CN107922873B

CN107922873B - Lubricant with calcium-containing detergent and its use for improving low-speed pre-ignition

Info

Publication number: CN107922873B
Application number: CN201680039372.2A
Authority: CN
Inventors: 克里斯汀·弗莱彻; 威廉·Y·拉姆; 杨孔盛; 杰瑞米·斯泰尔
Original assignee: Afton Chemical Corp
Current assignee: Afton Chemical Corp
Priority date: 2015-07-16
Filing date: 2016-07-14
Publication date: 2021-08-27
Anticipated expiration: 2036-07-14
Also published as: CN107922873A; RU2018104014A3; KR20180048596A; JP2018520240A; BR112018000353B1; EP3322781B1; JP6708831B2; RU2720202C2; EP3322781A1; KR102103653B1; RU2018104014A; CA2991769A1; MX2018000152A; CA2991769C; BR112018000353A2; MX371195B

Abstract

A lubricating oil composition and method of operating a boosted internal combustion engine. The lubricating oil composition comprises greater than 50 wt.% of a base oil, an overbased detergent having a TBN greater than 225mg KOH/g, and a low overbased/neutral detergent having a TBN of up to 175mg KOH/g. The total amount of calcium from the overbased and low-based/neutral detergents is from greater than 1100ppm to less than 2400ppm by weight based on the total weight of the lubricating oil composition. The lubricating oil composition and the method are effective to reduce low speed pre-ignition events in a boosted internal combustion engine lubricated with the lubricating oil composition relative to commercially available lubricating oil compositions.

Description

Lubricant with calcium-containing detergent and its use for improving low-speed pre-ignition

Technical Field

The present disclosure relates to lubricant compositions containing one or more oil soluble additives and the use of such lubricant compositions for improving low speed pre-ignition.

Background

Turbocharged or supercharged engines (i.e., boosted internal combustion engines) may experience an abnormal combustion event known as random pre-ignition or low speed pre-ignition (or "LSPI"). An LSPI is a pre-ignition event that may include very high pressure spikes, early combustion during improper crankshaft angles, and knock. All of these, individually and in combination, can cause engine degradation and/or severe damage. However, because LSPI events occur only sporadically in an uncontrolled manner, it is difficult to identify the cause of this phenomenon and to present a solution to contain it.

Pre-ignition is a form of combustion that results from the combustion of the air-fuel mixture within the combustion chamber prior to the desired ignition of the air-fuel mixture by the igniter. Pre-ignition is typically a problem during high engine speed operation, as the heat generated by engine operation heats a portion of the combustion chamber to a temperature sufficient to ignite the air-fuel mixture at contact. This type of pre-ignition is sometimes referred to as hot-spot pre-ignition.

Recently, intermittent abnormal combustion has been observed in a low-speed and medium-to-high-load intensified internal combustion engine. For example, during engine operation at 3,000rpm or less, low load, Brake Mean Effective Pressure (BMEP) of at least 10 bar, low-speed pre-ignition (LSPI) may occur in a random and random manner. During low engine speed operation, the compression stroke time is longest.

Several published studies have shown that the use of turbochargers, engine design, engine coatings, piston shape, fuel selection, and/or oil additives may contribute to an increase in LSPI events. One theory holds that auto-ignition of oil droplets entering the engine combustion chamber from the piston gap (the space between the piston ring set and the cylinder liner) may be one cause of an LSPI event. Accordingly, there is a need for an oil additive composition and/or combination that is effective in reducing or eliminating LSPI in boosted internal combustion engines.

Disclosure of Invention

The present disclosure relates to a lubricating oil composition and a method of operating a boosted internal combustion engine. The lubricating oil composition comprises greater than 50 wt.% of a base oil of lubricating viscosity, at least 0.3 wt.% of an overbased detergent having a Total Base Number (TBN) of greater than 225mg KOH/g, and at least 0.2 wt.% of a low-based/neutral detergent having a TBN of less than or equal to 175mg KOH/g, wherein the total amount of calcium of the overbased and low-based/neutral detergents ranges from greater than 1100ppm (by weight) to less than 2400ppm (by weight) based on the total weight of the lubricating oil composition. The lubricating oil composition may be effective in reducing low speed pre-ignition events in a boosted internal combustion engine lubricated with the lubricating oil composition.

In another embodiment, the present disclosure provides a method for reducing low speed pre-ignition events in a boosted internal combustion engine. The method comprises the step of lubricating a boosted internal combustion engine with a lubricating oil composition comprising greater than 50 wt.% of a base oil of lubricating viscosity, at least 0.3 wt.% of an overbased detergent having a TBN of greater than 225mg KOH/g, and at least 0.2 wt.% of a low based/neutral detergent having a TBN of up to 175mg KOH/g. The total amount of calcium of the overbased and low-based/neutral detergents ranges from greater than 1100ppm (by weight) to less than 2400ppm (by weight) based on the total weight of the lubricating oil composition. The boosted internal combustion engine is operated and lubricated with the lubricating oil composition such that low speed pre-ignition events may be reduced in engines lubricated with the lubricating oil composition.

In any of the preceding embodiments, the overbased detergent may comprise an overbased calcium-containing detergent. The overbased calcium-containing detergent may be selected from overbased calcium sulfonate detergents and overbased calcium phenate detergents. In each embodiment, the overbased detergent may be a calcium-containing detergent or a mixture of two or more overbased calcium-containing detergents. In each of the foregoing embodiments, the one or more overbased calcium-containing detergents may provide from about 900 to about 2000ppm (by weight) of calcium to the lubricating oil composition, based on the total weight of the lubricating oil composition.

In any of the preceding embodiments, the low-alkaline/neutral detergent may be a calcium-containing detergent, and the low-alkaline/neutral calcium-containing detergent may be a detergent selected from the group consisting of a calcium sulfonate detergent and a calcium phenate detergent. In the foregoing examples, at least 4 wt.% of the total detergent in the lubricating oil composition may be derived from the low-base/neutral detergent. In each of the foregoing embodiments, the ratio of total metal millimoles (M) of the lubricating oil composition to Total Base Number (TBN) may range from greater than 4.5 to about 10.0 or greater than 8 to about 10.

In each of the foregoing embodiments, the reduction in low speed pre-ignition (LSPI) events may be expressed as a ratio of test oil LSPI events relative to reference oil LSPI events (hereinafter "LSPI ratio"), where reference petroleum R-1 includes an overbased calcium-containing detergent as the sole detergent in the lubricating oil composition in an amount to provide about 2400ppm calcium to the lubricating oil composition. In the foregoing embodiment, the LSPI events may be represented as LSPI counts during 25,000 engine cycles, where the engine is operating at 2000 Revolutions Per Minute (RPM), Brake Mean Effective Pressure (BMEP) of 18,000 kPA.

In each of the foregoing embodiments, the base oil may be selected from group I, group II, group III, group IV, or group V base oils, and combinations of two or more of the foregoing. In other embodiments, greater than 50 wt.% of the base oil is selected from the group consisting of: group II, group III, group IV or group V base oils, and combinations of two or more of the foregoing, wherein greater than 50 wt.% of the base oil is not a diluent oil resulting from providing an additive component or viscosity index improver in the composition.

In each of the foregoing embodiments, the lubricating oil composition may include one or more components selected from the group consisting of friction modifiers, antiwear agents, dispersants, antioxidants, and viscosity index improvers.

In the foregoing embodiments of the methods described herein, the engine may produce a Brake Mean Effective Pressure (BMEP) level of greater than 1,500kPa during operation at an engine speed of less than 3000 revolutions per minute (rpm), or a BMEP of 1,800kPa at an engine speed of 2000 rpm.

In each of the foregoing examples, the lubricating oil composition may effectively pass the TEOST 33 bench oxidation test.

In each of the foregoing embodiments, the low-base/neutral detergent may comprise a low-base/neutral calcium-containing detergent, and the ratio of the ppm (by weight) of calcium provided to the lubricating oil composition by the low-base/neutral calcium-containing detergent to the ppm (by weight) of calcium provided to the lubricating oil composition by the overbased calcium-containing detergent may be from 0.05 to 1.0.

In each of the foregoing embodiments, the total calcium provided to the lubricating oil composition by the overbased detergent may be from 1100ppm to 1800ppm (by weight) based on the total weight of the lubricating oil composition.

In each of the foregoing embodiments, the total calcium provided to the lubricating oil composition by the low-basic/neutral calcium-containing detergent may be from 50ppm to 1000ppm (by weight) based on the total weight of the lubricating oil composition.

In each of the foregoing embodiments, the lubricating oil composition may comprise no more than 10 wt.% of a group IV base oil, a group V base oil, or a combination thereof. In each of the foregoing embodiments, the lubricating oil composition comprises less than 5 wt.% of group V base oil.

In each of the foregoing embodiments, the overbased calcium-containing detergent may be an overbased calcium sulfonate detergent.

In each of the foregoing embodiments, the overbased calcium-containing detergent may optionally not include an overbased calcium salicylate detergent.

In each of the foregoing embodiments, the lubricating oil composition may optionally not include any magnesium-containing detergent, or the lubricating oil composition may be magnesium-free.

In each of the foregoing embodiments, the lubricating oil composition may not contain any group IV base oil.

In each of the foregoing embodiments, the lubricating oil composition may not contain any group V base oil.

The following definitions of terms are provided to clarify the meaning of certain terms used herein.

The terms "oil composition", "lubricating oil", "lubricant composition", "lubricating composition", "fully formulated lubricant composition", "lubricant", "crankcase oil", "crankcase lubricant", "engine oil", "engine lubricant", "motor oil" and "motor lubricant" are considered as synonymous, fully interchangeable terms referring to a finished lubricating product comprising greater than 50 wt.% of a base oil and a minor amount of an additive composition.

As used herein, the terms "additive package", "additive concentrate", "additive composition", "oil additive package", "oil additive concentrate", "crankcase additive package", "crankcase additive concentrate", "motor oil additive package", "motor oil concentrate" are considered to be synonymous, fully interchangeable terms referring to the portion of the lubricating oil composition other than the greater than 50 wt.% base oil stock mixture. The additive package may or may not include a viscosity index improver or pour point depressant.

The term "overbased" refers to metal salts, such as those of sulfonic acids, formic acids, salicylic acids, and/or phenols, in which the amount of metal present is in excess of stoichiometric. Such salts may have conversion levels in excess of 100% (i.e., they may contain greater than 100% of the theoretical amount of metal required to convert the acid to its "positive", "neutral" salt). The expression "metal ratio" is often abbreviated MR and is used to refer to the ratio of the total stoichiometric amount of metal in the overbased salt to the stoichiometric amount of metal in the neutral salt, in accordance with known chemical reactivity and stoichiometry. The metal ratio is one in the positive or neutral salts and the MR is greater than one in the overbased salts. They are often referred to as overbased, superbased or superbased salts and may be salts of organic sulfuric, formic, salicylic and/or phenol acids. In the present disclosure, the TBN of overbased detergents is greater than 225mg KOH/g. The overbased detergent may be a combination of two or more overbased detergents each having a TBN greater than 225mg KOH/g.

In the present disclosure, the TBN of low alkaline/neutral detergents is up to 175mg KOH/g. The low-basic/neutral detergent can be a combination of two or more low-basic and/or neutral detergents each having a TBN of up to 175mg KOH/g. In some cases, "overbased" may be abbreviated "OB" and in some cases, "low basicity/neutral" may be abbreviated "LB/N".

The term "total metals" refers to the total metals, metalloids or transition metals in the lubricating oil composition, including the metals provided by the detergent component of the lubricating oil composition.

As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary sense as is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the rest of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include:

(a) hydrocarbon substituents, that is, aliphatic substituents (e.g., alkyl or alkenyl), alicyclic substituents (e.g., cycloalkyl, cycloalkenyl), and aromatic substituents substituted with aromatic, aliphatic, and alicyclic groups, as well as cyclic substituents wherein the ring is completed by another portion of the molecule (e.g., two substituents together form an alicyclic moiety);

(b) substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups that, in the context of this disclosure, do not alter the predominantly hydrocarbon substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, amine, alkylamino, and sulfoxy); and

(c) hetero substituents, that is, substituents that, in the context of this disclosure, have a predominantly hydrocarbon character while containing atoms other than carbon in a ring or chain otherwise composed of carbon atoms. Heteroatoms can include sulfur, oxygen, and nitrogen, and encompass substituents as pyridyl, furyl, thienyl, and imidazolyl. Generally, no more than two, such as no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; typically, no non-hydrocarbon substituents will be present in the hydrocarbyl group.

As used herein, unless expressly stated otherwise, the term "wt.%" means the percentage represented by the component in question relative to the weight of the total composition.

As used herein, the terms "soluble", "oil-soluble" or "dispersible" may but do not necessarily indicate that the compound or additive is soluble, miscible or capable of being suspended in all proportions in an oil. However, the foregoing terms all mean that they are, for example, soluble, suspendable, dissolvable or stably dispersible in the oil to an extent sufficient to perform their intended function in the environment in which the oil is utilized. Moreover, the additional incorporation of other additives may also allow for the incorporation of higher levels of particular additives, if desired.

The term "TBN" as used herein is used to denote the total base number in milligrams KOH/gram of composition as measured by the method of ASTM D2896.

The term "alkyl" as used herein refers to a straight, branched, cyclic, and/or substituted saturated chain moiety of from about 1 to about 100 carbon atoms.

The term "alkenyl" as used herein refers to straight, branched, cyclic, and/or substituted unsaturated chain moieties of about 3 to about 10 carbon atoms.

The term "aryl" as employed herein refers to mono-and polycyclic aromatic compounds that may include alkyl, alkenyl, alkaryl, amine, hydroxyl, alkoxy, halo substituents, and/or heteroatoms (including, but not limited to, nitrogen, oxygen, and sulfur).

The lubricants, combinations of components, or individual components of the present description may be suitable for use in various types of internal combustion engines. Suitable engine types may include, but are not limited to: heavy duty diesel engines, passenger cars, light duty diesel engines, medium speed diesel engines, marine engines, or motorcycle engines. The internal combustion engine may be a diesel engine, a gasoline engine, a natural gas engine, a biofuel engine, a diesel/biofuel hybrid engine, a gasoline/biofuel hybrid engine, an ethanol engine, a gasoline/ethanol hybrid engine, a Compressed Natural Gas (CNG) engine, or a mixture thereof. The diesel engine may be a compression ignition engine. The diesel engine may be a compression ignition engine with spark ignition assistance. The gasoline engine may be a spark ignition engine. Internal combustion engines may also be used in combination with electrical power or battery power. An engine so configured is commonly referred to as a hybrid engine. The internal combustion engine may be a 2-stroke, 4-stroke or rotary engine. Suitable internal combustion engines include marine diesel engines (e.g., inland marine), aviation piston engines, low-load diesel engines and motorcycle, automotive, locomotive and truck engines.

The internal combustion engine may contain components belonging to one or more of the following: aluminum alloys, lead, tin, copper, cast iron, magnesium, ceramics, stainless steel, composites, and/or mixtures thereof. The component may be coated, for example, with a diamond-like carbon coating, a lubricious coating, a phosphorous-containing coating, a molybdenum-containing coating, a graphite coating, a nanoparticle-containing coating, and/or mixtures thereof. The aluminum alloy may include aluminum silicate, aluminum oxide, or other ceramic materials. In one embodiment, the aluminum alloy is an aluminum silicate surface. As used herein, the term "aluminum alloy" is intended to be synonymous with "aluminum composite" to describe a component or surface comprising aluminum that intermixes or reacts with another component at a microscopic or near-microscopic level, regardless of its specific structure. This would include any conventional alloy having a metal other than aluminum and a composite or alloy-like structure having non-metallic elements or compounds (e.g., having a ceramic-like material).

Lubricating oil compositions for internal combustion engines may be suitable for use in any engine regardless of sulfur, phosphorus, or sulfated ash (ASTM D-874) content. The sulfur content of the engine oil lubricant may be about 1 wt% or less, or about 0.8 wt% or less, or about 0.5 wt% or less, or about 0.3 wt% or less, or about 0.2 wt% or less. The sulfur content may range from about 0.001 wt% to about 0.5 wt%, or from about 0.01 wt% to about 0.3 wt% in one embodiment. The phosphorus content can be about 0.2 wt% or less, or about 0.1 wt% or less, or about 0.085 wt% or less, or about 0.08 wt% or less, or even about 0.06 wt% or less, about 0.055 wt% or less, or about 0.05 wt% or less. In one embodiment the phosphorus content may be from about 50ppm to about 1000ppm, or from about 325ppm to about 850 ppm. The total sulfated ash content may be about 2 wt% or less, or about 1.5 wt% or less, or about 1.1 wt% or less, or about 1 wt% or less, or about 0.8 wt% or less, or about 0.5 wt% or less. The sulfated ash content in one embodiment may be about 0.05 wt% to about 0.9 wt%, or about 0.1 wt%, or about 0.2 wt% to about 0.45 wt%. In another embodiment, the sulfur content may be about 0.4 wt% or less, the phosphorus content may be about 0.08 wt% or less, and the sulfated ash is about 1 wt% or less. In another embodiment, the sulfur content can be about 0.3 wt% or less, the phosphorus content can be about 0.05 wt% or less, and the sulfated ash can be about 0.8 wt% or less.

In one embodiment, the lubricating oil composition is an engine oil, wherein the lubricating oil composition may have (i) a sulfur content of about 0.5 wt.% or less, (ii) a phosphorus content of about 0.1 wt.% or less, and (iii) a sulfated ash content of about 1.5 wt.% or less.

In some embodiments, the lubricating oil composition is suitable for use with engines powered by low sulfur fuels (e.g., fuels containing about 1% to about 5% sulfur). Highway vehicle fuels contain about 15ppm sulfur (or about 0.0015% sulfur). The lubricating oil composition is suitable for use with boosted internal combustion engines, including turbocharged or supercharged internal combustion engines.

Additionally, the lubricants of the present description may be adapted to meet one or more industry specification requirements, such as ILSAC GF-3, GF-4, GF-5, GF-6, PC-11, CI-4, CJ-4, ACEA A1/B1, A2/B2, A3/B3, A3/B4, A5/B5, C1, C2, C3, C4, C5, E4/E6/E7/E9, Euro 5/6, Jaso DL-1, Low SAPS, Medium SAPS, or original equipment manufacturer specifications, such as Dexos^TM 1、Dexos^TM2. MB-approved 229.51/229.31, VW 502.00, 503.00/503.01, 504.00, 505.00, 506.00/506.01, 507.00, 508.00, 509.00, BMW Longlife-04, Porsche C30, Peugeot

Automobiles B712290, B712296, B712297, B712300, B712302, B712312, B712007, B712008, Ford WSS-M2C153-H, WSS-M2C930-A, WSS-M2C945-A, WSS-M2C913A, WSS-M2C913-B, WSS-M2C-C, GM 6094-M, Chrysler MS-6395, or any past or future PCMO or HDD specifications not mentioned herein. In some embodiments, the amount of phosphorus in the finished fluid is 1000ppm or less, or 900ppm or less, or 800ppm or less for Passenger Car Motor Oil (PCMO) applications.

Other metal implements may not be suitable for use with the disclosed lubricant. "functional fluid" is a term encompassing various fluids including, but not limited to, tractor hydraulic fluid; a power transmission fluid comprising: automatic transmission fluid, continuously variable transmission fluid, and manual transmission fluid; hydraulic fluid, including tractor hydraulic fluid; some gear oil; a power steering fluid; fluids for wind turbines, compressors; some industrial fluids; and a fluid associated with a driveline component. It should be noted that within each of these fluids, such as within an automatic transmission fluid, there are a variety of different types of fluids, as the various transmissions have different designs resulting in the need for fluids having significantly different functional characteristics. This is in contrast to the term "lubricating fluid" which is not used to generate or transmit power.

With regard to tractor hydraulic fluids, for example, these fluids are common products for all lubrication applications in tractors except for lubricating the engine. These lubrication applications may include: the gearbox, power take off and clutch, rear axle, reduction gear, wet brake and hydraulic accessory lubrication.

When the functional fluid is an automatic transmission fluid, the automatic transmission fluid must have sufficient friction for the clutch plates to transmit power. However, the coefficient of friction of the fluid has a tendency to decrease because of the temperature effect caused by the fluid heating up during operation. It is important that the tractor hydraulic fluid or automatic transmission fluid maintain its high coefficient of friction at high temperatures, otherwise the brake system or automatic transmission may fail. This is not a function of the oil.

Tractor fluids, and such as Super Tractor Universal Oils (STUO) or Universal Tractor Transmission Oils (UTTO), combine the efficiency of the engine oil with the efficiency of the Transmission, differential, final drive planetary gears, wet brakes, and hydraulic efficiency. While many of the additives used to formulate a UTTO or STUO fluid are functionally similar, they can have deleterious effects if not properly combined. For example, some anti-wear and extreme pressure additives for engine oil can be extremely corrosive to copper components in hydraulic pumps. Detergents and dispersants that target gasoline or diesel engine performance may be detrimental to wet brake performance. Friction modifiers that are specifically designed to eliminate wet brake noise may lack the thermal stability necessary for oil performance. Each of these fluids, whether functional, tractor or lubricating, is designed to meet specific and stringent manufacturer requirements.

The present disclosure provides novel lubricating oil blends formulated for use as automotive crankcase lubricants. Embodiments of the present disclosure may provide a lubricating oil suitable for crankcase applications and having improvements in the following features: air incorporation, ethanol fuel compatibility, oxidation resistance, antiwear performance, biofuel compatibility, antifoaming properties, friction reduction, fuel economy, pre-ignition prevention, rust prevention, sludge and/or soot dispersibility, piston cleanliness, deposit formation, and water tolerance.

The engine oils of the present disclosure may be formulated by adding one or more additives to a suitable base oil formulation, as described in detail below. The additives may be combined with the base oil in the form of an additive package (or concentrate) or, alternatively, may be combined with the base oil alone (or as a mixture of the two). Fully formulated engine oils may exhibit improved performance characteristics depending on the additives added and their respective proportions.

Additional details and advantages of the disclosure will be set forth in part in the description which follows, and/or may be learned by practice of the disclosure. The details and advantages of the disclosure may be realized and obtained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure as claimed.

Detailed Description

Various embodiments of the present disclosure provide lubricating oil compositions and methods useful for reducing low speed pre-ignition events (LSPI) in boosted internal combustion engines. In particular, the enhanced internal combustion engine of the present disclosure includes turbocharged and supercharged internal combustion engines. Boosted internal combustion engines include spark-ignited direct injection and/or nozzle fuel injected engines. The spark ignition internal combustion engine may be a gasoline engine.

The compositions of the present invention include lubricating oil compositions comprising a base oil of lubricating viscosity and a specific additive composition. The methods of the present disclosure use lubricating oil compositions containing the additive composition. As described in more detail below, the lubricating oil composition may be unexpectedly effective for reducing low speed pre-ignition events in a boosted internal combustion engine lubricated with the lubricating oil composition.

In some embodiments, the combustion chamber or cylinder wall of a spark-ignition, direct-injection or nozzle-fuel-injection internal combustion engine configured with a turbocharger or supercharger is operated and lubricated with a lubricating oil composition, such that low-speed pre-ignition events may be reduced in engines lubricated with the lubricating oil composition.

Optionally, the method of the present invention may include the step of measuring a low speed pre-ignition event of an internal combustion engine lubricated with lubricating oil. In such methods, the internal combustion engine LSPI events are reduced by 50% or more, more preferably, by 75% or more, and the LSPI events are LSPI counts during 25,000 engine cycles, wherein the engine is operating at 2000 revolutions per minute and brake mean effective pressure of 18,000 kPa.

As described in more detail below, embodiments of the present disclosure may provide significant and unexpected improvements in reducing LSPI events while maintaining relatively high calcium detergent concentrations in lubricating oil compositions. Embodiments of the present disclosure may also provide unexpected improvements in TEOST 33 testing while also reducing LSPI events.

In embodiments of the present disclosure, the lubricating oil composition may also pass the TEOST 33 test.

Detergent

The lubricating oil composition comprises one or more overbased detergents and one or more low-based/neutral detergents. Suitable detergent bases include phenates, sulphur-containing phenates, sulphonates, calixarates, salicylates, carboxylic acids, phosphoric acids, mono-and/or dithiophosphoric acids, alkylphenols, sulphur-coupled alkylphenol compounds or methylene-bridged phenols. Suitable detergents and methods for their preparation are described in more detail in a number of patent publications, including US 7,732,390 and the references cited therein. The detergent matrix may be salted with alkali or alkaline earth metals such as, but not limited to: calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof. In some embodiments, the detergent is barium-free. Suitable detergents may include alkali or alkaline earth metal salts of petroleum sulfonic acid and long chain mono-or di-alkyl aryl sulfonic acids with the aryl groups being benzyl, tolyl and xylyl. Examples of suitable additional detergents include, but are not limited to: calcium phenate, sulfur-containing calcium phenate, calcium sulfonate, calix (calcium phosphates), calcium salicylate(s), calcium carboxylate, calcium phosphate, calcium mono-and/or di-thiophosphate, calcium alkyl phenate, sulfur-coupled calcium alkyl phenate compounds, methylene-bridged calcium phenate, magnesium phenate, sulfur-containing magnesium phenate, magnesium sulfonate, magnesium calixate(s), magnesium salicylate(s), magnesium carboxylates, magnesium phosphates, magnesium monothiophosphates and/or dithiophosphates, magnesium alkylphenates, sulfur-coupled magnesium alkylphenates compounds, methylene-bridged magnesium phenolates, sodium phenolates, sulfur-containing sodium phenolates, sodium sulfonates, sodium calixarates, sodium salicylate, sodium carboxylates, sodium phosphates, sodium monothiophosphates and/or sodium dithiophosphates, sodium alkylphenates, sulfur-coupled sodium alkylphenates compounds or methylene-bridged sodium phenolates.

Overbased detergents are well known in the art and may be alkali metal or alkaline earth metal overbased detergents. Such detergents can be prepared by reacting a metal oxide or metal hydroxide with a substrate and carbon dioxide gas. The substrate is typically an acid, for example, an acid such as an aliphatic substituted sulfonic acid, an aliphatic substituted formic acid, or an aliphatic substituted phenol.

The term "overbased" relates to metal salts, such as those of sulfonic acids, formic acids, and phenols, in which the amount of metal present is in excess of stoichiometric. Such salts may have conversion levels in excess of 100% (i.e., they may contain greater than 100% of the theoretical amount of metal required to convert the acid to its "positive", "neutral" salt). The expression "metal ratio" is often abbreviated MR and is used to refer to the ratio of the total stoichiometric amount of metal in the overbased salt to the stoichiometric amount of metal in the neutral salt, in accordance with known chemical reactivity and stoichiometry. The metal ratio is one in the positive or neutral salts and the MR is greater than one in the overbased salts. They are often referred to as overbased, superbased or superbased salts and may be organic salts of sulfuric, formic or phenol.

The overbased detergent has a TBN greater than 225mg KOH/g, or as another example, about 250 mg KOH/g or greater, or about 300 mg KOH/g or greater, or about 350 mg KOH/g or greater, or about 375 mg KOH/g or greater, or about 400 mg KOH/g or greater.

Examples of suitable overbased detergents include, but are not limited to: overbased calcium phenates, overbased sulfur-containing calcium phenates, overbased calcium sulfonates, overbased calcium calixarates (overrefined calcium phosphates), overbased calcium salicylates (overrefined calcium salicylates), overbased calcium salicylates, overbased calcium formates, overbased calcium phosphates, overbased mono-and/or calcium dithiophosphates, overbased calcium alkylphenates, overbased sulfur-coupled alkylphenol calcium compounds, overbased methylene-bridged calcium phenates, overbased magnesium phenates, overbased sulfur-containing magnesium phenates, overbased magnesium sulfonates, overbased magnesium calixarates, overbased magnesium salicylate (overrefined magnesium salicylates), overbased magnesium salicylate, overbased magnesium formate, overbased magnesium phosphate, overbased mono-and/or magnesium dithiophosphates, overbased magnesium alkylphenates, overbased sulfur-coupled alkylphenol magnesium compounds, or overbased magnesium methylene-bridged phenates.

The metal to substrate ratio of the overbased detergent may be 1.1:1, or 2:1, or 4:1, or 5:1, or 7:1, or 10: 1.

In some embodiments, the detergent is effective to reduce or prevent rust in the engine.

The detergent may be present at up to 10 wt.%, or about up to 8 wt.%, or up to about 4 wt.%, or greater than about 4 wt.% to about 8 wt.%, based on the total weight of the lubricating oil composition.

The detergent may be present in an amount capable of providing about 1100 to about 3500ppm of metal to the finished fluid. In other embodiments, the detergent may provide from about 1100 to about 3000ppm metal, or from about 1150 to about 2500ppm metal, or from about 1200 to about 2400ppm metal to the finished fluid.

The lubricating oil compositions of the present disclosure comprise at least one overbased detergent having a TBN greater than 225mg KOH/g and at least one neutral/overbased detergent having a TBN of up to 175mg KOH/g. The disclosure also includes methods of using such lubricating oil compositions in methods or lubricating engines by using the lubricating oil compositions to lubricate and run the engines.

The total amount of calcium of the overbased and low-based/neutral detergents of the lubricating oil compositions of the present disclosure ranges from greater than 1100ppm (by weight) to less than 2400ppm (by weight) based on the total weight of the lubricating oil composition.

The overbased detergent may be an overbased calcium-containing detergent. The overbased calcium-containing detergent may be selected from the group consisting of overbased calcium sulfonate detergents, overbased calcium phenate detergents, and overbased calcium salicylate detergents. In certain embodiments, the overbased calcium-containing detergent comprises an overbased calcium sulfonate detergent. In certain embodiments, the overbased detergent is one or more calcium-containing detergents, preferably, the overbased detergent is a calcium sulfonate detergent.

In certain embodiments, the one or more overbased calcium-containing detergents provide from about 900 to about 2400ppm calcium to the finished fluid. As another example, the one or more overbased calcium-containing detergents may be present in an amount capable of providing from about 900 to about 2000ppm calcium, or from about 900 to about 1800ppm calcium, or from about 1100 to 1600ppm calcium, or from about 1200 to 1500ppm calcium to the finished fluid.

The TBN of the low alkaline/neutral detergent is at most 175mg KOH/g or at most 150mg KOH/g. The low alkaline/neutral detergent may comprise a calcium-containing detergent. The low-alkaline neutral calcium-containing detergent may be selected from the group consisting of calcium sulfonate detergents, calcium phenate detergents, and calcium salicylate detergents. In some embodiments, the low alkaline/neutral detergent is a calcium-containing detergent or a mixture of calcium-containing detergents. In some embodiments, the low alkaline/neutral detergent is a calcium sulfonate detergent or a calcium phenate detergent.

The low-base/neutral detergent constitutes at least 2.5 wt.% of the total detergent in the lubricating oil composition. In some embodiments, at least 4 wt.%, or at least 6 wt.%, or at least 8 wt.%, or at least 10 wt.%, or at least 12 wt.%, or at least 20 wt.% of the total detergent in the lubricating oil composition is a low-base/neutral detergent, which optionally may be a low-base/neutral calcium-containing detergent.

In certain embodiments, the one or more low-basic/neutral calcium-containing detergents provide from about 50 to about 1000ppm calcium (by weight) to the lubricating oil composition, based on the total weight of the lubricating oil composition. In some embodiments, the one or more low-basic/neutral calcium-containing detergents provide from 75 to less than 800ppm, or from 100 to 600ppm, or from 125 to 500ppm (by weight) calcium to the lubricating oil composition, based on the total weight of the lubricating oil composition.

In some embodiments, the ratio of total metal millimoles (M) of the lubricating oil composition to TBN of the lubricating oil composition is in the range of greater than 4.5 to about 10.0. In some embodiments, the ratio of total metal millimoles (M) to TBN of the lubricating oil composition is in a range of greater than 8 to less than 10.0, or 8 to 9.5, or 8.1 to 9.0.

In some embodiments, the ratio of the ppm (by weight) of calcium provided to the lubricating oil composition by the low-base/neutral detergent to the ppm (by weight) of calcium provided to the lubricating oil composition by the overbased calcium detergent is from about 0.01 to about 1, or from about 0.03 to about 0.7, or from about 0.05 to about 0.5, or from about 0.08 to about 0.4.

The overbased calcium-containing detergent may be an overbased calcium sulfonate detergent. The overbased calcium-containing detergent may optionally exclude overbased calcium salicylate detergents. The lubricating oil may optionally not include any magnesium-containing detergent or contain no magnesium. In any of the embodiments of the present disclosure, the amount of sodium in the lubricating composition can be limited to no more than 150ppm of sodium, based on the total weight of the lubricating oil composition.

Base oil

The Base Oil used in the lubricating Oil compositions herein may be selected from any of group I to group V Base oils as specified in the American Petroleum Institute (API) Base Oil Interchangeability guide. The five base oil groups were as follows:

TABLE 1

Group I, II and III are mineral oil processing feedstocks. Group IV base oils contain homozygous component material and are produced by the polymerization of olefinically unsaturated hydrocarbons. Many group V base oils are also pure synthetic products and may include diesters, polyol esters, polyalkylene glycols, alkylated aromatics, polyphosphate esters, polyvinyl ethers and/or polyphenyl ethers, and the like, but may also be naturally occurring oils, such as vegetable oils. It should be noted that although group III base oils are derived from mineral oils, the rigorous processing experienced by these fluids results in physical properties that are very similar to some pure compositions, such as PAOs. Thus, in the industry, oils derived from group III base oils may be referred to as synthetic fluids.

The base oil used in the disclosed lubricating oil compositions can be a mineral oil, an animal oil, a vegetable oil, a synthetic oil, or mixtures thereof. Suitable oils may be derived from hydrocracked, hydrogenated, hydrofinished, unrefined, refined and rerefined oils, and mixtures thereof.

Unrefined oils are those derived from a natural, mineral, or synthetic source with little or no further purification treatment. Refined oils are similar to unrefined oils, although they have been subjected to one or more purification steps, potentially resulting in an improvement in one or more properties. Examples of suitable purification techniques are solvent extraction, secondary distillation, acid or base extraction, filtration, osmosis, and the like. Oils refined to food grade may or may not be suitable. Edible oils may also be referred to as white oils. In some embodiments, the lubricating oil composition is free of edible oil or white oil.

Rerefined oils are also known as reclaimed or reprocessed oils. These oils are obtained using the same or similar processes as the refined oils. Typically these oils are further processed by techniques directed to the removal of spent additives and oil breakdown products.

Mineral oil may include oil obtained by drilling or from plants and animals or any mixture thereof. For example, such oils may include, but are not limited to: castor oil, lard oil, olive oil, peanut oil, corn oil, soybean oil and linseed oil, as well as mineral lubricating oils, such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic naphthenic or mixed paraffinic-naphthenic types. Such oils may be partially or fully hydrogenated if desired. Oils derived from coal or shale may also be suitable.

Suitable synthetic lubricating oils may include: hydrocarbon oils such as polymeric, oligomeric or interpolyolefins (e.g., polybutylenes, polypropylenes, propylene/isobutylene copolymers); poly (1-hexene), poly (1-octene), trimers or oligomers of 1-decene, e.g., poly (1-decene), which are commonly referred to as alpha-olefins, and mixtures thereof; alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di (2-ethylhexyl) -benzene); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls); diphenyl alkanes, alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof or mixtures thereof. Polyalphaolefins are generally hydrogenated materials.

Other synthetic lubricating oils include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and diethyl ester of decane phosphionic acid), or polytetrahydrofuran. Synthetic oils may be produced by Fischer-Tropsch reactions and may typically be hydroisomerised Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil may be prepared by a fischer-tropsch gas-liquid synthesis step, as well as other natural gas synthetic oils.

More than 50 wt.% of the base oil comprised in the lubricating composition may be selected from the group consisting of: group I, group II, group III, group IV, group V, and combinations of two or more of the foregoing, and wherein greater than 50 wt.% of the base oil is not base oil resulting from the provision of an additive component or viscosity index improver in the composition. In another embodiment, greater than 50 wt.% of the base oil included in the lubricating composition may be selected from the group consisting of: group II, group III, group IV, group V, and combinations of two or more of the foregoing, and wherein greater than 50 wt.% of the base oil is not a diluent oil resulting from providing an additive component or viscosity index improver in the composition.

The amount of oil of lubricating viscosity present may be the remainder after subtraction of the sum of 100 wt% performance additives including viscosity index improver and/or pour point depressant and/or other pretreatment additives. For example, the oil of lubricating viscosity that may be present in the finished fluid may be substantial, such as greater than about 50 wt.%, greater than about 60 wt.%, greater than about 70 wt.%, greater than about 80 wt.%, greater than about 85 wt.%, or greater than about 90 wt.%.

The lubricating oil composition can comprise no more than 10 wt.% of a group IV base oil, a group V base oil, or a combination thereof. In each of the foregoing embodiments, the lubricating oil composition comprises less than 5 wt.% of group V base oil. The lubricating oil composition does not contain any group IV base oil. The lubricating oil composition does not contain any group V base oil.

The lubricating oil composition may further comprise one or more optional components selected from various additives described below.

Antioxidant agent

The lubricating oil compositions herein may also optionally contain one or more antioxidants. Antioxidant compounds are known and include, for example, phenolate, phenol sulfide, sulfurized olefin, thiophosphorylated terpene, sulfurized ester, aromatic amine, alkylated diphenylamine (e.g., nonyldiphenylamine, dinonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine), phenyl-alpha-naphthylamine, alkylated phenyl-alpha-naphthylamine, hindered non-aromatic amines, phenol, hindered phenol, oil-soluble molybdenum compounds, macromolecular antioxidants, or mixtures thereof. The antioxidant compounds may be used alone or in combination.

The hindered phenol antioxidant may contain a sec-butyl and/or tert-butyl group as a sterically hindered group. The phenolic group may be further substituted with a hydrocarbyl group and/or a bridging group attached to another aromatic group. Examples of suitable hindered phenol antioxidants include: 2, 6-di-tert-butylphenol, 4-methyl-2, 6-di-tert-butylphenol, 4-ethyl-2, 6-di-tert-butylphenol, 4-propyl-2, 6-di-tert-butylphenol, or 4-butyl-2, 6-di-tert-butylphenol, or 4-dodecyl-2, 6-di-tert-butylphenol. In one embodiment, the hindered phenol antioxidant may be an ester and may include, for example, IRGANOX available from BASF^TML-135 is derived from the addition product of 2, 6-di-tert-butylphenol and an alkyl acrylate, wherein the alkyl group can contain from about 1 to about 18, or from about 2 to about 12, or from about 2 to about 8, or from about 2 to about 6, or about 4 carbon atoms. Another commercially available hindered phenol antioxidant can be an ester, and can include ETHANOX, available from Albemarle Corporation^TM4716。

Suitable antioxidants may include diarylamines as well as high molecular weight phenols. In one embodiment, the lubricating oil composition may contain a mixture of diarylamines and high molecular weight phenols, such that each antioxidant may be present in an amount sufficient to provide up to about 5 wt.%, based on the final weight of the lubricating oil composition. In one embodiment, the antioxidant may be a mixture of about 0.3 to about 1.5 wt.% diarylamine and about 0.4 to about 2.5 wt.% high molecular weight phenol, based on the final weight of the lubricating oil composition.

Examples of suitable olefins that may be sulfurized to form sulfurized olefins include: propylene, butene, isobutylene, polyisobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof, as well as dimers, trimers, and tetramers thereof are particularly useful olefins. Alternatively, the olefin may be a Diels-Alder adduct of a diene (such as 1, 3-butadiene) and an unsaturated ester (such as butyl acrylate).

Another class of sulfurized olefins includes sulfurized fatty acids and esters thereof. The fatty acids are typically obtained from vegetable or animal oils and typically contain from about 4 to about 22 carbon atoms. Examples of suitable fatty acids and esters thereof include triglycerides, oleic acid, linoleic acid, palmitoleic acid, or mixtures thereof. Typically, the fatty acid is obtained from lard, pine oil, peanut oil, soybean oil, cottonseed oil, sunflower oil or mixtures thereof. The fatty acids and/or esters may be mixed with olefins, such as alpha-olefins.

The one or more antioxidants may be present in a range from about 0 wt.% to about 20 wt.%, or from about 0.1 wt.% to about 10 wt.%, or from about 1 wt.% to about 5 wt.% of the lubricating oil composition.

Antiwear agent

The lubricating oil compositions herein may also optionally contain one or more antiwear agents. Examples of suitable antiwear agents include, but are not limited to: a metal thiophosphate; a metal salt of a dialkyl dithiophosphate; a phosphate ester or a salt thereof; a phosphate ester; a phosphite ester; a phosphorus-containing carboxylic acid ester or amide; a sulfurized olefin; thiocarbamate-containing compounds including thiocarbamates, alkylene-coupled thiocarbamates, and bis (S-alkyldithiocarbamoyl) disulfides; and mixtures thereof. A suitable antiwear agent may be molybdenum dithiocarbamate. Phosphorus-containing antiwear agents are more fully described in european patent 612839. The metal in the dialkyldithiophosphates may be an alkali metal, an alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium or zinc. Suitable antiwear agents may be zinc dialkylthiophosphates.

Other examples of suitable antiwear agents include: titanium compounds, tartaric acid esters, tartaric imides, oil-soluble amine salts of phosphorus compounds, sulfurized olefins, phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate-containing compounds (such as thiocarbamates, thiocarbamate amides, thiocarbamate ethers, alkylene-coupled thiocarbamates and bis (S-alkyldithiocarbamoyl) disulfides). The tartrate or tartrimide may contain alkyl ester groups, wherein the sum of the carbon atoms in the alkyl groups may be at least 8. In one embodiment, the antiwear agent may include a citrate ester.

The antiwear agent may be present in a range including from about 0 wt.% to about 15 wt.%, or from about 0.01 wt.% to about 10 wt.%, or from about 0.05 wt.% to about 5 wt.%, or from about 0.1 wt.% to about 3 wt.% of the lubricating oil composition.

The antiwear agent compound may be Zinc Dihydrocarbyl Dithiophosphate (ZDDP) having a P: Zn ratio of from about 1:0.8 to about 1: 1.7.

Boron-containing compounds

The lubricating oil compositions herein may optionally contain one or more boron-containing compounds.

Examples of boron-containing compounds include borate esters, borated fatty amines, borated epoxides, borated detergents, and borated dispersants, such as borated succinimide dispersants, as disclosed in U.S. patent No. 5,883,057.

If present, the boron-containing compound may be used in an amount sufficient to provide up to about 8 wt.%, from about 0.01 wt.% to about 7 wt.%, from about 0.05 wt.% to about 5 wt.%, or from about 0.1 wt.% to about 3 wt.% of the lubricating oil composition.

Dispersing agent

The lubricating oil composition may optionally additionally comprise one or more dispersants or mixtures thereof. Dispersants are generally referred to as ashless-type dispersants because they do not contain ash-forming metals prior to use in lubricating oil compositions and they generally do not provide any ash when added to a lubricant. Ashless dispersants are characterized by having a polar group attached to a relatively high molecular weight hydrocarbon chain. Typical ashless dispersants include N-substituted long chain alkenyl succinimides. Examples of N-substituted long chain alkenyl succinimides include polyisobutylene succinimides having a number average molecular weight of the polyisobutylene substituent in the range of about 350 to about 50,000 or to about 5,000 or to about 3,000. Succinimide dispersants and their preparation are disclosed, for example, in U.S. patent No. 7,897,696 or U.S. patent No. 4,234,435. The polyolefin may be prepared from polymerizable monomers containing from about 2 to about 16, or from about 2 to about 8, or from about 2 to about 6 carbon atoms. Succinimide dispersants are typically imides formed from polyamines, typically poly (ethyleneamines).

In one embodiment the present disclosure additionally includes at least one polyisobutylene succinimide dispersant derived from polyisobutylene having a number average molecular weight in the range of about 350 to about 50,000 or to about 5000 or to about 3000. Polyisobutylene succinimides may be used alone or in combination with other dispersants.

In some embodiments, the polyisobutylene, if included, can have a terminal double bond content of greater than 50 mol%, greater than 60 mol%, greater than 70 mol%, greater than 80 mol%, or greater than 90 mol%. Such PIBs are also known as highly reactive PIBs ("HR-PIBs"). HR-PIB having a number average molecular weight in the range of about 800 to about 5000 is suitable for use in embodiments of the present disclosure. Conventional PIB typically has a terminal double bond content of less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, or less than 10 mol%.

HR-PIB having a number average molecular weight in the range of about 900 to about 3000 may be suitable. Such HR-PIB is commercially available or may be synthesized by polymerization of isobutylene in the presence of a non-chlorinated catalyst, such as boron trifluoride, as described in U.S. Pat. No. 4,152,499 to Boerzel et al and U.S. Pat. No. 5,739,355 to Gateau et al. HR-PIB, when used in the aforementioned thermal ene reactions, may result in higher reaction conversions and lower deposit formation due to increased reactivity. Suitable methods are described in U.S. patent No. 7,897,696.

In one embodiment, the present disclosure additionally includes at least one dispersant derived from polyisobutylene succinic anhydride ("PIBSA"). The PIBSA may have an average of between about 1.0 and about 2.0 succinic acid moieties per polymer.

The% activity of alkenyl or alkyl succinic anhydride can be determined using chromatographic techniques. This process is described in U.S. patent No. 5,334,321 at columns 5 and 6.

The percent conversion of the polyolefin is calculated from the activity% using the equations in columns 5 and 6 of U.S. patent No. 5,334,321.

Unless otherwise stated, all percentages are in weight percent and all molecular weights are number average molecular weights.

In one embodiment, the dispersant may be derived from Polyalphaolefin (PAO) succinic anhydride.

In one embodiment, the dispersant may be derived from an olefin maleic anhydride copolymer. For example, the dispersant may be described as poly PIBSA.

In one embodiment, the dispersant may be derived from an anhydride grafted to an ethylene-propylene copolymer.

One class of suitable dispersants may be Mannich bases (Mannich bases). Mannich bases are materials formed by the condensation of higher molecular weight alkyl-substituted phenols, polyalkylene polyamines, and aldehydes (e.g., formaldehyde). Mannich bases are described in more detail in U.S. patent No. 3,634,515.

One class of suitable dispersants may be high molecular weight esters or half ester amides.

Suitable dispersants may also be worked up by conventional methods by reaction with any of a variety of reagents. Among these are boron, urea, thiourea, thiodiazole, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, hindered phenolic esters, and phosphorus compounds. US 7,645,726, US 7,214,649 and US 8,048,831 are incorporated herein by reference in their entirety.

In addition to carbonate and borate post treatments, both compounds may be post treated or further post treated using various post treatments designed to improve or impart different properties. Such post-treatments include those outlined in columns 27 to 29 of U.S. patent No. 5,241,003, hereby incorporated by reference. Such treatments include, using the following treatments:

inorganic phosphorous acid or dehydrates (e.g., U.S. patent nos. 3,403,102 and 4,648,980);

organic phosphorus compounds (e.g., U.S. patent No. 3,502,677);

phosphorus pentasulfide;

boron compounds already mentioned above (e.g., U.S. Pat. nos. 3,178,663 and 4,652,387);

carboxylic acids, polycarboxylic acids, anhydrides, and/or acid halides (e.g., U.S. patent nos. 3,708,522 and 4,948,386);

epoxides, polyepoxides, or thioepoxides (e.g., U.S. patent nos. 3,859,318 and 5,026,495);

aldehydes or ketones (e.g., U.S. patent No. 3,458,530);

carbon disulfide (e.g., U.S. patent No. 3,256,185);

glycidol (e.g., U.S. patent No. 4,617,137);

urea, thiourea or guanidine (e.g. us patent nos. 3,312,619, 3,865,813 and british patent No. GB 1,065,595);

organic sulfonic acids (e.g., U.S. patent No. 3,189,544 and british patent No. GB 2,140,811);

alkenyl cyanides (e.g., U.S. patent nos. 3,278,550 and 3,366,569);

diacetylenones (e.g., U.S. patent No. 3,546,243);

diisocyanates (e.g., U.S. patent No. 3,573,205);

alkane sultones (e.g., U.S. patent No. 3,749,695);

1, 3-dicarbonyl compounds (e.g., U.S. Pat. No. 4,579,675);

sulfuric esters of alkoxylated alcohols or phenols (e.g., U.S. patent No. 3,954,639);

cyclic lactones (e.g., U.S. patent nos. 4,617,138, 4,645,515, 4,668,246, 4,963,275 and 4,971,711);

cyclic carbonates or thiocarbonates linear monocarbonates or polycarbonates or chloroformates (e.g. U.S. patent nos. 4,612,132, 4,647,390, 4,648,886, 4,670,170);

nitrogen-containing carboxylic acids (e.g., U.S. patent 4,971,598 and british patent GB 2,140,811);

hydroxy protected chlorodicarbonyloxy compounds (e.g., U.S. patent No. 4,614,522);

lactams, thiolactams, thiolactones, or dithiolactones (e.g., U.S. patent nos. 4,614,603 and 4,666,460);

cyclic carbonates or thiocarbonates linear monocarbonates or polycarbonates or chloroformates (e.g. U.S. patent nos. 4,612,132, 4,647,390, 4,646,886, 4,670,170);

nitrogen-containing carboxylic acids (e.g., U.S. patent No. 4,971,598 and british patent No. GB 2,440,811);

cyclic carbamates, thiocyclic carbamates, or dithiocyclic carbamates (e.g., U.S. patent nos. 4,663,062 and 4,666,459);

hydroxy aliphatic carboxylic acids (e.g., U.S. patent nos. 4,482,464, 4,521,318, 4,713,189);

oxidizing agents (e.g., U.S. patent No. 4,379,064);

phosphorus pentasulfide and polyalkylene polyamines (e.g., U.S. patent No. 3,185,647);

carboxylic acids or aldehydes or ketones in combination with sulfur or sulfur chloride (e.g., U.S. patent nos. 3,390,086, 3,470,098);

hydrazine in combination with carbon disulfide (e.g., U.S. patent No. 3,519,564);

combinations of aldehydes and phenols (e.g., U.S. patent nos. 3,649,229, 5,030,249, 5,039,307);

a combination of an aldehyde with an O-diester of a dithiophosphoric acid (e.g., U.S. patent No. 3,865,740);

a hydroxy aliphatic carboxylic acid in combination with boric acid (e.g., U.S. Pat. No. 4,554,086);

hydroxy aliphatic carboxylic acids and combinations of formaldehyde and phenol (e.g., U.S. Pat. No. 4,636,322);

a combination of a hydroxy aliphatic carboxylic acid and an aliphatic dicarboxylic acid (e.g., U.S. Pat. No. 4,663,064);

a combination of formaldehyde and phenol and glycolic acid (e.g., U.S. patent No. 4,699,724);

a combination of a hydroxy aliphatic carboxylic acid or oxalic acid and a diisocyanate (e.g., U.S. patent No. 4,713,191);

combinations of inorganic acids or anhydrides of phosphorus or its meta-or total sulfur analogs and boron compounds (e.g., U.S. Pat. No. 4,857,214);

a combination of an organic diacid and an unsaturated fatty acid and a nitrosoaromatic amine, optionally followed by a boron compound and a glycolating agent (e.g., U.S. patent No. 4,973,412);

combinations of aldehydes with triazoles (e.g., U.S. patent No. 4,963,278);

combinations of aldehydes and triazoles and boron compounds (e.g., U.S. Pat. No. 4,981,492);

cyclic lactones are combined with boron compounds and combinations (e.g., U.S. patent nos. 4,963,275 and 4,971,711). The above patents are incorporated herein in their entirety.

Suitable dispersants may have a TBN of from about 10 to about 65 on an oil-free basis, corresponding to a TBN of from about 5 to about 30 when measured on a dispersant sample containing about 50% diluent oil.

If present, the dispersant may be used in an amount sufficient to provide up to about 20 wt.%, based on the final weight of the lubricating oil composition. Another amount of dispersant that may be used may be from about 0.1 wt.% to about 15 wt.%, or from about 0.1 wt.% to about 10 wt.%, or from about 3 wt.% to about 10 wt.%, or from about 1 wt.% to about 6 wt.%, or from about 7 wt.% to about 12 wt.%, based on the final weight of the lubricating oil composition. In some embodiments, the lubricating oil composition employs a mixed dispersant system. A single type of dispersant or a mixture of two or more types of dispersants in any desired ratio may be used.

Friction modifiers

The lubricating oil compositions herein may also optionally contain one or more friction modifiers. Suitable friction modifiers may include metal-containing as well as metal-free friction modifiers, and may include, but are not limited to: imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated ether amines, amine oxides, amidoamines, nitriles, betaines, quaternary amines, imines, amine salts, aminoguanidines, alkanolamides, phosphonates, metal-containing compounds, glycerides, sulfurized fatty compounds and olefins, sunflower oil other naturally occurring vegetable or animal oils, dicarboxylic acid esters, esters or partial esters of polyols and one or more aliphatic or aromatic carboxylic acids, and the like.

Suitable friction modifiers may contain hydrocarbyl groups selected from straight chain, branched chain or aromatic hydrocarbyl groups or mixtures thereof and may be saturated or unsaturated. The hydrocarbyl group may be composed of carbon and hydrogen or heteroatoms such as sulfur or oxygen. The hydrocarbyl group may range from about 12 to about 25 carbon atoms. In some embodiments, the friction modifier may be a long chain fatty acid ester. In another embodiment, the long chain fatty acid ester may be a mono-or di-ester or a (tri) glyceride. The friction modifier may be a long chain fatty amide, a long chain fatty ester, a long chain fatty epoxide derivative, or a long chain imidazoline.

Other suitable friction modifiers may include organic ashless (metal-free) nitrogen-free organic friction modifiers. Such friction modifiers may include esters formed by reacting carboxylic acids and anhydrides with alkanols, and typically include a polar terminal group (e.g., carboxyl or hydroxyl) covalently bonded to an oleophilic hydrocarbon chain. An example of an organic ashless, nitrogen-free friction modifier is commonly known as Glycerol Monooleate (GMO), which may contain mono-, di-and triesters of oleic acid. Other suitable friction modifiers are described in U.S. patent No. 6,723,685, which is incorporated herein by reference in its entirety.

The amine friction modifier may include an amine or polyamine. Such compounds may have linear saturated or unsaturated hydrocarbon groups or mixtures thereof, and may contain from about 12 to about 25 carbon atoms. Other examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. Such compounds may have linear saturated or unsaturated hydrocarbon groups or mixtures thereof. They may contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.

The amines and amides may be used as such or in the form of adducts or reaction products with boron compounds, such as boron oxides, boron halides, metaborates, boric acid or mono-, di-or trialkyl borates. Other suitable friction modifiers are described in U.S. Pat. No. 6,300,291, which is incorporated herein by reference in its entirety.

The friction modifier may optionally be present in a range of from about 0 wt% to about 10 wt%, or from about 0.01 wt% to about 8 wt%, or from about 0.1 wt% to about 4 wt%.

Component containing molybdenum

The lubricating oil compositions herein may also optionally contain one or more molybdenum-containing compounds. The oil soluble molybdenum compound may have the functional effectiveness of an antiwear agent, an antioxidant, a friction modifier, or a mixture thereof. The oil soluble molybdenum compounds may include molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum dithiophosphinates, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, trinuclear organo-molybdenum compounds, and/or mixtures thereof. The molybdenum sulfide includes molybdenum disulfide. The molybdenum disulfide may be in the form of a stable dispersion. In one embodiment the oil soluble molybdenum compound may be selected from the group consisting of: molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment the oil soluble molybdenum compound may be molybdenum dithiocarbamate.

Suitable examples of molybdenum compounds that can be used include the commercial materials sold under the trade names: molyvan 822 from r.t.vanderbilt co., ltd^TM、Molyvan^TMA、Molyvan 2000^TMAnd Molyvan 855^TMAnd Sakura-Lube from Adeka Corporation^TMS-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710, and mixtures thereof. Suitable molybdenum components are described in US 5,650,381, US RE 37,363E 1, US RE 38,929E 1 and US RE 40,595E 1, which are incorporated herein by reference in their entirety。

Additionally, the molybdenum compound may be an acidic molybdenum compound. Including molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, such as sodium hydrogen molybdate, MoOCl₄、MoO₂Br₂、Mo₂O₃Cl₆Molybdenum trioxide or similar acidic molybdenum compounds. Alternatively, the composition may be provided with molybdenum from a molybdenum/sulfur complex of a basic nitrogen compound, as described in, for example, U.S. Pat. nos. 4,263,152, 4,285,822, 4,283,295, 4,272,387, 4,265,773, 4,261,843, 4,259,195, and 4,259,194, and U.S. patent publication No. 2002/0038525, incorporated herein by reference in their entirety.

Another class of suitable organo-molybdenum compounds are trinuclear molybdenum compounds, for example of the formula Mo₃S_kL_nQ_zWherein S represents sulfur, L represents an independently selected ligand having an organo group with a number of carbon atoms sufficient to render the compound soluble or dispersible in oil, n is 1 to 4, k is 4 to 7, Q is selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers, and z is in the range of 0 to 5 and includes non-stoichiometric values, and mixtures thereof. At least 21 total carbon atoms, such as at least 25, at least 30, or at least 35 carbon atoms, may be present in the organo groups of all ligands. Other suitable molybdenum compounds are described in U.S. patent No. 6,723,685, which is incorporated herein by reference in its entirety.

The oil soluble molybdenum compound may be present in an amount sufficient to provide about 0.5ppm to about 2000ppm, about 1ppm to about 700ppm, about 1ppm to about 550ppm, about 5ppm to about 300ppm, or about 20ppm to about 250ppm molybdenum.

Titanium-containing compound

Another class of additives includes oil soluble titanium compounds. The oil soluble titanium compound may serve as an antiwear agent, a friction modifier, an antioxidant, a deposit control additive, or more than one of these functions. In one embodiment, the oil soluble titanium compound may be a titanium (IV) alkoxide. The titanium alkoxide may be formed from a monohydric alcohol, a polyhydric alcohol, or mixtures thereof. The monoalkoxides may have 2 to 16, or 3 to 10 carbon atoms. In one embodiment, the titanium alkoxide may be titanium (IV) isopropoxide. In one embodiment, the titanium alkoxide may be titanium (IV) 2-ethylhexanoate. In one embodiment, the titanium compound may be a1, 2-diol or an alkoxide of a polyol. In one embodiment, the 1, 2-diol comprises a fatty acid monoglyceride, such as oleic acid. In one embodiment, the oil soluble titanium compound may be a titanium carboxylate. In one embodiment, the titanium (IV) carboxylate may be titanium neodecanoate.

In an embodiment, the oil soluble titanium compound may be present in the lubricating oil composition in an amount capable of providing zero to about 1500ppm by weight titanium, or about 10ppm to 500ppm by weight, or about 25ppm to about 150ppm by weight titanium.

Transition metal-containing compound

In another embodiment, the oil soluble compound may be a transition metal containing compound or metalloid. Transition metals may include, but are not limited to: titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, tungsten, and the like. Suitable metalloids include, but are not limited to: boron, silicon, antimony, tellurium, and the like.

In one embodiment, the oil soluble compound that may be used in a Ca/M weight ratio in the range of about 0.8:1 to about 70:1 is a titanium-containing compound, where M is the total metals in the lubricant composition as described above. The titanium-containing compound may serve as an antiwear agent, a friction modifier, an antioxidant, a deposit control additive, or more than one of these functions. Among the titanium-containing compounds that may be used in or for the preparation of the oil-soluble materials of the disclosed technology are various ti (IV) compounds, such as titanium (IV) oxide; titanium (IV) sulfide; titanium (IV) nitrate; titanium (IV) alkoxides, such as titanium methoxide, ethoxide, propoxide, isopropoxide, butoxide, 2-ethylhexoxide; and other titanium compounds or complexes including, but not limited to: titanium phenoxide; titanium carboxylates, such as titanium (IV) 2-ethyl-1-3-adipate or titanium citrate or oleate; and (triethanolamine acid radical) titanium (IV) isopropoxide. Other forms of titanium contemplated within the disclosed technology include titanium phosphates, such as titanium dithiophosphates (e.g., dialkyl dithiophosphates) and titanium sulfonates (e.g., alkyl benzene sulfonates), or generally the reaction products of titanium compounds with various acidic species to form salts (e.g., oil soluble salts). The titanium compound can thus be derived from, among others, organic acids, alcohols and diols. The Ti compound may also be present in dimeric or oligomeric form, containing a Ti- -O- -Ti structure. Such titanium species are commercially available or can be readily prepared by suitable synthetic techniques that will be apparent to those skilled in the art. They are present as solids or liquids at room temperature, depending on the particular compound. They may also be provided as solutions in suitable inert solvents.

In one embodiment, the titanium may be provided as a Ti modified dispersant, such as a succinimide dispersant. Such materials can be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride, such as an alkenyl (or alkyl) succinic anhydride. The resulting titanate-succinate intermediate may be used as such or it may be reacted with any of a number of materials: (a) polyamine succinimide/amide dispersants with free, condensable-NH functional groups; (b) components of polyamine succinimide/amide dispersants, i.e. alkenyl (or alkyl) succinic anhydrides and polyamines; (c) a hydroxyl-containing polyester dispersant prepared by the reaction of a substituted succinic anhydride with a polyol, aminoalcohol, polyamine or mixtures thereof. Alternatively, the titanate-succinate intermediate may be reacted with other reagents such as alcohols, aminoalcohols, ether alcohols, polyether alcohols or polyols, or fatty acids, and the product thereof used directly to impart Ti to a lubricant, or further reacted with a succinic acid dispersant as described above. For example, 1 part (by mole) tetraisopropyl titanate can be reacted with about 2 parts (by mole) polyisobutylene substituted succinic anhydride at 140 ℃ for 5 to 6 hours to provide a titanium modified dispersant or intermediate. The resulting material (30g) can be further reacted with a succinimide dispersant derived from polyisobutylene substituted succinic anhydride and a polyethylene polyamine mixture (127 g + diluent oil) at 150 ℃ for 1.5 hours to produce a titanium modified succinimide dispersant.

Another titanium-containing compound may be titanium alkoxide and C₆To C₂₅A reaction product of a carboxylic acid. The reaction product may be of the formulaRepresents:

wherein n is an integer selected from 2,3 and 4, and R is a hydrocarbyl group containing from about 5 to about 24 carbon atoms, or represented by the formula:

wherein each R¹、R²、R³And R⁴The same or different and are selected from hydrocarbyl groups containing from about 5 to about 25 carbon atoms. Suitable carboxylic acids may include, but are not limited to: caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, neodecanoic acid, and the like.

In an embodiment, the oil soluble titanium compound may be present in the lubricating oil composition in an amount capable of providing from 0 to 3000ppm by weight titanium, or from 25 to about 1500ppm by weight titanium, or from about 35ppm to 500ppm by weight titanium, or from about 50ppm to about 300ppm by weight.

Viscosity index improver

The lubricating oil compositions herein may also optionally contain one or more viscosity index improvers. Suitable viscosity index improvers may include polyolefins, olefin copolymers, ethylene/propylene copolymers, polyisobutylene, hydrogenated styrene-isoprene polymers, styrene/maleate copolymers, hydrogenated styrene/butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrogenated alkenyl aryl conjugated diene copolymers, or mixtures thereof. Viscosity index improvers may include star polymers, and suitable examples are described in U.S. patent No. 8,999,905B 2.

The lubricating oil compositions herein may also optionally contain one or more dispersant viscosity index improvers in addition to or in place of the viscosity index improvers. Suitable viscosity index improvers may include functionalized polyolefins, for example, ethylene-propylene copolymers that have been functionalized with the reaction product of an acylating agent (e.g., maleic anhydride) and an amine; amine or functionalized polymethacrylates, or esterified maleic anhydride-styrene copolymers reacted with amines.

The total amount of viscosity index improver and/or dispersant viscosity index improver can be from about 0 wt.% to about 20 wt.%, from about 0.1 wt.% to about 15 wt.%, from about 0.1 wt.% to about 12 wt.%, or from about 0.5 wt.% to about 10 wt.% of the lubricating oil composition.

Other optional additives

Other additives may be selected to perform one or more functions necessary for the lubricating fluid. In addition, one or more of the additives mentioned may be multifunctional and provide functions in addition to or different from those specified herein.

Lubricating oil compositions according to the present disclosure may optionally include other performance additives. Other performance additives may be in addition to the named additives of the present disclosure, and/or may include one or more of the following: metal deactivators, viscosity index improvers, ashless TBN synergists, friction modifiers, antiwear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, emulsifiers, pour point depressants, seal swell agents, and mixtures thereof. Typically, a fully formulated lubricating oil will contain one or more of these performance additives.

Suitable metal deactivators may include derivatives of benzotriazole (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2, 4-triazole, benzimidazole, 2-alkyldithiobenzimidazole or 2-alkyldithiobenzothiazole; a foam inhibitor comprising a copolymer of ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers; pour point depressants, including esters of maleic anhydride-styrene, polymethacrylates, polyacrylates or polyacrylamides.

Suitable foam inhibitors include silicon based compounds such as silicones.

Suitable pour point depressants may include polymethyl methacrylate or mixtures thereof. The pour point depressant can be present in an amount sufficient to provide from about 0 wt.% to about 1 wt.%, from about 0.01 wt.% to about 0.5 wt.%, or from about 0.02 wt.% to about 0.04 wt.%, based on the final weight of the lubricating oil composition.

Suitable rust inhibitors may be a single compound or a mixture of compounds having the property of inhibiting corrosion of ferrous metal surfaces. Non-limiting examples of rust inhibitors suitable for use herein include: oil-soluble high molecular weight organic acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, and cerotic acid; and oil-soluble polycarboxylic acids including dimer and trimer acids, such as those produced from tall oil fatty acids, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long chain alpha, omega-dicarboxylic acids having a molecular weight in the range of about 600 to about 3000 and alkenyl succinic acids wherein the alkenyl group contains about 10 or more carbon atoms, such as tetrapropenyl succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid. Another useful class of acidic corrosion inhibitors are half-esters of alkenyl succinic acids having about 8 to about 24 carbon atoms in the alkenyl group with alcohols such as polyethylene glycol. The corresponding half amides of such alkenyl succinic acids are also suitable. Suitable rust inhibitors are high molecular weight organic acids. In some embodiments, the engine oil is free of rust inhibitors.

If present, the rust inhibitor may be used in an amount sufficient to provide from about 0 wt.% to about 5 wt.%, from about 0.01 wt.% to about 3 wt.%, from about 0.1 wt.% to about 2 wt.%, based on the final weight of the lubricating oil composition.

In a general sense, suitable crankcase lubricants can include additive components in the ranges set forth in the following table.

TABLE 2

The above percentages of each component represent the weight percent of each component, based on the weight of the final lubricating oil composition. The remainder of the lubricating oil composition is made up of one or more base oils.

Additives used to formulate the compositions described herein can be blended into the base oil individually or in various sub-combinations. However, it may be suitable to blend all of the components simultaneously using an additive concentrate (i.e., additive and diluent, such as a hydrocarbon solvent). Additives used to formulate the compositions described herein can be blended into the base oil individually or in various sub-combinations. However, it may be suitable to blend all of the components simultaneously using an additive concentrate (i.e., additive and diluent, such as a hydrocarbon solvent).

The present disclosure provides novel lubricating oil blends formulated for use as automotive engine lubricants. Embodiments of the present disclosure may provide a lubricating oil suitable for engine applications, providing improvements in one or more of the following features: low speed pre-ignition events, antioxidants, anti-wear efficacy, rust protection, fuel economy, water tolerance, air incorporation, seal protection, reduced deposits, i.e. passing the TEOST 33 test, and anti-foaming properties.

Well-formulated lubricants conventionally contain an additive package, referred to herein as a dispersant/inhibitor package or DI package, which will provide the necessary characteristics for the formulation. Suitable DI packages are described, for example, in U.S. patent nos. 5,204,012 and 6,034,040. The types of additives included in the additive package may be dispersants, seal swelling agents, antioxidants, foam inhibitors, lubricants, rust inhibitors, corrosion inhibitors, demulsifiers, viscosity index improvers, and the like. Several of these components are well known to those skilled in the art and are typically used in conventional amounts with the additives and compositions described herein.

The following examples are illustrative of the methods and compositions of the present disclosure and are not limiting. Other suitable modifications and adaptations of various conditions and parameters normally encountered in the art and which are obvious to those skilled in the art are within the spirit and scope of the present disclosure. All patents and publications cited herein are fully incorporated by reference in their entirety.

Examples of the invention

Fully formulated lubricating oil compositions containing conventional additives were prepared and low speed pre-ignition events of the lubricating oil compositions were measured. Each lubricating oil composition contains a major amount of base oil, a base conventional Dispersant Inhibitor (DI) package, and a viscosity index improver, wherein the base DI package (less the viscosity index improver) comprises about 8 to 12 wt.% of the lubricating oil composition. The base DI contained conventional amounts of dispersants, anti-wear additives, anti-foam agents and antioxidants as illustrated in Table 3 below. Specifically, the base DI contains a succinimide dispersant, a borated succinimide dispersant, a molybdenum-containing compound in an amount to provide about 80ppm molybdenum of the lubricating oil composition, an organic friction modifier, one or more antioxidants, and one or more antiwear agents (unless otherwise specified). The base DI package also incorporates from about 5 to about 10 wt% of one or more viscosity index improvers. Group I base oils are used as diluents. A substantial amount of base oil (about 78 to about 87 weight percent) is group III base oil. The varying components are detailed in the following tables and in the discussion of the examples. Unless otherwise specified, all values listed are stated as weight percent of the components in the lubricating oil composition (i.e., active plus diluent oil, if present).

TABLE 3 basic DI packet composition

Components	Wt.％
		Antioxidant agent	0.5 to 2.5
Antiwear agents, including any dihydrocarbyl dithiophosphate metal salt	0.7 to 5.0
		Anti-foaming agent	0.001 to 0.01
Detergent	0.0
		Dispersing agent	2.0 to 6.0
Metal-containing friction modifiers	0.05 to 1.25
		Metal-free friction modifier	0.01 to 0.5
Pour point depressant	0.05 to 0.5
		Processing oil	0.25 to 1.0

Detergents were different in the following experiments, thus the detergent amount was set to zero for the purpose of the base formulation.

Low speed pre-ignition (LSPI) events were measured in GM 2.0 liter, 4 cylinder Ecotec turbocharged gasoline type direct injection (GDI) engines. A complete LSPI ignition engine test consists of 4 test cycles. Within a single test cycle, two phases or loops of operation are repeated to generate an LSPI event. In phase A, the engine was operated at about 2000rpm and about 18,000kPa Brake Mean Effective Pressure (BMEP) when LSPI was most likely to occur. In phase B, the engine was operated at about 1500rpm and about 17,000kPa BMEP when LSPI was unlikely to occur. For each stage, data was collected over 25,000 engine cycles. The structure of the test cycle is as follows: stage a-stage B-stage a. The phases are separated by idle periods. Because LSPI is statistically significant during phase a, the LSPI event data considered in this example includes only LSPI generated during phase a operations. Thus, for a complete LSPI ignition engine test, data is typically generated over a total of 16 stages and used to evaluate the efficacy of the comparative oil versus the oil of the present invention.

LSPI events are determined by monitoring peak cylinder pressure (Ρ) and when 2% of combustible material is combusted in the combustion chamber (MFB 02). The threshold value for peak cylinder pressure is calculated for each cylinder and each stage, and is typically 65,000 to 85,000 kPa. The threshold for MFB02 is calculated for each cylinder and each phase, and is typically in the range of about 3.0 to about 7.5 Crank Angle Degrees (CAD) After Top Dead Center (ATDC). LSPI is recorded when the thresholds for PP and MFB02 are exceeded during a single engine cycle. LSPI events may be reported in a number of ways. To remove the ambiguity involved in reporting the counts per engine cycle, where different ignition engine tests can be conducted using different numbers of engine cycles, the relative LSPI events of the comparison oil to the inventive oil are reported in the form of an "LSPI ratio". In this way, the improvement in response over some standards is clearly shown.

All reference oils are commercially available engine oils that meet all ILSAC GF-5 performance requirements, including passing the TEOST 33 test discussed below.

In the following examples, the basic formulation was used to test the combination of overbased calcium detergents with neutral/low-based calcium detergents. The LSPI ratio is reported as the ratio of LSPI events for the test oil relative to the LSPI events for the reference oil "R-1". R-1 is a lubricating oil composition formulated using a base DI package and an overbased calcium detergent in an amount to provide about 2400ppm Ca for the lubricating oil composition. More detailed blending information for reference oil R-1 is given below. A substantial improvement in LSPI is recognized when the reduction of LSPI events is greater than 50% relative to R-1 (LSPI ratio less than 0.5), a further improvement in LSPI is recognized when the reduction of LSPI events is greater than 70% (LSPI ratio less than 0.3), a further improvement in LSPI is recognized when the reduction of LSPI events is greater than 75% (LSPI ratio less than 0.25), and a further improvement in LSPI is recognized when the reduction of LSPI events is greater than 80% (LSPI ratio less than 0.20) relative to R-1, and a further improvement in LSPI is recognized when the reduction of LSPI events is greater than 90% (LSPI ratio less than 0.10) relative to R-1. The LSPI ratio for the apparent R-1 reference oil was therefore 1.00.

The TEOST-33 test is a bench test that can be used to evaluate the oxidative degradation and/or thermal coking of engine oils. According to the test, about 100mL of test oil was used in the 12-cycle/2-hour test. The test caused bulk oxidation of the oil (about 100 grams) on a hollow heating rod (TEOST deposition rod) that would accumulate deposits during the test. The test oil was flowed through the rod at about 0.5 grams per minute while the test part was cycled 12 times through the temperature range of 200 ℃ and 480 ℃. Total deposition is a measured performance parameter. The total deposit is the sum of the deposit on the rod and the deposit in the oil removed by filtration. More deposition measured indicates poorer efficacy of the additive composition. Specifically, test oils with weight gains of 30 milligrams or less pass the TEOST 33 test.

The TBN measurements given in the table below are based on ASTM D2896. TBN measurements are used to report the total metal millimoles of fully formulated example fluids in Table 4 below.

TABLE 4

Measurement using ICP analysis

Commercial oils R-1 and R-2 are currently the first to be displayedTechnical reference is included with reference to oil. Reference oil R-1 is made from about 80.7 wt.% group III base oil, 12.1 wt.% available from Afton Chemical Corporation

The 11150PCMO additive package was formulated with 7.2 wt.% 35SSI ethylene/propylene copolymer viscosity index improver.

The 11150 ride motor oil additive package is an API SN, ILSAC-GF-5, and ACEA A5/B5 quality DI package. R-1 also shows the following characteristics and partial elemental analysis:

reference oil R-1

R-2 contains only calcium-containing detergents with higher calcium loading than the tested oils of the invention. R-1 and R-2 meet all the potency requirements of ILSAC GF-5 and will therefore show passing performance in TEOST-33 bench oxidation tests. Comparative examples C-1, C-2, and C-3 are not commercially available fluids, but are designed to show the technical problems one skilled in the art experiences when modifying a detergent system to meet LSPI performance requirements.

As shown in Table 4, there was a significant improvement in LSPI efficacy when the amount of calcium from the overbased ("OB") detergent was reduced from about 2400ppm to about 1600ppm calcium. Comparing R-1 to C-1, the LSPI ratio decreased by about 78%, but the performance in the TEOST-33 test changed from pass to fail due to the decrease in calcium. If the amount of calcium from the OB detergent is further reduced to 1100ppm (C-2), the LSPI ratio improves even more significantly; however, at this calcium level, the performance in the TEOST-33 test is still poor. In C-3, the detergent system was completely removed, indicating that: without detergent, LSPI improved 100%. Again, however, TEOST 33 test failed performance. Example I-5 used low alkaline sodium sulfonate instead of the low alkaline calcium sulfonates used in inventive examples I-1, I-2, I-3, and I-4 and shows: using a sodium-containing low-alkaline/neutral detergent instead of a calcium-containing low-alkaline/neutral detergent can result in a significant reduction in LSPI ratio.

By combining low-basic or neutral ("LB/N") calcium detergents (I-1 to I-4) with OB calcium detergents, unexpected improvements in LSPI can be obtained without sacrificing performance in the TEOST-33 bench oxidation test. Inventive example I-1 was tested by TEOST-33 while providing a more significant improvement in LSPI events, with a reduction in LSPI ratio of almost 81% relative to R-1. Inventive examples I-2 and I-3 provided even greater reductions in LSPI ratios without losing performance in the TEOST-33 test. Example I-4 shows the use of LB/N calcium phenate instead of LB/N calcium sulfonate. I-4 also showed a significant improvement in LSPI ratio and passed the TEOST 33 test. The examples shown in table 4 clearly show that: by adding additional calcium from the LB/N calcium detergent, it is possible to keep the amount of calcium from the OB calcium detergent at higher levels while still passing the TEOST 33 test and ensuring a significant reduction in the LSPI ratio. In addition, unexpectedly, the results obtained in the TEOST 33 test can be improved even in the absence of significant amounts of OB calcium detergent. In fact, offsetting the OB calcium detergent with the LB/N calcium detergent unexpectedly and surprisingly improved the TEOST 33 test while also decreasing the LSPI ratio.

This data shows that compensating the OB Ca sulfonate with LB/N Ca sulfonate at an amount greater than 8% LB/N Ca sulfonate in the total detergent provides improvement of LSPI while maintaining performance in the TEOST 33 test.

Throughout this specification, reference is made to a number of U.S. patents and other documents. All such cited documents are expressly incorporated in full into this disclosure as if fully set forth herein.

Other embodiments of the disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the embodiments disclosed herein. As used throughout the specification and claims, "a" and/or "an" may mean one or more than one. Unless otherwise specified, all numbers expressing quantities of ingredients, properties, such as molecular weight, percentages, ratios, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about," whether or not the term "about" is present. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and claims are approximations that may vary depending upon the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the disclosure being indicated by the following claims.

In practice, the foregoing embodiments are susceptible to significant variation. Accordingly, the embodiments are not intended to be limited to the specific examples set forth above. Rather, the foregoing embodiments are within the spirit and scope of the appended claims, including the equivalents of the claims, as applicable.

The applicant does not intend to dedicate any disclosed embodiments to the public, and to the extent any disclosed modifications or alterations may not literally fall within the scope of the claims, they are considered to be part hereof under the doctrine of equivalents.

It is to be understood that each component, compound, substituent, or parameter disclosed herein is to be understood as being disclosed for use alone or in combination with one or more of each other component, compound, substituent, or parameter disclosed herein.

It will also be appreciated that each amount/value or range of amounts/values for each component, compound, substituent or parameter disclosed herein is to be understood as also disclosed in combination with each amount/value or range of amounts/values disclosed for any other component, compound, substituent or parameter disclosed herein, and any combination of amounts/values or ranges of amounts/values of two or more components, compounds, substituents or parameters disclosed herein for the purposes of this description is also hereby disclosed in combination with each other.

It is also to be understood that each range disclosed herein is to be understood as disclosing each specific value with the same number of significant digits within the range disclosed. Accordingly, a range of 1 to 4 should be understood as disclosing the values 1,2, 3 and 4.

It is also to be understood that each lower limit of each range disclosed herein is to be understood as being disclosed in combination with each upper limit of each range and each specific value within each range disclosed herein for the same component, compound, substituent or parameter. Thus, the disclosure should be understood as disclosing all ranges derived from combining each lower limit of each range with each upper limit of each range, or with each specific value within each range, or from combining each upper limit of each range with each specific value within each range.

Further, a particular amount/value of a component, compound, substituent, or parameter disclosed in the specification or examples is to be understood as disclosing the lower or upper limit of the range, and thus a range for a component, compound, substituent, or parameter described may be formed in combination with any other lower or upper limit disclosed elsewhere in this application for the same component, compound, substituent, or parameter, or particular amount/value.

Claims

1. A lubricating oil composition comprising:

greater than 50 wt.% of a base oil of lubricating viscosity;

at least 0.3 wt.% of an overbased calcium sulfonate detergent having a total base number greater than 225mg KOH/g as determined by the method of ASTM D-2896, and

at least 0.2 wt.% of a low-base/neutral detergent selected from the group consisting of calcium sulfonate detergents and calcium phenate detergents, having a total base number of at most 175mg KOH/g as determined by the method of ASTM D-2896, wherein the total amount of calcium from the overbased calcium sulfonate detergent and the low-base/neutral detergent ranges from greater than 1100ppm by weight to less than 2400ppm by weight based on the total weight of the lubricating oil composition,

the total amount of calcium from the overbased calcium sulfonate detergent is from 900ppm to no greater than 1800ppm by weight of calcium, based on the total weight of the lubricating oil composition; and

the ratio of ppm by weight of calcium provided to the lubricating oil composition by the low-base/neutral detergent to ppm by weight of calcium provided to the lubricating oil composition by the overbased calcium sulfonate detergent is from 0.08 to 0.4.

2. The lubricating oil composition of claim 1, wherein the reduction of LSPI events is 75% or more and the LSPI events are LSPI counts during 25,000 engine cycles, wherein the engine is operated at 2000 revolutions per minute and brake mean effective pressure of 18,000 kPa.

3. The lubricating oil composition of claim 1, wherein the lubricating oil composition has a ratio of total metal millimoles in the lubricating oil composition to the total base number of the lubricating oil composition in the range of greater than 4.5 to 10.0.

4. The lubricating oil composition of claim 1, wherein the lubricating oil composition is effective to pass the TEOST 33 bench oxidation test.

5. The lubricating oil composition of claim 1, further comprising one or more components selected from the group consisting of: friction modifiers, antiwear agents, dispersants, antioxidants, and viscosity index improvers.

6. The lubricating oil composition of claim 1, wherein the greater than 50 wt.% base oil is selected from the group consisting of: group II, group III, group IV, group V base oils, and combinations of two or more of the foregoing base oils, and wherein the greater than 50 wt.% base oil is not a diluent oil resulting from providing an additive component or viscosity index improver in the composition.

7. The lubricating oil composition of claim 1, wherein the ratio of total metal millimoles in the lubricating oil composition to TBN of a lubricant is greater than 8 to less than 10, and the lubricating oil composition comprises at least 0.25 wt.% of the low-base/neutral detergent.

8. The lubricating oil composition of claim 1, wherein the total calcium provided to the lubricating oil composition by the overbased calcium sulfonate detergent is from 1100ppm to 1800ppm by weight, based on the total weight of the lubricating oil composition.

9. The lubricating oil composition of claim 1, wherein the total calcium provided to the lubricating oil composition by the low-basic/neutral detergent is from 50ppm to 1000ppm by weight, based on the total weight of the lubricating oil composition.

10. The lubricating oil composition of claim 1, wherein the lubricating oil composition is effective to reduce low speed pre-ignition events in a boosted internal combustion engine lubricated with the lubricating oil composition relative to a plurality of low speed pre-ignition events in the same engine lubricated with reference lubricating oil R-1.

11. A method for reducing low speed pre-ignition events in a boosted internal combustion engine comprising:

lubricating an enhanced internal combustion engine using a lubricating oil composition comprising

Greater than 50 wt.% of a base oil of lubricating viscosity;

at least 0.2 wt.% of a low-alkaline/neutral detergent selected from the group consisting of calcium sulfonate detergents and calcium phenate detergents; the low-alkaline/neutral detergent has a total base number of up to 175mg KOH/g as measured by the method of ASTM D-2896; wherein the total amount of calcium from the overbased calcium sulfonate detergent and the overbased/neutral detergent is in the range of greater than 1100ppm by weight to less than 2400ppm by weight based on the total weight of the lubricating oil composition,

the ratio of ppm by weight of calcium provided to the lubricating oil composition by the low-base/neutral detergent to ppm by weight of calcium provided to the lubricating oil composition by the overbased calcium sulfonate detergent is from 0.08 to 0.4; and

operating the engine lubricated with the lubricating oil composition.

12. The method of claim 11, wherein the lubricant composition passes the TEOST 33 bench oxidation test.

13. The method of claim 12, wherein LSPI events are based on LSPI counts during 25,000 engine cycles, wherein the engine is operated at 2000 Revolutions Per Minute (RPM) and Brake Mean Effective Pressure (BMEP) of 18,000kPa, and the low speed pre-ignition events in the boosted internal combustion engine lubricated with the lubricating oil composition are reduced relative to a plurality of low speed pre-ignition events in the same engine lubricated with reference lubricating oil R-1,

wherein a reference lube R-1 was formulated with 80.7 wt.% group III base oil, 12.1 wt.% passenger car motor oil package, and 7.2 wt.% of a 35SSI ethylene/propylene copolymer viscosity index improver, and R-1 also showed the following characteristics and partial elemental analysis:

10.9 dynamic viscosity (mm) at 100 ℃²Second) 3.3 TBS, apparent viscosity, cPa 2438 Calcium (ppmw) <10 Magnesium (ppmw) 80 Molybdenum (ppmw) 772 Phosphorus (ppmw) 855 Zinc (ppmw) 9.0 Total base number ASTM D-2896(mg KOH/g) 165 Viscosity index

。

14. The method of claim 13, wherein the lubricating step lubricates a combustion chamber or cylinder wall of a spark-ignition direct-injection engine or a nozzle fuel-injected internal combustion engine equipped with a turbocharger or supercharger.

15. The method of claim 13, further comprising the step of measuring a low speed pre-ignition event of the internal combustion engine lubricated with the lubricating oil.

16. The lubricating oil composition of claim 1, wherein the low-base/neutral detergent is a low-base/neutral calcium sulfonate detergent.

17. The method of claim 11, wherein the low-alkaline/neutral detergent is a low-alkaline/neutral calcium sulfonate detergent.