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    • 专利摘要:
    LUBRICANT COMPOSITIONS FOR DIRECT INJECTION ENGINES The invention is directed to a method of reducing low speed pre-ignition events in a spark ignited direct injection internal combustion engine by providing the crankcase with a lubricating composition containing an oil of lubricating viscosity and an over-based metal detergent. The metal overbased detergent can be selected from sulphonate detergents, phenate detergents, and salicylate detergents, especially sulphonate detergents with a metal ratio of at least 5.
    公开号:BR112016006109B1
    申请号:R112016006109-8
    申请日:2014-09-19
    公开日:2021-05-18
    发明作者:Patrick E. Mosier；Jeffry G. Dietz；Alexander Sammut
    申请人:The Lubrizol Corporation；
    IPC主号:
    专利说明:

    Fundamentals of the Invention
    [0001] The disclosed technology refers to lubricants for internal combustion engines, particularly those for spark ignition direct injection engines.
    [0002] Modern engine designs are being developed to improve fuel economy without sacrificing performance or durability. Historically, gasoline has been injected through a fuel port (PFI), which is, injected through the air inlet and enters the combustion chamber through the air inlet valve. Direct Gasoline Injection (GDI) involves the direct injection of gasoline into the combustion chamber.
    [0003] In certain situations, the internal combustion engine may exhibit abnormal combustion. Abnormal combustion in a spark-initiated internal combustion engine can be understood as an uncontrolled explosion that occurs in the combustion chamber, as a result of ignition of combustible elements in it by a source other than the ignition device.
    [0004] Pre-ignition can be understood as an abnormal form of combustion resulting from the ignition of the air-fuel mixture prior to ignition by the ignition device. Whenever the mixture of air and fuel in the combustion chamber is ignited before ignition by the ignition device, this can be understood as pre-ignition.
    [0005] Without being bound by a particular theory, traditionally, pre-ignition has occurred during high-speed operation of an engine when a certain point inside the combustion chamber of a cylinder can become sufficiently hot during operation. at high speed than the engine effectively functions as a glow plug (eg overheated spark plug tip, overheated metal burr) to provide an ignition source, which causes the air and fuel mixture to ignite before ignition by the ignition device. Such pre-ignition may be more commonly referred to as hot-spot pre-ignition, and can be inhibited by simply locating the hot-spot and eliminating it.
    [0006] More recently, vehicle manufacturers have observed intermittent abnormal combustion in their production of turbo gasoline engines, especially at low speeds and medium to high loads. More particularly, when operating the engine at speeds less than or equal to 3000 rpm and with a load, with a mean effective braking pressure (BMEP) greater than or equal to 10 bar, a condition that may be referred to as pre-ignition at low speed (LSPI) can occur in a very random and stochastic way.
    [0007] The disclosed technology provides a method to reduce, inhibit, or even eliminate LSPI events in direct injection engines by operating the engines with a lubricant that contains a base excess detergent with metal. SUMMARY OF THE INVENTION
    [0008] The disclosed technology provides a method to reduce low-speed pre-ignition events of a combustion spark ignition internal direct injection engine comprising supplying the crankcase with a lubricating composition containing an oil of lubricating viscosity and a detergent with excess metal base. The metal-based excess detergent can be selected from sulphonate detergents, phenate detergents, and salicylate detergents, especially sulphonate detergents.
    [0009] The invention provides a method for reducing low speed pre-ignition events of a combustion spark ignition internal direct injection engine comprising providing the engine with a lubricating composition comprising a lubricating base oil of viscosity and a detergent with excess metal base.
    [0010] The invention further provides the method as described herein, in which the motor is operated under a load with a mean effective braking pressure (BMEP) greater than or equal to 10 bar.
    [0011] The invention further provides the method as described herein, wherein the engine is operated at speeds less than or equal to 3000 rpm.
    [0012] The invention further provides the method as described herein wherein the engine is fed with a liquid hydrocarbon fuel, non-liquid hydrocarbon fuel, or mixtures thereof.
    [0013] The invention further provides the method, as disclosed herein, in which the engine is powered by natural gas, liquefied petroleum gas (LPG), compressed natural gas (CNG), or mixtures thereof.
    The invention further provides the method as described herein wherein the metal base excess detergent comprises one or more of a phenolic antioxidant, a sulfonate detergent, a phenate detergent, a salicylate detergent and combinations thereof.
    [0015] The invention further provides the method as described herein wherein the lubricating composition further includes at least one other additive selected from an ash-free dispersant, an ash-free antioxidant, a phosphorus-containing antiwear additive, a phosphorus modifier. friction, and a polymeric viscosity modifier.
    The invention further provides the method as described herein wherein the detergent with excess metal base comprises a sulfonated detergent.
    The invention further provides the method as described herein wherein the metal base excess detergent comprises a salicylate detergent.
    [0018] The invention further provides the method described herein wherein the base metal excess detergent comprises an alkali metal or an alkaline earth metal detergent.
    [0019] The invention further provides the method described herein in which the detergent with excess metal base has a metal ratio of 5 to 30.
    [0020] The invention further provides the method as described herein wherein the ash-free dispersant is present in an amount 0.2 - 8 percent by weight of the lubricating composition.
    [0021] The invention further provides the method as described herein wherein the lubricating composition further includes a polyalkenyl succinimide dispersant in an amount of 0.5 to 4% by weight of the composition.
    [0022] The invention further provides the method described herein in which the lubricating composition includes at least 50% by weight of Group II base oil, Group III base oil, or mixtures thereof.
    The invention further provides the method as described herein wherein the metal base excess detergent comprises a sulfur-bound-a-phenate detergent.
    [0024] The invention further provides the method described herein in which the detergent with excess metal base is present in an amount to provide 0.1 weight percent to 0.9 weight percent sulfated ash for the lubrication composition.
    [0025] The invention further provides the method described herein in which there is a reduction in the number of LSPI events of at least 10 percent.
    [0026] The invention further provides the method described herein in which low velocity pre-ignition events are reduced to less than 20 LSPI events per 100,000 combustion events. DETAILED DESCRIPTION
    [0027] The various features and preferred embodiments will be described below by way of non-limiting illustration.
    [0028] As indicated above, when operating the engine at speeds less than or equal to 3000 rpm and with a load, with a mean effective braking pressure (BMEP) greater than or equal to 10 bar, a pre-ignition event at low speed (LSPI) can occur in the engine. An LSPI event can consist of one or more LSPI combustion cycles, and generally consists of several LSPI combustion cycles that occur alternately or consecutively with the normal combustion cycles in between. Without being bound by a particular theory, LSPI may result from a combustion of oil droplets(s), or a drop(s) of liquid fuel mixture, or combinations thereof, which may accumulate, for example, on top the volume of a piston's ground slots, or the ground-ring and segment-ring piston slots. Lubricating oil can be transferred from under the oil control ring to the ground area on top of the piston due to unusual piston ring movements. At low speed, high load conditions, dynamic pressures in cylinders (compression and firing pressures) can be considerably different from pressures in cylinders at lower loads, in particular due to strongly delayed combustion phasing and high thrust and peak pressures of compression that can influence the dynamic ring of movement.
    [0029] At earlier loads, LSPI, which may be accompanied by later detonation and/or severe engine detonation, can cause severe engine damage very quickly (often within 1 to 5 engine cycles). Engine detonation can occur with LSPI as, after the normal spark is supplied from the ignition device, multiple flames may be present. The present invention aims to provide a method for inhibiting or reducing LSPI events, the method involves supplying the engine with a lubricant comprising a detergent with excess metal base.
    [0030] In an embodiment of the invention, the engine is operated at speeds of between 500 rpm and 3000 rpm, or 800 rpm to 2800 rpm, 1000 rpm or even 2600 rpm for. In addition, the engine can be operated with an average effective braking pressure of 10 bar to 30 bar, or 12 bar and 24 bar.
    [0031] LSPI events, while relatively uncommon, can be catastrophic in nature. Hence drastic reduction or even elimination of LSPI events during normal or sustained operation of a direct fuel injection engine is desirable. In one embodiment, the method of the invention is such that there are less than 20 LSPI events per 100,000 combustion events or less than 10 LSPI events per 100,000 combustion events. In one modality, it can be less than 5 LSPI events per 100,000 combustion events, less than 3 per LSPI events 100,000 combustion events; or there can be 0 LSPI events per 100,000 combustion events.
    [0032] In one embodiment, the method of the present invention provides a reduction in the number of LSPI events of at least 10 percent, or at least 20 percent, or at least 30 percent, or at least less, 50 percent. Fuel
    [0033] The method of the present invention involves the operation of a spark ignition internal combustion engine. In addition to engine operating conditions and lubricant composition, fuel composition can impact LSPI events. In one embodiment, the fuel may comprise a fuel that is liquid at room temperature and is useful for powering a spark-ignition engine, a fuel that is gaseous at room temperature, or combinations thereof.
    [0034] Liquid fuel is normally a liquid at ambient conditions, eg ambient temperature (20 to 30°C). The fuel can be a hydrocarbon fuel, a non-hydrocarbon fuel, or a mixture of these. The hydrocarbon fuel can be a gasoline engine as defined by the ASTM D4814 standard. In one embodiment of the invention, the fuel is a gasoline engine, and in other embodiments the fuel is a leaded gasoline, or an unleaded gasoline.
    [0035] The non-hydrocarbon fuel can be an oxygen-containing composition, often referred to as an oxygenated additive, to include an alcohol, an ether, a ketone, an ester of a carboxylic acid, a nitroalkane, or a mixture thereof. Non-hydrocarbon fuels may include, for example, methanol, ethanol, methyl-t-butyl ether, methyl ethyl ketone, transesterified plant and animal oils and/or fats such as rapeseed methyl ester and soy methyl ester, and nitromethane. Blends of hydrocarbons and non-hydrocarbon fuels may include, for example, gasoline and methanol and/or ethanol. In one embodiment of the invention, the liquid fuel is a mixture of gasoline and ethanol, wherein the ethanol content is at least 5 percent by volume of the fuel composition, or at least 10 percent by volume of the composition, or at least 15 percent by volume, or 15 to 85 percent by volume of the composition. In one embodiment, liquid fuel that contains less than 15% by volume ethanol content, less than 10% by volume ethanol content, less than 5% ethanol content by volume, or is substantially free of (or ie, less than 0.5% by volume) of ethanol.
    [0036] In various embodiments of the present invention, the fuel may have a sulfur content on a weight basis that is 5000 ppm or less, 1000 ppm or less, 300 ppm or less, 200 ppm or less, 30 ppm or less, or 10 ppm or less. in another embodiment, the fuel may have a sulfur content on a weight basis of 1 to 100 ppm. In one embodiment, the fuel contains about 0ppm and about 1000ppm, from about 0 to about 500ppm, about 0 to about 100ppm, about 0 to about 50ppm, about 0 to about 25ppm , approximately 0 to about 10 ppm, or about 0 to 5 ppm of alkali metals, alkaline earth metals, transition metals or mixtures thereof. In another embodiment, the fuel contains from 1 to 10 ppm by weight of alkali metals, alkaline earth metals, transition metals or mixtures thereof.
    [0037] Gaseous fuel is normally a gas at ambient conditions, eg ambient temperature (20 to 30 °C). Suitable gaseous fuels include natural gas, liquefied petroleum gas (LPG), compressed natural gas (CNG), or mixtures thereof. In one mode, the engine is powered by natural gas.
    [0038] The fuel compositions of the present invention may further comprise one or more performance additives. Performance additives can be added to a fuel composition depending on several factors, including the type of internal combustion engine and the type of fuel being used in which the engine, the quality of the fuel, and the service conditions in which the engine is used. engine is being operated. In some embodiments, the added performance additives are nitrogen-free. In other embodiments, additional performance additives may contain nitrogen.
    [0039] Performance additives may include an antioxidant, such as a hindered phenol or its derivative and/or a diarylamine or derivative thereof; a corrosion inhibitor such as an alkenylsuccinic acid; and/or a detergent/dispersant additive, such as a polyetheramine or nitrogen-containing detergent, including but not limited to polyisobutylene (PIB) amine dispersants, detergents, Mannich dispersants of succinimide, and their respective quaternary ammonium salts .
    [0040] Performance additives may also include a cold flow enhancer such as an esterified copolymer of maleic anhydride and styrene and/or a copolymer of ethylene and vinyl acetate; a foam inhibitor such as a silicone fluid; a demulsifier such as a polyoxyalkylene and/or a polyether alkyl alcohol; a lubricating agent, such as a fatty carboxylic acid, ester and/or amide derivatives of fatty carboxylic acids, or ester and/or amide derivatives of substituted hydrocarbyl succinic anhydrides; a metal deactivator, such as an aromatic triazole or a derivative thereof, including but not limited to a benzotriazole, such as tolytriazole; and/or a valve seat recession additive, such as an alkali metal sulfosuccinate salt. Additives may also include a biocide, an antistatic agent, a deicer, a fluidizer such as a mineral oil and/or a poly(alpha-olefin) and/or a polyether, and a combustion enhancer such as an octane or cetane improver.
    [0041] The fluidizing agent can be a polyetheramine or a polyether compound. Polyetheramine can be represented by the formula R[-OCH2CH(R1)]nA, where R is a hydrocarbyl group, R1 is selected from the group consisting of hydrogen, hydrocarbyl groups of 1 to 16 carbon atoms, and mixtures thereof, n is a number from 2 to about 50, and a is selected from the group consisting of --OCH2CH2CH2NR2R2 and --NR3R3, where each R2 is independently hydrogen or hydrocarbyl, and each R3 is independently hydrogen, hydrocarbyl, or - [ R4N(R5)]pR6, where R4 is C2-C10 alkylene, R5 and R6 are independently hydrogen or hydrocarbyl, and p is a number from 1-7.
    [0042] The fluidizing agent can be a polyether, which can be represented by the formula R7O [CH2CH(R8)O]qH, where R7 is a hydrocarbyl group, R8 is selected from the group consisting of hydrogen, hydrocarbyl groups from 1 to 16 carbon atoms, and mixtures thereof, eq is a number from 2 to about 50. The fluidizing agent may be a hydrocarbyl-terminated poly(oxyalkylene) as described in U.S. Pat. No. 5,503,644. The fluidizer can be an alkoxylate, wherein the alkoxylate can comprise: (i) a polyether containing two or more terminal ester groups; (ii) a polyether containing one or more ester groups and one or more terminal ether groups; or (iii) a polyether containing one or more ester groups and one or more terminal amino groups, wherein a terminal group is defined as a linking group located within five carbon or oxygen atoms from the end of the polymer. . Bonding is defined as the sum of the bonding carbon and oxygen atoms of the polymer or final group.
    [0043] Performance additives that may be present in the fuel additive compositions and fuel compositions of the present invention include diester, diamide, ester-amide, and ester-imide friction modifiers prepared by reaction of a dicarboxylic acid ( such as tartaric acid) and/or a tricarboxylic acid (such as citric acid), with an amine and/or alcohol, optionally in the presence of a known esterification catalyst. These friction modifiers often derived from tartaric acid, citric acid, or their derivatives can be derived from amines and/or alcohols that are branched so that the friction modifier itself has significant amounts of branched hydrocarbyl groups present in its structure. Examples of suitable branched alcohols used to prepare these friction modifiers include 2-ethylhexanol, isotridecanol, Guerbet alcohols, or mixtures thereof.
    [0044] In different modes of fuel composition it can have a composition as described in the following table:

    [0045] The lubricant composition comprises an oil of lubricating viscosity. These oils include natural and synthetic oils, oils derived from hydrocracking, hydrogenation and hydrofinishing, unrefined, refined, re-refined oils or mixtures thereof. A more detailed description of unrefined, refined and re-refined oils is provided in International Publication WO2008/147704, paragraphs [0054] to [0056] (similar disclosure is provided in US patent publication 2010/0197536, see [0072] to [0073]). A more detailed description of natural and synthetic lubricating oils is described in paragraphs [0058] to [0059], respectively, of WO2008/147704 (similar disclosure is provided in US patent publication 2010/0197536, see [0075] to [ 0076]). Synthetic oils can also be produced through Fischer-Tropsch reactions and typically can be hydroisomerized with Fischer-Tropsch hydrocarbons or waxes. In one embodiment, oils can be prepared by a Fischer-Tropsch gas-to-liquid synthesis process, as well as other gas-to-liquid oils.
    [0046] Lubricant viscosity oils can also be defined as specified in the April 2008 version of "Appendix E - API Base Oil Interchangeability Guidelines for Passenger Car Engine Oils and Diesel Engine Oils", section 1.3 Sub -point 1.3. "Basic Stock Categories". API guidelines are also summarized in US Patent 7285516 (see column 11, line 64 through column 12, line 10). In one embodiment, the lubricating viscosity oil may be an API Group II, Group III or Group IV oil, or mixtures thereof. The five base oil groups are as follows:

    [0047] The amount of lubricating viscosity oil present is typically the balance remaining after subtracting from 100% by weight (% by weight) the sum of the amount of the compound of the invention and the other performance additives.
    [0048] The lubricating composition can be in the form of a concentrate and/or a fully formulated lubricant. If the lubricant composition of the invention (comprising the additives described herein) is in the form of a concentrate which can be combined with the additional oil to form, in whole or in part, a finished lubricant, the relationship between these additives to the lubricating oil and/or thinner oil include ranges from 1:99 to 99:1 by weight, or 80:20 to 10:90 by weight.
    [0049] In one modality, the base oil has a kinematic viscosity at 100 ° C from 2 mm2/s (centistokes - cSt) to 16 mm2/s, from 3 mm2/s to 10 mm2/s, or even from 4 mm2/s to 8 mm2/s.
    [0050] The ability of a base oil to act as a solvent (ie, solvency) can be a factor that contributes to the increased frequency of LSPI events during the operation of a direct fuel injection engine. Base oil solvency can be measured as the ability of an unadditivated base oil to act as a solvent for polar constituents. In general, the base oil Solvency decreases as the base oil group moves from Group I to Group IV (PAO). In other words, the solvency of base oils can be classified as follows for oil of a certain kinematic viscosity: Group I> Group II> Group III> Group IV. Base oil solvency also decreases as viscosity increases within a base oil group; Low viscosity base oil tends to have better solvency than similar higher viscosity base oil. Base oil solvency can be measured by aniline point (ASTM D611).
    [0051] In one embodiment, the base oil comprises at least 30% by weight of the Group II or Group III base oil. In another embodiment, the base oil comprises at least 60% by weight of the Group II or Group III base oil, or at least 80% by weight of the Group II or Group III base oil. In one embodiment, the lubricant composition comprises less than 20% by weight of Group IV base oil (i.e. polyalphaolefin). In another embodiment, the base oil comprises less than 10% by weight of Group IV base oil. In one embodiment, the lubricating composition is substantially free of (i.e., contains less than 0.5% by weight) of Group IV base oil.
    [0052] Ester-based fluids, which are characterized as Group V oils, have high levels of solvency as a result of their polar nature. The addition of low levels (typically less than 10% by weight) of ester to a lubricant composition can significantly increase the resulting solvency of the base oil blend. Esters can be grouped into two categories: synthetic and natural. An ester base fluid would have a kinematic viscosity at 100 °C suitable for use in an engine lubricating oil, such as between 2 cSt and 30 cSt, or from 3 cSt to 20 cSt, or even from 4 cSt to 12 cSt.
    [0053] Synthetic ester may comprise esters of dicarboxylic acids (for example, phthalic acid, succinic acid, alkyl and alkenyl succinic acids, succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, dimer linoleic acid, malonic acid, alkyl malonic acid, and alkenyl malonic acid), with any of a variety of monohydric alcohols (eg, butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, and propylene glycol). Specific examples of these esters include salts of dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl dioctyl azelate, didecyl phthalate, dieicosyl sebacate phthalate, diester of 2 -ethylhexyl linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid. Other synthetic esters include those made from C5 to C12 monocarboxylic acids and ether polyols and polyols such as neopentyl glycol, trimethylalpropane, pentaerythritol, dipentaerythritol, tripentaerythritol e.g. Esters can also be mono-esters of mono-carboxylic acids and mono-hydric alcohols.
    [0054] Natural esters (or bio derivatives) refer to materials derived from a renewable biological resource, organism or entity, distinct from petroleum-derived materials or equivalent raw materials. Natural esters include fatty acid triglycerides, hydrolyzed or partially hydrolyzed triglycerides, or transesterified triglyceride esters such as fatty acid methyl ester (or FAME). Suitable triglycerides include, but are not limited to palm oil, soybean oil, sunflower oil, rapeseed oil, olive oil, linseed oil, and related materials. Other sources of triglycerides include, but are not limited to algae, animal tallow, and zooplankton. Methods for producing natural triglyceride biolubricants are described in, for example, United States Patent Publication 2011/0009300A1.
    [0055] In one embodiment, the lubricating composition comprises at least 2% by weight of an ester-based fluid. In one embodiment the lubricant composition of the invention comprises at least 4% by weight of an ester base fluid, or at least 7% by weight of an ester base fluid, or even at least 10% by weight of an ester base fluid.
    [0056] Detergents with excess metal base, otherwise referred to as detergents with excess base, detergents with excess base containing metals or salts with excess base, are characterized by a higher metal content than would be necessary for the neutralization according to the stoichiometry of the metal and the particular acidic organic compound, ie the substrate, reacted with the metal. The base excess detergent can comprise one or more of the non-sulfur containing phenates, sulfur containing phenates, sulfonates, salicylates, and mixtures thereof.
    [0057] The amount of excess metal is usually expressed in terms of the ratio of substrate to metal. The terminology "metal ratio" is used in the prior art and here to define the ratio of the total chemical equivalents of metal in the salt with excess base to the chemical equivalents of metal in the salt that would be expected to result from the reaction between the hydrocarbyl substituted organic acid; the phenol or its mixtures substituted with hydrocarbyl to be with excess base, and the basic metal compound according to the known chemical reactivity and stoichiometry of the two reactants. Thus, in a normal or neutral salt (ie soaps) the metal ratio is one, in a salt with excess base the metal ratio is greater than one, especially greater than 1.3. The base excess detergent of the invention may have a metal ratio of 5 to 30, or a metal ratio of 7 to 22, or a metal ratio of at least 11.
    The metal-containing detergent may also include "hybrid" detergents formed with mixed surfactant systems, including phenate and/or sulfonate components, eg phenate-salicylates, sulfonate, sulfonate-phenate-salicylates, sulfonate-phenate-salicylates , as described, for example, in US Patents 6,429,178; 6,429,179; 6,153,565; and 6,281,179. Where, for example, a hybrid sulfonate/phenate detergent is employed, the hybrid detergent would be considered equivalent to distinct amounts of phenate and sulfonate detergents introducing as amounts of phenate and sulfonate soaps, respectively. Excess base phenates and salicylates typically have a total base number of 180450 TBN. Excess base sulphonates typically have a total base number of 250 to 600, or 300 to 500. Detergents with excess base are known in the art.
    [0059] Alkyl Phenols are often used as components in and/or building blocks for detergents with excess base. Alkylphenols can be used to prepare phenate, salicylate, salixarate, or saligenin detergents or mixtures thereof. Alkylphenols include para-substituted hydrocarbyl phenols. The hydrocarbyl group can be a linear or branched aliphatic group of 1 to 60 carbon atoms, 8 to 40 carbon atoms, 10 to 24 carbon atoms, 12 to 20 carbon atoms, or 16 to 24 carbon atoms. In one embodiment, the detergent with excess alkylphenol base is prepared from an alkylphenol or a mixture thereof that is free or substantially free of (i.e., contains less than 0.1 weight percent) of p- dodecylphenol. In one embodiment, the lubricant composition of the invention contains less than 0.3 percent by weight of alkylphenol, less than 0.1 percent by weight of alkylphenol, or less than 0.05 percent by weight of alkylphenol. .
    [0060] The detergent containing metal with excess base can be alkali metal salts or alkaline earth metals. In one embodiment, the detergent can be base-excess sodium salts, calcium salts, magnesium salts, or mixtures thereof of phenates, sulfur-containing phenates, sulfonates, salicylates and salixarates. In one embodiment, the detergent is a detergent with an excess of a calcium base, a magnesium detergent, or mixtures thereof. In one embodiment, the excess base calcium detergent can be present in an amount sufficient to provide at least 500 ppm by weight of calcium and no calcium more than 3000 ppm by weight, or at least 1000 ppm of calcium by weight or at least 2000 ppm calcium by weight or no calcium more than 2500 ppm by weight of the lubricating composition. In one embodiment, the detergent with excess base can be present in an amount to provide no more than 500 ppmw of magnesium for the lubricant composition, or no more than 330 ppmw, or no more than 125 ppm by weight, or no more than 45 ppm by weight. In one embodiment, the lubricating composition is essentially free of (i.e., contains less than 10 ppm) magnesium resulting from the detergent with excess base. In one embodiment, the detergent with excess base can be present in an amount sufficient to provide at least 200 ppm by weight of magnesium, or at least 450 ppm by weight of magnesium, or at least 700 ppm magnesium by weight of the lubricating composition. In one embodiment, both calcium and magnesium containing detergents can be present in the lubricant composition. Detergent calcium and magnesium may be present such that the calcium to magnesium weight ratio is 10: 1 to 1:10, or 8: 3-4: 5, or 1:1 to 1: 3. In one modality, the detergent with excess base is free or substantially free of sodium.
    [0061] In one embodiment, the sulfonate detergent may be predominantly a linear alkylbenzene sulfonate detergent having a metal ratio of at least 8, as described in paragraphs [0026] to [0037] of US Patent 2005/065045 Publication ( and granted as US 7,407,919). Linear alkylbenzene sulfonate detergent can be particularly useful to help improve fuel economy. The linear alkyl group can be attached to the benzene ring anywhere along the straight chain of the alkyl group, but often at the 2, 3 or 4 positions of the straight chain, and in some cases predominantly at the 2 position, resulting in linear alkylbenzene sulfonate detergent.
    [0062] Salicylate detergents and salicylate detergents with excess base can be prepared in at least two different ways. Carbonylation (also referred to as carboxylation) of a p-alkylphenol is described in many references, including US Patent 8,399,388. Carbonylation can be followed by excess basification to form salicylate detergent with excess base. Suitable p-alkylphenols include linear and/or branched hydrocarbyl groups of 1 to 60 carbon atoms. Salicylate detergent can also be prepared by alkylation of salicylic acid, followed by excess basification, as described in US Patent 7,009,072. Salicylate detergents prepared in this way can be prepared from linear and/or branched alkylating agents (generally 1-olefins) containing 6 to 50 carbon atoms, 10 to 30 carbon atoms, or 14 to 24 carbon atoms . In one embodiment, the base excess detergent of the invention is a salicylate detergent. In one embodiment, the salicylate detergent of the present invention is free of unreacted p-alkylphenol (i.e., contains less than 0.1 percent by weight). In one embodiment, the salicylate detergent of the present invention is prepared by alkylation of salicylic acid.
    [0063] The detergent with excess base may be present at 0.2% by weight to 15% by weight, or 0.3% by weight to 10% by weight, or 0.3% by weight to 8% by weight , or 0.4% by weight to 3% by weight. For example, in a heavy duty diesel engine, the detergent may be present at 2% by weight to 3% by weight of the lubricating composition. For a passenger car engine, the detergent may be present in 0.2% by weight to 1% by weight of the lubricating composition.
    [0064] Metal-containing detergents contribute sulphated ash to a lubricating composition. Sulphated ash can be determined by ASTM D874. In one embodiment, the lubricating composition of the present invention comprises a detergent containing a metal in an amount to provide at least 0.4 percent by weight of sulfated ash to the total composition. In another embodiment, the metal-containing detergent is present in an amount to provide at least 0.6 weight percent sulfated ash, or at least 0.75 weight percent sulfated ash, or even at least 0. 9 weight percent sulfated ash to the lubricating composition. In one embodiment, the metal-containing excess base detergent is present in an amount sufficient to provide 0.1 weight percent to 0.8 weight percent sulfated ash to the lubricating composition.
    [0065] In addition to ash and TBN, detergents with excess base contribute to detergent soap, also referred to as neutral detergent salt, to the lubricating composition. Soap, being a metal salt of the substrate, can act as a surface active agent in the lubricating composition. In one embodiment, the lubricating composition comprises from 0.05 percent by weight to 1.5 percent by weight of detergent soap, or 0.1 percent by weight to 0.9 percent by weight of detergent soap. In one embodiment, the lubricating composition contains no more than 0.5 percent by weight of detergent soap. Detergent with excess base may have an ash:soap weight ratio of 5:1 to 1: 2.3, or 3.5: 1 to 1: 2, or 2.9: 1 to 1:1 : 7. Other performance additives
    [0066] The compositions of the invention may optionally comprise one or more performance additives. These additional performance additives may include one or more metal deactivators, viscosity modifying agents, antioxidants, friction modifiers, antiwear agents, corrosion inhibitors, dispersants, dispersant viscosity modifiers, extreme pressure agents, antioxidants (except those herein invention), foam inhibitors, demulsifiers, pour point depressants, seal swelling agents, and any combination or mixture thereof. Typically, fully formulated lubricating oil will contain one or more of these performance additives, and often a package of multiple performance additives.
    [0067] In one embodiment, the invention provides a lubricating composition which further comprises a dispersing agent, an antiwear agent, a dispersing viscosity modifier, a friction modifier, a viscosity modifier, an antioxidant, a detergent (other than the invention) or a combination thereof, where each of said additives may be a mixture of two or more such additives. In one embodiment, the invention provides a lubricating composition which further comprises a polyisobutylene succinimide dispersant, an antiwear agent, a dispersant viscosity modifier, a friction modifier, a viscosity modifier (typically an olefin copolymer, such as an ethylene-propylene copolymer), an antioxidant (including phenolic and amine antioxidants), a detergent with excess base (including sulfonates and phenates with excess base), or a combination thereof, where each of said additives may be a mixture of two or more of this type of additive.
    [0068] In one embodiment, the invention provides a lubricating composition that further comprises ash-free antioxidants. Ash-free antioxidants one or more of arylamines, diarylamines, alkylated arylamines, amines, alkylated diaryl phenols, hindered phenols, sulfur olefins, or mixtures thereof. In one embodiment the lubricating composition includes an antioxidant, or mixtures thereof. The antioxidant may be present at 0% by weight to 15% by weight, or 0.1% by weight to 10% by weight, or 0.5% by weight to 5% by weight, or 0.5% by weight to 3% by weight, or 0.3% by weight to 1.5% by weight of the lubricating composition.
    The alkylated diarylamine or diarylamine can be a phenyl-α-naphthylamine (PANA), an alkylated diphenylamine, or an alkylated phenylnaptylamine, or mixtures thereof. The alkylated diphenylamine may include di-nonylated diphenylamine, nonyl diphenylamine, octyl diphenylamine, di-octylated diphenylamine, dideylated diphenylamine, decyl diphenylamine and mixtures thereof. In one embodiment, the diphenylamine can include nonyl diphenylamine, dinonyl diphenylamine, octyl diphenylamine, dioctyl diphenylamine, or mixtures thereof. In an alkylated diphenylamine embodiment it may include nonyl diphenylamine, or dinonyl diphenylamine. The alkylated diarylamine can include octyl, dioctyl, nonyl, di-nonyl, decyl or didecyl phenylnaptylamines.
    [0070] The diarylamine antioxidant of the invention may be present on a weight basis of the lubricating composition at 0.1% to 10%, 0.35% to 5%, or even 0.5% to 2%.
    [0071] The phenolic antioxidant can be a simple alkyl phenol, a hindered phenol, or coupled phenolic compounds.
    The hindered phenolic antioxidant often contains a secondary butyl group and/or a tertiary butyl group as a sterically hindering group. The phenol group may be further substituted with a hydrocarbyl group (typically linear or branched alkyl) and/or a bridging group linking to a second aromatic group. Examples of suitable hindered phenolic antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2, 6-di-tert-butyl-phenol or 4-butyl-2,6-di-tert-butyl-phenol, 4-dodecyl-2,6-di-tert-butyl-phenol, or 3-(3,5-ditert-butyl) ethyl -butyl-4-hydroxyphenyl)propanoate. In one embodiment, the phenol posterior antioxidant may be an ester and may include, for example, Ciba's Irganox™ G-135.
    [0073] Coupled phenols often contain two alkylphenols together with alkylene groups to form bisphenol compounds. Examples of suitable coupled phenolic compounds include 4,4'-methylene-bis-(2,6-di-tert-butyl phenol), 4-methyl-2,6-di-tert-butylphenol, 2,2'-bis- (6-t-butyl-4-heptylphenol); 4,4'-bis(2,6-di-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol) and 2,2'-methylene bis(4-ethyl-6 -t-butylphenol).
    [0074] The phenols of the invention also include polyhydric aromatic compounds and their derivatives. Examples of suitable polyhydric aromatic compounds include gallic acid esters and amides, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 1,4-dihydroxy-2-naphthoic acid, 3,5 -dihydroxynaphthoic, 3,7-dihydroxy naphthoic, and mixtures thereof.
    [0075] In one embodiment, the phenolic antioxidant comprises a hindered phenol. In another embodiment, the hindered phenol is derived from 2,6-ditertbutyl phenol.
    [0076] In one embodiment, the lubricating composition of the present invention comprises a phenolic antioxidant in a range of 0.01% by weight to 5% by weight, or 0.1% by weight to 4% by weight, or 0. 2% by weight to 3% by weight, or 0.5% by weight to 2% by weight of the lubricating composition.
    [0077] Sulfurated Olefins are well known commercial materials, and those that are substantially nitrogen free, ie not containing nitrogen functionality, are readily available. Olefin compounds that can be sulfured are of a different nature. They contain at least one olefinic double bond, which is defined as a non-aromatic double bond; that is, a bond between two aliphatic carbon atoms. These materials generally have sulfide bonds, having 1 to 10 sulfur atoms, for example 1 to 4, or 1 or 2.
    [0078] Ash-free antioxidants can be used separately or in combination. In one embodiment of the invention, two or more different antioxidants are used in combination, such that there is at least 0.1 percent by weight of each of the at least two antioxidants, and wherein the combined amount of the ash-free antioxidants is from 0.5 to 5 percent by weight. In one embodiment, there can be at least 0.25 to 3 percent by weight of each antioxidant ash-free.
    [0079] In one embodiment, the invention provides a lubricating composition further comprising a molybdenum compound. The molybdenum compound can be selected from the group consisting of molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, amine salts of molybdenum compounds, and mixtures thereof. The molybdenum compound can provide the lubricating composition with 0 to 1000 ppm, or 5 to 1000 ppm, or 10 to 750 ppm, or 5 ppm to 300 ppm, or 20 ppm to 250 ppm of molybdenum.
    [0080] Dispersants suitable for use in the compositions of the present invention include succinimide dispersing agents. In one embodiment, the dispersing agent can be present as a single dispersant. In one embodiment, the dispersing agent can be present as a mixture of two or three different dispersants, at least one of which can be a succinimide dispersant.
    [0081] The succinimide dispersant can be a derivative of an aliphatic polyamine, or mixtures thereof. The aliphatic polyamine can be an aliphatic polyamine such as an ethylenepolyamine, a propylenepolyamine, a butylenepolyamine, or mixtures thereof. In one embodiment, the aliphatic polyamine can be ethylenepolyamine. In one embodiment the aliphatic polyamine can be selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine distillation, and mixtures thereof.
    [0082] The dispersant may be an N-substituted long chain alkenyl succinimide. Examples of N-substituted long chain alkenyl succinimide include polyisobutylene succinimide. Typically, the polyisobutylene of polyisobutylene anhydride, which is succinic derivative has a number average molecular weight of 350-5000, or 550 to 3000 or 750 to 2500. Succinimide dispersants and their preparation are disclosed, for example in the US Patents 3,172,892, 3,219,666, 3,316,177, 3,340,281, 3351552, 3381022, 3433744, 3444170, 3467668, 3501405, 3542680, 3576743, 3632511, 4234435, Re 26433 and 6165235, 7238650 and in Patent EP 0 355 895B1.
    [0083] The dispersant can also be post-treated by conventional methods through a reaction with any of a variety of agents. Among these are boron compounds, urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, and phosphorus compounds.
    [0084] The dispersing agent may be present at 0.01% by weight to 20% by weight, or 0.1% by weight to 15% by weight, or 0.1% by weight to 10% by weight, or 1 % by weight to 6% by weight of the lubricating composition.
    [0085] In one embodiment, the lubricant composition of the invention further comprises a dispersant viscosity modifier. The dispersant viscosity modifier may be present at 0% by weight to 5% by weight, or 0% by weight to 4% by weight, or 0.05% by weight to 2% by weight of the lubricant composition.
    [0086] Suitable dispersant viscosity modifiers include functionalized polyolefins, for example ethylene-propylene copolymers that have been functionalized with an acylating agent such as maleic anhydride and an amine; polymethacrylates functionalized with an amine group, or copolymers of esterified styrene-maleic anhydride reacted with an amine. More detailed description of viscosity modifying dispersants are described in International Publication WO2006/015130 or U.S. Patents 4,863,623; 6,107,257; 6,107,258; and 6,117,825. In one embodiment, the dispersant viscosity modifier may include those described in US Patent 4,863,623 (see column 2, line 15 to column 3, line 52) or in WO2006 International Publication/015130 (see page 2, paragraph [0008] and the preparative examples are described in nos. [0065] to [0073]).
    [0087] In one embodiment, the invention provides a lubricating composition that further includes a phosphorus-containing anti-wear agent. Typically, the phosphorus-containing antiwear agent can be a zinc dialkyldithiophosphate. Zinc dialkyldithiophosphates are known in the art. The antiwear agent may be present at 0% by weight to 3% by weight, or 0.1% by weight to 1.5% by weight, or 0.5% by weight to 0.9% by weight of the composition. lubricant.
    [0088] In one embodiment, the invention provides a lubricating composition which further comprises a friction modifier. Examples of friction modifiers include long-chain fatty acid derivatives of amines, fatty acid esters, or epoxides; fatty imidazolines such as condensation products of carboxylic acids and polyalkylene polyamines; amine salts of alkyl phosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; or fatty alkyl tartramides. The term fatty acid, as used herein, can mean having a linear, C8-22 alkyl group.
    [0089] Friction modifiers can also include materials such as fatty sulfur compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, sunflower oil or monoester of a polyol and an aliphatic carboxylic acid.
    [0090] In one embodiment the friction modifier can be selected from the group consisting of long chain fatty acid derivatives of amines, long chain fatty acid esters, or long chain fatty epoxides; fatty imidazolines; amine salts of alkyl phosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; and fatty alkyl tartramides. The friction modifier may be present at 0% by weight to 6% by weight, or 0.05% by weight to 4% by weight, or 0.1% by weight to 2% by weight of the lubricant composition.
    [0091] In one embodiment, the friction modifier can be a long-chain fatty acid ester. In another embodiment, the long chain fatty acid ester can be a mono-ester or a diester or a mixture thereof, and in another embodiment the long chain fatty acid ester can be a triglyceride.
    [0092] Other performance additives such as corrosion inhibitors include those described in paragraphs 5 to 8 of US Application US05/038,319, published as WO2006/047486, octyl octanamide, condensation products of dodecenyl succinic acid or anhydride and a fatty acid such as oleic acid with a polyamine. In one embodiment, corrosion inhibitors include Synalox® (a registered trademark of The Dow Chemical Company) corrosion inhibitor. Synalox® corrosion inhibitor can be a homopolymer or copolymer of propylene oxide. Synalox® corrosion inhibitor is described in more detail in a Product Brochure Form No. 118-01453-0702 AMS, published by The Dow Chemical Company. The product brochure is titled "SYNALOX High Performance Polyglycol Lubricants for demanding applications."
    [0093] The lubricating composition may further include metal deactivators, including benzotriazole derivatives (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles or 2-alkyldithiobenzothiazoles; foam inhibitors, including ethyl acrylate 2-ethylhexylacrylate copolymers and ethyl acrylate 2-ethylhexyl vinyl acetate copolymers; demulsifiers, including trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and the oxide polymers (ethylene-propylene oxide); and pour point depressants, including maleic-styrene anhydride esters, polymethacrylates, polyacrylamides or polyacrylates.
    Pour point depressants that may be useful in the compositions of the invention further include polyalphaolefins, maleic anhydride-styrene esters, poly(meth)acrylates, polyacrylates or polyacrylamides.
    [0095] In different modalities of the lubricating composition may have a composition as described in the following table:

    [0096] The present invention provides a surprising ability to prevent damage to a running engine due to pre-ignition events resulting from direct injection of gasoline into the combustion chamber. This is achieved by keeping fuel economy performance, sulphated gray levels low, improved deposit control and other limitations required by increasingly stringent government regulations. industrial application
    [0097] As described above, the invention provides a method of lubricating an internal combustion engine which comprises providing the internal combustion engine with a lubricating composition as disclosed herein. Generally, lubricant is added to the internal combustion engine's lubrication system, which then supplies the lubricant composition to the critical parts of the engine, during its operation, that require lubrication.
    [0098] The lubrication compositions described above can be used in an internal combustion engine. Engine components can have a steel or aluminum surface (usually a steel surface), and can also be coated, for example, with a diamond-like carbon (DLC) coating.
    [0099] An aluminum surface may be comprised of an aluminum alloy which may be a hypereutectic or eutectic aluminum alloy (such as those derived from aluminum silicates, aluminum oxides, or other ceramic materials). The aluminum surface may be present in a cylinder bore, cylinder block, or piston ring having an aluminum alloy, or aluminum composite.
    [0100] An aluminum surface can consist of an aluminum alloy which can be a eutectic or hyper-eutectic aluminum alloy (such as those derived from aluminum silicates, aluminum oxides, or other ceramic materials). The aluminum surface may be present in a bore, cylinder block, or piston ring having an aluminum alloy, or aluminum composite.
    [0101] The internal combustion engine can be equipped with an emission control system and a turbocharger. Examples of the emission control system include diesel particulate filters (DPF), or systems that employ selective catalytic reduction (SCR).
    [0102] The internal combustion engine of the present invention is distinct from a gas turbine. In an internal combustion engine, individual combustion events translate from an alternate linear force to a rotational torque through the stem and crankshaft. In contrast, in a gas turbine (which may also be referred to as a jet engine) a continuous combustion process generates rotational torque continuously without translation, and can also build up pressure at the exhaust outlet. These differences in the operating conditions of a gas turbine and internal combustion engine result in different operating environments and voltages.
    [0103] The lubricant composition for an internal combustion engine may be suitable for any engine lubricant regardless of sulfur, phosphorus or sulphated ash (ASTM D 874) content. The sulfur content of the engine lubricating oil may be 1% by weight or less, or 0.8% by weight or less, or 0.5% by weight or less, or 0.3% by weight or less. In one embodiment, the sulfur content can range from 0.001% by weight to 0.5% by weight, or 0.01% by weight to 0.3% by weight. The phosphorus content may be 0.2% by weight or less, or 0.12% by weight or less, or 0.1% by weight or less, or 0.085% by weight or less, or 0.08% by weight. weight or less, or even 0.06% by weight or less, 0.055% by weight or less, or 0.05% by weight or less. In one embodiment, the phosphorus content can be from 100 ppm to 1000 ppm, or 200 ppm to 600 ppm. The total content of sulfated ash may be 2% by weight or less, or 1.5% by weight or less, or 1.1% by weight or less, or 1% by weight or less, or 0.8% by weight or less, or 0.5% by weight or less, or 0.4% by weight or less. In one embodiment, the sulfated ash content can be 0.05% by weight to 0.9% by weight, or 0.1% by weight to 0.2% by weight or 0.45% by weight.
    [0104] In one embodiment, the lubricant composition can be a motor oil, wherein the lubricant composition can be characterized as having at least one of (i) a sulfur content of 0.5% by weight or less , (ii) a phosphorus content of 0.1% by weight or less, (iii) a sulfated ash content of 1.5% by weight or less, or combinations thereof. EXAMPLES
    [0105] The invention will be further illustrated by the following examples, which set forth particularly advantageous embodiments. While examples are provided to illustrate the invention, they are not intended to limit it. Lubricating Compositions
    [0106] A series of 5W-20 engine lubricants in Group II lube viscosity base oil are prepared containing the additives described above, as well as conventional additives including polymeric viscosity modifier, ash-free succinimide dispersant, detergents with excess base, antioxidants (combination of phenolic ester and diarylamine), zinc dialkyldithiophosphate (ZDDP), as well as other performance additives as shown (Table 1). The phosphorus, sulfur and ash contents of each of the Examples are also shown in the Table in part to show that each example has a similar amount of these materials and thus provide a suitable comparison between the comparative examples and the invention.
    1 - All values shown above are in percent by weight and are on an oil free base unless otherwise indicated 2 - Ca 1 sulphonate: calcium sulphonate with excess base with oil free 520 TBN; metal ratio of 10 3- Sulfonate Ca 2: calcium sulfonate with excess base with TBN free oil of 690; metal ratio of 184 - Ca3 sulphonate: calcium sulphonate with excess base with TBN free oil of 160; metal ratio of 2.85 – Phenate Ca: “neutral” calcium phenate with 200 TBN free oil; metal ratio of 1.2 6 - Sulfonate Na: Sulfonate Na with excess base with oil free TBN of 650 7 - Sulfonate Mg: Sulfonate Mg with excess base with oil free 600 8 - Combination of alkylated diarylamine and oxidants of hindered phenol 9 - Dispersant: PIBsuccinimide prepared from 2000 Mn PIB 10 - Additional additives used in the examples include friction modifiers, pour point depressants, antifoam agents, corrosion inhibitors, and include some amount of thinner oil. Table 2 - Lubricating Oil Composition Formulations (5W-30)
    1 - All amounts shown above are in percent by weight and are on an oil-free basis unless otherwise noted. 11 - Ca sulphonate is one or more calcium alkylbenzene sulphonic acid with excess base with TBN of at least 300 and metal ratio of at least 10 12 - Magnesium sulphonate with excess base with TBN of ~600 13 - Alloyed phenate salt calcium sulfur with TBN of ~200 14 - Ash-free antioxidant - mixture of dinonylated and nonylated diphenylamine, hindered phenol ester and sulfurized olefin 15 - Additional additives used in the examples include friction modifiers, pour point depressants, agents anti-foam, corrosion inhibitors, and includes a certain amount of thinner oil. Rehearsal
    [0107] Low speed pre-ignition events are measured on two engines, a Ford 2.0L Ecoboost engine and a GM 2.0L Ecotec engine. Both engines are turbocharged gasoline direct injection (GDI) engines. The Ford Ecoboost engine is operated in two stages. In the first phase, the engine is operated at 1500 rpm and 14.4 bar of mean effective braking pressure (BMEP). During the second phase, the engine is operated at 1750 rpm and 17.0 bar PEMF. The engine runs for 25,000 combustion cycles in each stage, and LSPI events are counted.
    [0108] The GM Ecotec engine is operated at 2000 rpm and 22.0 bar BMEP with an oil sump temperature of 100oC. The test consists of nine phases of 15,000 combustion cycles with each phase separated by a rest period. Thus combustion events are counted over 135,000 combustion cycles.
    [0109] LSPI events are determined by monitoring peak cylinder pressure (PP) and burning mass fraction (MFB) of the fuel charge in the cylinder. When both criteria are met, it is determined that an LSPI event has occurred. The limit for peak cylinder pressure is typically 9,000 to 10,000 kPa. The threshold for MFB is typically such that at least 2% of the fuel charge is burned late, ie 5.5 degrees After Top Dead Center (CTDM). LSPI events can be reported as events per 100,000 combustion cycles, events per cycle, and/or combustion cycles per event.
    The data indicate that a reduction in a total detergent ash below 1 percent by weight results in a reduction in LSPI events. Partial replacement of calcium detergent with magnesium and/or sodium detergent also provided an observed reduction in LSPI events. In addition, partial replacement of sulfonate detergent with phenate-based detergent resulted in an observable reduction in LSPI events.
    [0110] It is known that some of the materials described above can interact in the final formulation, so that the components of the final formulation may be different from those that are initially added. The products so formed, including the products formed above employing the lubricant composition of the present invention in their intended use, may not be capable of easy description. However, all such modifications and reaction products are included within the scope of the present invention; the present invention encompasses the lubricating composition prepared by mixing the above-described components.
    [0111] Each of the above documents is incorporated herein by reference, as is the priority document and all related applications, if any, which this application claims the benefit of. Except in the examples, or where otherwise explicitly indicated, all numerical quantities in this description specifying quantities of materials, reaction conditions, molecular weight, number of carbon atoms, and the like, are to be understood as modified by the word "about ". Unless otherwise indicated, each chemical or composition referred to herein is to be construed as being a commercial grade material that may contain the isomers, by-products, derivatives, and other such materials that are commonly understood to be present in commercial grade. However, the amount of each chemical component is shown unique to any oil solvent or thinner, which may ordinarily be present in commercial material, unless otherwise indicated. It is to be understood that the amount, range, and upper and lower relationship limits set forth herein may be independently combined. Likewise, ranges and amounts for each element of the present invention can be used in conjunction with ranges of amounts or any of the other elements.
    [0112] As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its common sense, which is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and which is predominantly hydrocarbon in character. Examples of hydrocarbyl groups include: (i) hydrocarbon substituents, i.e., aliphatic (eg, alkyl or alkenyl), alicyclic (eg, cycloalkyl, cycloalkenyl), and aromatic-, aliphatic, and alicyclic-substituted aromatic substituents , as well as cyclic substituents in which the ring is completed through another portion of the molecule (for example, two substituents together form a ring); (ii) substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups which, in the context of this invention, do not change the predominantly hydrocarbon character of the substituent (e.g., halogen atoms (especially chlorine and fluorine), hydroxy , alkoxy, mercapto, alkyl mercapto, nitro, nitroso, and sulfoxide); (iii) heteroatom substituents, i.e., substituents which, although having a predominantly hydrocarbon character in the context of this invention, contain other than carbon in a ring or chain otherwise composed of carbon atoms.
    [0113] Heteroatoms include sulfur, oxygen, nitrogen, and embrace substituents such as pyridyl, furyl, thienyl, and imidazolyl. In general, no more than two, preferably no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; normally, there will be no non-hydrocarbon substituents on the hydrocarbyl group.
    [0114] Although the invention has been explained with respect to its preferred embodiments, it is to be understood that various modifications thereof will be apparent to those skilled in the art upon reading the specification. Therefore, it is to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.
    权利要求:
    Claims (8)
    [0001]
    1. Method of reducing low-speed pre-ignition events in a spark-ignition direct injection internal combustion engine, where the engine is equipped with a turbocharger and is operated under a load with an average effective braking pressure ( BMEP) greater than or equal to 12 bar (1.2 MPa) at speeds less than or equal to 3,000 rpm, the method characterized by the fact that it comprises providing the engine with a lubricating composition comprising: (a) a base oil of viscosity lubricant; (b) an excess base magnesium sulphonate detergent in an amount to provide at least 450 ppm of magnesium from the excess base magnesium sulphonate detergent to the lubricating composition; (c) an excess base calcium sulfonate detergent in an amount to provide at least 1,000 ppm of calcium from the excess base calcium sulfonate detergent to the lubricating composition; (d) 0.5% to 0.9% by weight of a zinc dialkyldithiophosphate antiwear additive; and (e) 0.5% to 15% by weight of one or more additional additives, wherein the excess base magnesium sulphonate detergent and the excess base calcium sulphonate detergent collectively contribute up to 0.8 % by weight of sulphated ash for the lubricating composition and wherein the lubricating composition has a phosphorus content of 0.12% by weight or less and total sulphated ash of 1.1% by weight or less.
    [0002]
    2. Method according to claim 1, characterized in that the engine is filled with a liquid hydrocarbon fuel, a liquid non-hydrocarbon fuel or their mixtures.
    [0003]
    3. Method according to claim 2, characterized in that the engine is fueled by natural gas, liquefied petroleum gas (LPG), compressed natural gas (CNG) or their mixtures.
    [0004]
    4. Method according to claim 1, characterized in that the one or more additional additives is selected from an ash-free dispersant, an ash-free antioxidant, a friction modifier and a polymeric viscosity modifier.
    [0005]
    5. Method according to claim 1, characterized in that the magnesium detergent with excess base has a metal ratio of 5 to 30.
    [0006]
    6. Method according to claim 1, characterized in that the magnesium detergent with excess base is present in an amount of 0.2% to 8% by weight of the lubricant composition.
    [0007]
    7. Method according to claim 1, characterized in that the one or more additional additives is a polyalkenyl succinimide dispersant in an amount of 0.5% to 4% by weight of the lubricant composition.
    [0008]
    8. Method according to claim 1, characterized in that the base oil comprises at least 50% by weight of a Group II base oil, a Group III base oil or mixtures thereof.
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    法律状态:
    2018-11-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-11-12| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-09-29| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2021-03-16| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-18| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/09/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201361879725P| true| 2013-09-19|2013-09-19|
    US61/879,725|2013-09-19|
    PCT/US2014/056445|WO2015042340A1|2013-09-19|2014-09-19|Lubricant compositions for direct injection engines|
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