from about 1.0 to about 2.0 liters.
- the engine can have two, three, four, five or six cylinders.
- the present disclosure provides the use of a at least one metal or metalloid hydrogen atom donor compound for preventing or reducing low speed pre-ignition in a direct injected, boosted, spark ignited internal combustion engine.
- the lubricating oil composition can comprise additional lubricating oil additives.
- the lubricating oil compositions of the present disclosure may also contain other conventional additives that can impart or improve any desirable property of the lubricating oil composition in which these additives are dispersed or dissolved.
- Any additive known to a person of ordinary skill in the art may be used in the lubricating oil compositions disclosed herein.
- Some suitable additives have been described in ortier et ai. ,“Chemistry and Technology of Lubricants,” 2nd Edition, London, Springer, (1996); and Leslie R. Rudnick,“Lubricant Additives: Chemistry and Applications,” New York, Mareei Dekker (2003), both of which are incorporated herein by reference.
- the lubricating oil compositions can be blended with antioxidants, anti-wear agents, metal detergents, rust inhibitors, dehazing agents, demuisifying agents, metal deactivating agents, friction modifiers, pour point depressants, antifoaming agents, co-solvents, corrosion-inhibitors, ashiess dispersants, muitifunctional agents, dyes, extreme pressure agents and the like and mixtures thereof.
- antioxidants anti-wear agents, metal detergents, rust inhibitors, dehazing agents, demuisifying agents, metal deactivating agents, friction modifiers, pour point depressants, antifoaming agents, co-solvents, corrosion-inhibitors, ashiess dispersants, muitifunctional agents, dyes, extreme pressure agents and the like and mixtures thereof.
- additives are known and commercially available. These additives, or their analogous compounds, can be employed for the preparation of the lubricating oil compositions of the disclosure by the usual blending procedures.
- the lubricating oil composition of the present invention can contain one or more detergents.
- Metal-containing or ash-forming detergents function as both detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life.
- Detergents generally comprise a polar head with a long hydrophobic tail.
- the polar head comprises a metal salt of an acidic organic compound.
- the salts may contain a substantially stoichiometric amount of the metal in which case they are usually described as normal or neutral salts.
- a large amount of a metal base may be Incorporated by reacting excess metal compound (e.g., an oxide or hydroxide) with an acidic gas (e.g., carbon dioxide).
- Detergents that may be used include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and naphthenates and other oil-soluble carboxylates of a metal, particularly the alkali or alkaline earth metals, e.g., barium, sodium, potassium, lithium, calcium, and magnesium.
- a metal particularly the alkali or alkaline earth metals, e.g., barium, sodium, potassium, lithium, calcium, and magnesium.
- the most commonly used metals are calcium and magnesium, which may both be present in detergents used in a lubricant, and mixtures of calcium and/or magnesium with sodium.
- the lubricating oil composition of the present invention can contain one or more anti-wear agents that can reduce friction and excessive wear.
- Any anti-wear agent known by a person of ordinary skill in the art may be used in the lubricating oil composition.
- suitable anti-wear agents include zinc dithiophosphate, metal (e.g., Pb, Sb, Mo and the like) salts of dithiophosphates, metal (e.g., Zn, Pb, Sb, Mo and the like) salts of dithiocarbamates, metal (e.g., Zn, Pb, Sb and the like) salts of fatty acids, boron compounds, phosphate esters, phosphite esters, amine salts of phosphoric acid esters or thiophosphoric acid esters, reaction products of dicyciopentadiene and thiophosphoric acids and combinations thereof.
- the amount of the anti-wear agent may vary from about 0 01 wt. % to about 5 wt. %, from about 0.05 wt. % to about 3 wt. %, or from about 0.1 wt. % to about 1 wt. %, based on the total weight of the lubricating oil composition.
- the anti-wear agent is or comprises a dihydrocarbyi dithiophosphate metal salt, such as zinc dialkyl dithiophosphate compounds.
- the metal of the dihydrocarbyi dithiophosphate metal salt may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper in some embodiments, the metal is zinc in other embodiments, the aikyi group of the dihydrocarbyi dithiophosphate metal salt has from about 3 to about 22 carbon atoms, from about 3 to about 18 carbon atoms, from about 3 to about 12 carbon atoms, or from about 3 to about 8 carbon atoms. In further embodiments, the aikyi group is linear or branched.
- the amount of the dihydrocarbyi dithiophosphate metal salt including the zinc dialkyl dithiophosphate salts in the lubricating oil composition disclosed herein is measured by its phosphorus content in some embodiments, the phosphorus content of the lubricating oil composition disclosed herein is from about 0.01 wt. % to about 0.14 wt. %, based on the total weight of the lubricating oil composition.
- the lubricating oil composition of the present invention can contain one or more friction modifiers that can lower the friction between moving parts.
- Any friction modifier known by a person of ordinary skill in the art may be used in the lubricating oil composition.
- suitable friction modifiers include fatty carboxylic acids; derivatives (e.g., alcohol, esters, borated esters, amides, metal salts and the like) of fatty carboxylic acid; mono-, di- or tri-alkyl substituted phosphoric acids or phosphonic acids; derivatives (e.g., esters, amides, metal salts and the like) of mono-, di- or tri-alkyl substituted phosphoric acids or phosphonic acids; mono-, di- or tri-a!ky!
- friction modifiers include, but are not limited to, aikoxyiated fatty amines; borated fatty epoxides; fatty phosphites, fatty epoxides, fatty amines, borated aikoxyiated fatty amines, metal salts of fatty acids, fatty acid amides, glycerol esters, borated glycerol esters; and fatty imidazolines as disclosed in U.S. Patent No.
- friction modifiers obtained from a reaction product of a C4 to C75, or a G0 to G24, or a Ge to C20, fatty acid ester and a nitrogen-containing compound selected from the group consisting of ammonia, and an a!kanolamine and the like and mixtures thereof.
- the amount of the friction modifier may vary from about 0.01 wt. % to about 10 wt. %, from about 0.05 wt. % to about 5 wt. %, or from about 0.1 wt. % to about 3 wt. %, based on the total weight of the lubricating oil composition.
- the lubricating oil composition of the disclosure can contain a molybdenum-containing friction modifier.
- the molybdenum-containing friction modifier can be any one of the known molybdenum-containing friction modifiers or the known molybdenum-containing friction modifier compositions.
- Preferred molybdenum-containing friction modifier is, for example, sulfurized oxymolybdenum dithiocarbamate, sulfurized oxymoiybdenum dithiophosphafe, amine-molybdenum complex compound, oxymoiybdenum diethylate amide, and oxymolybdenum monoglyceride. Most preferred is a molybdenum dithiocarbamate friction modifier.
- the lubricating oil composition of the invention generally contains the molybdenum-containing friction modifier in an amount of 0.01 to 0.15 wt. % in terms of the molybdenum content.
- the lubricating oil composition of the invention preferably contains an organic oxidation inhibitor in an amount of 0.01-5 wt. %, preferably 0.1-3 wt. %.
- the oxidation inhibitor can be a hindered phenol oxidation inhibitor or a diaryiamine oxidation inhibitor.
- the diaryiamine oxidation inhibitor is advantageous in giving a base number originating from the nitrogen atoms.
- the hindered phenol oxidation inhibitor is advantageous in producing no NOx gas.
- hindered phenol oxidation inhibitors examples include 2,6-di-t- buty!-p-creso!, 4,4 , -methylenebis(2,6-di-t-butylphenol), 4,4'-methylenebis(6-t-butyl-o- cresol), 4 4 , -isopropylidenebis(2,6-di-t-butylphenol), 4,4'-bis(2,6-di-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4'-thiobis(2-methyl-6-t-butylphenol), 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octyl 3-(3,5 ⁇ di ⁇ t- butyl-4-hydroxyphenyl)propionate, octadecyl 3-(3,5-di-t-butyl-4- hydroxyphen
- diaryiamine oxidation inhibitors examples include alkyldiphenyiamine having a mixture of alkyl groups of 3 to 9 carbon atoms, p,p ⁇ diocfyidiphenyiamine, pbenyi-naphthy!amine, pbeny!-napbfhyiamine, alkylated- naphthylamine, and alkylated phenyl-naphthyiamine.
- the diaryiamine oxidation inhibitors can have from 1 to 3 alkyl groups.
- Each of the hindered phenol oxidation inhibitor and diaryiamine oxidation inhibitor can be employed alone or in combination. If desired, other oil soluble oxidation inhibitors can be employed in combination with the above-mentioned oxidation inhibitor(s).
- the lubricating oil composition of the invention may further contain an oxymolybdenum complex of succlnimide, particularly a sulfur-containing oxymolybdenum complex of succinimide.
- the sulfur-containing oxymolybdenum complex of succinimide can provide increased oxidation inhibition when it is employed in combination with the above-mentioned phenolic or amine oxidation inhibitors.
- additives in the form of 10 to 80 wt. % active ingredient concentrates in hydrocarbon oil, e.g. mineral lubricating oil, or other suitable solvent.
- concentrates may be diluted with 3 to 100, e.g., 5 to 40, parts by weight of lubricating oil per part by weight of the additive package in forming finished lubricants, e.g. crankcase motor oils.
- the purpose of concentrates is to make the handling of the various materials less difficult and awkward as well as to facilitate solution or dispersion in the final blend.
- lubricating oil compositions disclosed herein can be prepared by any method known to a person of ordinary skill in the art for making lubricating oils.
- the base oil can be blended or mixed with the metal or metalloid hydrogen atom donor compounds described herein.
- one or more other additives in additional to the metal or metalloid hydrogen atom donor compounds can be added.
- the metal or metalloid hydrogen atom donor compounds and the optional additives may be added to the base oil individually or
- the metal or metalloid hydrogen atom donor compounds and the optional additives are added to the base oil individually in one or more additions and the additions may be in any order in other embodiments, the metal or metalloid hydrogen atom donor compounds and the additives are added to the base oil simultaneously, optionally in the form of an additive concentrate.
- the solubilizing of the metal or metalloid hydrogen atom donor compounds or any solid additives in the base oil may be assisted by heating the mixture to a temperature from about 25 °C to about 200 °C, from about 50 °C to about 150 °C or from about 75 °C to about 125 °C.
- Any mixing or dispersing equipment known to a person of ordinary skill in the art may be used for blending, mixing or solubilizing the ingredients.
- the blending, mixing or solubilizing may be carried out with a blender, an agitator, a disperser, a mixer (e.g , planetary mixers and double planetary mixers), a
- homogenizer e.g., Gaulin homogenizers and Rannie homogenizers
- a mill e.g., colloid mill, ball mill and sand mill
- any other mixing or dispersing equipment known in the art e.g., colloid mill, ball mill and sand mill
- the lubricating oil composition disclosed herein may be suitable for use as motor oils (that is, engine oils or crankcase oils), in a spark-ignited internal combustion engine, particularly a direct Injected, boosted, engine that is susceptible to low speed pre-ignition.
- motor oils that is, engine oils or crankcase oils
- test compounds were blended in lube oil and their capacity for reducing LSPI events were determined using the test method described below.
- This engine is a turbocharged gasoline direct injection (GDI) engine.
- the Ford Ecoboost engine is operated in four-roughly 4 hour iterations.
- the engine is operated at 1750 rpm and 1.7 MPa break mean effective pressure (BMEP) with an oil sump temperature of 95 °C.
- BMEP break mean effective pressure
- the engine is run for 175,000 combustion cycles in each stage, and LSPI events are counted.
- LSPI events are determined by monitoring peak cylinder pressure (PP) and the crank angle of 2% mass fraction burn (MFB02) of the fuel charge in the cylinder. When both criteria are met, it can be said that an LSPI event has occurred.
- the threshold for peak cylinder pressure varies by test, but is typically 4-5 standard deviations above the average cylinder pressure. Likewise, the MFB02 threshold is typically 4-5 standard deviations earlier than the average MFBQ2 (represented in crank angle degrees).
- LSPI events can be reported as average events per test, events per 100,000 combustion cycles, events per cycle, and/or combustion cycles per event. The results for this test is shown below.
- the base line formulation contained a Group 2 base oil, a mixture of primary and secondary dialkyl zinc dithiophosphates in an amount to provide 737-814 ppm phosphorus to the lubricating oil composition, a mixture of poiyisobuteny! succinimide dispersants (borated and ethylene carbonate post- treated), a molybdenum succinimide complex, an alkylated dipbenylamine antioxidant, a borated friction modifier, a foam inhibitor, a pour point depressant, and an olefin copolymer viscosity index improver.
- a Group 2 base oil a mixture of primary and secondary dialkyl zinc dithiophosphates in an amount to provide 737-814 ppm phosphorus to the lubricating oil composition
- a mixture of poiyisobuteny! succinimide dispersants borated and ethylene carbonate post- treated
- a molybdenum succinimide complex an alkylated dipbenyl
- the lubricating oil compositions were blended into a 5W-30 viscosity grade oil.
- Triphenylsilane was commercially available from Millipore Sigma® or Gelest®.
- Tributyigermane was commercially available from Millipore Sigma®.
- a lubricating oil composition was prepared by adding 458 ppm of silicon from the triphenylsilane and 2164 ppm of calcium from a combination of overbased Ca sulfonate and phenate detergents to the baseline formulation.
- a lubricating oil composition was prepared by adding 2255 ppm of calcium from a combination of overbased Ca sulfonate and phenate detergents to the baseline formulation.
- Example 2 A lubricating oil composition was prepared by adding 1483 ppm of germanium from the tributyigermane and 2204 ppm of calcium from a combination of overbased Ca sulfonate and phenate detergents to the baseline formulation.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Lubricants (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP20706017.9A EP3921395A1 (en) | 2019-02-08 | 2020-02-05 | Composition and method for preventing or reducing low speed pre-ignition in direct injected spark-ignited engines |
CA3128820A CA3128820A1 (en) | 2019-02-08 | 2020-02-05 | Composition and method for preventing or reducing low speed pre-ignition in direct injected spark-ignited engines |
CN202080015348.1A CN113454190A (en) | 2019-02-08 | 2020-02-05 | Compositions and methods for preventing or reducing low speed pre-ignition in direct injection spark-ignition engines |
SG11202108514WA SG11202108514WA (en) | 2019-02-08 | 2020-02-05 | Composition and method for preventing or reducing low speed pre-ignition in direct injected spark-ignited engines |
JP2021546266A JP2022520062A (en) | 2019-02-08 | 2020-02-05 | Compositions and Methods for Preventing or Reducing Low Speed Pre-ignition in Direct Injection Spark Ignition Engines |
KR1020217027651A KR20210121189A (en) | 2019-02-08 | 2020-02-05 | Compositions and methods for preventing or reducing low speed pre-ignition in direct injection spark-ignition engines |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201962802745P | 2019-02-08 | 2019-02-08 | |
US62/802,745 | 2019-02-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2020161635A1 true WO2020161635A1 (en) | 2020-08-13 |
Family
ID=69630561
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/IB2020/050913 WO2020161635A1 (en) | 2019-02-08 | 2020-02-05 | Composition and method for preventing or reducing low speed pre-ignition in direct injected spark-ignited engines |
Country Status (8)
Country | Link |
---|---|
US (1) | US20200255762A1 (en) |
EP (1) | EP3921395A1 (en) |
JP (1) | JP2022520062A (en) |
KR (1) | KR20210121189A (en) |
CN (1) | CN113454190A (en) |
CA (1) | CA3128820A1 (en) |
SG (1) | SG11202108514WA (en) |
WO (1) | WO2020161635A1 (en) |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE619908A (en) * | ||||
US4320019A (en) | 1978-04-17 | 1982-03-16 | The Lubrizol Corporation | Multi-purpose additive compositions and concentrates containing same |
US6127481A (en) * | 1995-08-04 | 2000-10-03 | Dsm Copolymer, Inc. | Branched polyolefin polymers as additives in fuel and lubricating oil compositions |
US6372696B1 (en) | 1999-11-09 | 2002-04-16 | The Lubrizol Corporation | Traction fluid formulation |
CN102408565B (en) * | 2011-09-09 | 2013-04-24 | 汕头市骏码凯撒有限公司 | Preparation method for phenyl hydrogen-containing silicone oil |
EP3366755A1 (en) * | 2017-02-22 | 2018-08-29 | Infineum International Limited | Improvements in and relating to lubricating compositions |
US20180245008A1 (en) * | 2016-12-30 | 2018-08-30 | Exxonmobil Research And Engineering Company | Method for improving lubricant antifoaming performance and filterability |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE475195A (en) * | 1942-10-28 | |||
DE102005025450A1 (en) * | 2005-06-02 | 2006-12-07 | Wacker Chemie Ag | defoamer |
US7867957B2 (en) * | 2007-03-30 | 2011-01-11 | Nippon Oil Corporation | Lubricating oil composition |
JP5249683B2 (en) * | 2008-08-29 | 2013-07-31 | Jx日鉱日石エネルギー株式会社 | Lubricating oil composition in contact with silver-containing material |
SG192237A1 (en) * | 2011-01-31 | 2013-08-30 | Lubrizol Corp | Lubricant composition comprising anti-foam agents |
JP2014534046A (en) * | 2011-09-19 | 2014-12-18 | ダウ コーニング コーポレーションDow Corning Corporation | Silicone foam control composition and method for producing the same |
US9896634B2 (en) * | 2014-05-08 | 2018-02-20 | Exxonmobil Research And Engineering Company | Method for preventing or reducing engine knock and pre-ignition |
US20180057769A1 (en) * | 2015-07-07 | 2018-03-01 | Exxonmobil Research And Engineering Company | Method and composition for preventing or reducing engine knock and pre-ignition in high compression spark ignition engines |
-
2020
- 2020-02-05 WO PCT/IB2020/050913 patent/WO2020161635A1/en unknown
- 2020-02-05 JP JP2021546266A patent/JP2022520062A/en active Pending
- 2020-02-05 SG SG11202108514WA patent/SG11202108514WA/en unknown
- 2020-02-05 US US16/782,211 patent/US20200255762A1/en active Pending
- 2020-02-05 CA CA3128820A patent/CA3128820A1/en active Pending
- 2020-02-05 EP EP20706017.9A patent/EP3921395A1/en active Pending
- 2020-02-05 CN CN202080015348.1A patent/CN113454190A/en active Pending
- 2020-02-05 KR KR1020217027651A patent/KR20210121189A/en unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE619908A (en) * | ||||
US4320019A (en) | 1978-04-17 | 1982-03-16 | The Lubrizol Corporation | Multi-purpose additive compositions and concentrates containing same |
US6127481A (en) * | 1995-08-04 | 2000-10-03 | Dsm Copolymer, Inc. | Branched polyolefin polymers as additives in fuel and lubricating oil compositions |
US6372696B1 (en) | 1999-11-09 | 2002-04-16 | The Lubrizol Corporation | Traction fluid formulation |
CN102408565B (en) * | 2011-09-09 | 2013-04-24 | 汕头市骏码凯撒有限公司 | Preparation method for phenyl hydrogen-containing silicone oil |
US20180245008A1 (en) * | 2016-12-30 | 2018-08-30 | Exxonmobil Research And Engineering Company | Method for improving lubricant antifoaming performance and filterability |
EP3366755A1 (en) * | 2017-02-22 | 2018-08-29 | Infineum International Limited | Improvements in and relating to lubricating compositions |
Non-Patent Citations (3)
Title |
---|
AMANN ET AL., SAE 2012-01-1140 |
LESLIE R. RUDNICK: "Lubricant Additives: Chemistry and Applications", 2003, MARCEL DEKKER |
MORTIER: "Chemistry and Technology of Lubricants", 1996, SPRINGER |
Also Published As
Publication number | Publication date |
---|---|
SG11202108514WA (en) | 2021-09-29 |
CA3128820A1 (en) | 2020-08-13 |
KR20210121189A (en) | 2021-10-07 |
EP3921395A1 (en) | 2021-12-15 |
JP2022520062A (en) | 2022-03-28 |
US20200255762A1 (en) | 2020-08-13 |
CN113454190A (en) | 2021-09-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3652283B1 (en) | Lubricating oil compositions containing zirconium and method for preventing or reducing low speed pre-ignition in direct injected spark-ignited engines | |
JP2024041811A (en) | Method for preventing or reducing low speed premature ignition in direct injection spark ignition engines using silane-containing lubricating oil | |
WO2019012450A1 (en) | Lubricating oil compositions containing non-sulfur-phosphorus containing zinc compounds and method for preventing or reducing low speed pre-ignition in direct injected spark-ignited engines | |
CA3041927C (en) | Lubricating oil compositions and method for preventing or reducing low speed pre-ignition in direct injected spark-ignited engines | |
CA2894238A1 (en) | Process for producing an overbased metal detergent | |
EP3921395A1 (en) | Composition and method for preventing or reducing low speed pre-ignition in direct injected spark-ignited engines | |
US11802255B2 (en) | Composition and method for preventing or reducing low speed pre-ignition in direct injected spark-ignited engines | |
JP7329545B2 (en) | Method for preventing or reducing low-speed pre-ignition in direct-injection spark-ignited engines using manganese-containing lubricants |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 20706017 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 3128820 Country of ref document: CA |
|
ENP | Entry into the national phase |
Ref document number: 2021546266 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20217027651 Country of ref document: KR Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2020706017 Country of ref document: EP Effective date: 20210908 |