KR20180048596A - Lubricants with calcium-containing detergents and their use for low speed early-ignition improvement - Google Patents

Abstract

LUBRICANT COMPOSITION AND VOLUME. The lubricating oil composition comprises a base oil of greater than 50 wt.%, An overbased detergent having a TBN of greater than 225 mg KOH / g, and a low basic / neutral detergent having a TBN of up to 175 mg KOH / g. The total calcium content of the overbased and low basic / neutral detergent is greater than 1100 ppm and less than 2400 ppm based on the total weight of the lubricating oil composition. Lubricant compositions and methods may be effective in reducing low speed pre-ignition events in a power internal combustion engine that is lubricated with a lubricant composition as compared to commercially available lubricant compositions.

Description

Lubricants with calcium-containing detergents and their use for low speed early-ignition improvement

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

A turbocharged or supercharged engine (ie a power internal combustion engine) may exhibit an abnormal combustion phenomenon known as stochastic early-ignition or low-velocity early-ignition (or "LSPI"). LSPI is an early-ignition event that involves a very high pressure rise, initial combustion at an unsuitable crank angle, and knocking. All of these, individually and in combination, can potentially cause deterioration and / or various damage to the engine. However, since LSPI events occur only sporadically and in a non-modulated manner, it is difficult to identify the cause of these phenomena and propose a solution to prevent them.

Early-ignition is a form of combustion due to the ignition of the air-fuel mixture in the combustion chamber prior to the preferred air-fuel mixture ignition by the igniter. Early-ignition is typically a problem in high-speed engine operation as heat from engine operation can heat a portion of the combustion chamber sufficiently to ignite the air-fuel mixture. This type of premature ignition is sometimes referred to as hot point premature ignition.

More recently, intermittent unsteady combustion at low and medium to high loads has been observed in a power internal combustion engine. For example, low engine pre-ignition (LSPI) may occur in a random and stochastic manner during engine operation below 3,000 rpm under load of a braking mean effective pressure (BMEP) of at least 10 bar. During low-speed engine operation, the compression stroke time is the longest.

Several public studies suggest that supercharger use, engine design, engine coating, piston geometry, fuel selection, and / or engine oil additives can contribute to increased LSPI events. One theory suggests that auto-ignition of engine oil droplets entering the engine combustion chamber from the piston clearance (the space between the piston ring pack and the cylinder liner) may be one cause of the LSPI event. Thus, there is a need for effective engine oil additive components and / or combinations that can reduce or eliminate LSPI in the internal combustion engine.

The present disclosure relates to a lubricating oil composition and a method for operating a power internal combustion engine. The lubricating oil composition comprises at least 0.3 wt.% Of an overbased detergent having a lubricating viscosity base oil of greater than 50 wt.%, A total base number (TBN) of greater than 225 mg KOH / g, and 175 mg of KOH / g, wherein the total calcium content of the overbased and low basic / neutral detergent ranges from greater than 1100 ppm to the total weight of the lubricating oil composition, Less than 2400 ppm. The lubricating oil composition can be effective in reducing low speed pre-ignition events in a power internal combustion engine that is lubricated with a lubricating oil composition.

In yet another embodiment, the present disclosure provides a method of reducing low speed pre-ignition events in a power internal combustion engine. The method includes lubrication of the internal combustion engine with a lubricating oil composition, wherein the composition comprises at least 0.3 wt.% Of an overbased detergent having a lubricating viscosity base oil in excess of 50 wt.%, A TBN in excess of 225 mg KOH / g, and At least 0.2 wt.% Of a low basic / neutral detergent having a TBN of at most 175 mg KOH / g. The overall calcium content range of the overbased and low basic / neutral detergents is from greater than 1100 ppm to less than 2400 ppm, based on the total weight of the lubricating oil composition, by weight. The internal combustion engine of the internal combustion engine is operated and lubricated with the lubricating oil composition so that the low speed early-ignition event can be reduced in the engine lubricated with the lubricating oil composition.

In certain electrical embodiments, the overbased detergent comprises an overbased calcium-containing detergent. The overbased calcium-containing detergent may be selected from an overbased calcium sulfonate detergent and an overbased calcium phenate detergent. In each embodiment, the overbased detergent can be a calcium-containing detergent or a mixture of two or more overbased calcium-containing detergents. In each of the electrical embodiments, the at least one overbased calcium-containing detergent (s) can provide about 900 to about 2000 ppm of calcium to the lubricating oil composition, based on the weight of the lubricating oil composition, based on the weight of the lubricating oil composition.

In certain electrical embodiments, the low basic / neutral detergent may be a calcium containing detergent and the low basic / neutral calcium containing detergent may be a detergent selected from calcium sulfonate detergents and calcium phenate detergents. In electrical embodiments, at least 4 wt.% Of the total detergent in the lubricating oil composition is a low basic / neutral detergent. In each electrical embodiment, the lubricating oil composition may have a range of ratios of total mmol metal (M) to total base number (TBN) of greater than 4.5 to about 10.0 or greater than 8 and about 10.

In each of the electrical implementations, the reduction in low speed early-ignition (LSPI) events is indicated by the ratio of the LSPI event of the test oil to the LSPI event of the reference oil (hereinafter "LSPI ratio"), Containing an overbearing calcium-containing detergent in an amount to provide about 2400 ppm calcium to the lubricating oil composition as the sole detergent in the composition. In electrical implementations, the LSPI event is represented by an LSPI count at 25,000 engine cycles, and the engine is operated at 2000 revolutions per minute (RPM) at a braking mean effective pressure (BMEP) of 18,000 kPA.

In each of the electrical embodiments, the base oil may be selected from Group I, Group II, Group III, Group IV, or Group V base oils, and a combination of two or more base oils. In other embodiments, base oils of greater than 50 wt.% Are selected from the group consisting of Group II, Group III, Group IV, or Group V base oils, and combinations of two or more base base oils, Quot; is outside of the diluent oil (diluent oil) due to the addition of the additive components or the viscosity index improver in the composition.

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

In the electrical embodiments of the method described herein, the operating engine has a braking mean effective pressure (BMEP) of greater than 1,500 kPa at engine speeds of revolutions per minute (rpm) of less than 3000 or a BMEP of 1,800 kPa at 2000 rpm engine speed Level. ≪ / RTI >

In each of the electrical embodiments, the lubricating oil composition may be effective in passing the TEOST 33 bench oxidation test.

In each of the electrical embodiments, the low basic / neutral detergent comprises a low basic / neutral calcium-containing detergent and comprises a low basic / neutral detergent on a weight basis with respect to ppm of calcium provided to the lubricating oil composition by the overbased calcium- The proportion of ppm calcium provided to the lubricating oil composition by the neutral calcium-containing detergent may be 0.05 to 1.0.

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

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

In each electrical embodiment, the lubricating oil composition may comprise up to 10 wt.% Of a Group IV base oil, a Group V base oil, or combinations thereof. In each electrical embodiment, the lubricating oil composition comprises less than 5 wt.% Of Group V base oil.

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

In each of the electrical embodiments, the overbased calcium-containing detergent may optionally exclude the overbased calcium salicylate detergents.

In each of the electrical embodiments, the lubricating oil composition may optionally exclude any magnesium-containing detergents, or the lubricating oil composition may be free of magnesium.

In each of the electrical embodiments, the lubricating oil composition may not contain any Group IV base oils.

In each of the electrical embodiments, the lubricating oil composition may not contain any Group V base oils.

Definitions of the following terms are provided to clarify the meaning of certain terms as used herein.

The terms "oil composition," "lubricating composition," "lubricating oil composition," "lubricating oil," "lubricating composition," "lubricating composition," "fully formulated lubricant composition," "lubricant," "crankcase oil, Quot ;, " crankcase lubricant ", " engine oil, " " engine lubricant, " " motor oil, " and " motor lubricant " are synonyms referring to finished lubricants comprising base oils in excess of 50 wt.% And minor amounts of additive composition And is considered to be a fully compatible term.

As used herein, the terms "additive package," "additive concentrate," "additive composition," "engine oil additive package," "engine oil additive concentrate," "crankcase additive package," "crankcase additive Concentrate, " " motor oil additive package, " " motor oil concentrate ", are considered synonymous and fully compatible terms that refer to a portion of a lubricating oil composition that excludes base oil stock mixtures in excess of 50 wt.%. The additive package may or may not include a viscosity index improver or a pour point depressant.

The term " overbased " relates to metal salts such as sulfonates, carboxylates, salicylates, and / or phenates, wherein the amount of metal present exceeds the stoichiometric amount. The salt may have an excess conversion level of 100% (i.e., it may comprise more than 100% of the theoretical amount of metal required to convert the acid to its "normal", "neutral" salt). The expression "metal ratio ", commonly abbreviated as MR, is used to specify the ratio of the total chemical equivalent of the metal in the overbased salt to the chemical equivalent of the metal in the neutral salt according to known chemical reactivity and stoichiometry. In normal or neutral salts, the metal ratio is 1 and the MR in the overbased salt is greater than 1. It is usually expressed as an overbased, hyper basic or super basic salt and may be a salt of organic sulfuric acid, carboxylic acid, salicylate, and / or phenol. In this disclosure, the TBN of the overbased detergent is greater than 225 mg KOH / g. The overbased detergent may be a combination of two or more overbased detergents and each TBN is greater than 225 mg KOH / g.

In the present disclosure, the TBN of the low basic / neutral detergent is at most 175 mg KOH / g. The low basic / neutral detergent may be a combination of two or more low basic and / or neutral detergents and each TBN has a maximum of 175 mg KOH / g. In some instances, " overbased " is outlined as "OB" and in some instances, "low basic / neutral" is outlined as "LB / N".

The term " whole metal " refers to the entire metal, semimetal, or transition metal of a lubricating oil composition, including metals contributed by the detergent component (s) 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 is referred to as a group having carbon atoms attached directly to the remainder of the molecule and usually having hydrocarbon character. Examples of hydrocarbyl groups include:

(a) a hydrocarbon substituent, i. e. an aliphatic (e.g., alkyl or alkenyl), an alicyclic (e.g., cycloalkyl, cycloalkenyl) substituent, and an aromatic, aliphatic, and alicyclic- , As well as cyclic substituents wherein the ring is completed through another moiety of the molecule (e.g., the two substituents together form an alicyclic moiety);

(b) a substituted hydrocarbon substituent, i.e., a non-hydrocarbon group (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto groups which do not alter the majority of the hydrocarbon substituents in the context of this disclosure A nitro group, a nitro group, a nitro group, a nitro group, an amino group, an alkylamino group, and a sulfoxy group); And

(c) Hetero substituents, that is, substituents containing carbon other than carbon in the ring or chain having carbon atoms in the context of the present disclosure, usually of hydrocarbon character but elsewhere. Hetero atoms can include sulfur, oxygen, and nitrogen and can include substituents such as pyridyl, furyl, thienyl, and imidazolyl. Generally, no more than two, for example no more than one, non-hydrocarbon substituent will be present for every 10 carbon atoms in the hydrocarbyl group; Typically, the non-hydrocarbon substituent in the hydrocarbyl group will not be present.

As used herein, the term "% by weight" means the percentage of the recited ingredient relative to the weight of the total composition, unless explicitly stated otherwise.

As used herein, the terms "solubility "," availability ", or "dispersibility" are not essential but may indicate that the compound or additive is soluble, miscible, or suspendable in oil in all proportions. However, the term is meant to be soluble, suspendable, soluble, or stably dispersible in the oil to an extent sufficient to, for example, exert its intended effect in the environment in which the oil is utilized. In addition, further incorporation of other additives may also allow incorporation of higher levels of the specified additive if desired.

The term "TBN " as utilized herein is used to denote the total base number as the KOH / g composition, as determined by the method of ASTM D2896.

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

As used herein, the term "alkenyl" is referred to as a straight, branched, cyclic, and / or substituted unsaturated chain portion of about 3 to about 10 carbon atoms.

The term "aryl" as used herein includes heteroatoms including, but not limited to, alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy, halo substituents, and / or nitrogen, Quot; mono- and multi-ring aromatic compounds "

The lubricants, combinations of components, or separate components of the present description may be suitable for use in various types of internal combustion engines. Suitable engine types may include, but are not limited to, heavy duty diesel, passenger car, light duty diesel, medium speed diesel, or marine engines. Internal combustion engines include diesel fueled engines, gasoline fueled engines, natural gas fueled engines, bio-fueled engines, mixed diesel / biofuel fueled engines, mixed gasoline / biofuel fueled engines, alcohol fueled engines, mixed gasoline / An engine, a compressed natural gas (CNG) fueling engine, or a mixture thereof. The diesel engine can be a compression ignition engine. The diesel engine can be a compression ignition engine with a spark-ignition assist. The gasoline engine can be a flame-ignition engine. The internal combustion engine can also be used in combination with an electrical or battery power source. The engine thus constructed is commonly known as a hybrid engine. The internal combustion engine may be a two-stroke, four-stroke, or rotary engine. Suitable internal combustion engines include marine diesel engines (e.g., internal), aviation piston engines, diesel engines in degradation, and motorcycles, automobiles, locomotives, and truck engines.

The internal combustion engine may contain one or more components of an aluminum-alloy, lead, tin, copper, cast iron, magnesium, ceramic, stainless steel, composites, and / or mixtures thereof. The component may be coated with, for example, a diamond-like carbon coating, a lubricating coating, a phosphorus-containing coating, a molybdenum-containing coating, a graphite coating, a nano-particle-containing coating, and / or mixtures thereof. The aluminum-alloy may comprise aluminum silicate, aluminum oxide, or other ceramic material. In one embodiment, the aluminum-alloy is an aluminum-silicate surface. As used herein, the term "aluminum alloy" is synonymous with the term "aluminum composite" and refers to a surface or component comprising aluminum and other components that are mixed or reacted at a microscopic or near microscopic level, Is intended to be described. This will include any conventional alloys with metals other than aluminum, as well as composite or alloy-like structures with non-metallic elements or compounds such as ceramic-like materials.

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

In one embodiment, the lubricating composition is an engine oil, wherein the lubricating composition comprises (i) a sulfur content of about 0.5 wt% or less, Lt; RTI ID = 0.0 > sulfated ash. ≪ / RTI >

In some embodiments, the lubricating oil composition is suitable for use in a low sulfur fuel, such as about 1 to about 5% sulfur containing fuel engines. Highway vehicle fuels contain about 15 ppm sulfur (or about 0.0015% sulfur). The lubricant composition is suitable for use in a power internal combustion engine including a turbocharged or supercharged internal combustion engine.

In addition, the lubricant of the present description may be used with one or more industrial specification requirements, such as ILSAC GF-3, GF-4, GF-5, GF-6, PC-11, CI-4, CJ- / 2, A3 / B3, A3 / B4, A5 / B5, C1, C2, C3, C4, C5, E4 / E6 / E7 / E9, Euro 5/6, Jaso DL- the original equipment manufacturer's specifications, for example ^{Dexos TM 1, Dexos TM 2,} MB-Approval 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 Citroen Automobiles B71 2290, B71 2296, B71 2297, B71 2300, B71 2302, B71 2312, B71 2007, B71 2008, Ford WSS-M2C153-H, WSS-M2C930-A, WSS- , WSS-M2C913-B, WSS-M2C913-C, GM 6094-M, Chrysler MS-6395, or any past or future PCMO or HDD specifications not mentioned herein. In some embodiments for passenger car motor oil (PCMO) applications, the amount of phosphorus in the finished fluid is 1000 ppm or less, or 900 ppm or less, or 800 ppm or less.

Other hardware may not be suitable for use with the disclosed lubricant. "Functional fluid" is used in tractor hydraulic fluids, power transmission fluids such as automatic transmission fluids, continuously variable transmission fluids and manual transmission fluids, hydraulic fluids such as tractor hydraulic fluids, some gear oils, power steering fluids, wind turbines, compressors Including fluids, some industrial fluids, and fluid associated with power train components. It should be noted that there are various and different types of fluids due to various transmissions having different designs that have led to the need for fluids of significantly different operating characteristics, for example, in each of these fluids such as automatic transmission fluids . This is in contrast to the term "lubricating fluid" which is not used to generate or move the power.

With respect to tractor hydraulic fluids, for example, these fluids are multipurpose products used in all lubricant applications in tractors, except that the engine is lubricated. These lubrication applications can include lubrication of gearboxes, power take-offs and clutches, rear axles, reduction gears, wet brakes, and hydraulic accessories.

When the functional fluid is an automatic transmission fluid, the automatic transmission fluid must have sufficient friction to allow the clutch plate to transmit power. However, the coefficient of friction of the fluid tends to decrease due to the temperature effect that the fluid is heated during operation. It is important for the tractor hydraulic fluid or automatic transmission fluid to maintain its high coefficient of friction at elevated temperatures, otherwise the brake system or automatic transmission may fail. This is not a function of engine oil.

Tractor fluids and, for example, Super Tractor Universal Oil (STUO) or Universal Tractor Transmission Oil (UTTO) can be used to optimize the performance of engine oils in transmissions, differentials, final-drive planetary gear, wet-brake, and hydraulic performance. Many of the additives used to formulate UTTO or STUO fluids are similar in function, but they can have a deleterious effect if not properly incorporated. For example, some anti-wear and extreme pressure additives used in engine oils may be extremely corrosive to the copper parts of hydraulic pumps. Detergents and dispersants used for gasoline or diesel engine performance can be detrimental to wet brake performance. A special friction modifier for quiet wet brake sound may lack the thermal stability required for engine oil performance. Each of these fluids is designed to meet specific, stringent manufacturer requirements, both for functionality, tractor, or lubricity.

The present disclosure provides a novel lubricant blend that is specially formulated for use as an automotive crankcase lubricant. Embodiments of the disclosure can provide lubricating oils that are suitable for crankcase applications and have improvements in properties such as: air entrainment, alcohol fuel compatibility, antioxidant, antiwear performance, biofuel compatibility, reduced foam properties, reduced friction , Fuel economy, premature ignition prevention, rust inhibition, sludge and / or soot dispersibility, piston cleanliness, deposition and water resistance.

The engine oil of the disclosure can be formulated by adding one or more additives as described in detail below to an appropriate base oil formulation. The additive 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 separately. The fully formulated engine oil may exhibit improved performance characteristics based on the additive to be added and their respective proportions.

Additional details and advantages of the disclosure will be set forth in part in the description that follows, and / or may be learned by practice of the present disclosure. The details and advantages of the disclosure can be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. As claimed, both the foregoing general description and the following detailed description are merely illustrative and explanatory and are not to be considered limiting of the present disclosure.

Various embodiments of the disclosure provide a lubricant composition and method that can be used to reduce low speed early-ignition events (LSPI) in a boosted internal combustion engine. In particular, the present internal combustion engine includes a turbo class and a supercharged internal combustion engine. The internal combustion engine includes a spark-ignition, direct injection, and / or port-fuel injection engine. The flame-ignition internal combustion engine can be a gasoline engine.

The composition of the present invention comprises a lubricating oil composition containing a lubricating viscosity base oil and a specific additive composition. The method of the disclosure applies a lubricating oil composition containing an additive composition. As will be described in more detail below, the lubricating oil composition is surprisingly effective at reducing low-early-ignition events in a power internal combustion engine lubricated with a lubricating oil composition.

In yet another embodiment, the present disclosure provides a method of reducing low speed pre-ignition events in a power internal combustion engine. The method includes lubrication of the internal combustion engine with a lubricating oil composition, wherein the composition comprises at least 0.3 wt.% Of an overbased detergent having a lubricating viscosity base oil in excess of 50 wt.%, A TBN in excess of 225 mg KOH / g, and At least 0.2 wt.% Of a low basic / neutral detergent having a TBN of at most 175 mg KOH / g. The overall calcium content range of the overbased and low basic / neutral detergents is from greater than 1100 ppm to less than 2400 ppm, based on the total weight of the lubricating oil composition, by weight. The low-early-ignition event can be reduced in an engine in which the internal combustion engine of the internal combustion engine is operated and lubricated with the lubricating oil composition.

In some embodiments, a combustion chamber or cylinder wall of a spark-ignition direct injection engine or a port fuel injected internal combustion engine provided with a turbocharger or supercharger is operated with a lubricant composition and lubricated with the lubricant composition by being lubricated Low-early-ignition events in the engine can be reduced.

Optionally, the method of the present invention may comprise the step of measuring a low-speed pre-ignition event of an internal combustion engine lubricated with lubricating oil. In this way, the LSPI event reduction of the internal combustion engine is reduced by 50% or more, or more preferably by 75% or more, and the LSPI event is the LSPI count at 25,000 engine cycles, and the engine is at the braking average effective pressure of 18,000 kPa It operates at 2000 revolutions per minute.

As will be discussed in more detail below, embodiments of the disclosure provide unexpected improvements while keeping in mind the reduction of LSPI events while maintaining a relatively high calcium detergent concentration in the lubricating oil composition. Implementations of the present disclosure may also provide unexpected TEOST 33 test improvements while reducing LSPI events.

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

Detergents

The lubricating oil composition comprises one or more overbased detergents and one or more low basic / neutral detergents. Suitable detergent substrates include, but are not limited to, phenate, sulfur containing phenates, sulfonates, calicarboxylate, salicylate, salicylate, carboxylic acid, phosphoric acid, mono- and / or di- Alkyl phenol compounds, or methylene bridged phenols. Suitable detergents and methods for their preparation are described in greater detail in many patents, including U.S. Patent No. 7,732,390 and references cited therein. The detergent substrate may be chlorinated with an alkali or alkaline earth metal, such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof. In some embodiments, the detergent does not contain barium. Suitable detergents may include alkaline or alkaline earth metal salts of long-chain mono- or di-alkylaryl sulfonic acids having petroleum sulfonic acid and benzyl, tolyl, and xylyl aryl groups. Examples of suitable additional detergents include, but are not limited to, calcium phenate, calcium sulfur containing phenate, calcium sulfonate, calcium calicarate, calcium salicylate, calcium salicylate, calcium carboxylic acid, calcium phosphate, Calcium mono- and / or di-thiophosphoric acid, calcium alkylphenol, calcium sulfur-coupled alkylphenol compounds, calcium methylene bridged phenol, magnesium phenate, magnesium sulfur-containing phenate, magnesium sulfonate, magnesium calixarate, magnesium Magnesium mono-and / or di-thiophosphoric acid, magnesium alkylphenol, magnesium sulfur-coupled alkylphenol compounds, magnesium methylene-bridged phenol, sodium phenate, magnesium stearate, magnesium stearate, magnesium silicate, magnesium carboxylate, magnesium phosphate, magnesium mono- and / , Sodium sulfur-containing phenate, sodium sulfonate, sodium calicylate, sodium salicylate, sodium salicylate, Acrylate, sodium acid, sodium phosphate, sodium mono- include thio phosphate, sodium alkyl phenol, a sodium sulfur coupled alkyl phenol compounds, or sodium methylene bridged phenol-and / or di.

The overbased detergents are well known in the art and can be alkali metal or alkaline earth metal and basic detergents. These detergents can be prepared by reacting metal oxides or metal hydroxides with substrate and carbon dioxide gases. The substrate may typically be an acid, such as an acid such as an aliphatic substituted sulfonic acid, an aliphatic substituted carboxylic acid, or an aliphatically substituted phenol.

The term " overbased " relates to metal salts of metal salts, such as sulfonates, carboxylates, and phenates, wherein the amount of metal present exceeds the stoichiometric amount. Such salts may have an excess conversion level of 100% (i. E., It may comprise more than 100% of the theoretical amount of metal required to convert the acid to its "normal", "neutral" salt). The expression "metal ratio ", commonly abbreviated as MR, is used to specify the ratio of the total chemical equivalent of the metal in the overbased salt to the chemical equivalent of the metal in the neutral salt according to known chemical reactivity and stoichiometry. In normal or neutral salts, the metal ratio is 1, and the MR in the overbased salt exceeds 1. It is usually expressed as an overbased, hyper basic or super basic salt and may be a salt of organic sulfuric acid, carboxylic acid, or phenol.

TBN with an overbased detergent greater than 225 mg KOH / gram, or, as additional examples, TBN greater than about 250 mg KOH / gram, or TBN greater than about 300 mg KOH / gram, or greater than about 350 mg KOH / gram, or about 375 mg TBN above KOH / gram, or TBN above about 400 mg KOH / gram.

Examples of suitable overbased detergents include, but are not limited to, an overbased calcium phenate, an overbased calcium sulphate containing phenate, an overbased calcium sulphonate, an overbased calcium calicarate, an overbased calcium sialicarboxylate, an overbased Overbased calcium-phosphorus acid, overbased calcium mono- and / or di-thiophosphoric acid, overbased calcium alkylphenol, overbased calcium sulfur-coupled alkylphenol compounds, overbased calcium phosphate, Methylene bridged phenol, an overbased magnesium penneate, an overbased magnesium sulfur containing phenate, an overbased magnesium sulphonate, an overbased magnesium calixate, an overbased magnesium salicylate, an overbased magnesium salicylate, an overbased magnesium carbonate Unsaturated acid, unsaturated acid, unsaturated acid, unsaturated acid, unsaturated acid, It includes castle magnesium alkyl phenols, overbased magnesium sulfur coupled alkyl phenol compounds, or magnesium overbased methylene bridged phenol.

The overbased detergent has a metal to base ratio of from 1.1: 1, or from 2: 1, or from 4: 1, or from 5: 1, or from 7: 1 or from 10: 1.

In some embodiments, the detergent is effective in reducing or preventing rust in the engine.

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

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

The lubricating oil composition of the disclosure comprises at least one overbased detergent having a TBN greater than 225 mg KOH / gram and at least one neutral / low basic detergent having a TBN of up to 175 mg KOH / gram. The disclosure also includes a method of using such a lubricating composition in a method of lubricating the engine and lubricating the engine with a lubricating composition and operating the engine.

The total calcium content range from the overbased and low basic / neutral detergents in the lubricating oil compositions of this disclosure is greater than 1100 ppm and less than 2400 ppm 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 an overbased calcium sulfonate detergent, an overbased calcium phenate detergent, and an overbased calcium salicylate detergent. 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 at least one overbased calcium-containing detergent provides from about 900 to about 2400 ppm of calcium to the finished fluid. As a further example, the at least one overbased calcium-containing detergent may comprise from about 900 to about 2000 ppm of calcium, or from about 900 to about 1800 ppm of calcium, or from about 1100 to 1600 ppm of calcium, or from about 1200 to 1500 ppm of calcium It is present in a content that can be supplied to the finished fluid.

The low basic / neutral detergent has a TBN of up to 175 mg KOH / g, or up to 150 mg KOH / g. Low base / neutral detergents include calcium-containing detergents. The low basic neutral calcium-containing detergent may be selected from calcium sulfonate detergents, calcium phenate detergents and calcium salicylate detergents. In some embodiments, the low basic / neutral detergent is a calcium-containing detergent or a mixture of calcium-containing detergents. In some embodiments, the low basic / neutral detergent is a calcium sulfonate detergent or a calcium phenate detergent.

A low basic / neutral detergent is included in the lubricant composition at least 2.5 wt.% Of the total detergent. 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 lubricant composition, Is a low basic / neutral detergent and may optionally be a low basic / neutral calcium-containing detergent.

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

In some embodiments, the lubricating oil composition has a range of ratios of total millimolar (M) to lubricant composition TBN of from greater than 4.5 to about 10.0. In some embodiments, the ratio of total millimolar (M) to lubricant composition TBN ranges from greater than 8 to less than 10.0 or from 8 to 9.5 or 8.1 to 9.0.

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

The overbased calcium-containing detergent may be an overbased calcium sulfonate detergent. The overbased calcium-containing detergent optionally excludes the overbased calcium salicylate detergent. The lubricating oil optionally excludes any magnesium-containing detergent or is free of magnesium. In certain embodiments of the disclosure, the sodium content in the lubricating composition may be limited to less than 150 ppm sodium based on the total weight of the lubricating oil composition.

Base oil

The base oils used in the lubricating oil compositions herein may be selected from any of the base oils listed in Groups I-V as set forth in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five groups of base oils are:

Base oil classification Sulfur (%) Saturation (%) Viscosity index Group I > 0.03 And / or <90 80 to 120 Group II 0.03 And ≥ 90 80 to 120 Group III 0.03 And ≥ 90 ≥120 Group IV All poly alpha-olefin (PAO) Group V All other base oils not included in Group I, II, III, or IV

Groups I, II, and III are mineral oil process stocks. Group IV base oils contain true synthetic molecular species produced by polymerization of olefinically unsaturated hydrocarbons. Many group V base oils are also true synthetic products and may include diesters, polyol esters, polyalkylene glycols, alkylated aromatics, polyphosphate esters, polyvinyl ethers, and / or polyphenyl ethers, For example, plants may be unique. Group III base oils are derived from mineral oil, but it should be noted that the rigorous processing experienced by these fluids makes their physical properties very similar to some of the true synthetic products such as PAO. Therefore, oils derived from Group III base oils can be referred to in the industry as synthetic fluids.

Base oils used in the disclosed lubricating oil compositions may be mineral oils, animal oils, vegetable oils, synthetic oils, or mixtures thereof. Suitable oils can be derived from hydrocracking, hydrogenation, hydrofinishing, unrefined, refined, and re-refined oils, and mixtures thereof.

Unrefined oils are derived from natural, mineral, or synthetic sources with little or no further purification. Refined oils are similar to unfixed oils except that they have been treated in one or more purification steps which may result in the improvement of one or more properties. Examples of suitable purification techniques are solvent extraction, secondary distillation, acid or base extraction, filtration, exudate, and the like. Refined oils of acceptable quality may or may not be useful. Edible oil may also be referred to as white oil. In some embodiments, the lubricant composition is free of cooking oil or white oil.

The re-refined oil is also known as regenerated or remanufactured oil. Such oils are obtained using the same or similar processes similar to refined oils. Often these oils are additionally processed by techniques for the removal of spent additives and oil degradation products.

The mineral oil may comprise oils obtained from excavation or from plants and animals or any mixture thereof. For example, such oils may be mineral-based lubricants such as castor oil, lard oil, olive oil, peanut oil, corn oil, soybean oil and linseed oil as well as mineral oil lubricants such as liquid petroleum and paraffin, naphthene, But are not limited to, acid-treated mineral lubricating oils. Such oils may be partially or fully hydrogenated as needed. Oils derived from coal or shale may also be useful.

Useful synthetic lubricating oils include hydrocarbon oils such as polymerized, oligomerized, or copolymerized olefins (e.g., polybutylene, polypropylene, propylene isobutylene copolymers); Trimers or oligomers of poly (1-hexene), poly (1-octene), 1-decene, such as poly (1-decene) (these materials are often referred to as alpha-olefins), and mixtures thereof; Alkyl-benzene (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di- (2-ethylhexyl) -benzene); Polyphenyls (e.g., biphenyl, terphenyl, alkylated polyphenyls); Diphenylalkanes, alkylated diphenylalkanes, alkylated diphenyl ethers and alkylated diphenyl sulfides and derivatives, analogs and analogs thereof or mixtures thereof. Polyalphaolefins are typically 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 phosphonic acid), or polymeric tetrahydrofuran . The synthetic oil may be produced by a Fischer-Tropsch reaction, typically a hydroisomerized Fischer-Tropsch hydrocarbon or wax. In one embodiment, the oil may be prepared by Fischer-Tropsch gas-to-liquid synthesis procedures as well as other gas-to-liquid oils.

The base oil of greater than 50 wt.% Contained in the lubricating composition is selected from the group consisting of Group I, Group II, Group III, Group IV, Group V, and combinations of two or more electrical base oils, Is other than base oils due to the addition of additive components or viscosity index improvers in the composition. In yet another embodiment, the base oil of greater than 50 wt.% Contained in the lubricating composition is selected from the group consisting of Group II, Group III, Group IV, Group V, and combinations of two or more electrical base oils, Excess base oils are other than diluent oils due to the addition of additive ingredients or viscosity index improvers in the composition.

The amount of oil present in the lubricating viscosity present is determined by subtracting the sum of the amount of the performance additive comprising the viscosity index improver (s) and / or pour point depressant (s) and / or other top treat additives from 100% Lt; / RTI &gt; For example, the lubricating viscosity oil that may be present in the finished fluid may be a large amount, such as greater than about 50 weight percent, greater than about 60 weight percent, greater than about 70 weight percent, greater than about 80 weight percent, greater than about 85 weight percent, May be more than 90% by weight.

The lubricating oil composition comprises up to 10 wt.% Of Group IV base oils, Group V base oils, or combinations thereof. In each electrical embodiment, 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 oils. The lubricating oil composition does not contain any Group V base oils.

The lubricating oil composition also includes one or more optional components selected from the various additives set forth below.

Antioxidant

The lubricating oil composition herein may also optionally contain one or more antioxidants. The antioxidant compounds are known and are known, for example, phenate, phenate sulfide, sulfurized olefin, phosphosulfurized terpene, sulfated ester, aromatic amine, alkylated diphenylamine (for example, nonyldiphenylamine, Phenylamine, phenylamine, octyldiphenylamine, di-octyldiphenylamine), phenyl-alpha-naphthylamine, alkylated phenyl-alpha-naphthylamine, disordered nonaromatic amine, phenol, disturbing phenol, useful molybdenum compound, Antioxidants, or mixtures thereof. Antioxidant compounds may be used alone or in combination.

The inhibitory phenolic antioxidants may contain secondary butyl and / or tertiary butyl groups as steric hindrance groups. The phenol group may be further substituted with a crosslinking group and / or a hydrocarbyl group connected to the second aromatic group. Examples of suitable phenolic antioxidants suitable for use in the present invention are 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl- Butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the disorder phenolic antioxidant may be an ester, for example IRGANOX ^TM L-135 (available from BASF) or 2,6-di-tert-butylphenol and alkyl acrylate, 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. Other commercially available phenolic antioxidants may be esters and may include ETHANOX ^TM 4716 (available from Albemarle Corporation)

Useful antioxidants may include diarylamines and high molecular weight phenols. In embodiments, the lubricating oil composition may contain a mixture of diaryl amines and high molecular weight phenols such that each antioxidant may be present in an amount sufficient to provide up to about 5 weight percent based on the final weight of the lubricating oil composition. In embodiments, the antioxidant may be a mixture of about 0.3 to about 1.5% diarylamine and about 0.4 to about 2.5% (by weight) high molecular weight phenol, based on the final weight of the lubricating oil composition.

Examples of suitable olefins that can be sulfided to form sulfided olefins include propylene, butylene, isobutylene, polyisobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, Decene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecene, nonadecene, eicosene or mixtures thereof and dimers, trimers and tetramers are particularly useful olefins. Alternatively, the olefin may be Diels-Alder adducts of dienes such as 1,3-butadiene and unsaturated esters such as butyl acrylate.

Another class of sulfurized olefins includes sulfurized fatty acids and esters thereof. Fatty acids are often obtained from vegetable oils or animal fats and typically contain from about 4 to about 22 carbon atoms. Examples of suitable fatty acids and esters thereof include triglycerides, oleic, linoleic, palmitoleic, or mixtures thereof. Often, fatty acids are obtained from lard oil, tall 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 antioxidant (s) may be present in the range of about 0 wt% to about 20 wt%, or about 0.1 wt% to about 10 wt%, or about 1 wt% to about 5 wt% of the lubricating composition.

Antimatter

The lubricating oil composition herein may optionally also optionally contain one or more anti-wear agents. Examples of suitable antiwear agents include, but are not limited to, metal thiophosphates; Metal dialkyl dithiophosphates; Phosphoric acid esters or salts thereof; Phosphate ester (s); Phosphite; Phosphorus-containing carboxyl esters, ethers, or amides; Olefin sulfide; A thiocarbamate-containing compound comprising a thiocarbamate ester, an alkylene-coupled thiocarbamate and bis (S-alkyldithiocarbamyl) disulfide; And mixtures thereof. A suitable antiwear agent may be molybdenum dithiocarbamate. Phosphorous-containing anti-wrinkle agents are fully described in European Patent 612 839. In the dialkyldithiophosphate salt, the metal can be an alkali metal, an alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc. A useful antiwear agent can be zinc dialkyl thiophosphate.

Additional examples of suitable antiwear agents include, but are not limited to, titanium compounds, tartrates, tartrates, useful amine salts of phosphorus compounds, sulfurized olefins, phosphites (e.g., dibutylphosphite), phosphonates, thiocarbamate- , Such as thiocarbamate esters, thiocarbamate amides, thiocarbamate ethers, alkylene-coupled thiocarbamates, and bis (S-alkyldithiocarbamyl) disulfides. Tartrate or tartrate may contain an alkyl-ester group, wherein the total number of carbon atoms on the alkyl group may be at least 8. Anti-abrasives can include citrates in one embodiment.

The antiwear agent may comprise 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 And the like.

The antiwear compound may be zinc dihydrocarbyl dithiophosphate (ZDDP) having a P: Zn ratio of about 1: 0.8 to about 1: 1.7.

Boron-containing compound

The lubricating oil composition 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, for example, borated succinimide dispersants as described in U.S. Patent No. 5,883,057.

The boron-containing compound, if present, can 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% Can be used in a sufficient amount.

Dispersant

The lubricant composition may optionally further comprise one or more dispersants or mixtures thereof. Dispersants are commonly known as ashless-type dispersants, since they do not contain ash-forming metals prior to mixing into the lubricant composition and they do not contribute to any ash when they are generally added to the lubricant. The ashless dispersant is characterized by 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 wherein the number average molecular weight of the polyisobutylene substituent ranges from about 350 to about 50,000, or from about 5,000 to about 3,000 . Succinimide dispersants and their preparation are disclosed, for example, in U.S. Pat. No. 7,897,696 or U.S. Pat. No. 4,234,435. The polyolefin may be prepared from a polymerizable monomer having from about 2 to about 16 carbon atoms, or from about 2 to about 8, or from about 2 to about 6 carbon atoms. The succinimide dispersant is typically an imide formed from a polyamine, typically poly (ethyleneamine).

In embodiments, the disclosure further comprises one or more polyisobutylene succinimide dispersants derived from polyisobutylene having a number average molecular weight in the range of from about 350 to about 50,000, or from about 5000 to about 3000 do. The polyisobutylene succinimide may be used alone or in combination with other dispersants.

In some embodiments, polyisobutylene, when included, may 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%. The PIB is also represented as a highly reactive PIB ("HR-PIB"). HR-PIB having a number average molecular weight of from about 800 to about 5000 is suitable for use in the embodiments of this disclosure. Typical PIBs typically have 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 ranging from about 900 to about 3000 may be suitable. The HR-PIB is commercially available or can be synthesized by polymerization of isobutene in the presence of a non-chlorinated catalyst such as boron trifluoride (U.S. Patent No. 4,152,499 (Boerzel, et al.) And U.S. Patent No. 5,739,355 (Gateau, Lt; / RTI &gt; When used in the above-mentioned thermal enantiomeric reaction, HR-PIB can induce a low amount of precipitate formation as well as a high conversion in the reaction due to increased reactivity. A suitable method is described in U.S. Patent No. 7,897,696.

In one embodiment, the disclosure also includes one or more dispersants derived from polyisobutylene succinic anhydride ("PIBSA"). PIBSA may have an average of from about 1.0 to about 2.0 succinic acid moieties per polymer.

The% activity of alkenyl or alkyl succinic anhydride can be determined using chromatographic techniques. Such methods are described in columns 5 and 6 of U.S. Patent No. 5,334,321.

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

Unless otherwise indicated, all percentages are by weight and all molecular weights are number average molecular weights.

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

In one embodiment, the dispersing agent may be derived from an olefin maleic anhydride copolymer. By way of example, the dispersant may be described as poly-PIBSA.

In embodiments, 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 are substances which are formed by condensation of high molecular weight, alkyl substituted phenols, polyalkylene polyamines, and aldehydes such as formaldehyde. Mannich bases are described in more detail in U.S. Patent No. 3,634,515.

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

Suitable dispersing agents may also be post-treated by conventional methods by reaction with any of a variety of agonists. Among these, boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehyde, ketone, carboxylic acid, hydrogen carbonate-substituted succinic anhydride, maleic anhydride, nitrile, epoxide, carbonate, cyclic Carbonate, disturbed phenol 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 the carbonate and boric acid follow-up treatments, all compounds may be post-treated or further post-treated by various post-treatments designed to improve or impart different properties. This post-treatment includes those summarized in columns 27-29 of U.S. Pat. No. 5,241,003, which is incorporated herein by reference. The treatment includes treatment with: inorganic phosphorous acid or anhydride (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); Pentasulfide; The boron compounds already shown (for example, U.S. Patent Nos. 3,718,663 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); Epoxide polyepoxyates 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 (for example, U.S. Patent No. 3,256,185); Glycidol (e.g., U.S. Patent No. 4,617,137); Urea, thiourea or guanidine (e.g., U.S. Pat. No. 3,312,619; 3,865,813; and British Patent GB 1,065,595); Organic sulfonic acids (e.g., U.S. Pat. No. 3,189,544 and British Patent GB 2,140,811); Alkenyl cyanide (e.g., U.S. Patent Nos. 3,278,550 and 3,366,569); Diketene (e.g., U.S. Patent No. 3,546,243); Diisocyanates (e.g., U.S. Pat. No. 3,573,205); Alkanesulfones (e.g., U.S. Patent No. 3,749,695); 1,3-dicarbonyl compounds (e.g., U.S. Patent No. 4,579,675); Sulfates 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 thiocarbonate linear mono- or polycarbonates, or chloroformates (e.g., U.S. Pat. Nos. 4,612,132; 4,647,390; 4,648,886; 4,670,170); Nitrogen-containing carboxylic acids (e.g., U.S. 4,971,598 and GB 2,140,811); Hydroxy-protected chlorodicarbonyloxy compounds (e.g., U.S. Patent No. 4,614,522); Lactam, thiolactam, thiolactone or dithiolactone (e.g., U.S. Patent Nos. 4,614,603 and 4,666,460); Cyclic carbonates or thiocarbonates, linear mono- or polycarbonates, or chloroformates (e.g., U.S. Pat. Nos. 4,612,132; 4,647,390; and 4,670,170); Cyclic carbamates, cyclic thiocarbamates or cyclic dithiocarbamates (e.g., U.S. Pat. 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); Oxidants (e.g., U.S. Patent No. 4,379,064); A combination of phosphorus pentasulfide and polyalkylene polyamine (e.g., U.S. Patent No. 3,185,647); Combinations of carboxylic acids or aldehydes or ketones and sulfur or sulfur chlorides (e.g., U.S. Pat. No. 3,390,086; 3,470,098); A combination of hydrazine and 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 and an O-diester of dithiophosphoric acid (e.g., U.S. Patent No. 3,865,740); A combination of a hydroxy aliphatic carboxylic acid and a boric acid (e.g., U.S. Patent No. 4,554,086); A hydroxy aliphatic carboxylic acid, followed by a combination of formaldehyde and phenol (e.g., U.S. Patent No. 4,636,322); A combination of a hydroxy aliphatic carboxylic acid and a subsequent aliphatic dicarboxylic acid (e.g., U.S. Patent No. 4,663,064); A combination of formaldehyde and phenol and subsequent glycolic acid (e.g., U.S. Patent No. 4,699,724); A hydroxy aliphatic carboxylic acid or a combination of oxalic acid and subsequent diisocyanate (e.g., U.S. Patent No. 4,713,191); A phosphorus acid or anhydride or a part or whole sulfur analog thereof and a combination of boron compounds (e.g., U.S. Patent No. 4,857,214); Unsaturated fatty acids after organic diacids and then nitrosoaromatic amines are optionally followed by a combination of a boron compound and a subsequent glycosylation agent (e.g., U.S. Patent No. 4,973,412); Combinations of aldehydes and triazoles (e.g., U.S. Patent No. 4,963,278); Combinations of aldehydes and boron compounds after triazole (e.g., U.S. Patent No. 4,981,492); Combinations of cyclic lactones and boron compounds (e.g., U.S. Pat. Nos. 4,963,275 and 4,971,711). These patents are incorporated herein by reference in their entirety.

The TBN of a suitable dispersant may be from about 10 to about 65, on a no-oil basis, comparable to about 5 to about 30 TBN, as measured for a dispersant sample containing about 50% diluent oil.

The dispersant, when present, 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 can be used is 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 0.1 wt% to about 10 wt%, based on the final weight of the lubricating oil composition From about 1 wt% to about 6 wt%, or from about 7 wt% to about 12 wt%. In one embodiment, the lubricating oil composition utilizes a mixed dispersant system. Mixtures of two or more types of dispersants in a single type or in any desired ratio may be used.

Friction modifier

The lubricating oil composition herein may also optionally contain one or more friction modifiers. Suitable friction modifiers can include metal-containing and metal-free friction modifiers and include, without limitation, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated ether amines, amine oxides, amidoamines, nitriles, Phosphorus compounds and olefins, sunflower oils and other naturally occurring plants or animal oils, dicarboxylic acids, such as dicarboxylic acids, Acid esters, esters or some esters of polyols, and at least one aliphatic or aromatic carboxylic acid.

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 a heteroatom such as sulfur or oxygen. The hydrocarbyl group may have 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-ester, or a di-ester or (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 (no metal), non-nitrogen organic friction modifiers. The friction modifier may include an ester formed by reacting a carboxylic acid and anhydride with an alkanol, and generally includes a polar end group (e.g., carboxyl or hydroxyl) covalently bonded to a lipophilic hydrocarbon chain. Examples of organic ashless nitrogen friction modifiers are generally known as glycerol monooleate (GMO), which may contain mono-, di-, and tri-esters of oleic acid. Other suitable friction modifiers are described in U.S. Pat. No. 6,723,685, which is incorporated herein by reference in its entirety.

The amine-based friction modifier may include an amine or a polyamine. The compound may have a hydrocarbyl group that is saturated or unsaturated linear, or a mixture thereof, and may contain from about 12 to about 25 carbon atoms. Further examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. The compound may have a hydrocarbyl group that is linear or saturated, or a mixture thereof. Which may contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.

Amines and amides can be used in the form of adducts or reaction products with boron compounds such as boron oxide, boron halides, metaborates, boric acids or mono-, di- or tri-alkyl borates or on their own. Other suitable friction modifiers are described in U.S. Pat. No. 6,300,291, which is incorporated herein by reference.

The friction modifier may optionally be present in the 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%.

Molybdenum-containing component

The lubricating oil composition herein may also optionally contain at least one molybdenum-containing compound. Utility Molybdenum compounds can have functional performance of anti-abrasives, antioxidants, friction modifiers, or mixtures thereof. Usability The molybdenum compound is selected from the group consisting of molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, molybdenum dithiophosphate, amine salts of molybdenum compounds, molybdenum titanate, A molybdenum alkoxide, a 3-nuclear organo-molybdenum compound, and / or a mixture thereof. Molybdenum sulphide includes molybdenum disulphide. 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 dithiocarbamate, molybdenum dialkyldithiophosphate, 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 may be used include commercially available materials commercially available under the trade names Molyvan 822, Molyvan TM A, Molyvan 2000 ^TM and Molyvan 855 ^TM from RT Vanderbilt Co., And Sakura-Lube ™ S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710, and mixtures thereof, available from Adeka Corporation. Suitable molybdenum components are described in U.S. Pat. Nos. 5,650,381; US RE 37,363 E1; US RE 38,929 E1; And US RE 40,595 E1.

Further, the molybdenum compound may be an acidic molybdenum compound. Included are molybdodenic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts such as hydrogensodium molybdate, MoOCl ₄ , MoO ₂ Br ₂ , Mo ₂ O ₃ Cl ₆ , molybdenum trioxide, or similar acidic molybdenum compounds. Alternatively, the compositions may include, for example, those described in U.S. Patent 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 molybdenum / sulfur complexes of basic nitrogen compounds as described in U.S. Patent Publication No. 2002/0038525.

Another class of suitable organo-molybdenum compounds is a 3-nuclear molybdenum compound such as those of the formula Mo ₃ S _k L _n Q _z and mixtures thereof wherein S represents sulfur and L represents a compound in an oil N is from 1 to 4, k varies from 4 to 7, Q is selected from the group of neutral electron donating compounds, Such as water, amines, alcohols, phosphines and ethers, z ranges from 0 to 5, and includes non-stoichiometric values. 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 group of all the ligands. Additional suitable molybdenum compounds are described in U.S. Patent No. 6,723,685, which is incorporated herein by reference in its entirety.

The useful molybdenum compounds include about 0.5 ppm to about 2000 ppm, about 1 ppm to about 700 ppm, about 1 ppm to about 550 ppm, about 5 ppm to about 300 ppm, or about 20 ppm to about 250 ppm molybdenum &Lt; / RTI &gt;

Titanium-containing compounds

Another class of additives includes an oil-soluble titanium compound. The oil-soluble titanium compound may function as an anti-wear agent, a friction modifier, an antioxidant, a deposition control additive, or more than one of these functions. In an embodiment, the usable titanium compound may be titanium (IV) alkoxide. The titanium alkoxide may be formed from a monohydric alcohol, a polyol, or a mixture thereof. The monovalent alkoxide may have 2 to 16 carbon atoms, or 3 to 10 carbon atoms. In an embodiment, the titanium alkoxide may be titanium (IV) isopropoxide. In an embodiment, the titanium alkoxide may be titanium (IV) 2-ethylhexoxide. In an embodiment, the titanium compound may be a 1,2-diol or an alkoxide of a polyol. In embodiments, the 1,2-diol includes glycerol fatty acid mono-esters such as oleic acid. In an embodiment, the usable titanium compound may be a titanium carboxylate. In an embodiment, the titanium (IV) carboxylate may be titanium neodecanoate.

In an embodiment, the usable titanium compound may be present in the lubricating composition in an amount to provide from 0 to about 1500 weight ppm titanium or from about 10 weight ppm to 500 weight ppm titanium or from about 25 weight ppm to about 150 weight ppm .

Transition metal-containing compound

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

In one embodiment, the oil-soluble compound that can be used in a Ca / M weight ratio of about 0.8: 1 to about 70: 1 is a titanium-containing compound, wherein M is the total metal in the lubricant composition. The titanium-containing compound may function as an anti-abrasive, a friction modifier, an antioxidant, a deposition control additive, or more than one of these functions. Uses of Initiation Techniques Among the titanium-containing compounds used in or used in the manufacture of materials, various Ti (IV) compounds such as titanium (IV) oxide; Titanium (IV) sulfide; Titanium (IV) nitrate; Titanium (IV) alkoxides such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium 2-ethylhexoxide; And other titanium compounds or complexes such as, but not limited to, titanium phenate; Titanium carboxylates such as titanium (IV) 2-ethyl-1, 3-hexanedioate or titanium citrate or titanium oleate; And titanium (IV) (triethanolaminato) isopropoxide. Other forms of titanium encompassed within the disclosure include titanium phosphate such as titanium dithiophosphate (e.g., dialkyldithiophosphate) and titanium sulfonate (e.g., alkylbenzenesulfonate), or generally titanium Compounds and salts with various acidic substances, such as reaction products to form an oil-soluble salt. Titanium compounds can thus be derived, among other things, from organic acids, alcohols, and glycols. The Ti compound may also be present in the form of a dendritic or oligomer having a Ti - O - Ti structure. The titanium material is commercially available or can be readily prepared by suitable synthetic techniques as will be apparent to those skilled in the art. They may be present as solids or liquids at room temperature depending on the particular compound. They may also be provided in solution form in a suitable inert solvent.

In one embodiment, the titanium may be supplied as a Ti-modified dispersant, such as a succinimide dispersant. The material may be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride such as an alkenyl- (or alkyl) succinic anhydride. The resulting titanate-succinate intermediates may be used directly or in combination with any of a number of materials such as (a) a polyamine-based succinimide / amide dispersant having a free, condensable-NH functional group; (b) reaction of polyamine-based succinimide / amide dispersant components, i.e., alkenyl- (or alkyl-) succinic anhydrides and polyamines, (c) reaction of substituted succinic anhydrides with polyols, aminoalcohols, polyamines, Lt; RTI ID = 0.0 &gt; hydroxy-containing &lt; / RTI &gt; Alternatively, the titanate-succinate intermediate reacts with other agents such as alcohols, amino alcohols, ether alcohols, polyether alcohols or polyols, or fatty acids, the products of which are used directly to impart Ti to the lubricant, Lt; / RTI &gt; As an illustration, one part (molar basis) of tetraisopropyl titanate is reacted with about 2 parts (by mole) of polyisobutene-substituted succinic anhydride at 140-150 ° C for 5-6 hours to form a titanium reforming dispersant or intermediate Lt; / RTI &gt; The resulting material (30 g) was further reacted with a succinimide dispersant from polyisobutene-substituted succinic anhydride and a polyethylene polyamine mixture (127 grams + dilution oil) at 150 ° C for 1.5 hours to give titanium- A mid dispersant is produced.

Another titanium-containing compound is the reaction product of a titanium alkoxide and a C ₆ to C ₂₅ carboxylic acid. The reaction product is represented by the following formula:

Wherein n is an integer selected from 2, 3 and 4, and R represents a hydrocarbyl group having from about 5 to about 24 carbon atoms, or a formula:

Wherein each R ¹ , R ² , R ³ , and R ⁴ is the same or different and is selected from hydrocarbyl groups having from about 5 to about 25 carbon atoms. Suitable carboxylic acids 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 embodiments, the oil-soluble titanium compound may be present in the lubricating oil composition in an amount of from 0 to 3000 ppm titanium by weight, or from 25 to about 1500 ppm titanium by weight, or from about 35 ppm to 500 ppm titanium or from about 50 ppm to about 300 ppm by weight And may be present in an amount that can be achieved.

Viscosity index improver

The lubricating oil composition herein may also optionally contain one or more viscosity index improvers. Suitable viscosity index improvers include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutene, hydrogenated styrene-isoprene polymers, styrene / maleic ester copolymers, hydrogenated styrene / butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic acid Anhydride copolymers, polymethacrylates, polyacrylates, polyalkyl styrenes, hydrogenated alkenyl aryl conjugated diene copolymers, or mixtures thereof. The viscosity index improver may comprise a star polymer and a suitable example is described in U.S. Patent No. 8,999,905 B2.

The lubricating oil composition herein may also optionally contain one or more dispersant viscosity index improvers other than or in place of the viscosity index improvers. Suitable viscosity index improvers include ethylene-propylene copolymers that are functionalized with the reaction product of a functionalized polyolefin, such as an acrylating agent (e.g., maleic anhydride) and an amine; An amine-functionalized polymethacrylate, or an esterified maleic anhydride-styrene copolymer reacted with an amine.

The total amount of the viscosity index improver and / or the dispersant viscosity index improver is 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%.

Other optional additives

Other additives may be selected to perform one or more of the required functions of the lubricating fluid. In addition, one or more of the mentioned additives may be multifunctional and provide functions other than those specified herein or other functions.

The lubricating composition according to the present disclosure may optionally comprise other performance additives. Other performance additives may be other than the additives specified in this disclosure and / or may include additives such as metal deactivators, viscosity index improvers, detergents, ashless TBN promoters, friction modifiers, antiwear agents, corrosion inhibitors, rust inhibitors, dispersants, , An extreme pressure agent, an antioxidant, a foaming inhibitor, a bleaching agent, an emulsifier, a pour point depressant, a seal swelling agent, and mixtures thereof. Typically, the fully-formulated lubricant will contain one or more of these performance additives.

Suitable metal deactivators include, but are not limited to, derivatives of benzotriazole (typically, tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, Or 2-alkyldithiobenzothiazole; The foaming inhibitor is a copolymer of ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate; The demulsifiers include trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers; Pour point depressants may include esters of maleic anhydride-styrene, polymethacrylates, polyacrylates or polyacrylamides.

Suitable foaming inhibitors include silicon-based compounds such as siloxanes.

Suitable pour point depressants may include polymethyl methacrylate or mixtures thereof. The pour point depressant may 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 mixture of compounds with properties that inhibit corrosion of the ferrous metal surface. Non-limiting examples of rust inhibitors useful herein include but are not limited to 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, Carboxylic acids such as dimer and trimer acids such as tall oil fatty acid, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long chain alpha, omega-dicarboxylic acids (molecular weight ranges from about 600 to about 3000) and alkenyl succinic acids wherein alkenyl groups contain at least about 10 carbon atoms, such as tetrapropenyl Succinic acid, tetradecenylsuccinic acid, and hexadecenylsuccinic acid. Another useful type of acidic corrosion inhibitor is the half ester of alkenyl succinic acid having from about 8 to about 24 carbon atoms in the alcohol and alkenyl groups such as polyglycols. The corresponding half-amides of the alkenyl succinic acids are also useful. Useful rust inhibitors are high molecular weight organic acids. In some embodiments, the engine oil is deficient in a rust inhibitor.

The rust inhibitor, when present, will 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 .

As a general term, crankcase lubricants may contain additive components in the ranges listed in the table below.

ingredient Wt. %
(Comprehensive) Wt. %
(Typical) The dispersant (s) 0.0 - 10% 1.0 -8.5% Antioxidant (s) 0.0 - 5.0 0.01 - 3.0 Metal detergent (s) 0.1 - 15.0 0.2 - 8.0 Non-TBN promoter (s) 0.0 - 1.0 0.01 - 0.5 Corrosion inhibitor (s) 0.0 - 5.0 0.0 - 2.0 The metal dihydrocarbyl dithiophosphate (s) 0.1 to 6.0 0.1 - 4.0 The asuamine amine phosphate salt (s) 0.0 - 3.0 0.0 - 1.5 Defoamer (s) 0.0 - 5.0 0.001 - 0.15 Anti-abrasive agent (s) 0.0 - 10.0 0.0 - 5.0 The pour point depressant (s) 0.0 - 5.0 0.01 - 1.5 The viscosity index improver (s) 0.0 - 20.00 0.25 - 10.0 The dispersant viscosity index improver (s) 0.0 - 10.0 0.0 - 5.0 The friction modifier (s) 0.01 - 5.0 0.05 - 2.0 Base oil (s) Remainder Remainder all 100 100

The percentage of each component represents the weight percentage of each component based on the weight of the final lubricating oil composition. The remainder of the lubricant composition consists of one or more base oils.

The additives used to formulate the compositions described herein may be incorporated into the base oil either individually or in various sub-combinations. However, it may be appropriate to blend all the ingredients simultaneously using additive concentrates (i.e., additives + diluents, such as hydrocarbon solvents). The additives used to formulate the compositions described herein may be incorporated into the base oil either individually or in various sub-combinations. However, it may be appropriate to blend all the ingredients simultaneously using additive concentrates (i.e., additives + diluents, such as hydrocarbon solvents).

The present disclosure provides new lubricant blends that are specifically formulated for use as automotive engine lubricants. Embodiments of the disclosure can provide a lubricant suitable for engine applications that provide improvements to one or more of the following properties: low speed early-ignition events, antioxidant, antiwear performance, rust prevention, fuel economy, Air inlets, airtight protection, reduced deposition, ie TEOST 33 test pass, and bubble reduction characteristics.

The fully formulated lubricant typically contains an additive package referred to hereinafter as a dispersant / inhibitor package or DI package to provide the properties desired in the formulation. Suitable DI packages are described, for example, in U.S. Patent Nos. 5,204,012 and 6,034,040. Among the types of additives included in the additive package, there are dispersants, sealants and swelling agents, antioxidants, foam inhibitors, lubricity improvers, rust inhibitors, corrosion inhibitors, anti-fogging agents, viscosity index improvers, and others. These various ingredients are well known to those of ordinary skill in the art and are generally used in customary amounts with the additives and compositions described herein.

The following examples are illustrative of the methods and compositions of the present disclosure, but are not limited thereto. Other suitable variations and adaptations of the various conditions and parameters generally encountered in the art and apparent to those skilled in the art are within the spirit and scope of the present disclosure. All patents and documents mentioned herein are fully incorporated by reference in their entirety.

Examples

A fully formulated lubricating oil composition containing conventional additives was prepared and low velocity early-ignition events of the lubricating oil composition were measured. Each lubricant composition contains a base oil, a basic conventional dispersant inhibitor (DI) package and a viscosity index improver (s), and a basic DI package (less than a viscosity index improver) contains about 8 to 12 wt% %. The basic DI package contains the usual amounts of dispersant (s), antiwear additive (s), defoamer (s), and antioxidant (s) shown in Table 3 below. Specifically, the basic DI package comprises a succinimide dispersant, a borated succinimide dispersant, a molybdenum-containing compound capable of delivering about 80 ppm of molybdenum to the lubricating oil composition, an organic friction modifier, one or more Antioxidants, and one or more anti-wrinkle agents (unless otherwise specified). The basic DI package was also blended with about 5 to about 10 wt% of one or more viscosity index improvers. Group I base oils were used as diluents. Most base oils (about 78 to about 87 wt%) are Group III base oils. The components to be changed are specified in the table and in the discussion of the examples below. All values listed are referred to as component weight percent in the lubricating oil composition (i. E., Diluent oil if active ingredient + if present), unless otherwise specified.

Table 3 - Basic DI Package Composition

ingredient Wt. % Antioxidant (s) 0.5 to 2.5 Antiwear agent (s), any metal dihydrocarbyl dithiophosphate 0.7 to 5.0 Defoamer (s) 0.001 to 0.01 Detergent (s) * 0.0 The dispersant (s) 2.0 to 6.0 The metal-containing friction modifier (s) 0.05 to 1.25 The metal-free friction modifier (s) 0.01 to 0.5 The pour point depressant (s) 0.05 to 0.5 Process oil 0.25 to 1.0

The detergent is varied in the following experiments and for the purpose of basic formulation, the detergent content is set to zero.

Low-speed early-ignition (LSPI) events were measured in GM 2.0-liter, four-cylinder Ecotec turbo and gasoline direct injection (GDI) engines. One complete LSPI combustion engine test consists of four test cycles. In a single test cycle, two operating steps or segments are repeated to generate an LSPI event. At stage A, where LSPI is most likely to occur, the engine is operated at a braking mean effective pressure (BMEP) of about 2000 rpm and about 18,000 kPa. At stage B, where LSPI is unlikely to occur, the engine operates at about 1500 rpm and about 17,000 kPa BMEP. At each step, data is collected over 25,000 engine cycles. The test cycle structure is as follows: Step A - Step A - Step B - Step B - Step A - Step A. Each step is divided by the idle period. In step A, the LSPI is statistically significant, and the LSPI event data considered in the present embodiments include only the LSPI generated in the step A operation. Thus, in one complete LSPI combustion engine test, the data typically occurred over a total of 16 steps and comparative and performance evaluations of the inventive oils were utilized.

The LSPI event was determined by monitoring the peak cylinder pressure (P P) and when 2% of the combustible material was burned in the combustion chamber (MFB 02). The threshold for peak cylinder pressure is calculated for each cylinder and each step and is typically 65,000 to 85,000 kPa. The threshold for MFB02 is calculated for each cylinder and each step and typically ranges from about 3.0 to about 7.5 crank angle (CAD) top dead center (ATDC). The LSPI was recorded when both the PP and MFB02 thresholds were exceeded in a single engine cycle. LSPI events can be reported in several ways. To eliminate the ambiguity associated with counting per engine cycle, where different combustion engine tests may be performed with different number of engine cycles, the relative LSPI events of the comparative and inventive oils were reported as &quot; LSPI ratios &quot;. In this way improvements to some standard responses are clearly determined.

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

In the following examples, a combination of an overbased calcium detergent and a neutral / low basic calcium detergent was tested with the base formulation. The LSPI ratio was reported as the ratio of the LSPI event of the test oil to the LSPI event of the reference oil &quot; R-1 &quot;. R-1 was a basic DI package and a lubricating oil composition formulated with an overbased calcium detergent in an amount to provide about 2400 ppm of Ca to the lubricating oil composition. More detailed formulation information for reference oil R-1 is given below. Significant improvements in LSPI are recognized when there is an LSPI event reduction (ratio of LSPI less than 0.5) in excess of 50% for R-1. Additional improvements in LSPI are recognized when there is an LSPI event reduction in excess of 70% (ratio of LSPI less than 0.3), and when there is a decrease in LSPI events above 75% (LSPI ratio less than 0.25) Further improvements are recognized in the LSPI when LSPI event reduction (RSPI ratio less than 0.20) exceeds 80% for R-1, and more than 90% LSPI events for R-1 Further reductions in LSPI are recognized when there is a decrease (LSPI ratio less than 0.10). The ratio of LSPI to R-1 reference oil is therefore considered to be 1.00.

The TEOST-33 test is a bench test for evaluating oxidative degradation and / or thermal coking of engine oil. According to the test, about 100 mL of test oil is used in the 12 cycles / 2 hour test. The test shows bulk oxidation of oil (about 100 grams) in a hollow heating rod (TEOST deposition rod) where deposits are deposited during the test cycle. The test oil flows about 0.5 grams per minute on the rod while the specimen circulates 12 times at 200-480 ° C. It is the performance parameter at which the entire deposit is measured. The total deposit is the sum of the deposit on the rod and the oil removed by filtration. If more deposits are measured, it means poorer additive composition performance. Specifically, a test oil with a weight gain of 30 mg or less passes the TEOST 33 test.

The TBN measurements provided in the table below are in accordance with ASTM D2896. The TBN measurements were used to report TBN of whole metal: fully-formulated fluid in mmol in Table 4 below.

ingredient R-1 R-2 C-1 C-2 C-3 I-1 I-2 I-3 I-4 I-5 OB Ca sulphonate, ppmw Ca
(TBN = 300 mg KOH / g) 2400 1600 1100 0 1625 1375 1200 1500 1450 LB / N Ca sulphonate, ppmw Ca
(TBN = 45 mg KOH / g) 0 0 0 0 125 125 500 LB / N Ca phenate, ppmw Ca
(TBN = 150 mg KOH / g) 125 LB / N Na sulphonate, ppmw Na
(TBN < 5 mg KOH / g) 91 Total Ca, ppmw 2400 2300 * 1600 1100 0 1750 1500 1700 1625 1450 LSPI ratio 1.00 1.38 0.22 0.05 0 0.19 0.15 0.06 0.25 0.35 TEOST 33, Total Deposits, mg pass pass fail fail fail pass pass pass pass pass mmol total metal: ratio of lubricating oil TBN 8.0 8.6 7.9 8.2 2.3 8.2 8.2 9.0 8.1 7.9 Ratio ppm LB / N Ca vs ppm OB Ca 0 0 0 0 0.08 0.09 0.4 0.08

* Values measured by ICP analysis

Commercial oils, R-1 and R-2, are included as reference oils and present state of the art in the art. The reference oil R-1 contains about 80.7 wt.% Group III base oil, 12.1 wt.% HiTEC 11150 PCMO additive package from Afton Chemical Corporation and 7.2 wt.% 35 SSI ethylene / propylene copolymer viscosity index improver . HiTEC® 11150 passenger car motor oil additive package is 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

10.9 Kinematic viscosity at 100 ° C, (mm ² / sec) 3.3 TBS, APPARENT_ viscosity, cPa 2438 Calcium (ppmw) <10 Magnesium (ppmw) 80 Molybdenum (ppmw) 772 (Ppmw) 855 Zinc (ppmw) 9.0 Total basic salt ASTM D-2896 (mg KOH / g) 165 Viscosity index

R-2 contains only a calcium-containing detergent with a higher calcium loading than the inventive subject oil. R-1 and R-2 meet all performance requirements for ILSAC GF-5 and therefore will pass the performance on the TEOST-33 bench oxidation test. COMPARATIVE EXAMPLES C-1, C-2, C-3, and C-4 are not commercially available fluids, but show a technical problem experienced by those skilled in the art when the detergent system is modified to meet LSPI performance requirements It is designed.

As shown in Table 4, there is significant LSPI performance improvement when the calcium content of the overbased (&quot; OB &quot;) detergent is reduced from about 2400 to about 1600 ppm calcium. Comparing R-1 and C-1, the LSPI ratio is reduced by about 78%, but with reduced calcium, the performance in the TEOST-33 test fails to pass. If the calcium content of the OB detergent is further reduced to 1100 ppm (C-2), the LSPI ratio is further improved; However, TEOST-33 test performance at this calcium level is still poor. At C-3, when the detergent system is completely excluded and becomes non-detergent, the LSPI is improved by 100%. However, again, TEOST 33 test performance is sacrificed. Example I-5 was prepared by using a low basic sodium sulfonate in place of the low basic calcium sulfonate used in Examples I-1, I-2, I-3 and I-4 of the present invention, Using a sodium-containing low basic / neutral detergent instead of a neutral detergent shows that a significant LSPI ratio reduction is achieved.

An unexpected LSPI improvement is achieved without sacrificing the TEOST-33 bench oxidation test performance with the combination of low basic or neutral ("LB / N") calcium detergents (I-1 to I-4) and OB calcium detergent. Example I-1 of the invention passes the TEOST-33 test while achieving a significant LSPI event improvement with a reduction of the LSPI ratio of nearly 81% over R-I. Embodiments I-2 and I-3 provide greater LSPI ratio reduction without loss of TEOST-33 test performance. Example I-4 shows the use of LB / N calcium phenate instead of LB / N calcium sulfonate. The I-4 also shows a significant LSPI improvement as well as a TEOST 33 test pass. The embodiments shown in Table 4 clearly show that the calcium content of the OB calcium detergent can be maintained at a higher level by adding additional calcium of the LB / N calcium detergent while assuring TEOST 33 test acceptance and significant LSPI ratio reduction. In addition, unexpectedly, the TEOST 33 test results can be improved without the presence of high levels of OB calcium detergent. In fact, off-setting the OB calcium detergent with an LB / N calcium detergent could unexpectedly and surprisingly improve the TEOST 33 test while also reducing the LSPI ratio.

This data shows that replacing OB Ca sulphonate with LB / N Ca sulphonate so that LB / N Ca sulphonate exceeds 8% of the total detergent improves LSPI and maintains TEOST 33 test performance.

In numerous places throughout the specification, reference has been made to a number of US patents and other documents. All such referenced documents are expressly incorporated into this disclosure as if fully set forth herein.

Other implementations 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, the singular &lt; RTI ID = 0.0 &gt; expression &lt; / RTI &gt; Unless otherwise indicated, all numbers expressing quantities of ingredients, such as molecular weight, percentages, ratios, reaction conditions, etc., used in the specification and claims are to be construed in a manner similar to that of the term &quot; about " As will be understood by those skilled in the art. 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 this 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 is understood in light of the number of reported significant digits and by applying ordinary rounding techniques. Although numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, numerical values set forth in the specific examples are reported as precisely as possible. However, any numerical value implicitly includes a specific error necessarily resulting from the standard deviation found in its respective test measurement. It is intended that the specification and examples be considered as exemplary only, with the true scope and spirit of the disclosure being indicated by the following claims.

The embodiment can be varied considerably when practiced. Accordingly, there is no intention to limit the embodiments to the specific examples presented hereinabove. Rather, the embodiments are within the subject matter and scope of the claims, including equivalents thereof, which are available in law.

Those of ordinary skill in the art will recognize that any disclosed embodiment is not intended to be dedicated to the public, and that any disclosed formulas or alterations may not necessarily fall within the scope of the claims, they are considered to be part of the disclosure under the doctrine of equivalents.

It is understood that each component, compound, substituent or parameter disclosed herein is used alone or in combination with any and all other ingredients, compounds, substituents or parameters disclosed herein.

(S), compound (s), substituent (s), or mediator (s) disclosed herein for each component, compound, substituent or parameter disclosed herein, (S), substituent (s), or parameter (s) / value (s) disclosed and combined in the context of the present invention and the respective ranges of values / values or amounts / Any combination of ranges of values / values is therefore to be construed as being disclosed as being combined with each other in accordance with the purpose of the present disclosure.

Further, each scope disclosed herein is understood to be the beginning of each particular value having the same significance within the scope of the disclosure. Thus, a range of 1-4 is interpreted as an explicit disclosure of the values 1, 2, 3 and 4.

Further, each lower limit for each range disclosed herein is disclosed in combination with each specific value within each upper limit and each range within each range disclosed herein for the same component, compound, substituent or parameter . Accordingly, it is understood that each lower limit of each range and each upper limit of each range or combination with each specific value within each range, or a combination of each upper limit of each range and each specific value within each range It is interpreted as the start of all ranges derived.

In addition, the specific amounts / values of the components, compounds, substituents or parameters disclosed in the description or the examples are to be construed as an initiation of the lower or upper limit of the range and accordingly, the ranges for the same components, compounds, substituents or parameters as disclosed herein Compounds, substituents or parameters in combination with any other lower or upper limit or specific content / value.

Claims (22)

As a lubricating oil composition,
Base oils with a lubricating viscosity of greater than 50 wt.%;
At least 0.3 wt.% Of an overbased detergent having a total basis weight of greater than 225 mg KOH / g, as measured by the ASTM D-2896 method, and
At least 0.2 wt.% Of a low basic / neutral detergent having a total base number of at most 175 mg KOH / g, as measured by the ASTM D-2896 method, wherein the total amount of the overbased detergent and the whole of the low basic / Wherein the calcium content ranges from greater than 1100 ppm to less than 2400 ppm, based on the total weight of the lubricating oil composition, by weight. The lubricating oil composition of claim 1, wherein the overbased detergent comprises an overbased calcium-containing detergent. The lubricating oil composition of claim 2, wherein the overbased calcium-containing detergent comprises a compound selected from an overbased calcium sulfonate detergent, and an overbased calcium phenate detergent. The method of claim 1, wherein the LSPI event reduction is greater than or equal to 75% reduction and the LSPI event is an LSPI count for an engine cycle of 25,000, the engine operating at 2000 revolutions per minute and the braking mean effective pressure of 18,000 kPa. . The lubricating oil composition of claim 1, wherein the low basic / neutral detergent comprises a low basic / neutral calcium-containing detergent. The lubricating oil composition of claim 1, wherein the low basic / neutral detergent comprises a detergent selected from the group consisting of calcium sulfonate detergents and calcium phenate detergents. The lubricating oil composition of claim 1, wherein the at least one overbased calcium-containing detergent (s) provides from about 900 to less than about 2000 ppm calcium to the lubricating oil composition, based on the total weight of the lubricating oil composition. The lubricating oil composition of claim 1, wherein the lubricating oil composition has a ratio of total mmol metal in the lubricating oil composition to total base water of the lubricating oil composition in the range of more than 4.5 to less than about 10.0. The lubricating oil composition of claim 1, wherein the lubricating oil composition is effective in passing the TEOST 33 bench oxidation test. The lubricating oil composition of claim 1, further comprising one or more components selected from the group consisting of a friction modifier, an antiwear agent, a dispersant, an antioxidant, and a viscosity index improver. The method of claim 1, wherein the base oil in excess of 50% 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 base oils, Wherein the lubricant composition is other than the diluent oil due to the addition of the additive components or the viscosity index improver in the composition. The lubricating composition of claim 1, wherein the ratio of total metal to mmol in the lubricating oil composition to TBN of the lubricant is greater than 8 and less than 10, and wherein the lubricating oil composition comprises at least 0.25 wt. % Of said low basic / neutral detergent. 3. The composition of claim 2, wherein the low basic / neutral detergent comprises a low basic / neutral calcium-containing detergent and comprises, based on the weight of the low basic / A neutral calcium-containing detergent, wherein the ratio of ppm of calcium provided to the lubricating oil composition is 0.05 to 1.0. 3. The lubricating oil composition of claim 2, wherein the total calcium provided to the lubricating oil composition by the at least one overbased detergent is from about 1100 ppm to about 1800 ppm, based on the total weight of the lubricating oil composition. 7. The lubricating oil composition according to claim 6, wherein the total calcium provided to the lubricating oil composition by the at least one low basic / neutral calcium-containing detergent is from 50 ppm to 1000 ppm based on the total weight of the lubricating oil composition. 2. The method of claim 1, wherein the lubricating oil composition is effective to reduce low-speed pre-ignition events in a power internal combustion engine lubricated with the lubricating composition, which results in a plurality of low-speed early-ignition events in the same engine lubricated with reference lubricant R- Lubricant composition relative to ignition events. CLAIMS What is claimed is: 1. A method for reducing a low speed pre-ignition event in a power internal combustion engine,
Lubricating the internal combustion engine with a lubricating oil composition;
Operating said engine lubricated with said lubricating oil composition, said lubricating oil composition comprising:
Base oils with a lubricating viscosity of greater than 50 wt.%;
At least 0.3 wt.% Of an overbased detergent having a total basis weight of greater than 225 mg KOH / g, as measured by the ASTM D-2896 method, and
At least 0.2 wt.% Of a low basic / neutral detergent having a total base number of at most 175 mg KOH / g, as measured by the ASTM D-2896 method, wherein the total amount of the overbased detergent and the whole of the low basic / Wherein the calcium content ranges from greater than 1100 ppm to less than 2400 ppm, based on the total weight of the lubricating oil composition, by weight. 18. The method of claim 17, wherein the lubricant composition passes the TEOST 33 bench oxidation test. 19. The method of claim 18, wherein the LSPI event is based on an LSPI count for a 25,000 engine cycle, the engine operating at 2000 revolutions per minute (RPM) and a braking mean effective pressure (BMEP) of 18,000 kPa, Wherein the low-speed pre-ignition event in the internal combustion engine being lubricated is reduced in comparison to a plurality of low-speed early-ignition events in the same engine lubricated with the reference lubricant R-I. 20. The lubricating oil composition of claim 19, wherein the low basic neutral detergent comprises a calcium-containing detergent, wherein the overbased detergent comprises a calcium-containing detergent and the overbased detergent comprises from about 900 to about &lt; RTI ID = Providing less than about 2000 ppm calcium to the lubricating oil composition. 20. The method according to claim 19, wherein the lubricating step lubes the combustion chamber or cylinder wall of a spark-ignition direct injection engine or a port fuel injected internal combustion engine provided with a turbocharger or a supercharger. 20. The method of claim 19, further comprising measuring the low-speed pre-ignition event of the internal combustion engine lubricated with the lubricating oil.