WO2019112711A1 - Procédé de prévention ou de réduction de pré-allumage à faible vitesse - Google Patents

Procédé de prévention ou de réduction de pré-allumage à faible vitesse Download PDF

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Publication number
WO2019112711A1
WO2019112711A1 PCT/US2018/058355 US2018058355W WO2019112711A1 WO 2019112711 A1 WO2019112711 A1 WO 2019112711A1 US 2018058355 W US2018058355 W US 2018058355W WO 2019112711 A1 WO2019112711 A1 WO 2019112711A1
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lubricating
oil
engine
lubricating oil
engine oil
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PCT/US2018/058355
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English (en)
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Jordan C. SMITH
Raymond G. BURNS, III
Smruti A. DANCE
Douglas E. Deckman
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Exxonmobil Research And Enginerring Company
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Publication of WO2019112711A1 publication Critical patent/WO2019112711A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • 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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • 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
    • C10M125/02—Carbon; Graphite
    • 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
    • C10M125/10—Metal oxides, hydroxides, carbonates or bicarbonates
    • 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
    • C10M2201/041—Carbon; Graphite; Carbon black
    • 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
    • C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
    • 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
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/0206—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • 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
    • C10N2010/06—Groups 3 or 13
    • 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
    • C10N2010/14—Group 7
    • 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
    • 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
    • C10N2030/08—Resistance to extreme temperature
    • 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
    • C10N2030/40—Low content or no content compositions
    • C10N2030/45—Ash-less or low ash content
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/52—Base number [TBN]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—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 method for preventing or reducing low speed pre-ignition (LSPI) in an engine lubricated with a lubricating oil by using as the lubricating oil a formulated oil that has at least one metal or metalloid present in a particular amount in the formulated oil.
  • the lubricating oils of this disclosure are useful as passenger vehicle engine oil (PVEO) products.
  • Pre-ignition in a flame propagation (or "spark-ignition”) engine describes an event wherein the air/fuel mixture in the cylinder ignites before the spark plug fires. Pre-ignition is initiated by an ignition source other than the spark, such as hot spots in the combustion chamber, a spark plug that runs too hot for the application, or carbonaceous deposits in the combustion chamber heated to incandescence by previous engine combustion events.
  • Pre-ignition can sharply increase combustion chamber temperatures and lead to rough engine operation or loss of performance.
  • Traditional methods of eliminating pre-ignition include, for example, proper spark plug selection, proper fuel/air mixture adjustment, and periodic cleaning of the combustion chambers.
  • Hardware solutions such as cooled exhaust gas recirculation (EGR) are known, but these can be costly to implement and present packaging problems.
  • Low speed pre-ignition is a type of abnormal combustion affecting engines operating at high brake mean effective pressure (BMEP) and low engine speed (RPM).
  • BMEP high brake mean effective pressure
  • RPM low engine speed
  • Downsized, downspeeded, turbocharged engines are most susceptible to operating under these engine conditions and are thus more susceptible to LSPI.
  • the concern over LSPI continues to grow.
  • This disclosure relates in part to new lubricating oil formulations which are particularly useful in internal combustion engines and, when used in internal combustion engines will prevent or minimize pre-ignition problems.
  • the lubricating oil compositions of this disclosure are useful in lubricating gasoline-fueled, spark-ignited engines.
  • the lubricant formulation chemistry of this disclosure can be used to prevent or control the detrimental effect of LSPI in engines which have already been designed or sold in the marketplace as well as future engine technology.
  • the lubricant formulation chemistry of this disclosure removes barriers for OEM technology and efficiency improvement, and enables further development of downspeeded, turbocharged gasoline engines that is currently being impeded by LSPI.
  • the lubricant formulation solution afforded by this disclosure for preventing or reducing LSPI enables product differentiation with regard to LSPI.
  • the lubricating oil formulations of this disclosure can also achieve desired performance characteristics in terms of wear, cleanliness, fuel economy, and the like.
  • formulators have increased flexibility to maximize other performance attributes, while minimizing LSPI activity.
  • This disclosure also relates in part to a method for preventing or reducing low speed pre-ignition in an engine lubricated with a lubricating oil by using as the lubricating oil a formulated oil.
  • the formulated oil has a composition comprising a lubricating oil base stock as a major component, and at least one lubricating oil additive, as a minor component.
  • the lubricating oil contains at least one metal or metalloid in an amount sufficient that, in thermogravimetric measurements of the lubricating oil by a Thermogravimetric Engine Oil Simulation Test, carbon black decomposition temperature is increased as compared to the carbon black decomposition temperature in a lubricating oil containing calcium or magnesium.
  • This disclosure further relates in part to a lubricating engine oil having a composition comprising a lubricating oil base stock as a major component, and at least one lubricating oil additive, as a minor component.
  • the lubricating engine oil contains at least one metal or metalloid in an amount sufficient that, in thermogravimetric measurements of the lubricating engine oil by a Thermogravimetric Engine Oil Simulation Test, carbon black decomposition temperature is increased as compared to the carbon black decomposition temperature in a lubricating engine oil containing calcium or magnesium.
  • prevention or reduction of LSPI can be attained in an engine lubricated with a lubricating oil by using as the lubricating oil a formulated oil having at least one metal or metalloid in an amount sufficient that, in thermogravimetric measurements of the lubricating oil by a Thermogravimetric Engine Oil Simulation Test, the carbon black decomposition temperature is increased by at least l0°C, or by at least 25°C, as compared to the carbon black decomposition temperature in a lubricating oil containing calcium or magnesium.
  • the carbon black decomposition temperature is an indicator of the catalytic activity of the metal oxide for promoting auto-ignition.
  • An increase in the decomposition temperature of a lubricant corresponds to an increase of the auto-ignition temperature of the LSPI precursors resulting in less LSPI activity.
  • lubricant compositions containing at least one of sodium, manganese, titanium, aluminum, or mixtures thereof, in combination with other typical lubricating oil additives, and in amounts from about 100 ppm to about 25,000 ppm provide improved LSPI performance.
  • Fig. 1 shows carbon decomposition temperatures of various metal oxides in a carbon black/P AO mixture, in accordance with the Examples.
  • Fig. 2 shows carbon decomposition temperatures of various metal oxides in a carbon black/base stock mixture in which barium and titanium and various base stocks were used, in accordance with the Examples.
  • Fig. 3 shows carbon decomposition temperatures of various metal oxides in a carbon black mixture in which barium and titanium and PAO base stock were used with varying concentrations of metal oxide, in accordance with the Examples.
  • minor amount or“minor component” as it relates to components included within the lubricating oils of the specification and the claims means less than 50 wt.%, or less than or equal to 40 wt.%, or less than or equal to 30 wt.%, or greater than or equal to 20 wt.%, or less than or equal to 10 wt.%, or less than or equal to 5 wt.%, or less than or equal to 2 wt.%, or less than or equal to 1 wt.%, based on the total weight of the lubricating oil.
  • phrases“essentially free” as it relates to components included within the lubricating oils of the specification and the claims means that the particular component is at 0 weight % within the lubricating oil, or alternatively is at impurity type levels within the lubricating oil (less than 100 ppm, or less than 20 ppm, or less than 10 ppm, or less than 1 ppm).
  • the phrase“other lubricating oil additives” as used in the specification and the claims means other lubricating oil additives that are not specifically recited in the particular section of the specification or the claims.
  • lubricating oil additives may include, but are not limited to, antioxidants, detergents, dispersants, antiwear additives, corrosion inhibitors, viscosity modifiers, metal passivators, pour point depressants, seal compatibility agents, antifoam agents, extreme pressure agents, friction modifiers and combinations thereof.
  • the carbon black decomposition temperature is increased by at least l0°C as compared to the carbon black decomposition temperature in a lubricating oil containing calcium or magnesium.
  • the carbon black decomposition temperature is increased by at least 25°C as compared to the carbon black decomposition temperature in a lubricating oil containing calcium or magnesium.
  • Illustrative metals and metalloids useful in the lubricating oils of this disclosure include, for example, sodium, manganese, titanium, aluminum, or mixtures thereof.
  • the at least one metal or metalloid is present in the lubricating oils of this disclosure in an amount from about 10 ppm to about 25,000 ppm, preferably from about 50 ppm to about 10,000 ppm, and more preferably from about 100 ppm to about 5,000 ppm, and more preferably from about 100 ppm to about 1,000 ppm, and more preferably from about 100 ppm to about 500 ppm.
  • the total base number (TBN), as measured by ASTM D2896, of the lubricating oil ranges from about 2 mg KOH to about 17 mg KOH, preferably from about 3 mg KOH to about 16 mg KOH, and more preferably from about 4 mg KOH to about 16 mg KOH.
  • the total sulfated ash of the lubricating oil ranges from about 0.01 to about 1 wt%, preferably from about 0.01 to about 0.8 wt%, more preferably from about 0.01 to about 0.6 wt%, more preferably from about 0.01 to about 0.4 wt%, more preferably from about 0.01 to about 0.17 wt%, more preferably from about 0.05 to about 0.16 wt%, and more preferably from about 0.1 to about 0.15 wt%.
  • the at least one metal or metalloid can be incorporated into the lubricating oil by several methods, for example, by maintaining constant ash, maintaining constant detergent metal, maintaining constant total base number (TBN), top treating, and the like.
  • the at least one metal or metalloid can be incorporated into the lubricating oil through at least one lubricating oil additive (e.g., metal-containing detergent).
  • the at least one lubricating oil additive is preferably selected from a salicylate, a carboxylate, a sulfonate, a phenate, a stearate, an oxide, and the like.
  • the at least one lubricating oil additive can have a total sulfated ash content from about 0.02 to about 0.17 wt%, preferably from about 0.05 to about 0.16 wt%, and more preferably from about 0.1 to about 0.15 wt%.
  • LSPI reduction of LSPI can be attained in an engine lubricated with a lubricating oil by using as the lubricating oil a formulated oil that has a particular base stock (e.g., Group IV base stock) and at least one metal or metalloid in an amount from about 100 ppm to about 25,000 ppm.
  • the lubricating oils of this disclosure are particularly advantageous in internal combustion engines using a variety of fuels including natural gas, gasoline, diesel, biofuels and the like, and for a variety of applications including passenger vehicle engine oils and natural gas engine oils.
  • the lubricating oils of this disclosure are particularly useful in internal combustion engines and, when used in internal combustion engines, will prevent or minimize pre-ignition problems.
  • the lubricating oil compositions of this disclosure are useful in lubricating gasoline- fueled, spark-ignited engines.
  • the lubricant formulation chemistry of this disclosure can be used to prevent or control the detrimental effect of LSPI in engines which have already been designed or sold in the marketplace as well as future engine technology.
  • the lubricant formulation chemistry of this disclosure removes barriers for OEM technology and efficiency improvement, and enables further development of downspeeded, turbocharged gasoline engines that is currently being impeded by LSPI.
  • the lubricant formulation solution afforded by this disclosure for preventing or reducing LSPI enables product differentiation with regard to LSPI.
  • Lubricating base oils that are useful in the present disclosure are both natural oils, and synthetic oils, and unconventional oils (or mixtures thereof) can be used unrefined, refined, or rerefmed (the latter is also known as reclaimed or reprocessed oil).
  • Unrefined oils are those obtained directly from a natural or synthetic source and used without added purification. These include shale oil obtained directly from retorting operations, petroleum oil obtained directly from primary distillation, and ester oil obtained directly from an esterification process. Refined oils are similar to the oils discussed for unrefined oils except refined oils are subjected to one or more purification steps to improve at least one lubricating oil property.
  • Groups I, II, III, IV, and V are broad base oil stock categories developed and defined by the American Petroleum Institute (API Publication 1509; www.API.org) to create guidelines for lubricant base oils.
  • Group I base stocks have a viscosity index of between 80 to 120 and contain greater than 0.03% sulfur and/or less than 90% saturates.
  • Group II base stocks have a viscosity index of between about 80 to 120, and contain less than or equal to 0.03% sulfur and greater than or equal to 90% saturates.
  • Group III stocks have a viscosity index greater than or equal to 120 and contain less than or equal to 0.03% sulfur and greater than or equal to 90% saturates.
  • Group IV includes polyalphaolefms (PAO).
  • Group V base stock includes base stocks not included in Groups I-IV. The table below summarizes properties of each of these five groups.
  • Natural oils include animal oils, vegetable oils (castor oil and lard oil, for example), and mineral oils. Animal and vegetable oils possessing favorable thermal oxidative stability can be used. Of the natural oils, mineral oils are preferred. Mineral oils vary widely as to their crude source, for example, as to whether they are paraffinic, naphthenic, or mixed paraffinic-naphthenic. Oils derived from coal or shale are also useful. Natural oils vary also as to the method used for their production and purification, for example, their distillation range and whether they are straight run or cracked, hydrorefmed, or solvent extracted.
  • Group II and/or Group III hydroprocessed or hydrocracked base stocks including synthetic oils such as polyalphaolefms, alkyl aromatics and synthetic esters are also well known base stock oils.
  • Synthetic oils include hydrocarbon oil.
  • Hydrocarbon oils include oils such as polymerized and interpolymerized olefins (polybutylenes, polypropylenes, propylene isobutylene copolymers, ethylene-olefin copolymers, and ethylene-alphaolefm copolymers, for example).
  • Polyalphaolefm (PAO) oil base stocks are commonly used synthetic hydrocarbon oil.
  • PAOs derived from C 6 , Cs, Cio, C 12, C14 olefins or mixtures thereof may be utilized. See U.S. Patent Nos. 4,956,122; 4,827,064; and 4,827,073.
  • the number average molecular weights of the PAOs typically vary from about 250 to about 3,000, although PAO’s may be made in viscosities up to about 150 cSt (l00°C).
  • the PAOs are typically comprised of relatively low molecular weight hydrogenated polymers or oligomers of alphaolefms which include, but are not limited to, C2 to about C32 alphaolefms with the C6 to about Ci 6 alphaolefms, such as 1 -hexene, l-octene, l-decene, l-dodecene, l-tetradocene, and the like, being preferred.
  • the preferred polyalphaolefms are poly- 1 -hexene, poly- l-octene, poly-l- decene and poly- l-dodecene and mixtures thereof and mixed olefin-derived polyolefins.
  • the dimers of higher olefins in the range of C14 to Cis may be used to provide low viscosity base stocks of acceptably low volatility.
  • the PAOs may be predominantly trimers and tetramers of the starting olefins, with minor amounts of the higher oligomers, having a viscosity range of 1.5 to 12 cSt.
  • PAO fluids of particular use may include 3.0 cSt, 3.4 cSt, and/or 3.6 cSt and combinations thereof.
  • Bi-modal mixtures of PAO fluids having a viscosity range of 1.5 to 150 cSt may be used if desired.
  • the PAO fluids may be conveniently made by the polymerization of an alphaolefin in the presence of a polymerization catalyst such as the Friedel-Crafts catalysts including, for example, aluminum trichloride, boron trifluoride or complexes of boron trifluoride with water, alcohols such as ethanol, propanol or butanol, carboxylic acids or esters such as ethyl acetate or ethyl propionate.
  • a polymerization catalyst such as the Friedel-Crafts catalysts including, for example, aluminum trichloride, boron trifluoride or complexes of boron trifluoride with water, alcohols such as ethanol, propanol or butanol, carboxylic acids or esters such as ethyl acetate or ethyl propionate.
  • a polymerization catalyst such as the Friedel-Crafts catalysts including, for example, aluminum trichloride, boro
  • Other useful lubricant oil base stocks include wax isomerate base stocks and base oils, comprising hydroisomerized waxy stocks (e.g. waxy stocks such as gas oils, slack waxes, fuels hydrocracker bottoms, etc.), hydroisomerized Fischer-Tropsch waxes, Gas-to-Liquids (GTL) base stocks and base oils, and other wax isomerate hydroisomerized base stocks and base oils, or mixtures thereof Fischer-Tropsch waxes, the high boiling point residues of Fischer-Tropsch synthesis, are highly paraffinic hydrocarbons with very low sulfur content.
  • hydroisomerized waxy stocks e.g. waxy stocks such as gas oils, slack waxes, fuels hydrocracker bottoms, etc.
  • hydroisomerized Fischer-Tropsch waxes e.g. waxy stocks such as gas oils, slack waxes, fuels hydrocracker bottoms, etc.
  • GTL Gas-to-Liquids
  • the hydroprocessing used for the production of such base stocks may use an amorphous hydrocracking/hydroisomerization catalyst, such as one of the specialized lube hydrocracking (LHDC) catalysts or a crystalline hydrocracking/hydroisomerization catalyst, preferably a zeolitic catalyst.
  • an amorphous hydrocracking/hydroisomerization catalyst such as one of the specialized lube hydrocracking (LHDC) catalysts or a crystalline hydrocracking/hydroisomerization catalyst, preferably a zeolitic catalyst.
  • LHDC specialized lube hydrocracking
  • a zeolitic catalyst preferably ZSM-48 as described in U.S. Patent No. 5,075,269, the disclosure of which is incorporated herein by reference in its entirety.
  • Processes for making hydrocracked/hydroisomerized distillates and hydrocracked/hydroisomerized waxes are described, for example, in U.S. Patent Nos.
  • Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base oils, and other wax- derived hydroisomerized (wax isomerate) base oils be advantageously used in the instant disclosure, and may have useful kinematic viscosities at l00°C of about 3 cSt to about 50 cSt, preferably about 3 cSt to about 30 cSt, more preferably about 3.5 cSt to about 25 cSt, as exemplified by GTL 4 with kinematic viscosity of about 4.0 cSt at l00°C and a viscosity index of about 141.
  • Gas-to-Liquids (GTL) base oils may have useful pour points of about -20°C or lower, and under some conditions may have advantageous pour points of about -25°C or lower, with useful pour points of about -30°C to about -40°C or lower.
  • Useful compositions of Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base oils, and wax-derived hydroisomerized base oils are recited in U.S. Patent Nos. 6,080,301; 6,090,989, and 6, 165,949 for example, and are incorporated herein in their entirety by reference.
  • the hydrocarbyl aromatics can be used as base oil or base oil component and can be any hydrocarbyl molecule that contains at least about 5% of its weight derived from an aromatic moiety such as a benzenoid moiety or naphthenoid moiety, or their derivatives.
  • These hydrocarbyl aromatics include alkyl benzenes, alkyl naphthalenes, alkyl diphenyl oxides, alkyl naphthols, alkyl diphenyl sulfides, alkylated bis-phenol A, alkylated thiodiphenol, and the like.
  • the aromatic can be mono-alkylated, dialkylated, polyalkylated, and the like.
  • the aromatic can be mono- or poly- functionalized.
  • the hydrocarbyl groups can also be comprised of mixtures of alkyl groups, alkenyl groups, alkynyl, cycloalkyl groups, cycloalkenyl groups and other related hydrocarbyl groups.
  • the hydrocarbyl groups can range from about C6 up to about C6o with a range of about Cx to about C20 often being preferred. A mixture of hydrocarbyl groups is often preferred, and up to about three such substituents may be present.
  • the hydrocarbyl group can optionally contain sulfur, oxygen, and/or nitrogen containing substituents.
  • the aromatic group can also be derived from natural (petroleum) sources, provided at least about 5% of the molecule is comprised of an above-type aromatic moiety.
  • Viscosities at l00°C of approximately 3 cSt to about 50 cSt are preferred, with viscosities of approximately 3.4 cSt to about 20 cSt often being more preferred for the hydrocarbyl aromatic component.
  • an alkyl naphthalene where the alkyl group is primarily comprised of l-hexadecene is used.
  • Other alkylates of aromatics can be advantageously used.
  • Naphthalene or methyl naphthalene, for example, can be alkylated with olefins such as octene, decene, dodecene, tetradecene or higher, mixtures of similar olefins, and the like.
  • Useful concentrations of hydrocarbyl aromatic in a lubricant oil composition can be about 2% to about 25%, preferably about 4% to about 20%, and more preferably about 4% to about 15%, depending on the application.
  • Alkylated aromatics such as the hydrocarbyl aromatics of the present disclosure may be produced by well-known Friedel-Crafts alkylation of aromatic compounds. See Friedel-Crafts and Related Reactions, Olah, G. A. (ed.), Inter-science Publishers, New York, 1963.
  • an aromatic compound such as benzene or naphthalene
  • an olefin, alkyl halide or alcohol in the presence of a Friedel-Crafts catalyst. See Friedel-Crafts and Related Reactions, Vol. 2, part 1, chapters 14, 17, and 18, See Olah, G. A. (ed.), Inter-science Publishers, New York, 1964.
  • catalysts are known to one skilled in the art.
  • the choice of catalyst depends on the reactivity of the starting materials and product quality requirements.
  • strong acids such as AlCb, BF 3 , or HF may be used.
  • milder catalysts such as FeCb or SnCb are preferred.
  • Newer alkylation technology uses zeolites or solid super acids.
  • Esters comprise a useful base stock. Additive solvency and seal compatibility characteristics may be secured by the use of esters such as the esters of dibasic acids with monoalkanols and the polyol esters of mono-carboxylic acids.
  • Esters of the former type include, for example, the esters of dicarboxylic acids such as phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, etc., with a variety of alcohols such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, etc.
  • dicarboxylic acids such as phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, etc
  • esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n- hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, etc.
  • Particularly useful synthetic esters are those which are obtained by reacting one or more polyhydric alcohols, preferably the hindered polyols (such as the neopentyl polyols, e.g., neopentyl glycol, trimethylol ethane, 2-methyl-2-propyl-l, 3 -propanediol, trimethylol propane, pentaerythritol and dipentaerythritol) with alkanoic acids containing at least about 4 carbon atoms, preferably Cs to C30 acids such as saturated straight chain fatty acids including caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, and behenic acid, or the corresponding branched chain fatty acids or unsaturated fatty acids such as oleic acid, or mixtures of any of these materials.
  • the hindered polyols such as the neopentyl polyo
  • Suitable synthetic ester components include the esters of trimethylol propane, trimethylol butane, trimethylol ethane, pentaerythritol and/or dipentaerythritol with one or more monocarboxylic acids containing from about 5 to about 10 or more carbon atoms. These esters are widely available commercially, for example, the Mobil P-41 and P-51 esters of ExxonMobil Chemical Company.
  • Preferred synthetic esters useful in this disclosure have a kinematic viscosity at l00°C of about 3 cSt to about 50 cSt, preferably about 3 cSt to about 30 cSt, more preferably about 3.5 cSt to about 25 cSt, and even more preferably about 2 cSt to about 8 cSt.
  • Group V base oils useful in this disclosure preferably comprise an ester at a concentration of about 2% to about 20%, preferably from about 5% to about 15%.
  • esters derived from renewable material such as coconut, palm, rapeseed, soy, sunflower and the like. These esters may be monoesters, di-esters, polyol esters, complex esters, or mixtures thereof. These esters are widely available commercially, for example, the Mobil P-51 ester of ExxonMobil Chemical Company.
  • Engine oil formulations containing renewable esters are included in this disclosure.
  • the renewable content of the ester is typically greater than about 70 weight percent, preferably more than about 80 weight percent and most preferably more than about 90 weight percent.
  • Other useful fluids of lubricating viscosity include non-conventional or unconventional base stocks that have been processed, preferably catalytically, or synthesized to provide high performance lubrication characteristics.
  • Non-conventional or unconventional base stocks/base oils include one or more of a mixture of base stock(s) derived from one or more Gas-to-Liquids (GTL) materials, as well as isomerate/isodewaxate base stock(s) derived from natural wax or waxy feeds, mineral and or non mineral oil waxy feed stocks such as slack waxes, natural waxes, and waxy stocks such as gas oils, waxy fuels hydrocracker bottoms, waxy raffinate, hydrocrackate, thermal crackates, or other mineral, mineral oil, or even non-petroleum oil derived waxy materials such as waxy materials received from coal liquefaction or shale oil, and mixtures of such base stocks.
  • GTL Gas-to-Liquids
  • GTL materials are materials that are derived via one or more synthesis, combination, transformation, rearrangement, and/or degradation/deconstructive processes from gaseous carbon- containing compounds, hydrogen-containing compounds and/or elements as feed stocks such as hydrogen, carbon dioxide, carbon monoxide, water, methane, ethane, ethylene, acetylene, propane, propylene, propyne, butane, butylenes, and butynes.
  • GTL base stocks and/or base oils are GTL materials of lubricating viscosity that are generally derived from hydrocarbons; for example, waxy synthesized hydrocarbons, that are themselves derived from simpler gaseous carbon-containing compounds, hydrogen-containing compounds and/or elements as feed stocks.
  • GTL base stock(s) and/or base oil(s) include oils boiling in the lube oil boiling range (1) separated/fractionated from synthesized GTL materials such as, for example, by distillation and subsequently subjected to a final wax processing step which involves either or both of a catalytic dewaxing process, or a solvent dewaxing process, to produce lube oils of reduced/low pour point; (2) synthesized wax isomerates, comprising, for example, hydrodewaxed or hydroisomerized cat and/or solvent dewaxed synthesized wax or waxy hydrocarbons; (3) hydrodewaxed or hydroisomerized cat and/or solvent dewaxed Fischer-Tropsch (F-T) material (i.e., hydrocarbons, waxy hydrocarbons, waxes and possible analogous oxygenates); preferably hydrodewaxed or hydroisomerized/followed by cat and/or solvent dewaxing dewaxed F-T waxy hydrocarbons, or hydrodewaxed
  • GTL base stock(s) and/or base oil(s) derived from GTL materials are characterized typically as having kinematic viscosities at l00°C of from about 2 mm 2 /s to about 50 mm 2 /s (ASTM D445). They are further characterized typically as having pour points of -5°C to about -40°C or lower (ASTM D97). They are also characterized typically as having viscosity indices of about 80 to about 140 or greater (ASTM D2270).
  • GTL base stock and/or base oil and/or wax isomerate base stock and/or base oil is to be understood as embracing individual fractions of such materials of wide viscosity range as recovered in the production process, mixtures of two or more of such fractions, as well as mixtures of one or two or more low viscosity fractions with one, two or more higher viscosity fractions to produce a blend wherein the blend exhibits a target kinematic viscosity.
  • the GTL material, from which the GTL base stock(s) and/or base oil(s) is/are derived is preferably an F-T material (i.e., hydrocarbons, waxy hydrocarbons, wax).
  • the GTL base stock(s) and/or base oil(s) are typically highly paraffinic (>90% saturates), and may contain mixtures of monocycloparaffms and multicycloparaffms in combination with non-cyclic isoparaffins.
  • the ratio of the naphthenic (i.e., cycloparaffm) content in such combinations varies with the catalyst and temperature used.
  • GTL base stock(s) and/or base oil(s) and hydrodewaxed, or hydroisomerized/cat (and/or solvent) dewaxed base stock(s) and/or base oil(s) typically have very low sulfur and nitrogen content, generally containing less than about 10 ppm, and more typically less than about 5 ppm of each of these elements.
  • the sulfur and nitrogen content of GTL base stock(s) and/or base oil(s) obtained from F-T material, especially F-T wax, is essentially nil.
  • the absence of phosphorous and aromatics make this material especially suitable for the formulation of low sulfur, sulfated ash, and phosphorus (low SAP) products.
  • Base oils for use in the formulated lubricating oils useful in the present disclosure are any of the variety of oils corresponding to API Group I, Group II, Group III, Group IV, and Group V oils and mixtures thereof, preferably API Group II, Group III, Group IV, and Group V oils and mixtures thereof, more preferably the Group III to Group V base oils due to their exceptional volatility, stability, viscometric and cleanliness features.
  • the base oil constitutes the major component of the engine oil lubricant composition of the present disclosure and typically is present in an amount ranging from about 50 to about 99 weight percent, preferably from about 70 to about 95 weight percent, and more preferably from about 85 to about 95 weight percent, based on the total weight of the composition.
  • the base oil may be selected from any of the synthetic or natural oils typically used as crankcase lubricating oils for spark-ignited and compression-ignited engines.
  • the base oil conveniently has a kinematic viscosity, according to ASTM standards, of about 2.5 cSt to about 12 cSt (or mm 2 /s) at l00°C and preferably of about 2.5 cSt to about 9 cSt (or mm 2 /s) at l00°C.
  • a kinematic viscosity according to ASTM standards, of about 2.5 cSt to about 12 cSt (or mm 2 /s) at l00°C and preferably of about 2.5 cSt to about 9 cSt (or mm 2 /s) at l00°C.
  • Mixtures of synthetic and natural base oils may be used if desired.
  • Mixtures of Group III, IV, and V may be preferably used if desired.
  • the formulated lubricating oil useful in the present disclosure may additionally contain one or more of the other commonly used lubricating oil performance additives including but not limited to antiwear agents, dispersants, detergents, corrosion inhibitors, rust inhibitors, metal deactivators, extreme pressure additives, anti-seizure agents, wax modifiers, viscosity index improvers, viscosity modifiers, fluid-loss additives, seal compatibility agents, friction modifiers, lubricity agents, anti-staining agents, chromophoric agents, defoamants, demulsifiers, emulsifiers, densifiers, wetting agents, gelling agents, tackiness agents, colorants, and others.
  • the other commonly used lubricating oil performance additives including but not limited to antiwear agents, dispersants, detergents, corrosion inhibitors, rust inhibitors, metal deactivators, extreme pressure additives, anti-seizure agents, wax modifiers, viscosity index improvers, viscosity modifiers
  • a metal alkylthiophosphate and more particularly a metal dialkyl dithio phosphate in which the metal constituent is zinc, or zinc dialkyl dithio phosphate can be a useful component of the lubricating oils of this disclosure.
  • ZDDP can be derived from primary alcohols, secondary alcohols or mixtures thereof.
  • ZDDP compounds generally are of the formula
  • R 1 and R 2 are C I -C I X alkyl groups, preferably C2-C12 alkyl groups. These alkyl groups may be straight chain or branched.
  • Alcohols used in the ZDDP can be propanol, 2-propanol, butanol, secondary butanol, pentanols, hexanols such as 4-methyl-2-pentanol, n-hexanol, n-octanol, 2-ethyl hexanol, alkylated phenols, and the like. Mixtures of secondary alcohols or of primary and secondary alcohol can be preferred. Alkyl aryl groups may also be used.
  • Preferable zinc dithiophosphates which are commercially available include secondary zinc dithiophosphates such as those available from for example, The Lubrizol Corporation under the trade designations“LZ 677A”,“LZ 1095” and“LZ 1371”, from for example Chevron Oronite under the trade designation“OLOA 262” and from for example Afton Chemical under the trade designation“HITEC 7169”.
  • the ZDDP is typically used in amounts of from about 0.3 weight percent to about 1.5 weight percent, preferably from about 0.4 weight percent to about 1.2 weight percent, more preferably from about 0.5 weight percent to about 1.0 weight percent, and even more preferably from about 0.6 weight percent to about 0.8 weight percent, based on the total weight of the lubricating oil, although more or less can often be used advantageously.
  • the ZDDP is a secondary ZDDP and present in an amount of from about 0.6 to 1.0 weight percent of the total weight of the lubricating oil.
  • Dispersants help keep these byproducts in solution, thus diminishing their deposition on metal surfaces.
  • Dispersants used in the formulation of the lubricating oil may be ashless or ash-forming in nature.
  • the dispersant is ashless.
  • So called ashless dispersants are organic materials that form substantially no ash upon combustion.
  • non-metal-containing or borated metal-free dispersants are considered ashless.
  • metal-containing detergents discussed above form ash upon combustion.
  • Suitable dispersants typically contain a polar group attached to a relatively high molecular weight hydrocarbon chain.
  • the polar group typically contains at least one element of nitrogen, oxygen, or phosphorus.
  • Typical hydrocarbon chains contain 50 to 400 carbon atoms.
  • a particularly useful class of dispersants are the (poly)alkenyl succinic derivatives, typically produced by the reaction of a long chain hydrocarbyl substituted succinic compound, usually a hydrocarbyl substituted succinic anhydride, with a polyhydroxy or polyamino compound.
  • the long chain hydrocarbyl group constituting the oleophilic portion of the molecule which confers solubility in the oil, is normally a polyisobutylene group.
  • Many examples of this type of dispersant are well known commercially and in the literature. Exemplary ET.S. patents describing such dispersants are U.S. Patent Nos.
  • Hydrocarbyl-substituted succinic acid and hydrocarbyl-substituted succinic anhydride derivatives are useful dispersants.
  • succinimide, succinate esters, or succinate ester amides prepared by the reaction of a hydrocarbon-substituted succinic acid compound preferably having at least 50 carbon atoms in the hydrocarbon substituent, with at least one equivalent of an alkylene amine are particularly useful.
  • Succinimides are formed by the condensation reaction between hydrocarbyl substituted succinic anhydrides and amines. Molar ratios can vary depending on the polyamine. For example, the molar ratio of hydrocarbyl substituted succinic anhydride to TEPA can vary from about 1 : 1 to about 5:1. Representative examples are shown in ET.S. Patent Nos. 3,087,936; 3,172,892; 3,219,666; 3,272,746; 3,322,670; and 3,652,616, 3,948,800; and Canada Patent No. 1,094,044.
  • Succinate esters are formed by the condensation reaction between hydrocarbyl substituted succinic anhydrides and alcohols or polyols. Molar ratios can vary depending on the alcohol or polyol used. For example, the condensation product of a hydrocarbyl substituted succinic anhydride and pentaerythritol is a useful dispersant.
  • Succinate ester amides are formed by condensation reaction between hydrocarbyl substituted succinic anhydrides and alkanol amines.
  • suitable alkanol amines include ethoxylated polyalkylpolyamines, propoxylated polyalkylpolyamines and polyalkenylpolyamines such as polyethylene polyamines.
  • propoxylated hexamethylenediamine Representative examples are shown in ET.S. Patent No. 4,426,305.
  • the molecular weight of the hydrocarbyl substituted succinic anhydrides used in the preceding paragraphs will typically range between 800 and 2,500 or more.
  • the above products can be post-reacted with various reagents such as sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid.
  • the above products can also be post reacted with boron compounds such as boric acid, borate esters or highly borated dispersants, to form borated dispersants generally having from about 0.1 to about 5 moles of boron per mole of dispersant reaction product.
  • Mannich base dispersants are made from the reaction of alkylphenols, formaldehyde, and amines. See ET.S. Patent No. 4,767,551, which is incorporated herein by reference. Process aids and catalysts, such as oleic acid and sulfonic acids, can also be part of the reaction mixture. Molecular weights of the alkylphenols range from 800 to 2,500. Representative examples are shown in U.S. Patent Nos. 3,697,574; 3,703,536; 3,704,308; 3,751,365; 3,756,953; 3,798,165; and 3,803,039.
  • Typical high molecular weight aliphatic acid modified Mannich condensation products useful in this disclosure can be prepared from high molecular weight alkyl-substituted hydroxyaromatics or HNR2 group-containing reactants.
  • Hydrocarbyl substituted amine ashless dispersant additives are well known to one skilled in the art; see, for example, U.S. Patent Nos. 3,275,554; 3,438,757; 3,565,804; 3,755,433, 3,822,209, and 5,084,197.
  • Preferred dispersants include borated and non-borated succinimides, including those derivatives from mono-succinimides, bis-succinimides, and/or mixtures of mono- and bis- succinimides, wherein the hydrocarbyl succinimide is derived from a hydrocarbylene group such as polyisobutylene having a Mn of from about 500 to about 5000, or from about 1000 to about 3000, or about 1000 to about 2000, or a mixture of such hydrocarbylene groups, often with high terminal vinylic groups.
  • Other preferred dispersants include succinic acid-esters and amides, alkylphenol-polyamine-coupled Mannich adducts, their capped derivatives, and other related components.
  • Polymethacrylate or polyacrylate derivatives are another class of dispersants. These dispersants are typically prepared by reacting a nitrogen containing monomer and a methacrylic or acrylic acid esters containing 5 -25 carbon atoms in the ester group. Representative examples are shown in U.S. Patent Nos. 2, 100, 993, and 6,323,164. Polymethacrylate and polyacrylate dispersants are normally used as multifunctional viscosity modifiers. The lower molecular weight versions can be used as lubricant dispersants or fuel detergents.
  • Illustrative preferred dispersants useful in this disclosure include those derived from polyalkenyl-substituted mono- or dicarboxylic acid, anhydride or ester, which dispersant has a polyalkenyl moiety with a number average molecular weight of at least 900 and from greater than 1.3 to 1.7, preferably from greater than 1.3 to 1.6, most preferably from greater than 1.3 to 1.5, functional groups (mono- or dicarboxylic acid producing moieties) per polyalkenyl moiety (a medium functionality dispersant).
  • Functionality (F) can be determined according to the following formula:
  • SAP is the saponification number (i.e., the number of milligrams of KOH consumed in the complete neutralization of the acid groups in one gram of the succinic-containing reaction product, as determined according to ASTM D94); M n is the number average molecular weight of the starting olefin polymer; and A.I. is the percent active ingredient of the succinic-containing reaction product (the remainder being unreacted olefin polymer, succinic anhydride and diluent).
  • the polyalkenyl moiety of the dispersant may have a number average molecular weight of at least 900, suitably at least 1500, preferably between 1800 and 3000, such as between 2000 and 2800, more preferably from about 2100 to 2500, and most preferably from about 2200 to about 2400.
  • the molecular weight of a dispersant is generally expressed in terms of the molecular weight of the polyalkenyl moiety. This is because the precise molecular weight range of the dispersant depends on numerous parameters including the type of polymer used to derive the dispersant, the number of functional groups, and the type of nucleophilic group employed.
  • Polymer molecular weight can be determined by various known techniques.
  • One convenient method is gel permeation chromatography (GPC), which additionally provides molecular weight distribution information (see W. W. Yau, J. J. Kirkland and D. D. Bly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979).
  • GPC gel permeation chromatography
  • Another useful method for determining molecular weight, particularly for lower molecular weight polymers is vapor pressure osmometry (e.g., ASTM D3592).
  • the polyalkenyl moiety in a dispersant preferably has a narrow molecular weight distribution (MWD), also referred to as polydispersity, as determined by the ratio of weight average molecular weight (M w ) to number average molecular weight (M n ).
  • MWD molecular weight distribution
  • M w weight average molecular weight
  • M n number average molecular weight
  • Suitable polymers have a polydispersity of from about 1.5 to 2.1, preferably from about 1.6 to about 1.8.
  • Suitable polyalkenes employed in the formation of the dispersants include homopolymers, interpolymers or lower molecular weight hydrocarbons.
  • such polymers comprise interpolymers of ethylene and at least one alpha-olefin of the above formula, wherein R 1 is alkyl of from 1 to 18 carbon atoms, and more preferably is alkyl of from 1 to 8 carbon atoms, and more preferably still of from 1 to 2 carbon atoms.
  • Another useful class of polymers is polymers prepared by cationic polymerization of monomers such as isobutene and styrene.
  • monomers such as isobutene and styrene.
  • Common polymers from this class include polyisobutenes obtained by polymerization of a C 4 refinery stream having a butene content of 35 to 75% by wt., and an isobutene content of 30 to 60% by wt.
  • a preferred source of monomer for making poly-n-butenes is petroleum feedstreams such as Raffinate II. These feed stocks are disclosed in the art such as in U.S. Pat. No. 4,952,739.
  • a preferred embodiment utilizes polyisobutylene prepared from a pure isobutylene stream or a Raffinate I stream to prepare reactive isobutylene polymers with terminal vinylidene olefins.
  • Polyisobutene polymers that may be employed are generally based on a polymer chain of from 1500 to 3000.
  • the dispersant(s) are preferably non-polymeric (e.g., mono- or bis-succinimides). Such dispersants can be prepared by conventional processes such as disclosed in U.S. Patent Application Publication No. 2008/0020950, the disclosure of which is incorporated herein by reference.
  • the dispersant(s) can be borated by conventional means, as generally disclosed in U.S. Patent Nos. 3,087,936, 3,254,025 and 5,430,105.
  • Such dispersants may be used in an amount of about 0.01 to 20 weight percent or 0.01 to 10 weight percent, preferably about 0.5 to 8 weight percent, or more preferably 0.5 to 4 weight percent. Or such dispersants may be used in an amount of about 2 to 12 weight percent, preferably about 4 to 10 weight percent, or more preferably 6 to 9 weight percent. On an active ingredient basis, such additives may be used in an amount of about 0.06 to 14 weight percent, preferably about 0.3 to 6 weight percent.
  • the hydrocarbon portion of the dispersant atoms can range from C60 to Cioo, or from C70 to C300, or from C70 to C200. These dispersants may contain both neutral and basic nitrogen, and mixtures of both.
  • Dispersants can be end-capped by borates and/or cyclic carbonates.
  • Nitrogen content in the finished oil can vary from about 200 ppm by weight to about 2000 ppm by weight, preferably from about 200 ppm by weight to about 1200 ppm by weight.
  • Basic nitrogen can vary from about 100 ppm by weight to about 1000 ppm by weight, preferably from about 100 ppm by weight to about 600 ppm by weight.
  • the dispersant concentrations are given on an“as delivered” basis.
  • the active dispersant is delivered with a process oil.
  • The“as delivered” dispersant typically contains from about 20 weight percent to about 80 weight percent, or from about 40 weight percent to about 60 weight percent, of active dispersant in the“as delivered” dispersant product.
  • Illustrative detergents useful in this disclosure include, for example, alkali metal detergents, alkaline earth metal detergents, or mixtures of one or more alkali metal detergents and one or more alkaline earth metal detergents.
  • a typical detergent is an anionic material that contains a long chain hydrophobic portion of the molecule and a smaller anionic or oleophobic hydrophilic portion of the molecule.
  • the anionic portion of the detergent is typically derived from an organic acid such as a sulfur-containing acid, carboxylic acid (e.g., salicylic acid), phosphorus-containing acid, phenol, or mixtures thereof.
  • the counterion is typically an alkaline earth or alkali metal.
  • the detergent can be overbased as described herein.
  • the detergent is preferably a metal salt of an organic or inorganic acid, a metal salt of a phenol, or mixtures thereof.
  • the metal is preferably selected from an alkali metal, an alkaline earth metal, and mixtures thereof.
  • the organic or inorganic acid is selected from an aliphatic organic or inorganic acid, a cycloaliphatic organic or inorganic acid, an aromatic organic or inorganic acid, and mixtures thereof.
  • the metal is preferably selected from an alkali metal, an alkaline earth metal, and mixtures thereof. More preferably, the metal is selected from calcium (Ca), magnesium (Mg), and mixtures thereof.
  • the organic acid or inorganic acid is preferably selected from a sulfur-containing acid, a carboxylic acid, a phosphorus-containing acid, and mixtures thereof.
  • the metal salt of an organic or inorganic acid or the metal salt of a phenol comprises calcium phenate, calcium sulfonate, calcium salicylate, magnesium phenate, magnesium sulfonate, magnesium salicylate, an overbased detergent, and mixtures thereof.
  • Salts that contain a substantially stochiometric amount of the metal are described as neutral salts and have a total base number (TBN, as measured by ASTM D2896) of from 0 to 80.
  • TBN total base number
  • Many compositions are overbased, containing large amounts of a metal base that is achieved by reacting an excess of a metal compound (a metal hydroxide or oxide, for example) with an acidic gas (such as carbon dioxide).
  • Useful detergents can be neutral, mildly overbased, or highly overbased. These detergents can be used in mixtures of neutral, overbased, highly overbased calcium salicylate, sulfonates, phenates and/or magnesium salicylate, sulfonates, phenates.
  • the TBN ranges can vary from low, medium to high TBN products, including as low as 0 to as high as 600.
  • the TBN delivered by the detergent is between 1 and 20. More preferably between 1 and 12.
  • Mixtures of low, medium, high TBN can be used, along with mixtures of calcium and magnesium metal based detergents, and including sulfonates, phenates, salicylates, and carboxylates.
  • a detergent mixture with a metal ratio of 1, in conjunction of a detergent with a metal ratio of 2, and as high as a detergent with a metal ratio of 5, can be used. Borated detergents can also be used.
  • Alkaline earth phenates are another useful class of detergent. These detergents can be made by reacting alkaline earth metal hydroxide or oxide (CaO, Ca(OH) 2 , BaO, Ba(OH) 2 , MgO, Mg(OH) 2 , for example) with an alkyl phenol or sulfurized alkylphenol.
  • alkyl phenol or sulfurized alkylphenol Useful alkyl groups include straight chain or branched C1-C3 0 alkyl groups, preferably, C 4 -C 2 o or mixtures thereof. Examples of suitable phenols include isobutylphenol, 2-ethylhexylphenol, nonylphenol, dodecyl phenol, and the like.
  • starting alkylphenols may contain more than one alkyl substituent that are each independently straight chain or branched and can be used from 0.5 to 6 weight percent.
  • the sulfurized product may be obtained by methods well known in the art. These methods include heating a mixture of alkylphenol and sulfurizing agent (including elemental sulfur, sulfur halides such as sulfur dichloride, and the like) and then reacting the sulfurized phenol with an alkaline earth metal base.
  • metal salts of carboxylic acids are preferred detergents.
  • carboxylic acid detergents may be prepared by reacting a basic metal compound with at least one carboxylic acid and removing free water from the reaction product. These compounds may be overbased to produce the desired TBN level.
  • Detergents made from salicylic acid are one preferred class of detergents derived from carboxylic acids.
  • Useful salicylates include long chain alkyl salicylates.
  • One useful family of compositions is of the formula
  • R is an alkyl group having 1 to about 30 carbon atoms
  • n is an integer from 1 to 4
  • M is an alkaline earth metal.
  • Preferred R groups are alkyl chains of at least C11, preferably C1 3 or greater. R may be optionally substituted with substituents that do not interfere with the detergent’ s function.
  • M is preferably, calcium, magnesium, barium, or mixtures thereof. More preferably, M is calcium.
  • Hydrocarbyl-substituted salicylic acids may be prepared from phenols by the Kolbe reaction (see U.S. Patent No. 3,595,791).
  • the metal salts of the hydrocarbyl-substituted salicylic acids may be prepared by double decomposition of a metal salt in a polar solvent such as water or alcohol.
  • Alkaline earth metal phosphates are also used as detergents and are known in the art.
  • Detergents may be simple detergents or what is known as hybrid or complex detergents. The latter detergents can provide the properties of two detergents without the need to blend separate materials. See U.S. Patent No. 6,034,039.
  • Preferred detergents include calcium sulfonates, magnesium sulfonates, calcium salicylates, magnesium salicylates, calcium phenates, magnesium phenates, and other related components (including borated detergents), and mixtures thereof.
  • Preferred mixtures of detergents include magnesium sulfonate and calcium salicylate, magnesium sulfonate and calcium sulfonate, magnesium sulfonate and calcium phenate, calcium phenate and calcium salicylate, calcium phenate and calcium sulfonate, calcium phenate and magnesium salicylate, calcium phenate and magnesium phenate.
  • Overbased detergents are also preferred.
  • the detergent concentration in the lubricating oils of this disclosure can range from about 0.5 to about 6.0 weight percent, preferably about 0.6 to 5.0 weight percent, and more preferably from about 0.8 weight percent to about 4.0 weight percent, based on the total weight of the lubricating oil.
  • the detergent concentrations are given on an“as delivered” basis.
  • the active detergent is delivered with a process oil.
  • The“as delivered” detergent typically contains from about 20 weight percent to about 100 weight percent, or from about 40 weight percent to about 60 weight percent, of active detergent in the“as delivered” detergent product.
  • Viscosity index improvers also known as VI improvers, viscosity modifiers, and viscosity improvers
  • VI improvers also known as VI improvers, viscosity modifiers, and viscosity improvers
  • Viscosity index improvers provide lubricants with high and low temperature operability. These additives impart shear stability at elevated temperatures and acceptable viscosity at low temperatures.
  • Suitable viscosity index improvers include high molecular weight hydrocarbons, polyesters and viscosity index improver dispersants that function as both a viscosity index improver and a dispersant.
  • Typical molecular weights of these polymers are between about 10,000 to 1,500,000, more typically about 20,000 to 1,200,000, and even more typically between about 50,000 and 1,000,000.
  • suitable viscosity index improvers are linear or star-shaped polymers and copolymers of methacrylate, butadiene, olefins, or alkylated styrenes.
  • Polyisobutylene is a commonly used viscosity index improver.
  • Another suitable viscosity index improver is polymethacrylate (copolymers of various chain length alkyl methacrylates, for example), some formulations of which also serve as pour point depressants.
  • Other suitable viscosity index improvers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (copolymers of various chain length acrylates, for example). Specific examples include styrene-isoprene or styrene-butadiene based polymers of 50,000 to 200,000 molecular weight.
  • Olefin copolymers are commercially available from Chevron Oronite Company LLC under the trade designation“PARATONE®” (such as“PARATONE® 8921” and“PARATONE® 8941”); from Afton Chemical Corporation under the trade designation“Hi TEC®” (such as “HiTEC® 5850B”; and from The Lubrizol Corporation under the trade designation“Lubrizol® 7067C”.
  • Polyisoprene polymers are commercially available from Infmeum International Limited, e.g. under the trade designation“SV200”; diene-styrene copolymers are commercially available from Infmeum International Limited, e.g. under the trade designation“SV 260”.
  • the viscosity index improvers may be used in an amount of less than about 2.0 weight percent, preferably less than about 1.0 weight percent, and more preferably less than about 0.5 weight percent, based on the total weight of the formulated oil or lubricating engine oil. Viscosity improvers are typically added as concentrates, in large amounts of diluent oil.
  • the viscosity index improvers may be used in an amount of from 0.25 to about 2.0 weight percent, preferably 0.15 to about 1.0 weight percent, and more preferably 0.05 to about 0.5 weight percent, based on the total weight of the formulated oil or lubricating engine oil.
  • Antioxidants retard the oxidative degradation of base oils during service. Such degradation may result in deposits on metal surfaces, the presence of sludge, or a viscosity increase in the lubricant.
  • One skilled in the art knows a wide variety of oxidation inhibitors that are useful in lubricating oil compositions. See, Klamann in Lubricants and Related Products, op cite, and ET.S. Patent Nos. 4,798,684 and 5,084,197, for example.
  • ETseful antioxidants include hindered phenols. These phenolic antioxidants may be ashless (metal-free) phenolic compounds or neutral or basic metal salts of certain phenolic compounds. Typical phenolic antioxidant compounds are the hindered phenolics which are the ones which contain a sterically hindered hydroxyl group, and these include those derivatives of dihydroxy aryl compounds in which the hydroxyl groups are in the o- or p-position to each other. Typical phenolic antioxidants include the hindered phenols substituted with C6+ alkyl groups and the alkylene coupled derivatives of these hindered phenols.
  • phenolic materials of this type 2-t-butyl-4-heptyl phenol; 2-t-butyl-4-octyl phenol; 2-t-butyl-4-dodecyl phenol; 2,6-di-t- butyl-4-heptyl phenol; 2,6-di-t-butyl-4-dodecyl phenol; 2-methyl-6-t-butyl-4-heptyl phenol; and 2-methyl-6-t-butyl-4-dodecyl phenol.
  • Other useful hindered mono-phenolic antioxidants may include for example hindered 2,6-di-alkyl-phenolic propionic ester derivatives.
  • Bis-phenolic antioxidants may also be advantageously used in combination with the instant disclosure.
  • ortho-coupled phenols include: 2,2’-bis(4-heptyl-6-t-butyl-phenol); 2,2’-bis(4-octyl- 6-t-butyl-phenol); and 2,2’-bis(4-dodecyl-6-t-butyl-phenol).
  • Para-coupled bisphenols include for example 4,4’-bis(2,6-di-t-butyl phenol) and 4,4’-methylene-bis(2,6-di-t-butyl phenol).
  • catalytic antioxidants comprise an effective amount of a) one or more oil soluble polymetal organic compounds; and, effective amounts ofb) one or more substituted N,N'-diaryl-o-phenylenediamine compounds or c) one or more hindered phenol compounds; or a combination of both b) and c).
  • Catalytic antioxidants are more fully described in ET.S. Patent No. 8,048,833, herein incorporated by reference in its entirety.
  • Non-phenolic oxidation inhibitors which may be used include aromatic amine antioxidants and these may be used either as such or in combination with phenolics.
  • Typical examples of non-phenolic antioxidants include: alkylated and non-alkylated aromatic amines such as aromatic monoamines of the formula R 8 R 9 R 10 N where R 8 is an aliphatic, aromatic or substituted aromatic group, R 9 is an aromatic or a substituted aromatic group, and R 10 is H, alkyl, aryl or R u S(0)xR 12 where R 11 is an alkylene, alkenylene, or aralkylene group, R 12 is a higher alkyl group, or an alkenyl, aryl, or alkaryl group, and x is 0, 1 or 2.
  • the aliphatic group R 8 may contain from 1 to 20 carbon atoms, and preferably contains from 6 to 12 carbon atoms.
  • the aliphatic group is a saturated aliphatic group.
  • both R 8 and R 9 are aromatic or substituted aromatic groups, and the aromatic group may be a fused ring aromatic group such as naphthyl.
  • Aromatic groups R 8 and R 9 may be joined together with other groups such as S.
  • Typical aromatic amines antioxidants have alkyl substituent groups of at least 6 carbon atoms.
  • Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl, and decyl. Generally, the aliphatic groups will not contain more than 14 carbon atoms.
  • the general types of amine antioxidants useful in the present compositions include diphenylamines, phenyl naphthylamines, phenothiazines, imidodibenzyls and diphenyl phenylene diamines. Mixtures of two or more aromatic amines are also useful. Polymeric amine antioxidants can also be used.
  • aromatic amine antioxidants useful in the present disclosure include: p,p’- dioctyldiphenylamine; t-octylphenyl-alpha-naphthylamine; phenyl-alphanaphthylamine; and p-octylphenyl-alpha-naphthylamine.
  • Sulfurized alkyl phenols and alkali or alkaline earth metal salts thereof also are useful antioxidants.
  • Preferred antioxidants include hindered phenols, arylamines. These antioxidants may be used individually by type or in combination with one another. Such additives may be used in an amount of 0.01 to 5 weight percent, preferably 0.01 to 2 weight percent, more preferably zero to 1.5 weight percent, more preferably zero to less than 1 weight percent.
  • pour point depressants also known as lube oil flow improvers
  • pour point depressants may be added to lubricating compositions of the present disclosure to lower the minimum temperature at which the fluid will flow or can be poured.
  • suitable pour point depressants include polymethacrylates, polyacrylates, polyarylamides, condensation products of haloparaffm waxes and aromatic compounds, vinyl carboxylate polymers, and terpolymers of dialkylfumarates, vinyl esters of fatty acids and allyl vinyl ethers.
  • 1,815,022; 2,015,748; 2,191,498; 2,387,501; 2,655,479; 2,666,746; 2,721,877; 2,721,878; and 3,250,715 describe useful pour point depressants and/or the preparation thereof.
  • Such additives may be used in an amount of about 0.01 to 5 weight percent, preferably about 0.01 to 1.5 weight percent.
  • Seal compatibility agents help to swell elastomeric seals by causing a chemical reaction in the fluid or physical change in the elastomer.
  • Suitable seal compatibility agents for lubricating oils include organic phosphates, alkoxysulfolanes, aromatic esters, aromatic hydrocarbons, esters (butylbenzyl phthalate, for example), and polybutenyl succinic anhydride. Such additives may be used in an amount of about 0.01 to 3 weight percent, preferably about 0.01 to 2 weight percent.
  • Anti-foam agents may advantageously be added to lubricant compositions. These agents retard the formation of stable foams. Silicones and organic polymers are typical anti-foam agents. For example, polysiloxanes, such as silicon oil or polydimethyl siloxane, provide antifoam properties. Anti-foam agents are commercially available and may be used in conventional minor amounts along with other additives such as demulsifiers; usually the amount of these additives combined is less than 1 weight percent and often less than 0.1 weight percent.
  • Antirust additives are additives that protect lubricated metal surfaces against chemical attack by water or other contaminants. A wide variety of these are commercially available.
  • One type of antirust additive is a polar compound that wets the metal surface preferentially, protecting it with a film of oil.
  • Another type of antirust additive absorbs water by incorporating it in a water-in-oil emulsion so that only the oil touches the metal surface.
  • Yet another type of antirust additive chemically adheres to the metal to produce a non-reactive surface.
  • suitable additives include zinc dithiophosphates, metal phenolates, basic metal sulfonates, fatty acids and amines. Such additives may be used in an amount of about 0.01 to 5 weight percent, preferably about 0.01 to 1.5 weight percent.
  • a friction modifier is any material or materials that can alter the coefficient of friction of a surface lubricated by any lubricant or fluid containing such material(s).
  • Friction modifiers also known as friction reducers, or lubricity agents or oiliness agents, and other such agents that change the ability of base oils, formulated lubricant compositions, or functional fluids, to modify the coefficient of friction of a lubricated surface may be effectively used in combination with the base oils or lubricant compositions of the present disclosure if desired. Friction modifiers that lower the coefficient of friction are particularly advantageous in combination with the base oils and lube compositions of this disclosure.
  • Illustrative friction modifiers may include, for example, organometallic compounds or materials, or mixtures thereof.
  • Illustrative organometallic friction modifiers useful in the lubricating engine oil formulations of this disclosure include, for example, molybdenum amine, molybdenum diamine, an organotungstenate, a molybdenum dithiocarbamate, molybdenum dithiophosphates, molybdenum amine complexes, molybdenum carboxylates, and the like, and mixtures thereof. Similar tungsten based compounds may be preferable.
  • illustrative friction modifiers useful in the lubricating engine oil formulations of this disclosure include, for example, alkoxylated fatty acid esters, alkanolamides, polyol fatty acid esters, borated glycerol fatty acid esters, fatty alcohol ethers, and mixtures thereof.
  • Illustrative alkoxylated fatty acid esters include, for example, polyoxyethylene stearate, fatty acid polyglycol ester, and the like. These can include polyoxypropylene stearate, polyoxybutylene stearate, polyoxyethylene isosterate, polyoxypropylene isostearate, polyoxyethylene palmitate, and the like.
  • Illustrative alkanolamides include, for example, lauric acid diethylalkanolamide, palmic acid diethylalkanolamide, and the like. These can include oleic acid diethyalkanolamide, stearic acid diethylalkanolamide, oleic acid diethylalkanolamide, polyethoxylated hydrocarbylamides, polypropoxylated hydrocarbylamides, and the like.
  • Illustrative polyol fatty acid esters include, for example, glycerol mono-oleate, saturated mono-, di-, and tri-glyceride esters, glycerol mono-stearate, and the like. These can include polyol esters, hydroxyl -containing polyol esters, and the like.
  • Illustrative borated glycerol fatty acid esters include, for example, borated glycerol mono-oleate, borated saturated mono-, di-, and tri-glyceride esters, borated glycerol mono-sterate, and the like.
  • glycerol polyols these can include trimethylolpropane, pentaerythritol, sorbitan, and the like.
  • esters can be polyol monocarboxylate esters, polyol dicarboxylate esters, and on occasion polyoltricarboxylate esters.
  • Preferred can be the glycerol mono-oleates, glycerol dioleates, glycerol trioleates, glycerol monostearates, glycerol distearates, and glycerol tristearates and the corresponding glycerol monopalmitates, glycerol dipalmitates, and glycerol tripalmitates, and the respective isostearates, linoleates, and the like.
  • the glycerol esters can be preferred as well as mixtures containing any of these. Ethoxylated, propoxylated, butoxylated fatty acid esters of polyols, especially using glycerol as underlying polyol can be preferred.
  • Illustrative fatty alcohol ethers include, for example, stearyl ether, myristyl ether, and the like. Alcohols, including those that have carbon numbers from C3 to C50, can be ethoxylated, propoxylated, or butoxylated to form the corresponding fatty alkyl ethers.
  • the underlying alcohol portion can preferably be stearyl, myristyl, C11 - C13 hydrocarbon, oleyl, isosteryl, and the like.
  • Useful concentrations of friction modifiers may range from 0.01 weight percent to 5 weight percent, or about 0.1 weight percent to about 2.5 weight percent, or about 0.1 weight percent to about 1.5 weight percent, or about 0.1 weight percent to about 1 weight percent. Concentrations of molybdenum-containing materials are often described in terms of Mo metal concentration. Advantageous concentrations of Mo may range from 25 ppm to 700 ppm or more, and often with a preferred range of 50-200 ppm. Friction modifiers of all types may be used alone or in mixtures with the materials of this disclosure. Often mixtures of two or more friction modifiers, or mixtures of friction modifier(s) with alternate surface active material(s), are also desirable.
  • the weight amounts in the table below, as well as other amounts mentioned herein, are directed to the amount of active ingredient (that is the non-diluent portion of the ingredient).
  • the weight percent (wt%) indicated below is based on the total weight of the lubricating oil composition.
  • Anti-foam Agent 0.001-3 0.001-0.15
  • additives are all commercially available materials. These additives may be added independently but are usually precombined in packages which can be obtained from suppliers of lubricant oil additives. Additive packages with a variety of ingredients, proportions and characteristics are available and selection of the appropriate package will take the requisite use of the ultimate composition into account.
  • LSPI testing can be used for LSPI testing.
  • a six segment test procedure can be used to determine the number of LSPI events that occur at two different specified engine load and speed conditions. Each segment of the test procedure comprises 25,000 engine cycles, where one cycle corresponds to 720 degrees of crank shaft rotation. The first set of conditions is 2000 RPM and 18 bar BMEP, hereafter referred to as“High Load”.
  • the second set of conditions is 1500 RPM and 12.5 bar BMEP, hereafter referred to as“Low Load”.
  • the test procedure comprises two segments of High Load, followed by two segments of Low Load, followed by two segments of High Load.
  • a 30 minute warm up at 2000 RPM and 4 bar BMEP is also conducted prior to commencing the test procedure.
  • This test procedure is repeated four times for each of the lubricants tested.
  • LSPI events are counted during the High Load segments only, using pressure transducers placed in each of the 4 cylinders to monitor the peak cylinder pressure. Peak pressures in the cylinder that are greater than 4.7 standard deviations above the mean peak cylinder pressure, or more than 4.7 standard deviations below the mean peak cylinder pressure are counted as an LSPI event.
  • the engine can exhibit greater than about 10%, or greater than about 25%, reduced low speed pre-ignition, based on normalized low speed pre- ignition (LSPI) counts per 25,000 engine cycles, engine operation at 2000 revolutions per minute (RPM) and brake mean effective pressure (BMEP) at 18 bar, as compared to low speed pre-ignition performance achieved in an engine using a lubricating oil containing calcium or magnesium.
  • LSPI normalized low speed pre- ignition
  • RPM revolutions per minute
  • BMEP brake mean effective pressure
  • Formulations were prepared as simple blends with 10% carbon black (Cabot Vulcan XC72R), a metal oxide, and base stock (balance) as shown in Figs. 1-3. All of the ingredients used herein are commercially available.
  • TGA thermogravimetric analysis
  • Fig. 1 shows carbon decomposition temperatures of various metal oxides in a carbon black/P AO mixture. Most notable among the oxide results are sodium, manganese, titanium, and aluminum. These four metals show low catalytic activity, even below that of magnesium, which in the form of a detergent, is well known to have significantly lower LSPI activity than calcium detergents.
  • Fig. 2 shows carbon decomposition temperatures of various metal oxides in a carbon black/base stock mixture in which barium oxide and titanium(IV) oxide and various base stocks were used. Barium oxide was selected because of its poor performance while titanium(IV) oxide was selected for its strong performance. Base stock selection impacted the decomposition temperature with Visom (Group III) performing the worst, EHC (Group II) in the middle, and GTL and PAO (Group III+ and Group IV) having the highest decomposition temperatures. Titanium has higher decomposition temperatures than barium across the spectrum and also has less variability between the different base stocks.
  • Fig. 3 shows carbon decomposition temperatures of various metal oxides in a carbon black/formulated mixture in which barium and titanium and PAO base stock were used with varying concentrations of metal oxide. Titanium has higher decomposition temperatures than barium, and both sets of samples remain fairly constant regardless of concentration.
  • a method for preventing or reducing low speed pre-ignition in an engine lubricated with a lubricating oil by using as the lubricating oil a formulated oil, said formulated oil having a composition comprising a lubricating oil base stock as a major component; and at least one lubricating oil additive, as a minor component; wherein said lubricating oil contains at least one metal or metalloid in an amount sufficient that, in thermogravimetric measurements of the lubricating oil by a Thermogravimetric Engine Oil Simulation Test, carbon black decomposition temperature is increased as compared to the carbon black decomposition temperature in a lubricating oil containing calcium or magnesium.
  • a lubricating engine oil having a composition comprising a lubricating oil base stock as a major component; and at least one lubricating oil additive, as a minor component; wherein said lubricating engine oil contains at least one metal or metalloid in an amount sufficient that, in thermogravimetric measurements of the lubricating engine oil by a Thermogravimetric Engine Oil Simulation Test, carbon black decomposition temperature is increased as compared to the carbon black decomposition temperature in a lubricating engine oil containing calcium or magnesium.

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Abstract

L'invention concerne un procédé de prévention ou de réduction de pré-allumage à faible vitesse dans un moteur lubrifié par une huile lubrifiante en faisant appel à une huile formulée comme huile lubrifiante. L'huile formulée possède une composition comprenant une huile de base lubrifiante en tant que constituant principal et au moins un additif d'huile lubrifiante, en tant que constituant secondaire. L'huile lubrifiante contient au moins un métal ou un métalloïde en une quantité suffisante pour que, dans des mesures thermogravimétriques de l'huile lubrifiante au moyen d'un test de simulation d'huile de moteur thermogravimétrique, la température de décomposition du noir de carbone soit augmentée par rapport à la température de décomposition du noir de carbone dans une huile lubrifiante contenant du calcium ou du magnésium. La présente invention concerne également une huile lubrifiante utile pour prévenir ou réduire le pré-allumage à faible vitesse dans un moteur lubrifié par une huile lubrifiante. Les huiles lubrifiantes de la présente invention sont particulièrement avantageuses en tant que produits d'huiles de moteurs pour véhicules de tourisme (PVEO).
PCT/US2018/058355 2017-12-04 2018-10-31 Procédé de prévention ou de réduction de pré-allumage à faible vitesse WO2019112711A1 (fr)

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Citations (102)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1815022A (en) 1930-05-03 1931-07-14 Standard Oil Dev Co Hydrocarbon oil and process for manufacturing the same
US2015748A (en) 1933-06-30 1935-10-01 Standard Oil Dev Co Method for producing pour inhibitors
US2100993A (en) 1934-12-14 1937-11-30 Rohm & Haas Process for preparing esters and products
US2191498A (en) 1935-11-27 1940-02-27 Socony Vacuum Oil Co Inc Mineral oil composition and method of making
US2387501A (en) 1944-04-04 1945-10-23 Du Pont Hydrocarbon oil
US2655479A (en) 1949-01-03 1953-10-13 Standard Oil Dev Co Polyester pour depressants
US2666746A (en) 1952-08-11 1954-01-19 Standard Oil Dev Co Lubricating oil composition
US2721877A (en) 1951-08-22 1955-10-25 Exxon Research Engineering Co Lubricating oil additives and a process for their preparation
US2721878A (en) 1951-08-18 1955-10-25 Exxon Research Engineering Co Strong acid as a polymerization modifier in the production of liquid polymers
US2817693A (en) 1954-03-29 1957-12-24 Shell Dev Production of oils from waxes
US3036003A (en) 1957-08-07 1962-05-22 Sinclair Research Inc Lubricating oil composition
US3087936A (en) 1961-08-18 1963-04-30 Lubrizol Corp Reaction product of an aliphatic olefinpolymer-succinic acid producing compound with an amine and reacting the resulting product with a boron compound
US3172892A (en) 1959-03-30 1965-03-09 Reaction product of high molecular weight succinic acids and succinic anhydrides with an ethylene poly- amine
US3200107A (en) 1961-06-12 1965-08-10 Lubrizol Corp Process for preparing acylated amine-cs2 compositions and products
US3214570A (en) 1962-03-06 1965-10-26 Gen Electric Heating device control
US3250715A (en) 1964-02-04 1966-05-10 Lubrizol Corp Terpolymer product and lubricating composition containing it
US3272746A (en) 1965-11-22 1966-09-13 Lubrizol Corp Lubricating composition containing an acylated nitrogen compound
US3275554A (en) 1963-08-02 1966-09-27 Shell Oil Co Polyolefin substituted polyamines and lubricants containing them
US3316177A (en) 1964-12-07 1967-04-25 Lubrizol Corp Functional fluid containing a sludge inhibiting detergent comprising the polyamine salt of the reaction product of maleic anhydride and an oxidized interpolymer of propylene and ethylene
US3322670A (en) 1963-08-26 1967-05-30 Standard Oil Co Detergent-dispersant lubricant additive having anti-rust and anti-wear properties
US3329658A (en) 1962-05-14 1967-07-04 Monsanto Co Dispersency oil additives
US3382291A (en) 1965-04-23 1968-05-07 Mobil Oil Corp Polymerization of olefins with bf3
US3413347A (en) 1966-01-26 1968-11-26 Ethyl Corp Mannich reaction products of high molecular weight alkyl phenols, aldehydes and polyaminopolyalkyleneamines
US3438757A (en) 1965-08-23 1969-04-15 Chevron Res Hydrocarbyl amines for fuel detergents
US3444170A (en) 1959-03-30 1969-05-13 Lubrizol Corp Process which comprises reacting a carboxylic intermediate with an amine
US3449250A (en) 1962-05-14 1969-06-10 Monsanto Co Dispersency oil additives
US3454555A (en) 1965-01-28 1969-07-08 Shell Oil Co Oil-soluble halogen-containing polyamines and polyethyleneimines
US3454607A (en) 1969-02-10 1969-07-08 Lubrizol Corp High molecular weight carboxylic compositions
US3519565A (en) 1967-09-19 1970-07-07 Lubrizol Corp Oil-soluble interpolymers of n-vinylthiopyrrolidones
US3541012A (en) 1968-04-15 1970-11-17 Lubrizol Corp Lubricants and fuels containing improved acylated nitrogen additives
US3595791A (en) 1969-03-11 1971-07-27 Lubrizol Corp Basic,sulfurized salicylates and method for their preparation
US3630904A (en) 1968-07-03 1971-12-28 Lubrizol Corp Lubricating oils and fuels containing acylated nitrogen additives
US3632511A (en) 1969-11-10 1972-01-04 Lubrizol Corp Acylated nitrogen-containing compositions processes for their preparationand lubricants and fuels containing the same
US3652616A (en) 1969-08-14 1972-03-28 Standard Oil Co Additives for fuels and lubricants
US3687849A (en) 1968-06-18 1972-08-29 Lubrizol Corp Lubricants containing oil-soluble graft polymers derived from degraded ethylene-propylene interpolymers
US3697574A (en) 1965-10-22 1972-10-10 Standard Oil Co Boron derivatives of high molecular weight mannich condensation products
US3702300A (en) 1968-12-20 1972-11-07 Lubrizol Corp Lubricant containing nitrogen-containing ester
US3703536A (en) 1967-11-24 1972-11-21 Standard Oil Co Preparation of oil-soluble boron derivatives of an alkylene polyamine-substituted phenol-formaldehyde addition product
US3704308A (en) 1965-10-22 1972-11-28 Standard Oil Co Boron-containing high molecular weight mannich condensation
US3725480A (en) 1968-11-08 1973-04-03 Standard Oil Co Ashless oil additives
US3726882A (en) 1968-11-08 1973-04-10 Standard Oil Co Ashless oil additives
US3742082A (en) 1971-11-18 1973-06-26 Mobil Oil Corp Dimerization of olefins with boron trifluoride
US3751365A (en) 1965-10-22 1973-08-07 Standard Oil Co Concentrates and crankcase oils comprising oil solutions of boron containing high molecular weight mannich reaction condensation products
US3755433A (en) 1971-12-16 1973-08-28 Texaco Inc Ashless lubricating oil dispersant
US3756953A (en) 1965-10-22 1973-09-04 Standard Oil Co Vatives of high molecular weight mannich reaction condensation concentrate and crankcase oils comprising oil solutions of boron deri
US3769363A (en) 1972-03-13 1973-10-30 Mobil Oil Corp Oligomerization of olefins with boron trifluoride
US3787374A (en) 1971-09-07 1974-01-22 Lubrizol Corp Process for preparing high molecular weight carboxylic compositions
US3798165A (en) 1965-10-22 1974-03-19 Standard Oil Co Lubricating oils containing high molecular weight mannich condensation products
US3803039A (en) 1970-07-13 1974-04-09 Standard Oil Co Oil solution of aliphatic acid derivatives of high molecular weight mannich condensation product
GB1350257A (en) 1970-06-05 1974-04-18 Shell Int Research Process for the preparation of a lubricating oil
US3822209A (en) 1966-02-01 1974-07-02 Ethyl Corp Lubricant additives
US3876720A (en) 1972-07-24 1975-04-08 Gulf Research Development Co Internal olefin
GB1390359A (en) 1971-05-13 1975-04-09 Shell Int Research Process for the preparation of lubricating oil with high viscosity index
GB1429494A (en) 1972-04-06 1976-03-24 Shell Int Research Process for the preparation of a lubricating oil
US3948800A (en) 1971-07-01 1976-04-06 The Lubrizol Corporation Dispersant compositions
GB1440230A (en) 1972-08-04 1976-06-23 Shell Int Research Process for the preparation of lubricating oils
US4100082A (en) 1976-01-28 1978-07-11 The Lubrizol Corporation Lubricants containing amino phenol-detergent/dispersant combinations
US4149178A (en) 1976-10-05 1979-04-10 American Technology Corporation Pattern generating system and method
US4218330A (en) 1978-06-26 1980-08-19 Ethyl Corporation Lubricant
US4234435A (en) 1979-02-23 1980-11-18 The Lubrizol Corporation Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation
US4239930A (en) 1979-05-17 1980-12-16 Pearsall Chemical Company Continuous oligomerization process
CA1094044A (fr) 1977-02-25 1981-01-20 Norman A. Meinhardt Traduction non-disponible
US4367352A (en) 1980-12-22 1983-01-04 Texaco Inc. Oligomerized olefins for lubricant stock
US4413156A (en) 1982-04-26 1983-11-01 Texaco Inc. Manufacture of synthetic lubricant additives from low molecular weight olefins using boron trifluoride catalysts
US4426305A (en) 1981-03-23 1984-01-17 Edwin Cooper, Inc. Lubricating compositions containing boronated nitrogen-containing dispersants
US4434408A (en) 1980-03-11 1984-02-28 Sony Corporation Oscillator having capacitor charging and discharging controlled by non-saturating switches
US4454059A (en) 1976-11-12 1984-06-12 The Lubrizol Corporation Nitrogenous dispersants, lubricants and concentrates containing said nitrogenous dispersants
US4594172A (en) 1984-04-18 1986-06-10 Shell Oil Company Process for the preparation of hydrocarbons
US4767551A (en) 1985-12-02 1988-08-30 Amoco Corporation Metal-containing lubricant compositions
US4798684A (en) 1987-06-09 1989-01-17 The Lubrizol Corporation Nitrogen containing anti-oxidant compositions
US4827064A (en) 1986-12-24 1989-05-02 Mobil Oil Corporation High viscosity index synthetic lubricant compositions
US4827073A (en) 1988-01-22 1989-05-02 Mobil Oil Corporation Process for manufacturing olefinic oligomers having lubricating properties
US4897178A (en) 1983-05-02 1990-01-30 Uop Hydrocracking catalyst and hydrocracking process
US4910355A (en) 1988-11-02 1990-03-20 Ethyl Corporation Olefin oligomer functional fluid using internal olefins
US4921594A (en) 1985-06-28 1990-05-01 Chevron Research Company Production of low pour point lubricating oils
US4943672A (en) 1987-12-18 1990-07-24 Exxon Research And Engineering Company Process for the hydroisomerization of Fischer-Tropsch wax to produce lubricating oil (OP-3403)
US4952739A (en) 1988-10-26 1990-08-28 Exxon Chemical Patents Inc. Organo-Al-chloride catalyzed poly-n-butenes process
US4956122A (en) 1982-03-10 1990-09-11 Uniroyal Chemical Company, Inc. Lubricating composition
US4975177A (en) 1985-11-01 1990-12-04 Mobil Oil Corporation High viscosity index lubricants
US5068487A (en) 1990-07-19 1991-11-26 Ethyl Corporation Olefin oligomerization with BF3 alcohol alkoxylate co-catalysts
US5075269A (en) 1988-12-15 1991-12-24 Mobil Oil Corp. Production of high viscosity index lubricating oil stock
EP0464547A1 (fr) 1990-07-05 1992-01-08 Mobil Oil Corporation Production de lubrifiants à haute indice de viscosité
EP0464546A1 (fr) 1990-07-05 1992-01-08 Mobil Oil Corporation Production de lubrifiants à haut indice de viscosité
US5084197A (en) 1990-09-21 1992-01-28 The Lubrizol Corporation Antiemulsion/antifoam agent for use in oils
EP0471071A1 (fr) 1990-02-23 1992-02-19 Lubrizol Corp Fluides fonctionnels a hautes temperatures.
US5430105A (en) 1992-12-17 1995-07-04 Exxon Chemical Patents Inc. Low sediment process for forming borated dispersant
US5705458A (en) 1995-09-19 1998-01-06 The Lubrizol Corporation Additive compositions for lubricants and functional fluids
US6034039A (en) 1997-11-28 2000-03-07 Exxon Chemical Patents, Inc. Lubricating oil compositions
US6080301A (en) 1998-09-04 2000-06-27 Exxonmobil Research And Engineering Company Premium synthetic lubricant base stock having at least 95% non-cyclic isoparaffins
US6090989A (en) 1997-10-20 2000-07-18 Mobil Oil Corporation Isoparaffinic lube basestock compositions
US6165949A (en) 1998-09-04 2000-12-26 Exxon Research And Engineering Company Premium wear resistant lubricant
US6323164B1 (en) 2000-11-01 2001-11-27 Ethyl Corporation Dispersant (meth) acrylate copolymers having excellent low temperature properties
US20030090807A1 (en) 2001-11-14 2003-05-15 Morgan John Paul Anti-PDL beam swapping
WO2004101717A2 (fr) * 2003-05-12 2004-11-25 Southwest Research Institute Lubrifiants a indice d'octane eleve destines a une attenuation de la detonation dans des moteurs a propagation de la flamme
US20080020950A1 (en) 2006-07-19 2008-01-24 Christopher Gray Lubricating Oil Composition
US7704930B2 (en) 2002-01-31 2010-04-27 Exxonmobil Research And Engineering Company Mixed TBN detergents and lubricating oil compositions containing such detergents
US8048833B2 (en) 2007-08-17 2011-11-01 Exxonmobil Research And Engineering Company Catalytic antioxidants
US20120186225A1 (en) 2011-01-25 2012-07-26 Southwest Research Institute Methods And Apparatus To Detect And Inhibit Low-Speed Pre-Ignition In An Engine
WO2015042340A1 (fr) * 2013-09-19 2015-03-26 The Lubrizol Corporation Compositions lubrifiantes pour moteurs à injection directe
US20160186089A1 (en) * 2014-12-30 2016-06-30 Exxonmobil Research And Engineering Company Lubricating oil compositions with engine wear protection
WO2017011689A1 (fr) * 2015-07-16 2017-01-19 Afton Chemical Corporation Lubrifiants à base de titane et/ou de tungstène et leur utilisation pour améliorer un pré-allumage à basse vitesse
WO2017147380A1 (fr) * 2016-02-24 2017-08-31 The Lubrizol Corporation Compositions lubrifiantes pour moteurs à injection directe

Patent Citations (108)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1815022A (en) 1930-05-03 1931-07-14 Standard Oil Dev Co Hydrocarbon oil and process for manufacturing the same
US2015748A (en) 1933-06-30 1935-10-01 Standard Oil Dev Co Method for producing pour inhibitors
US2100993A (en) 1934-12-14 1937-11-30 Rohm & Haas Process for preparing esters and products
US2191498A (en) 1935-11-27 1940-02-27 Socony Vacuum Oil Co Inc Mineral oil composition and method of making
US2387501A (en) 1944-04-04 1945-10-23 Du Pont Hydrocarbon oil
US2655479A (en) 1949-01-03 1953-10-13 Standard Oil Dev Co Polyester pour depressants
US2721878A (en) 1951-08-18 1955-10-25 Exxon Research Engineering Co Strong acid as a polymerization modifier in the production of liquid polymers
US2721877A (en) 1951-08-22 1955-10-25 Exxon Research Engineering Co Lubricating oil additives and a process for their preparation
US2666746A (en) 1952-08-11 1954-01-19 Standard Oil Dev Co Lubricating oil composition
US2817693A (en) 1954-03-29 1957-12-24 Shell Dev Production of oils from waxes
US3036003A (en) 1957-08-07 1962-05-22 Sinclair Research Inc Lubricating oil composition
US3341542A (en) 1959-03-30 1967-09-12 Lubrizol Corp Oil soluble acrylated nitrogen compounds having a polar acyl, acylimidoyl or acyloxy group with a nitrogen atom attached directly thereto
US3172892A (en) 1959-03-30 1965-03-09 Reaction product of high molecular weight succinic acids and succinic anhydrides with an ethylene poly- amine
US3444170A (en) 1959-03-30 1969-05-13 Lubrizol Corp Process which comprises reacting a carboxylic intermediate with an amine
US3219666A (en) 1959-03-30 1965-11-23 Derivatives of succinic acids and nitrogen compounds
US3200107A (en) 1961-06-12 1965-08-10 Lubrizol Corp Process for preparing acylated amine-cs2 compositions and products
US3254025A (en) 1961-08-18 1966-05-31 Lubrizol Corp Boron-containing acylated amine and lubricating compositions containing the same
US3087936A (en) 1961-08-18 1963-04-30 Lubrizol Corp Reaction product of an aliphatic olefinpolymer-succinic acid producing compound with an amine and reacting the resulting product with a boron compound
US3214570A (en) 1962-03-06 1965-10-26 Gen Electric Heating device control
US3329658A (en) 1962-05-14 1967-07-04 Monsanto Co Dispersency oil additives
US3449250A (en) 1962-05-14 1969-06-10 Monsanto Co Dispersency oil additives
US3275554A (en) 1963-08-02 1966-09-27 Shell Oil Co Polyolefin substituted polyamines and lubricants containing them
US3322670A (en) 1963-08-26 1967-05-30 Standard Oil Co Detergent-dispersant lubricant additive having anti-rust and anti-wear properties
US3250715A (en) 1964-02-04 1966-05-10 Lubrizol Corp Terpolymer product and lubricating composition containing it
US3316177A (en) 1964-12-07 1967-04-25 Lubrizol Corp Functional fluid containing a sludge inhibiting detergent comprising the polyamine salt of the reaction product of maleic anhydride and an oxidized interpolymer of propylene and ethylene
US3454555A (en) 1965-01-28 1969-07-08 Shell Oil Co Oil-soluble halogen-containing polyamines and polyethyleneimines
US3382291A (en) 1965-04-23 1968-05-07 Mobil Oil Corp Polymerization of olefins with bf3
US3438757A (en) 1965-08-23 1969-04-15 Chevron Res Hydrocarbyl amines for fuel detergents
US3565804A (en) 1965-08-23 1971-02-23 Chevron Res Lubricating oil additives
US3697574A (en) 1965-10-22 1972-10-10 Standard Oil Co Boron derivatives of high molecular weight mannich condensation products
US3756953A (en) 1965-10-22 1973-09-04 Standard Oil Co Vatives of high molecular weight mannich reaction condensation concentrate and crankcase oils comprising oil solutions of boron deri
US3798165A (en) 1965-10-22 1974-03-19 Standard Oil Co Lubricating oils containing high molecular weight mannich condensation products
US3751365A (en) 1965-10-22 1973-08-07 Standard Oil Co Concentrates and crankcase oils comprising oil solutions of boron containing high molecular weight mannich reaction condensation products
US3704308A (en) 1965-10-22 1972-11-28 Standard Oil Co Boron-containing high molecular weight mannich condensation
US3272746A (en) 1965-11-22 1966-09-13 Lubrizol Corp Lubricating composition containing an acylated nitrogen compound
US3725277A (en) 1966-01-26 1973-04-03 Ethyl Corp Lubricant compositions
US3413347A (en) 1966-01-26 1968-11-26 Ethyl Corp Mannich reaction products of high molecular weight alkyl phenols, aldehydes and polyaminopolyalkyleneamines
US3822209A (en) 1966-02-01 1974-07-02 Ethyl Corp Lubricant additives
US3666730A (en) 1967-09-19 1972-05-30 Lubrizol Corp Oil-soluble interpolymers of n-vinylthiopyrrolidones
US3519565A (en) 1967-09-19 1970-07-07 Lubrizol Corp Oil-soluble interpolymers of n-vinylthiopyrrolidones
US3703536A (en) 1967-11-24 1972-11-21 Standard Oil Co Preparation of oil-soluble boron derivatives of an alkylene polyamine-substituted phenol-formaldehyde addition product
US3541012A (en) 1968-04-15 1970-11-17 Lubrizol Corp Lubricants and fuels containing improved acylated nitrogen additives
US3687849A (en) 1968-06-18 1972-08-29 Lubrizol Corp Lubricants containing oil-soluble graft polymers derived from degraded ethylene-propylene interpolymers
US3630904A (en) 1968-07-03 1971-12-28 Lubrizol Corp Lubricating oils and fuels containing acylated nitrogen additives
US3725480A (en) 1968-11-08 1973-04-03 Standard Oil Co Ashless oil additives
US3726882A (en) 1968-11-08 1973-04-10 Standard Oil Co Ashless oil additives
US3702300A (en) 1968-12-20 1972-11-07 Lubrizol Corp Lubricant containing nitrogen-containing ester
US3454607A (en) 1969-02-10 1969-07-08 Lubrizol Corp High molecular weight carboxylic compositions
US3595791A (en) 1969-03-11 1971-07-27 Lubrizol Corp Basic,sulfurized salicylates and method for their preparation
US3652616A (en) 1969-08-14 1972-03-28 Standard Oil Co Additives for fuels and lubricants
US3632511A (en) 1969-11-10 1972-01-04 Lubrizol Corp Acylated nitrogen-containing compositions processes for their preparationand lubricants and fuels containing the same
GB1350257A (en) 1970-06-05 1974-04-18 Shell Int Research Process for the preparation of a lubricating oil
US3803039A (en) 1970-07-13 1974-04-09 Standard Oil Co Oil solution of aliphatic acid derivatives of high molecular weight mannich condensation product
GB1390359A (en) 1971-05-13 1975-04-09 Shell Int Research Process for the preparation of lubricating oil with high viscosity index
US3948800A (en) 1971-07-01 1976-04-06 The Lubrizol Corporation Dispersant compositions
US3787374A (en) 1971-09-07 1974-01-22 Lubrizol Corp Process for preparing high molecular weight carboxylic compositions
US3742082A (en) 1971-11-18 1973-06-26 Mobil Oil Corp Dimerization of olefins with boron trifluoride
US3755433A (en) 1971-12-16 1973-08-28 Texaco Inc Ashless lubricating oil dispersant
US3769363A (en) 1972-03-13 1973-10-30 Mobil Oil Corp Oligomerization of olefins with boron trifluoride
GB1429494A (en) 1972-04-06 1976-03-24 Shell Int Research Process for the preparation of a lubricating oil
US3876720A (en) 1972-07-24 1975-04-08 Gulf Research Development Co Internal olefin
GB1440230A (en) 1972-08-04 1976-06-23 Shell Int Research Process for the preparation of lubricating oils
US4100082A (en) 1976-01-28 1978-07-11 The Lubrizol Corporation Lubricants containing amino phenol-detergent/dispersant combinations
US4149178A (en) 1976-10-05 1979-04-10 American Technology Corporation Pattern generating system and method
US4454059A (en) 1976-11-12 1984-06-12 The Lubrizol Corporation Nitrogenous dispersants, lubricants and concentrates containing said nitrogenous dispersants
CA1094044A (fr) 1977-02-25 1981-01-20 Norman A. Meinhardt Traduction non-disponible
US4218330A (en) 1978-06-26 1980-08-19 Ethyl Corporation Lubricant
US4234435A (en) 1979-02-23 1980-11-18 The Lubrizol Corporation Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation
US4239930A (en) 1979-05-17 1980-12-16 Pearsall Chemical Company Continuous oligomerization process
US4434408A (en) 1980-03-11 1984-02-28 Sony Corporation Oscillator having capacitor charging and discharging controlled by non-saturating switches
US4367352A (en) 1980-12-22 1983-01-04 Texaco Inc. Oligomerized olefins for lubricant stock
US4426305A (en) 1981-03-23 1984-01-17 Edwin Cooper, Inc. Lubricating compositions containing boronated nitrogen-containing dispersants
US4956122A (en) 1982-03-10 1990-09-11 Uniroyal Chemical Company, Inc. Lubricating composition
US4413156A (en) 1982-04-26 1983-11-01 Texaco Inc. Manufacture of synthetic lubricant additives from low molecular weight olefins using boron trifluoride catalysts
US4897178A (en) 1983-05-02 1990-01-30 Uop Hydrocracking catalyst and hydrocracking process
US4594172A (en) 1984-04-18 1986-06-10 Shell Oil Company Process for the preparation of hydrocarbons
US4921594A (en) 1985-06-28 1990-05-01 Chevron Research Company Production of low pour point lubricating oils
US4975177A (en) 1985-11-01 1990-12-04 Mobil Oil Corporation High viscosity index lubricants
US4767551A (en) 1985-12-02 1988-08-30 Amoco Corporation Metal-containing lubricant compositions
US4827064A (en) 1986-12-24 1989-05-02 Mobil Oil Corporation High viscosity index synthetic lubricant compositions
US4798684A (en) 1987-06-09 1989-01-17 The Lubrizol Corporation Nitrogen containing anti-oxidant compositions
US4943672A (en) 1987-12-18 1990-07-24 Exxon Research And Engineering Company Process for the hydroisomerization of Fischer-Tropsch wax to produce lubricating oil (OP-3403)
US4827073A (en) 1988-01-22 1989-05-02 Mobil Oil Corporation Process for manufacturing olefinic oligomers having lubricating properties
US4952739A (en) 1988-10-26 1990-08-28 Exxon Chemical Patents Inc. Organo-Al-chloride catalyzed poly-n-butenes process
US4910355A (en) 1988-11-02 1990-03-20 Ethyl Corporation Olefin oligomer functional fluid using internal olefins
US5075269A (en) 1988-12-15 1991-12-24 Mobil Oil Corp. Production of high viscosity index lubricating oil stock
EP0471071A1 (fr) 1990-02-23 1992-02-19 Lubrizol Corp Fluides fonctionnels a hautes temperatures.
EP0464547A1 (fr) 1990-07-05 1992-01-08 Mobil Oil Corporation Production de lubrifiants à haute indice de viscosité
EP0464546A1 (fr) 1990-07-05 1992-01-08 Mobil Oil Corporation Production de lubrifiants à haut indice de viscosité
US5068487A (en) 1990-07-19 1991-11-26 Ethyl Corporation Olefin oligomerization with BF3 alcohol alkoxylate co-catalysts
US5084197A (en) 1990-09-21 1992-01-28 The Lubrizol Corporation Antiemulsion/antifoam agent for use in oils
US5430105A (en) 1992-12-17 1995-07-04 Exxon Chemical Patents Inc. Low sediment process for forming borated dispersant
US5705458A (en) 1995-09-19 1998-01-06 The Lubrizol Corporation Additive compositions for lubricants and functional fluids
US6090989A (en) 1997-10-20 2000-07-18 Mobil Oil Corporation Isoparaffinic lube basestock compositions
US6034039A (en) 1997-11-28 2000-03-07 Exxon Chemical Patents, Inc. Lubricating oil compositions
US6080301A (en) 1998-09-04 2000-06-27 Exxonmobil Research And Engineering Company Premium synthetic lubricant base stock having at least 95% non-cyclic isoparaffins
US6165949A (en) 1998-09-04 2000-12-26 Exxon Research And Engineering Company Premium wear resistant lubricant
US6323164B1 (en) 2000-11-01 2001-11-27 Ethyl Corporation Dispersant (meth) acrylate copolymers having excellent low temperature properties
US20030090807A1 (en) 2001-11-14 2003-05-15 Morgan John Paul Anti-PDL beam swapping
US7704930B2 (en) 2002-01-31 2010-04-27 Exxonmobil Research And Engineering Company Mixed TBN detergents and lubricating oil compositions containing such detergents
WO2004101717A2 (fr) * 2003-05-12 2004-11-25 Southwest Research Institute Lubrifiants a indice d'octane eleve destines a une attenuation de la detonation dans des moteurs a propagation de la flamme
US20080020950A1 (en) 2006-07-19 2008-01-24 Christopher Gray Lubricating Oil Composition
US8048833B2 (en) 2007-08-17 2011-11-01 Exxonmobil Research And Engineering Company Catalytic antioxidants
US20120186225A1 (en) 2011-01-25 2012-07-26 Southwest Research Institute Methods And Apparatus To Detect And Inhibit Low-Speed Pre-Ignition In An Engine
WO2015042340A1 (fr) * 2013-09-19 2015-03-26 The Lubrizol Corporation Compositions lubrifiantes pour moteurs à injection directe
US20160186089A1 (en) * 2014-12-30 2016-06-30 Exxonmobil Research And Engineering Company Lubricating oil compositions with engine wear protection
WO2017011689A1 (fr) * 2015-07-16 2017-01-19 Afton Chemical Corporation Lubrifiants à base de titane et/ou de tungstène et leur utilisation pour améliorer un pré-allumage à basse vitesse
WO2017147380A1 (fr) * 2016-02-24 2017-08-31 The Lubrizol Corporation Compositions lubrifiantes pour moteurs à injection directe

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
"Friedel-Crafts and Related Reactions", 1963, INTER-SCIENCE PUBLISHERS
"Friedel-Crafts and Related Reactions", vol. 2, 1964, INTER-SCIENCE PUBLISHERS
KLAMANN: "Lubricants and Related Products", VERLAG CHEMIE
KO ONODERA ET AL.: "Engine Oil Formulation Technology to Prevent Pre-ignition in Turbocharged Direct Injection Spark Ignition Engines", JSAE 20159071
M. W. RANNEY: "Lubricant Additives", 1973, NOYES DATA CORPORATION OF PARKRIDGE
W. W. YAU; J. J. KIRKLAND; D. D. BLY: "Modern Size Exclusion Liquid Chromatography", 1979, JOHN WILEY AND SONS

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