JP2019506512A - Lubricant for use in boosted engines - Google Patents

Abstract

A lubricating oil composition and method of operating a boosted internal combustion engine. The lubricating oil composition is boosted as indicated by its ability to ensure a TCO temperature rise of less than 9.0% as measured using the 2015 edition of the General Motors dexos1® turbocharger coking test Formulated to be resistant to turbocharger deposit formation in internal combustion engines. The lubricating oil composition may also have a low NOACK volatility as measured by the ASTM D-5800 method at 250 ° C.
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Description

  The present disclosure relates to a lubricant composition having improved resistance to formation of engine deposits, including turbocharger deposits, when used in boosted internal combustion engines.

  Turbocharged or supercharged engines (ie, boosted or forced induction internal combustion engines) experience very high operating temperatures. The lubricant used in these engines is exposed to extreme conditions when the engine is stopped, and the lubricant remains in the hot turbocharger when cooled. Lubricants in this environment tend to form hard deposits in the turbocharger. This phenomenon can cause significant degradation of turbocharger efficiency and can cause performance degradation and / or serious damage to the engine.

  Some published studies can contribute to the use of turbochargers, engine design, engine coating, piston geometry, fuel selection, and / or the formation of these deposits in engines where engine oil additives are turbocharged. I have demonstrated that. Accordingly, there is a need for engine oil additive components and / or combinations that are effective in reducing or preventing deposit formation in turbocharged gasoline engines.

  Recent specifications, such as the 2015 version of the General Motors dexos1® specification, require passing the turbocharger coking test. One parameter that determines the passing result in the General Motors dexos1® turbocharger coking test is the percent from 100 cycle TCO temperature to 1800 cycle TCO temperature to less than 13% increase in turbo coolant external (TCO) temperature. To maintain the rise.

  In order to provide a lubricating oil composition capable of recording a passing rating of less than 9.0% increase in turbo coolant external (TCO) temperature from 100 cycle TCO temperature to 1800 cycle TCO temperature, General Motors dexos1® There is a need for improvement over the mere passing of the 2015 edition of the turbocharger coking test. As used herein, “TCO temperature rise” refers to the percent increase in TCO temperature from 100 cycle TCO temperature to 1800 cycle TCO temperature, as defined by the following equation:

SUMMARY AND TERMS The present disclosure provides a first lubricating oil composition, a method of operating an internal combustion engine boosted using the first lubricating oil composition (hereinafter referred to as invention A), and a second lubrication. A method of operating an internal combustion engine that is boosted with an oil composition and a second lubricating oil composition (hereinafter referred to as Invention B).

Invention A
In an embodiment of Invention A, the lubricating oil composition comprises a base oil having a lubricating viscosity of greater than 50% by weight. The lubricating oil composition has a ratio of total metals in ppm from one or more metal-containing detergents in the lubricating oil composition to total nitrogen in ppm in the lubricating oil composition of less than 1.9, and lubrication The ratio of total metal in ppm from one or more metal-containing detergents in the lubricating oil composition to total boron in ppm in the oil composition is less than 7.5, and in ppm in the lubricating oil composition The ratio of total metal in ppm from one or more metal-containing detergents in the lubricating oil composition to total molybdenum is less than 23.8. The lubricating oil composition also has a NOACK volatility of less than 11.0% by weight as measured by ASTM D-5800 method at 250 ° C., and the lubricating oil composition is a General Motors dexos1® turbocharger. It is effective to ensure a TCO temperature rise of less than 9.0% measured using the 2015 version of the coking test (TC test).

  In another embodiment of Invention A, the present disclosure provides a method for reducing or preventing deposit formation in a boosted internal combustion engine. The method includes lubricating the boosted internal combustion engine with a lubricating oil composition comprising a base oil having a lubricating viscosity of greater than 50% by weight. The lubricating oil composition has a ratio of total metals in ppm from one or more metal-containing detergents in the lubricating oil composition to total nitrogen in ppm in the lubricating oil composition of less than 1.9, and lubrication The ratio of total metal in ppm from one or more metal-containing detergents in the lubricating oil composition to total boron in ppm in the oil composition is less than 7.5, and in ppm in the lubricating oil composition The ratio of total metal in ppm from one or more metal-containing detergents in the lubricating oil composition to total molybdenum is less than 23.8. The lubricating oil composition also has a NOACK volatility of less than 11.0% by weight as measured by the ASTM D-5800 method at 250 ° C. By lubricating an internal combustion engine that is boosted with this lubricating oil composition, a TCO temperature increase of less than 9.0% measured using the 2015 version of the General Motors dexos1® turbocharger coking test There is improved resistance to deposit formation in boosted internal combustion engines, as shown by its ability to ensure.

  In each of the foregoing embodiments, the ratio of total metal in ppm from one or more metal-containing detergents in the lubricating oil composition to total nitrogen in ppm in the lubricating oil composition is less than 1.8. It can be 0.1 or more and less than 1.9, or 0.1 or more and less than 1.8, or 0.1 to 1.7.

  In each of the foregoing embodiments, the ratio of total metal in ppm from one or more metal-containing detergents in the lubricating oil composition to total boron in ppm in the lubricating oil composition is less than 7.3 or It may be from 0.1 to less than 7.5, or from 0.1 to less than 7.3, or from 0.1 to 7.0.

  In each of the foregoing embodiments, the ratio of total metal in ppm from one or more metal-containing detergents in the lubricating oil composition to total molybdenum in ppm in the lubricating oil composition is less than 20.0, Or less than 15.0, or 0.1 or more and less than 23.8, or 0.1 or more and less than 20.0, or 0.1 or more and less than 15.0, or 0.1 to 13.0, or 1.0 to It can be 13.0.

  In each of the foregoing embodiments, the lubricating oil composition is 2.0 wt% or more and less than 11.0 wt%, or 2.0 wt% to 10.9 wt% as measured by the method of ASTM D-5800 at 250 ° C. It may have a NOACK volatility of wt%, or 5.0 wt% to 10.9 wt%.

  In each of the foregoing embodiments, the lubricating oil composition is less than 8.0%, or less than 7.0%, as measured using the 2015 edition of the General Motors dexos1® turbocharger coking test, or 0% 0.01% or more and less than 9.0%, or 0.01% or more and less than 7.0%, or 0.1% or more and less than 7.0%, or 1.0% or more and less than 6.0%. It can be effective to secure.

Invention B
In one embodiment of Invention B, the lubricating oil composition comprises a base oil having a lubricating viscosity of greater than 50% by weight and one or more borated compounds. The lubricating oil composition also includes one or more molybdenum-containing compounds in an amount sufficient to provide the lubricating oil composition with greater than about 40 ppm by weight of molybdenum, based on the total weight of the lubricating composition. The lubricating oil composition also includes one or more magnesium-containing cleaning agents. The lubricating oil composition also includes one or more overbased calcium-containing detergents in an amount sufficient to provide the lubricating oil composition with less than about 1800 ppm by weight of calcium, based on the total weight of the lubricating composition. including.

  In another embodiment of invention B, the present disclosure provides a method for reducing or preventing deposit formation in a boosted internal combustion engine. The method includes lubricating a boosted internal combustion engine with a lubricating oil composition comprising a base oil having a lubricating viscosity of greater than 50% by weight and one or more boronated compounds. The lubricating oil composition includes one or more molybdenum-containing compounds in an amount sufficient to provide the lubricating oil composition with greater than about 40 ppm by weight of molybdenum, based on the total weight of the lubricating composition. The lubricating oil composition also includes one or more magnesium-containing cleaning agents. The lubricating oil composition also includes one or more overbased calcium-containing detergents in an amount sufficient to provide the lubricating oil composition with less than about 1800 ppm by weight of calcium, based on the total weight of the lubricating composition. including. By lubricating an internal combustion engine that is boosted with this lubricating oil composition, a TCO temperature increase of less than 9.0% measured using the 2015 version of the General Motors dexos1® turbocharger coking test There is improved resistance to deposit formation in boosted internal combustion engines, as shown by its ability to ensure.

  In each of the foregoing embodiments, the one or more molybdenum-containing compounds include at least about 50 ppm by weight of molybdenum in the lubricating oil composition, or at least about 80 ppm by weight, or 40 based on the total weight of the lubricating composition. May be present in an amount sufficient to provide the lubricating oil composition with greater than ppm by weight and less than or equal to 1200 ppm by weight, or greater than 40 ppm by weight and less than or equal to 900 ppm by weight, or at least about 80 to 800 ppm by weight molybdenum. .

  In each of the foregoing embodiments, the one or more calcium-containing overbased detergents are selected from overbased calcium sulfonate detergents, overbased calcium phenate detergents, and overbased calcium salicylate detergents. Can be done. In each of the foregoing embodiments, the one or more overbased calcium-containing detergents may comprise about 1000 to about 1750 ppm by weight, or 1100 to 1700 ppm by weight of calcium based on the total weight of the lubricating oil composition. It can be provided in the composition.

  In each of the foregoing embodiments, the one or more magnesium-containing detergents can be overbased, and the one or more overbased calcium-containing detergents and the one or more overbased magnesium-containing detergents are each A total base number (TBN) greater than 225 mg KOH / g as measured by the method of ASTM D-2896, or a TBN of greater than or equal to about 250 mg KOH / gram, as measured by the method of ASTM D-2896, or a TBN greater than or equal to about 300 mg KOH / gram, Or about 350 mg KOH / gram or more TBN, or about 375 mg KOH / gram or more TBN, or about 400 mg KOH / gram or more TBN, or more than 225 mg KOH / g to 425 mg KOH / gram TBN, or about 250 mg KOH / gram to 425 mg KOH / gram Gram TBN, or about 300 mg KOH / gram to 425 mg KOH / gram TBN, or about 350 mg KOH / gram to 425 mg KOH / gram TBN, or about 375 mg KOH / gram to 425 mg KOH / gram TBN, or about 400 mg KOH / gram to 425 mg KOH / gram. Can have TBN.

  In each of the foregoing embodiments, the one or more overbased magnesium-containing detergents can be an overbased magnesium sulfonate. In each of the foregoing embodiments, the one or more magnesium-containing detergents are 20 ppm to 1800 ppm by weight of magnesium, based on the total weight of the lubricating composition, or 100 based on the total weight of the lubricating composition. Weight ppm to 1200 ppm by weight of magnesium, or greater than about 140 ppm by weight and less than or equal to about 550 ppm by weight of magnesium may be present in an amount sufficient to provide the lubricating oil composition.

  In each of the foregoing embodiments, the ratio of total boron in weight ppm to total nitrogen in weight ppm can be less than about 0.29, or 0.01 to 0.28 or 0.05 to 0.28. .

  In each of the foregoing embodiments, the ratio of total calcium in weight ppm to total boron in weight ppm is greater than about 4.9 and less than about 9.7, or 5.0 to 9.0, or 5.0 to May be 7.5.

  In each of the foregoing embodiments, one or more overbased calcium-containing detergents and one or more overbased calcium-containing detergents based on total calcium and magnesium from one or more overbased magnesium-containing detergents The percent calcium from the cleaning agent can be greater than 50%, or greater than 50% and 99% or less, or 60% -99%, or 65% -95%, respectively.

  In each of the foregoing embodiments, the one or more borated compounds comprise more than 50 ppm boron in the lubricating oil composition, or more than 100 ppm boron, more than 50 ppm and less than 1000 ppm boron, or more than 100 ppm and less than 800 ppm boron. Or 110 ppm to 600 ppm boron, or 120 ppm to 500 ppm boron, in the lubricating oil composition in an amount sufficient to provide the lubricating oil composition.

  In each of the foregoing embodiments, the lubricating oil composition is less than 8.5%, or less than 8.0%, or 7, as measured using the 2015 edition of the General Motors dexos1® turbocharger coking test. Effective for securing a TCO temperature rise of less than 5%, or 0.01% or more and less than 9.0%, or 0.05% or more and less than 8.5%, or 0.1% or more and less than 7.5%. possible.

  The following description relates to both Invention A and Invention B unless stated otherwise.

  In each of the foregoing embodiments, the lubricating oil composition may also optionally contain one or more low basic / neutral detergents, wherein the low basic / neutral detergent is a method of ASTM D-2896. With a TBN of at most 175 mg KOH / g, or at most 150 mg KOH / g. In each of the foregoing embodiments, the low basic / neutral detergent may include a calcium-containing detergent. In each of the foregoing embodiments, the low basic / neutral calcium-containing detergent may be selected from a calcium sulfonate detergent, a calcium phenate detergent, a calcium salicylate detergent, or a mixture thereof. In each of the foregoing embodiments, the low basic / neutral detergent may be a calcium sulfonate detergent or a calcium phenate detergent. In some cases, “overbasic” can be abbreviated as “OB”, and in some cases, “low basicity / neutral” can be abbreviated as “LB / N”.

  In each of the foregoing embodiments, the low basic / neutral detergent may comprise at least 0.1% by weight of the lubricating oil composition. In some embodiments, the low basic / neutral detergent is at least 0.25 wt%, or 0.1 wt% to 5.0 wt%, or 0.15 wt% to 3.0 wt%, Alternatively, it may contain from 0.15% to 1.0% by weight of the lubricating oil composition.

  In each of the foregoing embodiments, the one or more low basic / neutral calcium-containing detergents provide the lubricating oil composition with about 10 to about 1000 ppm by weight of calcium, based on the total weight of the lubricating oil composition. Can do. In each of the foregoing embodiments, the one or more low basic / neutral calcium-containing detergents are less than 25-800 ppm by weight, or 50-600 ppm by weight, or 100, based on the total weight of the lubricating oil composition. ˜500 ppm by weight of calcium may be provided to the lubricating oil composition.

  In each of the foregoing embodiments, one of the one or more overbased calcium-containing detergents can be an overbased calcium sulfonate.

  In each of the foregoing embodiments, the total TBN of the lubricating oil composition is measured by at least 6.0 mg KOH / g of the lubricating oil composition as measured by ASTM D-2896, or by the method of ASTM D-2896. It can be 6.4 to 12.0 mg KOH / g of the lubricating oil composition, or 6.5 to 12.0 mg KOH / g of the lubricating oil composition.

  In each of the foregoing embodiments, the lubricating oil composition may include a dispersant. In each of the foregoing embodiments, the dispersant can be a boron-containing dispersant. In each of the foregoing embodiments, the boron-containing dispersant may be present in an amount of 1.0 to 10% by weight, based on the total weight of the lubricating oil composition. In each of the foregoing embodiments, the boron-containing dispersant may be present in an amount of 1.0 to 8.5% by weight, based on the total weight of the lubricating oil composition.

  In each of the foregoing embodiments, the lubricating oil composition is all in an amount from about 500 ppm to about 2500 ppm, or from about 700 ppm to about 2000 ppm, or from about 900 ppm to about 1600 ppm, all based on the total weight of the lubricating oil composition. Can have nitrogen present.

  In each of the foregoing embodiments, “total metal from one or more metal-containing detergents” refers to about 100 ppm to about 3500 ppm metal in the lubricating oil composition, or about 1100 to about 3000 ppm metal, or about 1150. To about 2500 ppm of metal, or about 1200 to about 2400 ppm of metal, or less than 1800 ppm of metal may be present in an amount that provides the lubricating oil composition.

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

  In each of the foregoing embodiments, the lubricating oil comprises greater than 50% base oil, the base oil comprising a Group II, Group III, Group IV, or Group V base oil, and a combination of two or more of the foregoing. The base oil in excess of 50% by weight can be other than the diluent oil resulting from providing the additive component or viscosity index improver to the composition. In each of the foregoing embodiments, the lubricating oil composition comprises greater than 50% by weight Group II base oil, Group III base oil, or a combination thereof, or greater than 70% by weight, or greater than 75% by weight. Or more than 80 wt%, or more than 85 wt%, or more than 90 wt% Group II base oil, Group III base oil, or a combination thereof, or more than 97 wt% Group II base oil and III A combination with a group of base oils may be included.

  In each of the foregoing embodiments of the method, the lubricating step comprises a turbocharger or supercharger component and a combustion chamber or cylinder wall of a spark ignition direct injection engine or spark ignition port fuel injection internal combustion engine comprising the turbocharger or supercharger. Lubricate (passages, bushings and other parts found in turbochargers or superchargers).

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

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

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

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

  “Oil composition”, “lubricating composition”, “lubricating oil composition”, “lubricating oil”, “lubricant composition”, “lubricating composition”, “fully formulated lubricant” The terms “composition”, “lubricant”, “crankcase oil”, “crankcase lubricant”, “engine oil”, “engine lubricant”, “motor oil”, and “motor lubricant” are 50 weights. It is considered to be a synonymous, fully interchangeable terminology that refers to a final lubricating product that contains a minor amount of additive composition in addition to greater than% base oil.

  As used herein, “additive package”, “additive concentrate”, “additive composition”, “engine oil additive package”, “engine oil additive concentrate”, “crankcase addition” The terms “agent package”, “crankcase additive concentrate”, “motor oil additive package”, “motor oil concentrate” are part of a lubricating oil composition that excludes a base oil stock mixture of greater than 50% by weight. Is considered to be a synonymous, fully interchangeable terminology. The additive package may or may not include a viscosity index improver or pour point depressant.

  The term “overbased” refers to metal salts such as sulfonates, carboxylates, salicylates, and / or metal salts of phenates, and the amount of metal present exceeds the stoichiometric amount. Such salts may have conversion levels in excess of 100% (ie they are 100 of the theoretical amount of metal required to convert the acid to its “normal” salt, “neutral” salt. % May be included). The expression “metal ratio”, often abbreviated as MR, refers to 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. Used for. In the normal or neutral salt, the metal ratio is 1, and in the overbased salt, the MR is greater than 1. They are commonly referred to as overbased salts, overbased salts, or superbasic salts, and can be salts of organic sulfur acids, carboxylic acids, salicylates, and / or phenols. In the present disclosure, the lubricating oil composition may contain one or more overbased metal salts. The one or more overbased metal salts can include an overbased detergent having a TBN of greater than 225 mg KOH / g. The overbased detergent can be a combination of two or more overbased detergents each having a TBN of greater than 225 mg KOH / g. The one or more overbased detergents may include one or more overbased calcium-containing detergents having a TBN greater than 225 mg KOH / g as measured by the method of ASTM D-2896.

As used herein, the term “hydrocarbyl substituent” or “hydrocarbyl group” or “alkyl group” is used in its ordinary sense, which is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom bonded directly to the rest of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include
(A) hydrocarbon substituents, ie, aliphatic (eg, alkyl or alkenyl), alicyclic (eg, cycloalkyl, cycloalkenyl) substituents, and aromatic, aliphatic, and alicyclic substituted aromatic substitutions A group, as well as a cyclic substituent in which the ring is completed by another part of the molecule (eg, two substituents together form an alicyclic moiety),
(B) Substituted hydrocarbon substituents, ie non-hydrocarbon groups (eg, halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkyl mercapto, which do not change primarily hydrocarbon substituents in the context of this disclosure, Nitro, nitroso, amino, alkylamino, and sulfoxy) containing substituents, and (c) hetero substituents, i.e. having predominantly hydrocarbon character, while in the context of this disclosure, otherwise with carbon atoms And substituents containing other than carbon in the ring or chain. Heteroatoms include sulfur, oxygen, and nitrogen and can cover substituents such as pyridyl, furyl, thienyl, and imidazolyl. Generally, for every 10 carbon atoms in a hydrocarbyl group, there are no more than two, for example no more than one non-hydrocarbon substituent, and typically there are no non-hydrocarbon substituents in the hydrocarbyl group. do not do.

  As used herein, unless expressly stated otherwise, the term “weight percent” means the percentage that the described ingredients represent relative to the weight of the entire composition. Also, all values reported herein using “ppm” refer to ppm by weight of the total weight of the lubricating oil composition, unless expressly stated otherwise.

  As used herein, the terms “soluble”, “oil-soluble”, or “dispersible” refer to the compound or additive being soluble, soluble, miscible, or suspended in oil in all proportions. It can be shown that it can become turbid, but not necessarily. However, the above terms are used to the extent that they are sufficient to exert their intended effect in the environment in which the oil is used, eg, soluble, suspendable, soluble, or stable in the oil. Means dispersibility. Furthermore, additional incorporation of other additives may also allow for the incorporation of higher levels of specific additives, if desired.

  As used herein, the transitional phrase “consisting essentially of” substantially affects the scope of embodiments of the present invention to a particular material or process, and the basic and novel features of the present invention. Limit to not. As used herein, the basic and novel features of the present invention may be one or more of NOACK volatility and TC test performance.

  As used herein, the term “TBN” is used to represent the total base number in a mg KOH / g composition as measured by the method of ASTM D-2896.

  As used herein, the term “alkyl” refers to a linear, branched, cyclic, and / or substituted saturated chain moiety of about 1 to about 100 carbon atoms.

  As used herein, the term “alkenyl” refers to a linear, branched, cyclic, and / or substituted unsaturated moiety of about 3 to about 10 carbon atoms.

  As used herein, the term “aryl” refers to an alkyl substituent, an alkenyl substituent, an alkylaryl substituent, an amino substituent, a hydroxyl substituent, an alkoxy substituent, a halo substituent, and / or nitrogen, oxygen And monocyclic and polycyclic aromatic compounds that may include heteroatoms, including but not limited to sulfur.

  The lubricants, component combinations, or individual components herein may be suitable for use in various types of internal combustion engines. Suitable engine types include, but are not limited to, large diesel cars, passenger cars, small diesel cars, medium speed diesel cars, marine engines, or motorcycle engines. Internal combustion engine is diesel fuel engine, gasoline fuel engine, natural gas fuel engine, bio fuel engine, mixed diesel / bio fuel engine, mixed gasoline / bio fuel engine, alcohol fuel engine, mixed gasoline / alcohol fuel engine, compressed natural gas It can be a (CNG) fuel engine or a mixture thereof. The diesel engine may be a compression ignition engine. The diesel engine may be a compression ignition engine with spark ignition assist. The gasoline engine can be a spark ignition engine. The internal combustion engine may also be used in combination with a power source or battery source. An engine so configured is generally known as a hybrid engine. The internal combustion engine can be a two-stroke engine, a four-stroke engine, or a rotary engine. Suitable internal combustion engines include marine diesel engines (such as Inland Marine), aircraft piston engines, low load diesel engines, and motorcycle, automobile, engine cars, and truck engines.

  The internal combustion engine may contain one or more components of aluminum alloy, lead, tin, copper, cast iron, magnesium, ceramic, stainless steel, composite materials and / or mixtures thereof. The component can be coated with, for example, a diamond-like carbon coating, a lubricious coating, a phosphorus-containing coating, a molybdenum-containing coating, a graphite coating, a nanoparticle-containing coating, and / or mixtures thereof. The aluminum alloy may include aluminum silicate, aluminum oxide, or other ceramic material. In one embodiment, the aluminum alloy is an aluminum silicate surface. As used herein, the term “aluminum alloy” is synonymous with “aluminum composite” and, regardless of its detailed structure, aluminum and other materials that are mixed or reacted at the microscopic or near microscopic level. It is intended to describe a component or surface comprising the following components. This includes any conventional alloy having a metal other than aluminum, and composite or alloy-like structures having non-metallic elements or compounds such as ceramic-like materials.

  Lubricating oil compositions for internal combustion engines may be suitable for any engine regardless of sulfur, phosphorus, or sulfated ash (ASTM D-874) content. The sulfur content of the engine oil lubricant is about 1 wt% or less, or about 0.8 wt% or less, or about 0.5 wt% or less, or about 0.3 wt% or less, or about 0.2 wt% It can be: In one embodiment, the sulfur content can be in the range of about 0.001% to about 0.5%, or about 0.01% to about 0.3% by weight. The phosphorus content is about 0.2% or less, or about 0.1% or less, or about 0.085% or less, or about 0.08% or less, or about 0.06% or less, about It can be 0.055 wt% or less, or about 0.05 wt% or less. 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 is about 2% or less, or about 1.5% or less, or about 1.1% or less, or about 1% or less, or about 0.8% or less, or about 0%. .5% by weight or less. In one embodiment, the sulfated ash content can be from about 0.05 wt% to about 0.9 wt%, or from about 0.1 wt% or from about 0.2 wt% to about 0.45 wt%. In another embodiment, the sulfur content can be about 0.4 wt% or less, the phosphorus content can be about 0.08 wt% or less, and the sulfated ash is about 1 wt% or less. In yet another embodiment, the sulfur content can be about 0.3 wt% or less, the phosphorus content can be about 0.05 wt% or less, and the sulfated ash can be about 0.8 wt% or less. ASTM D4951 is a test method that covers eight elements and can provide elemental composition data. ASTM D5185 can be used to measure 22 elements in used and unused lubricants and base oils and can provide a screen for used oils for signs of wear.

  In some embodiments, the total TBN of the lubricating oil composition is at least 6.0 mg KOH / g as measured by the method of ASTM D-2896, or 6.4-12.12 as measured by the method of ASTM D-2896. It can be 0 mg KOH / g, or 6.5 to 12.0 mg KOH / g.

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

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

  Further, the lubricants herein include ILSAC GF-3, GF-4, GF-5, GF-6, PC-11, CI-4, CJ-4, CK-4, FA-4, ACEA A1 / B1, A2 / B2, A3 / B3, A3 / B4, A5 / B5, C1, C2, C3, C4, C5, E4 / E6 / E7 / E9, Euro5 / 6, Jaso DL-1, Low SAPS, Mid SAPS One or more industry standard requirements such as, or Dexos ™ 1, Dexos ™ 2, MB-Approval 229.51 / 2229.31, 229.71, 229.3 / 229.5, VW 502.00, 503.000 / 503.01, 504.00, 505.00, 506.00 / 506.01, 507.00, 508.00, 509.00, BMW Longlife-0 , Porsche C30, Peugeot Citroen Automobiles B71 2290, B71 2296, B71 2297, B71 2300, B71 2302, B71 2312, B71 2007, B71 2008, Ford WSS-M2C15-H, WSS-M2C9-M, WSS-M2C9-M Original equipment manufacturing standards such as WSS-M2C913A, WSS-M2C913-B, WSS-M2C913-C, GM6094-M, Chrysler MS-6395, or any past or future PCMO standard or HDD not mentioned herein It may be suitable to meet the standard. In some embodiments, for passenger car motor oil (PCMO) applications, the amount of phosphorus in the final 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 lubricants. “Functional fluid” means tractor hydraulic fluid; power transmission fluid (including automatic transmission fluid, continuously variable transmission fluid, and manual transmission fluid); hydraulic fluid (including tractor hydraulic fluid) ); Some gear oils; power steering fluids; fluids used in wind turbines, compressors; some industrial fluids; and various fluids including, but not limited to, fluids related to components of the power transmission system It is a term that covers fluid. For each of these fluids, such as, for example, automatic transmission fluids, there are a variety of different types of fluids because the various transmissions have different designs resulting in the need for fluids with significantly different functional characteristics. Please note that. This is contrasted by the term “lubricating fluid” that is not used to generate or transmit power.

  For example, with respect to tractor hydraulic fluids, these fluids are versatile products used for all lubricant applications in tractors other than engine lubrication. These lubrication applications can include gearboxes, power take-off devices and clutches, rear axles, reduction gears, wet brakes, and hydraulic oil accessories.

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

  Tractor fluids and, for example, Super Tractor Universal Oil (STUO) or Universal Tractor Transmission Oil (UTTO) may combine engine oil performance with transmission, differential, 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 can have detrimental effects if not properly incorporated. For example, some antiwear and extreme pressure additives used in engine oils can be extremely corrosive to the copper component in hydraulic pumps. Cleaning agents and dispersants used for gasoline or diesel engine performance can be detrimental to wet brake performance. Friction modifiers specific to quiet wet brake noise may lack the thermal stability required for engine oil performance. Each of these fluids is designed to meet certain stringent manufacturer requirements, whether functional, tractor, or lubricious.

  The present disclosure provides a novel lubricant blend formulated for use as an automotive crankcase lubricant. Embodiments of the present disclosure are suitable for crankcase applications and have the following characteristics: aeration, alcohol fuel compatibility, antioxidant properties, anti-wear performance, biofuel compatibility, foam reduction properties, friction reduction, fuel economy Lubricants can be provided that have improvements in performance, pre-ignition prevention, rust control, sludge and / or smoke dispersibility, piston cleanliness, turbocharger deposit formation, and water resistance.

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

  Additional details and advantages of the present disclosure will be set forth in part in the following description and / or may be understood by practice of the disclosure. Additional details and advantages of the disclosure may be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It should be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the claimed disclosure.

  Various embodiments of the present disclosure provide lubricating oil compositions and methods that can be used to reduce or prevent deposit formation in boosted internal combustion engines that include turbocharger or supercharger components. In particular, the boosted internal combustion engine of the present disclosure includes turbocharged and supercharged internal combustion engines. Boosted internal combustion engines include spark ignition engines, direct injection engines, and / or spark ignition port fuel injection engines. The spark ignition internal combustion engine may be a gasoline engine.

  The composition of the present invention comprises a lubricating oil composition containing a base oil of lubricating viscosity and a specific additive composition. The method of the present disclosure employs a lubricating oil composition containing an additive composition. As described in more detail below, the lubricating oil composition surprisingly includes a boosted internal combustion engine that includes carbonaceous deposits in turbocharger or supercharger parts lubricated with the lubricating oil composition. Can be effective for use in reducing or preventing the formation of carbonaceous deposits. Because the deposit acts as a thermal insulator, the amount of deposit can be measured indirectly by measuring the temperature rise in one of the turbocharger coolant passages. The greater the amount of deposit, the greater the increase in temperature outside the turbocharger coolant during use of the engine (TCO temperature). The lubricating oil composition of the present invention is effective in ensuring a TCO temperature rise of less than 9.0% as measured using the 2015 edition of the General Motors dexos1® turbocharger coking test.

  In an embodiment of invention A, the present disclosure provides a method for reducing or preventing deposit formation in a boosted internal combustion engine. The method includes lubricating a boosted internal combustion engine with a lubricating oil composition comprising a base oil having a lubricating viscosity of greater than 50% by weight, the lubricating oil composition relative to total nitrogen in ppm in the lubricating oil composition. One or more metals in the lubricating oil composition having a ratio of total metals in ppm from one or more metal-containing detergents in the oil to less than 1.9 and total boron in ppm in the lubricating oil composition The ratio of total metal in ppm from the containing detergent is less than 7.5, in ppm from one or more metal-containing detergents in the lubricating oil composition to total molybdenum in ppm in the lubricating oil composition. And the lubricating oil composition has a NOACK volatility of less than 11.0% by weight as measured by the method of ASTM D-5800 at 250 ° C. By lubricating an internal combustion engine that is boosted with this lubricating oil composition, a TCO temperature increase of less than 9.0% measured using the 2015 version of the General Motors dexos1® turbocharger coking test There is improved resistance to deposit formation in boosted internal combustion engines, including turbocharger or supercharger parts, as shown by its ability to ensure. Boosted internal combustion engines are operated and lubricated with the lubricating oil composition, thereby reducing or preventing the amount of deposits in the engine that comprise in turbocharger or supercharger parts lubricated with the lubricating oil composition. Can be done.

  In an embodiment of invention B, the present disclosure provides a method for reducing or preventing deposit formation in a boosted internal combustion engine. The method provides the lubricating oil composition with greater than about 50 weight percent of a base oil having a lubricating viscosity of greater than about 40 ppm by weight, based on the total weight of the lubricating composition, and one or more boronated compounds. Providing the lubricating oil composition with less than about 1800 ppm by weight of calcium, based on the total weight of the lubricating composition, in an amount sufficient for the one or more molybdenum-containing compounds, the one or more magnesium-containing detergents, and Lubricating the boosted internal combustion engine with a lubricating oil composition comprising a sufficient amount of one or more overbased calcium-containing detergents. By lubricating an internal combustion engine that is boosted with this lubricating oil composition, a TCO temperature increase of less than 9.0% measured using the 2015 version of the General Motors dexos1® turbocharger coking test There is improved resistance to deposit formation in boosted internal combustion engines, as shown by its ability to ensure. Boosted internal combustion engines are operated and lubricated with the lubricating oil composition, thereby reducing or preventing the amount of deposits in the engine that comprise in turbocharger or supercharger parts lubricated with the lubricating oil composition. Can be done.

  The following description relates to both Invention A and Invention B unless stated otherwise.

  In some embodiments of the method, a combustion chamber or cylinder wall of a spark ignition direct injection engine or spark ignition port fuel injection internal combustion engine with a turbocharger or supercharger, and a turbocharger or supercharger passage, bushing, and others These parts are lubricated with a lubricating oil composition and a lubricated spark ignition direct injection engine is operated to reduce or prevent deposits in the turbocharger of the engine lubricated with the lubricating oil composition.

  Calcium in the lubricating oil composition can be provided by a variety of sources including detergents. In some embodiments, the lubricating oil composition comprises one or more overbased calcium-containing detergents having a TBN of greater than 225 mg KOH / g, and optionally ASTM D-, as measured by the method of ASTM D-2896. It may comprise at least one detergent selected from one or more low basic / neutral calcium containing detergents having a TBN of up to 175 mg KOH / g as measured by the 2896 method.

  The lubricating oil composition contains both boron and nitrogen. One source for providing boron and / or nitrogen to the lubricating oil composition is a boron-containing dispersant. In some embodiments, the lubricating oil composition can include a dispersant that can be a boron-containing dispersant. In some embodiments, the boron-containing dispersant may be present in an amount of 1.0 to 10% by weight, based on the total weight of the lubricating oil composition, and even more preferably, the boron-containing dispersant is lubricated. It can be in an amount of 1.0-8.5% by weight, based on the total weight of the oil composition.

  In some embodiments, nitrogen can be present in the lubricating oil composition in an amount of about 500 ppm to about 2500 ppm, or about 700 ppm to about 2000 ppm, or about 900 ppm to about 1600 ppm. In some embodiments, nitrogen present in the lubricating oil composition may be added as part of one or more of a dispersant, an antioxidant, and a friction modifier.

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

  Groups I, II, and III are mineral oil process stocks. Group IV base oils contain pure synthetic molecular species produced by the polymerization of olefinically unsaturated hydrocarbons. Many Group V base oils are also pure synthetic products and may include diesters, polyol esters, polyalkylene glycols, alkylated aromatics, polyphosphate esters, polyvinyl ethers, and / or polyphenyl ethers, etc. It can also be a naturally occurring oil such as Note that Group III base oils are derived from mineral oils, but due to the rigorous processing these fluids undergo, their physical properties are very similar to some pure compounds such as PAO. I want to be. Therefore, oils derived from Group III base oils may be referred to as synthetic fluids in the industry.

  The base oil used in the disclosed lubricating oil composition can be mineral oil, animal oil, vegetable oil, synthetic oil, or mixtures thereof. Suitable oils can be derived from hydrocracking, hydrogenation, hydrofinishing, unrefined, refined, and rerefined oils, and mixtures thereof.

  Unrefined oils are derived from natural, mineral or synthetic sources with little or no further refining treatment. Refined oils are similar to unrefined oils, except that they have been treated with one or more refining steps that can result in an improvement in one or more properties. Examples of suitable purification techniques are solvent extraction, secondary distillation, acid or base extraction, filtration, leaching and the like. Oils refined to edible quality may or may not be useful. Edible oil is also called white oil. In some embodiments, the lubricating oil composition does not include edible oil or white oil.

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

  Mineral oils may include oils obtained from rock drilling or from plants and animals, and mixtures thereof. For example, such oils include castor oil, lard oil, olive oil, peanut oil, corn oil, soybean oil, and linseed oil, as well as liquid petroleum and paraffinic, naphthenic, or paraffin-naphthenic types. Non-limiting examples include mineral lubricating oils such as solvent-treated or acid-treated mineral lubricating oils. Such oils may be partially or fully hydrogenated if desired. Oils derived from coal or shale may also be useful.

  Useful synthetic lubricating oils include hydrocarbon oils such as polymerized, oligomerized, or internally polymerized olefins (eg, polybutylene, polypropylene, propylene / isobutylene copolymers); poly (1-hexene), poly (1-octene), 1 -Decene trimers or oligomers, such as poly (1-decene) (such materials are often referred to as α-olefins), and mixtures thereof; alkyl-benzenes (eg, dodecylbenzene, tetradecylbenzene, di- Nonylbenzene, di- (2-ethylhexyl) -benzene); polyphenyl (eg, biphenyl, terphenyl, alkylated polyphenyl); diphenylalkane, alkylated diphenylalkane, alkylated diphenyl ether, and alkylated diphenyl sulfide, These derivatives Rabbi, can be cited analogs, and homologs or mixtures thereof. Polyalphaolefins are typically hydrogenated materials.

  Other synthetic lubricating oils include polyol esters, diesters, liquid esters of phosphorus-containing acids (eg, tricresyl phosphate, trioctyl phosphate, diethyl ester of decanephosphonic acid), or polymeric tetrahydrofuran. Synthetic oils can be produced by a Fischer-Tropsch reaction and typically can be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil may be prepared by Fischer-Tropsch gas-liquid procedures and other gas-liquid oils.

  The base oil in excess of 50% by weight contained in the lubricating composition may be selected from the group consisting of Group I, Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, wherein 50% by weight The excess base oil is other than the base oil resulting from the provision of an additive component or viscosity index improver in the composition. In another embodiment, the base oil in excess of 50% by weight included in the lubricating composition may be selected from the group consisting of Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, Base oils in excess of weight percent are other than diluent oils resulting from the provision of additive components or viscosity index improvers in the composition.

  The amount of oil of lubricating viscosity present is the balance remaining after subtracting the total amount of performance additives including viscosity index improvers and / or pour point depressants and / or other top treatment additives from 100% by weight. It can be. For example, oils of lubricating viscosity that may be present in the final fluid are all greater than about 50%, greater than about 60%, greater than about 70%, greater than about 80% by weight, based on the total weight of the lubricating oil composition. , Greater than about 85 wt%, or greater than about 90 wt%.

  The lubricating oil composition may comprise up to 10% by weight of a Group IV base oil, a Group V base oil, or a combination thereof. In each of the foregoing embodiments, the lubricating oil composition may comprise less than 5% by weight of Group V base oils. In some embodiments, the lubricating oil composition does not contain a Group IV base oil and / or the lubricating oil composition does not contain a Group V base oil.

Detergent The lubricating oil composition may comprise one or more detergents. In some embodiments, the lubricating oil composition may include one or more overbased calcium-containing detergents and optionally other detergents. Suitable detergent substrates include phenates, sulfur-containing phenates, sulfonates, calixates, salixates, salicylates, carboxylic acids, phosphoric acids, monothiophosphoric acids and / or dithiophosphoric acids, alkylphenols, sulfur-bonded alkylphenol compounds, or methylene bridged phenols. It is done. Suitable detergents and methods for their preparation are described in detail in numerous patent publications including US 7,732,390 and references cited therein. The detergent substrate can be salinized with an alkali metal or alkaline earth metal such as, but not limited to, calcium, magnesium, potassium, sodium, lithium, barium, or mixtures thereof. In some embodiments, the cleaning agent does not include barium. Suitable detergents may include petroleum sulfonic acids and alkali or alkaline earth metal salts of long chain mono- or dialkylaryl sulfonic acids where the aryl group is benzyl, tolyl, and xylyl.

  Examples of suitable additional detergents include calcium phenate, calcium sulfur-containing phenate, calcium sulfonate, calcium calixarate, calcium salixarate, calcium salicylate, calcium carboxylic acid, calcium phosphate, calcium monothiophosphate and / Or dithiophosphoric acid, calcium alkylphenol, calcium sulfur-bonded alkylphenol compound, calcium methylene crosslinked phenol, magnesium phenate, magnesium sulfur-containing phenate, magnesium sulfonate, magnesium calixarate, magnesium salixate, magnesium salicylate, magnesium carboxylic acid, Magnesium phosphate, magnesium monothiophosphate and / or dithiophosphate, magnesium alkyl phosphate Diol, magnesium sulfur bond alkylphenol compound, magnesium methylene bridged phenol, sodium phenate, sodium sulfur containing phenate, sodium sulfonate, sodium calixate, sodium salixate, sodium salicylate, sodium carboxylic acid, sodium phosphate, sodium mono Examples include, but are not limited to, thiophosphoric acid and / or dithiophosphoric acid, sodium alkylphenol, sodium sulfur-bonded alkylphenol compound, or sodium methylene bridged phenol.

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

  The term “overbased” refers to metal salts such as metal salts of sulfonates, carboxylates, and phenates, and the amount of metal present exceeds the stoichiometric amount. Such salts may have conversion levels in excess of 100% (ie they are 100 of the theoretical amount of metal required to convert the acid to its “normal” salt, “neutral” salt. % May be included). The expression “metal ratio”, often abbreviated as MR, refers to 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. Used for. In the normal or neutral salt, the metal ratio is 1, and in the overbased salt, the MR is greater than 1. They are commonly referred to as overbased, overbased, or superbasic salts and can be salts of organic sulfur acids, carboxylic acids, or phenols.

  The overbased detergent may have a TBN greater than 225 mg KOH / gram as measured by the method of ASTM D-2896, or as a further example, an overbased detergent may have a TBN greater than about 250 mg KOH / gram, Alternatively, it may have a TBN of about 300 mg KOH / gram or more, or a TBN of about 350 mg KOH / gram or more, or a TBN of about 375 mg KOH / gram or more, or a TBN of about 400 mg KOH / gram or more.

  Examples of suitable overbased detergents include overbased calcium phenate, overbased calcium sulfur containing phenate, overbased calcium sulfonate, overbased calcium calixarate, overbased calcium salixate, overbased calcium sulfonate. Basic calcium salicylate, overbased calcium carboxylic acid, overbased calcium phosphoric acid, overbased calcium monothiophosphoric acid and / or dithiophosphoric acid, overbased calcium alkylphenol, overbased calcium sulfur-bonded alkylphenol compound, Basic calcium methylene bridged phenol, overbased magnesium phenate, overbased magnesium sulfur-containing phenate, overbased magnesium sulfonate, overbased magnesium calixate, overbased magnesium salixate, overbased Magnesium salicylate, overbased magnesium carboxylic acid, overbased magnesium phosphoric acid, overbased magnesium monothiophosphoric acid and / or dithiophosphoric acid, overbased magnesium alkylphenol, overbased magnesium sulfur-bonded alkylphenol compound, or overbased Examples include, but are not limited to, soluble magnesium methylene crosslinked phenol.

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

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

  The total detergent is based on the total weight of the lubricating oil composition, up to 10%, or up to about 8%, or up to about 4%, or more than about 1% and up to about 8% by weight Or greater than about 1 wt% and up to about 4 wt%.

  In each of the foregoing embodiments, “total metal from one or more metal-containing detergents” may be present in an amount that provides about 100 ppm to about 3500 ppm of metal to the final fluid. In other embodiments, the metal-containing 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, or less than 1800 ppm metal to the final fluid. .

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

  In each of the foregoing embodiments, the total magnesium provided to the lubricating oil composition by the overbased magnesium detergent is 20 ppm to 1500 ppm by weight of the lubricating oil composition, based on the total weight of the lubricating composition. Magnesium, or magnesium from 100 ppm to 800 ppm by weight, or greater than about 140 ppm by weight and up to about 550 ppm by weight, based on the total weight of the lubricating composition. In each of the foregoing embodiments, the overbased magnesium detergent may have a TBN greater than 225 mg KOH / gram as measured by the method of ASTM D-2896, or as a further example, an overbased magnesium detergent Can have a TBN of about 250 mg KOH / gram or more, or a TBN of about 300 mg KOH / gram or more, or a TBN of about 350 mg KOH / gram or more, or a TBN of about 400 mg KOH / gram or more, or a TBN of about 425 mg KOH / gram or more.

  In some embodiments, the lubricating oil composition of the present disclosure comprises one or more overbased calcium-containing detergents having a TBN of greater than 225 mg KOH / g as measured by the method of ASTM D-2896, and optionally At least one detergent selected from one or more low basic / neutral calcium containing detergents having a TBN of at most 175 mg KOH / g as measured by the method of ASTM D-2896. The present disclosure also includes a method of lubricating a boosted engine by using such a lubricating oil composition in the method or lubricating the engine with the lubricating oil composition and operating the engine.

  The lubricating oil composition of the present disclosure has an overbased calcium-containing detergent selected from an overbased calcium sulfonate detergent, an overbased calcium phenate detergent, and an overbased calcium salicylate detergent. obtain. In certain embodiments, the overbased calcium-containing detergent comprises an overbased calcium sulfonate detergent. In certain embodiments, the overbased detergent is one or more calcium-containing detergents. Preferably, the overbased detergent is a calcium sulfonate detergent.

  In certain embodiments, the one or more overbased calcium-containing detergents includes less than about 1800 ppm by weight of calcium in the lubricating oil composition, or total lubricating oil composition, based on the total weight of the lubricating composition. The amount may be sufficient to provide the lubricating oil composition with about 1000 to about 1750 ppm by weight, or 1100 to 1700 ppm by weight calcium, based on weight.

  The lubricating oil composition of the present invention may also optionally contain one or more low basic / neutral detergents. The low basic / neutral detergent has a TBN of up to 175 mg KOH / g, or up to 150 mg KOH / g. The low basic / neutral detergent may comprise a calcium-containing detergent. 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 may be a calcium-containing detergent or a mixture of calcium-containing detergents. In some embodiments, the low basic / neutral detergent may be a calcium sulfonate detergent or a calcium phenate detergent. In some embodiments, the lubricating oil composition does not contain a low basic / neutral detergent.

  The low basic / neutral detergent, when present, can comprise at least 0.1% by weight of the lubricating oil composition. In some embodiments, the low basic / neutral detergent is at least 0.25 wt%, or 0 wt% to 5.0 wt%, or 0.15 wt% to 3.0 wt%, or 0 .15% to 1.0% by weight of the lubricating oil composition. The low basic / neutral detergent may optionally include one or more low basic / neutral calcium containing detergents.

  In certain embodiments, the one or more low basic / neutral calcium-containing detergents provide the lubricating oil composition with about 0 to about 1000 ppm by weight of calcium, based on the total weight of the lubricating oil composition. In some embodiments, the one or more low basic / neutral calcium containing detergents is less than 25 to 800 ppm by weight, or 50 to 600 ppm by weight, or 100 to 100 ppm based on the total weight of the lubricating oil composition. 500 ppm by weight of calcium can be provided to the lubricating oil composition.

  In some embodiments, the ratio of the weight ppm of calcium provided to the lubricating oil composition by the low basicity / neutral detergent to the weight ppm of calcium provided to the lubricating oil composition by the overbased calcium detergent. Can be 0 to about 1, or about 0.03 to about 0.7, or about 0.05 to about 0.5, or about 0.08 to about 0.4.

One or more molybdenum-containing compounds The lubricating oil compositions herein contain molybdenum, which can be provided to the lubricating oil composition in the form of one or more molybdenum-containing compounds. The oil soluble molybdenum compound may have the functional performance of an antiwear agent, an antioxidant, a friction modifier, or a mixture thereof. Oil-soluble molybdenum compounds are molybdenum dithiocarbamate, molybdenum dialkyldithiophosphate, molybdenum dithiophosphinate, amine salt of molybdenum compound, molybdenum xanthate, molybdenum thioxanthate, molybdenum sulfide, molybdenum carboxylate, molybdenum alkoxide, trinuclear organic molybdenum compound And / or mixtures thereof. Molybdenum sulfide includes molybdenum disulfide. Molybdenum disulfide can 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 can be molybdenum dithiocarbamate.

  Preferable examples of the molybdenum compound that can be used include R.I. under the trade names such as Polyvan 822 (trademark), Polyvan (trademark) A, Polyvan2000 (trademark), and Polyvan 855 (trademark). T.A. Vanderbilt Co. , Ltd., Ltd. And products such as Sakura-Lube (TM) S-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710 available from Adeka Corporation Commercially available materials sold by name, as well as mixtures thereof. Suitable molybdenum components are described in US 5,650,381, USRE 37,363E1, USRE 38,929E1, and USRE 40,595E1.

The molybdenum compound may be an acidic molybdenum compound. Included are molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts such as sodium hydrogen molybdate, MoOCl ₄ , MoO ₂ Br ₂ , Mo _2. O ₃ Cl ₆ , molybdenum trioxide, or similar acidic molybdenum compounds. Alternatively, the composition may be, for example, U.S. Pat. Nos. 4,263,152, 4,285,822, 4,283,295, 4,272,387, 4,265,773, Molybdenum by a molybdenum / sulfur complex of a basic nitrogen compound described in US Pat. Nos. 4,261,843, 4,259,195, and 4,259,194, and US 2002/0038525. May be provided.

Another class of preferred organo-molybdenum compounds are those of formula _{Mo 3 S k L n Q z} , and trinuclear molybdenum compounds, such as mixtures thereof, wherein, S is represents sulfur, L is compound Represents an independently selected ligand having an organic group with a sufficient number of carbon atoms to render the oil soluble or dispersible, n is 1-4 and k is 4-7 Vary, Q is selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5, including non-stoichiometric values. There may be at least 21 total carbon atoms, such as at least 25, at least 30, or at least 35 carbon atoms in all of the organic groups of the ligand. Further suitable molybdenum compounds are described in US Pat. No. 6,723,685.

  The one or more molybdenum-containing compounds are based on the total weight of the lubricating composition and include greater than about 40 ppm by weight of molybdenum in the lubricating oil composition, or at least about 50 ppm by weight of molybdenum in the lubricating oil composition, or lubrication. At least about 80 ppm by weight, based on the total weight of the composition, or greater than 40 ppm to 1200 ppm, or greater than 40 ppm to 900 ppm, or at least about 80 ppm to 800 ppm of molybdenum. It can be present in an amount sufficient to provide a lubricating oil composition.

Boron-containing compounds The lubricating oil compositions herein are composed of one or more boron-containing compounds (also referred to herein as one or more boronated compounds), such as a boron-containing dispersant, as discussed above. Boron that may be provided in a lubricating oil composition in form.

  Examples of boron-containing compounds include boronated esters, boronated fatty amines, boronated epoxides, boronated detergents, and boronated dispersants (borated succinimide dispersants disclosed in US Pat. No. 5,883,057). Etc.).

  The boron-containing compound provides about 0.01% to about 10%, about 0.05% to about 8.5%, or about 0.1% to about 3% by weight of the lubricating oil composition It can be used in an amount sufficient to do. The boron-containing compound is based on the total weight of the lubricating composition, more than 50 ppm boron in the lubricating oil composition, more than 100 ppm boron, more than 50 ppm and less than 1000 ppm boron, or more than 100 ppm and less than 800 ppm boron, or The lubricating oil composition may be included in an amount sufficient to provide 110 ppm to 600 ppm boron, or 120 ppm to 500 ppm boron to the lubricating oil composition.

  The lubricating oil composition may also include one or more optional ingredients selected from the various additives described below.

Antioxidants The lubricating oil compositions herein may also optionally contain one or more antioxidants. Antioxidant compounds are known, such as phenates, phenate sulfides, sulfurized olefins, phosphosulfurized terpenes, sulfurized esters, aromatic amines, alkylated diphenylamines (eg, nonyldiphenylamine, di-nonyldiphenylamine, octyldiphenylamine, di- Octyldiphenylamine), phenyl-alpha-naphthylamine, alkylated phenyl-alpha-naphthylamine, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, macromolecular antioxidants, or mixtures thereof. Antioxidant compounds may be used alone or in combination.

  The hindered phenol antioxidant may contain a secondary butyl group and / or a tertiary butyl group as a steric hindrance group. The phenol group can be further substituted with a bridging group that binds to the hydrocarbyl group and / or the second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol, or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol. In one embodiment, the hindered phenol antioxidant can be an ester, such as an addition product derived from IRGANOX ™ L-135 or 2,6-di-tert-butylphenol and alkyl acrylate available from BASF. The alkyl group can contain about 1 to about 18, or about 2 to about 12, or about 2 to about 8, or about 2 to about 6, or about 4 carbon atoms. Another commercially available hindered phenol antioxidant may be an ester and may include ETHANOX ™ 4716 available from Albemarle Corporation.

  Useful antioxidants can include diarylamines and high molecular weight phenols. In one embodiment, the lubricating oil composition may contain a mixture of diarylamine and high molecular weight phenol, so that each antioxidant is up to about 5 weight based on the total weight of the lubricating oil composition. % May be present in an amount sufficient to provide%. In one embodiment, the antioxidant is from about 0.3 to about 1.5 weight percent diarylamine and from about 0.4 to about 2.5 weight percent high, based on the total weight of the lubricating oil composition. It can be a mixture with molecular weight phenol.

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

  Another class of sulfurized olefins includes sulfurized fatty acids and their esters. Fatty acids are often obtained from vegetable and animal oils and typically contain from about 4 to about 22 carbon atoms. Examples of suitable fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid, or mixtures thereof. Often, the fatty acids are obtained from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil, or mixtures thereof. Fatty acids and / or esters can be mixed with olefins such as α-olefins.

  The one or more antioxidants are from about 0% to about 5.0%, or from about 0.1% to about 4.0% by weight of the lubricating oil composition, based on the total weight of the lubricating composition. Or in the range of about 0.5 wt% to about 3 wt%.

Antiwear Agents The lubricating oil compositions herein may also optionally contain one or more antiwear agents. Examples of suitable antiwear agents include metal thiophosphates, metal dialkyldithiophosphates, phosphate esters or salts thereof, phosphate esters, phosphites, phosphorus-containing carboxylic acid esters, ethers or amides, sulfurized olefins, thiocarbamate esters Thiocarbamate-containing compounds including, but not limited to, alkylene-linked thiocarbamates, and bis (S-alkyldithiocarbamyl) disulfides. A suitable antiwear agent may be molybdenum dithiocarbamate. Phosphorus-containing antiwear agents are more fully described in European Patent 612839. The metal in the dialkyldithiophosphate salt can be an alkali metal, alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc. A useful antiwear agent can be a zinc dialkylthiophosphate.

  Further examples of suitable antiwear agents include titanium compounds, tartrate salts, tartaric imides, oil soluble amine salts of phosphorus compounds, sulfurized olefins, phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate containing compounds (thiocarbamates) Ester, thiocarbamate amide, carbamine ether, alkylene-linked thiocarbamate, and bis (S-alkyldithiocarbamyl) disulfide). The tartrate or tartrate imide can contain alkyl-ester groups, where the total number of carbon atoms on the alkyl group can be at least 8. The antiwear agent may include citrate in one embodiment.

  The antiwear agent is about 0% to about 10%, or about 0.01% to about 8%, or about 0.05% by weight of the lubricating oil composition, based on the total weight of the lubricating composition. May be present in a range including from about 5 wt%, or from about 0.1 wt% to about 3 wt%, or less than 2 wt%

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

Dispersant The lubricating oil composition may optionally further comprise one or more dispersants or mixtures thereof. Dispersants are often known as ashless dispersants because they do not contain ash-forming metals prior to mixing into the lubricating oil composition, and they usually do not contribute to any ash upon addition to the lubricant. Ashless type dispersants are characterized by polar groups attached to relatively high molecular weight hydrocarbon chains. Typical ashless dispersants include N-substituted long chain alkenyl succinimides. Examples of N-substituted long chain alkenyl succinimides include polyisobutylene having a number average molecular weight of the polyisobutylene substituent in the range of about 350 to about 50,000, or about 5,000, or about 3,000. Succinimide is mentioned. Succinimide dispersants and their preparation are disclosed, for example, in US Pat. No. 7,897,696 or US Pat. No. 4,234,435. Polyolefins can be prepared from polymerizable monomers containing about 2 to about 16, or about 2 to about 8, or about 2 to about 6 carbon atoms. Succinimide dispersants are typically imides formed from polyamines, typically poly (ethyleneamine).

  In one embodiment, the disclosure provides at least one polyisobutylene succinimide dispersion derived from polyisobutylene having a number average molecular weight in the range of about 350 to about 50,000, or about 5000, or about 3000. An agent is further included. Polyisobutylene succinimide may be used alone or in combination with other dispersants.

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

  HR-PIB having a number average molecular weight in the range of about 900 to about 3000 may be suitable. Such HR-PIBs are commercially available, such as boron trifluoride, as described in US Pat. No. 4,152,499 to Boerzel et al. And US Pat. No. 5,739,355 to Gateau et al. It can be synthesized by polymerization of isobutene in the presence of a non-chlorinated catalyst. When used in the aforementioned heat-ene reaction, HR-PIB can result in higher conversion in the reaction and less amount of sediment formation due to increased reactivity. A suitable method is described in US Pat. No. 7,897,696.

  In one embodiment, the present disclosure further comprises at least one dispersant derived from polyisobutylene succinic anhydride (“PIBSA”). The PIBSA can have an average of between about 1.0 and about 2.0 succinic acid moieties per polymer.

  The% activity of alkenyl succinic anhydride or alkyl succinic anhydride can be determined using chromatographic techniques. This method is described in US Pat. No. 5,334,321, columns 5 and 6.

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

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

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

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

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

  One class of suitable dispersants can be Mannich bases. Mannich bases are materials formed by the condensation of higher molecular weight alkyl-substituted phenols, polyalkylene polyamines, and aldehydes (such as formaldehyde). Mannich bases are described in more detail in US Pat. No. 3,634,515.

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

  Suitable dispersants can also be post-treated by conventional methods by reaction with various agents. Among these, boron, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehyde, ketone, carboxylic acid, hydrocarbon-substituted succinic anhydride, maleic anhydride, nitrile, epoxide, carbonate, cyclic carbonate, There are hindered phenolic esters and phosphorus compounds. US 7,645,726, US 7,214,649 and US 8,048,831 disclose suitable dispersants and post treatments.

In addition to carbonate and boric acid post-treatments, both compounds can be post-treated with various post-treatments designed to improve or provide different properties, or can be further post-treated. Such post treatments include those summarized in US Pat. No. 5,241,003, columns 27-29. As such processing,
Inorganic phosphoric acid or anhydride (eg, US Pat. Nos. 3,403,102 and 4,648,980),
Organophosphorus compounds (eg, US Pat. No. 3,502,677),
Phosphorus pentasulfide,
Boron compounds as already described above (eg, US Pat. Nos. 3,178,663 and 4,652,387),
Carboxylic acids, polycarboxylic acids, anhydrides, and / or acid halides (eg, US Pat. Nos. 3,708,522 and 4,948,386),
Epoxides, polyepoxides, or thioepoxides (eg, US Pat. Nos. 3,859,318 and 5,026,495),
Aldehydes or ketones (eg, US Pat. No. 3,458,530),
Carbon disulfide (eg, US Pat. No. 3,256,185),
Glycidol (eg, US Pat. No. 4,617,137),
Urea, thiourea, or guanidine (eg, US Pat. Nos. 3,312,619, 3,865,813, and British Patent GB1,065,595),
Organic sulfonic acids (eg, US Pat. No. 3,189,544 and British Patent GB 2,140,811),
Alkenyl cyanide (eg, US Pat. Nos. 3,278,550 and 3,366,569),
Diketene (eg, US Pat. No. 3,546,243),
Diisocyanates (eg, US Pat. No. 3,573,205),
Alkane sultone (eg, US Pat. No. 3,749,695),
1,3-dicarbonyl compounds (eg, US Pat. No. 4,579,675),
Alkoxylated alcohols or phenol sulfates (eg, US Pat. No. 3,954,639),
Cyclic lactones (eg, US Pat. Nos. 4,617,138, 4,645,515, 4,668,246, 4,963,275, and 4,971,711),
Cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (eg, US Pat. Nos. 4,612,132, 4,647,390, 4,648,886) No. 4,670,170),
Nitrogen-containing carboxylic acids (eg, US Pat. No. 4,971,598 and British Patent GB 2,140,811),
Hydroxy protected chlorodicarbonyloxy compounds (eg, US Pat. No. 4,614,522),
Lactam, thiolactam, thiolactone, or ditholactone (eg, US Pat. Nos. 4,614,603 and 4,666,460),
Cyclic carbonates or thiocarbonates, linear monocarbonates or polycarbonates, or chloroformates (eg, US Pat. Nos. 4,612,132, 4,647,390, 4,646,886) No. and No. 4,670,170),
Nitrogen-containing carboxylic acids (eg, US Pat. No. 4,971,598 and British Patent GB 2,440,811),
Hydroxy protected chlorodicarbonyloxy compounds (eg, US Pat. No. 4,614,522),
Lactam, thiolactam, thiolactone, or dithiolactone (eg, US Pat. Nos. 4,614,603 and 4,666,460),
Cyclic carbamates, cyclic thiocarbamates, or cyclic dithiocarbamates (eg, US Pat. Nos. 4,663,062 and 4,666,459),
Hydroxy aliphatic carboxylic acids (eg, US Pat. Nos. 4,482,464, 4,521,318, 4,713,189),
Oxidizing agents (eg, US Pat. No. 4,379,064),
Combinations of phosphorus pentasulfide and polyalkylene polyamines (eg, US Pat. No. 3,185,647),
Combinations of carboxylic acids or aldehydes or ketones and sulfur or sulfur chloride (eg, US Pat. Nos. 3,390,086, 3,470,098),
A combination of hydrazine and carbon disulfide (eg, US Pat. No. 3,519,564),
Combinations of aldehydes and phenols (eg, US Pat. Nos. 3,649,229, 5,030,249, 5,039,307),
Combinations of aldehydes and dithiophosphoric acid O-diesters (eg, US Pat. No. 3,865,740),
Combinations of hydroxy aliphatic carboxylic acids and boric acids (eg, US Pat. No. 4,554,086),
A hydroxy aliphatic carboxylic acid followed by a combination of formaldehyde and phenol (eg, US Pat. No. 4,636,322),
Combinations of hydroxy aliphatic carboxylic acids and subsequent aliphatic dicarboxylic acids (eg, US Pat. No. 4,663,064),
A combination of formaldehyde and phenol, followed by glycolic acid (eg, US Pat. No. 4,699,724),
Combinations of hydroxy aliphatic carboxylic acids or oxalic acids followed by diisocyanates (eg, US Pat. No. 4,713,191),
A combination of an inorganic acid or anhydride of phosphorus or a partial or total sulfur analog thereof and a boron compound (eg, US Pat. No. 4,857,214),
A combination of an organic diacid, followed by an unsaturated fatty acid, followed by a nitroso aromatic amine, optionally followed by a boron compound, followed by a glycolating agent (eg, US Pat. No. 4,973,412),
Combinations of aldehydes and triazoles (eg, US Pat. No. 4,963,278),
A combination of an aldehyde and a triazole, followed by a boron compound (eg, US Pat. No. 4,981,492),
Treatment with a combination of a cyclic lactone and a boron compound (eg, US Pat. Nos. 4,963,275 and 4,971,711) can be mentioned.

  A suitable dispersant TBN may be from about 10 to about 65 when oil free, which is from about 5 to about 30 as measured on a dispersant sample containing about 50% diluent oil. Equivalent to TBN.

  When present, the dispersant may be used in an amount sufficient to provide up to about 10% by weight, based on the total weight of the lubricating oil composition. Another amount of dispersant that may be used is about 0.1% to about 10%, or about 1% to about 9%, or about 2% by weight, based on the total weight of the lubricating oil composition. To about 8.5 wt%, or about 2.75 wt% to about 6.5 wt%. In some embodiments, the lubricating oil composition utilizes a mixed dispersant system. A single type or a mixture of two or more dispersants in any desired ratio may be used.

  If the dispersant contains nitrogen, then the amount of dispersant used in the lubricating oil composition depends on the ratio of all metals from one or more metal-containing detergents to total nitrogen in the lubricating oil composition. Can be constrained.

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

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

  Other suitable friction modifiers include organic, ashless (metal free), and nitrogen-free organic friction modifiers. Such friction modifiers can include esters formed by reacting carboxylic acids and anhydrides with alkanols and generally have polar end groups (eg, carboxyl or hydroxyl) covalently attached to the lipophilic hydrocarbon chain. Including. An example of an organic ashless and nitrogen-free friction modifier is commonly known as glycerol monooleate (GMO), which may contain monoesters, diesters, and triesters of oleic acid. Other suitable friction modifiers are described in US Pat. No. 6,723,685.

  The amine friction modifier can include an amine or a polyamine. Such compounds can be linear, have a hydrocarbyl group that is either saturated or unsaturated, or a mixture thereof, and can contain from about 12 to about 25 carbon atoms. Further examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. Such compounds are linear and can have hydrocarbyl groups that are either saturated or unsaturated, or a mixture thereof. They can contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.

  Amines and amides, if used as such, are adducts with boron oxide, boron halide, metaborate, boric acid, or boron compounds such as monoalkyl borate, dialkyl borate, or trialkyl borate Alternatively, it may be used in the form of a reaction product. Other suitable friction modifiers are described in US Pat. No. 6,300,291.

  The friction modifier is about 0% to about 10%, or about 0.01% to about 8%, or about 0.05% to about 4% by weight, based on the total weight of the lubricating composition. Or optionally in the range of about 0.05 to about 2% by weight or the like.

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

  In one embodiment, the oil-soluble compound that can be used at a weight ratio of Ca / M in the range of about 0.8: 1 to about 70: 1 is a titanium-containing compound, where M is as described above. It is the total metal in the lubricant composition. The titanium-containing compound may function as an antiwear agent, friction modifier, antioxidant, deposit control additive, or one or more of these functions.

  Among the titanium-containing compounds that can be used in the disclosed technology or can be used to prepare the oil-soluble materials of the disclosed technology, various Ti (IV) compounds such as titanium (IV) oxide, titanium (IV) sulfide, titanium (IV) nitrate, titanium (IV) alkoxide, such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium 2-ethylhexoxide, and titanium Other titanium compounds or complexes, including but not limited to phenates, titanium carboxylates such as titanium (IV) 2-ethyl-1--3-hexanedioate or titanium citrate, or titanium oleate, and titanium ( IV) (Triethanolaminato) isopropoxide . The monovalent alkoxide can have 2 to 16, or 3 to 10 carbon atoms. In one embodiment, the titanium compound can be a 1,2-diol or an alkoxide of a polyol. In one embodiment, the 1,2-diol comprises a fatty acid monoester of glycerol, such as oleic acid. In one embodiment, the oil-soluble titanium compound can be a titanium carboxylate. In one embodiment, the titanium (IV) carboxylate can be titanium neodecanoate.

  Other forms of titanium encompassed by the disclosed technology include titanium phosphates, such as titanium dithiophosphates (eg, dialkyldithiophosphates) and titanium sulfonates (eg, alkylbenzene sulfonates), or generally titanium compounds and oils Reaction products with various acid materials that form salts such as soluble salts are included. Therefore, titanium compounds can be derived from organic acids, alcohols, and glycols, among others. Ti compounds may also be present in the form of dimers or oligomers containing a Ti-O-Ti structure. Such titanium materials are commercially available or can be readily prepared by suitable synthetic techniques apparent to those skilled in the art. They can exist at room temperature as solids or liquids, depending on the particular compound. They may also be provided in solution form in a suitable inert solvent.

  In one embodiment, titanium can be supplied as a Ti-modified dispersant such as a succinimide dispersant. Such materials can be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl substituted succinic anhydride such as an alkenyl (or alkyl) succinic anhydride. The resulting titanate-succinate intermediate may be used directly or may be reacted with any of a number of materials, such as (a) a polyamine having a free condensable -NH functional group. -Based succinimide / amide dispersant, (b) components of polyamine-based succinimide / amide dispersant, ie alkenyl- (or alkyl-) succinic anhydride and polyamine, (c) substituted succinic anhydride and polyol, amino alcohol, polyamine Or a hydroxy-containing polyester dispersant prepared by reaction with a mixture thereof. Alternatively, the titanate-succinate intermediate may be reacted with other agents such as alcohols, amino alcohols, ether alcohols, polyether alcohols or polyols, or fatty acids and Ti as a lubricant. Those products that are used directly to apply or are further reacted with the succinic dispersants described above. As an example, 1 part (by mole) of tetraisopropyl titanate is reacted with about 2 parts (by mole) of a polyisobutene-substituted succinic anhydride at 140-150 ° C. for 5-6 hours to form a titanium modified dispersant or intermediate. May be provided. The resulting material (30 g) was further reacted with a succinimide dispersant from a polyisobutene substituted succinic anhydride and polyethylene polyamine mixture (127 grams + diluent oil) at 150 ° C. for 1.5 hours to obtain a titanium modified succinimide dispersant. It may be generated.

Another titanium-containing compound may be the reaction product of a titanium alkoxide and C ₆ -C ₂₅ carboxylic acid. The reaction product has the following formula:

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

Wherein m + n = 4, n is in the range of 1 to 3, R ₄ is an alkyl moiety having a carbon atom in the range of 1 to 8, and R ₁ is about 6 to 25 carbons. Selected from hydrocarbyl groups containing atoms, wherein R ₂ and R ₃ are the same or different and are selected from hydrocarbyl groups containing 1 to 6 carbon atoms.) Or formula:

Wherein x ranges from 0 to 3, R ₁ is selected from hydrocarbyl groups containing about 6 to 25 carbon atoms, R ₂ and R ₃ are the same or different and are about 1 to Selected from hydrocarbyl groups containing 6 carbon atoms, R ₄ may be selected from the group consisting of H, any of C ₆ -C ₂₅ carboxylic acid moieties.

  Suitable carboxylic acids include 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, Although neodecanoic acid etc. may be mentioned, it is not limited to these.

  In one embodiment, the oil-soluble titanium compound is from 0 to 3000 ppm titanium, or from 25 to about 1500 ppm titanium, or from about 35 ppm to 500 ppm titanium, or from about 50 ppm to about 300 ppm, based on the total weight of the lubricating composition. It can be present in the lubricating oil composition in an amount that provides titanium.

Viscosity Index Improving Agent The lubricating oil composition herein may also optionally contain one or more viscosity index improving agents. 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-olefins. Mention may be made of maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrogenated alkenyl aryl conjugated copolymers, or mixtures thereof. Viscosity index improvers can include star polymers, suitable examples are described in US Pat. No. 8,999,905 B2.

  The lubricating oil compositions herein may also optionally contain one or more dispersant viscosity index improvers in addition to or instead of viscosity index improvers. Suitable viscosity index improvers are functionalized polyolefins such as ethylene-propylene copolymers functionalized with reaction products of acylating agents (such as maleic anhydride) and amines, polymethacrylates functionalized with amines. Or an esterified maleic anhydride-styrene copolymer reacted with an amine.

  The total amount of viscosity index improver and / or dispersant viscosity index improver is about 0% to about 20%, about 0.1% to about 15%, about 0.1% by weight of the lubricating oil composition. To about 13 wt%, or 0.25 wt% to about 12 wt%, or about 0.5 wt% to about 11 wt%, or about 3.0 wt% to about 10.5 wt%.

Other Optional Additives Other additives may be selected to perform one or more functions required for the lubricating fluid. In addition, one or more of the mentioned additives are multi-functional and may provide additional functionality or other functionality to the functionality defined herein.

  The lubricating oil composition according to the present disclosure may optionally include other performance additives. Other performance additives may be in addition to the additives specified in this disclosure and / or metal deactivators, viscosity index improvers, ashless TBN boosters, friction modifiers, antiwear agents, corrosion inhibitors 1 of agents, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, emulsifiers, pour point depressants, seal swell agents, and mixtures thereof It may contain more than seeds. Typically, fully formulated lubricating oils contain one or more of these performance additives.

  Suitable metal deactivators are derivatives of benzotriazole (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazole, benzimidazole, 2-alkyldithiobenzimidazole, or 2-alkyldithiobenzo Thiazoles; foam suppressors including copolymers of ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycol, polyethylene oxide, polypropylene oxide, and (ethylene oxide-propylene oxide) polymers; anhydrous Pour point depressants may be included, including maleic acid-styrene esters, polymethacrylates, polyacrylates, or polyacrylamides.

  Suitable suds suppressors include silicon compounds such as siloxane.

  Suitable pour point depressants may include polymethyl methacrylate or mixtures thereof. The pour point depressant is about 0% to about 5%, about 0.01% to about 3%, or about 0.01% to about 1% by weight, based on the total weight of the lubricating oil composition. % May be present in an amount sufficient to provide%.

  Suitable rust inhibitors may be a single compound or a mixture of compounds having the property of inhibiting the corrosion of the divalent iron metal surface. Non-limiting examples of rust inhibitors useful herein include 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, and serotic acid. Oil soluble high molecular weight organic acids and oil soluble polycarboxylic acids including dimer acids and trimer acids such as those generated from tall oil fatty acids, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long chain alpha, omega-dicarboxylic acid in the molecular weight range of about 600 to about 3000, and tetrapropenyl succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid. Alkenyl succinic acid in which the alkenyl group contains about 10 or more carbon atoms. Another useful class of acidic corrosion inhibitors are half esters of alkenyl succinic acids having from about 8 to about 24 carbon atoms in the alkenyl group and alcohols such as polyglycols. The corresponding half amides of such alkenyl succinic acids are also useful. Useful rust inhibitors are high molecular weight organic acids. In some embodiments, the engine oil lacks a rust inhibitor.

  When present, the rust inhibitor is from about 0% to about 5%, from about 0.01% to about 3%, from about 0.1% to about 0.1% by weight, based on the total weight of the lubricating oil composition. It can be used in an amount sufficient to provide 2% by weight.

  In general terms, suitable crankcase lubricants may include additive components within the ranges listed in the table below.

  The percentages of each component above represent the weight percent of each component, based on the total weight of the lubricating oil composition. The balance of the lubricating oil composition consists of one or more base oils.

  The additives used in formulating the compositions described herein can be blended into the base oil individually or in various partial combinations. However, it may be preferable to blend all of the ingredients simultaneously using an additive concentrate (ie, an additive plus a diluent such as a hydrocarbon solvent). The additives used in formulating the compositions described herein can be blended into the base oil individually or in various partial combinations. However, it may be preferable to blend all of the ingredients simultaneously using an additive concentrate (ie, an additive plus a diluent such as a hydrocarbon solvent).

  The present disclosure provides a novel lubricating oil blend specifically formulated for use as an automotive engine lubricant. Embodiments of the present disclosure may provide a lubricating oil suitable for engine applications, the lubricating oil having the following characteristics: antioxidant, anti-wear performance, rust control, fuel economy, water resistance, aeration, sealing Provides one or more improvements in protection and turbocharger deposit reduction, ie, resistance to elevated TCO temperature.

  Fully formulated lubricants conventionally contain an additive package referred to herein as a dispersant / inhibitor package or DI package that provides the properties required in the formulation. Suitable DI packages are described, for example, in US Pat. Nos. 5,204,012 and 6,034,040. Among the types of additives included in the additive package are dispersants, seal swelling agents, antioxidants, foam inhibitors, lubricants, rust inhibitors, corrosion inhibitors, demulsifiers, viscosity index improvers, etc. possible. Some of these ingredients are well known to those skilled in the art and are generally used in conventional amounts with the additives and compositions described herein.

  The following examples are illustrative, but not limiting, of the methods and compositions of the present disclosure. Other suitable modifications and adaptations of the various conditions and parameters normally encountered in the art will be apparent to those skilled in the art and are within the scope of this disclosure.

  Fully formulated lubricating oil compositions containing additives were made and tested to determine their impact on turbocharger deposit formation by determining TCO temperature rise in boosted internal combustion engines. . The increased TCO temperature provides an indication that turbocharger deposits in the engine are creating an adiabatic effect. Therefore, an increase in the TCO temperature of the boosted internal combustion engine turbocharger indicates an increase in the amount of turbocharger deposits.

  Each of the lubricating oil compositions contains a major amount of base oil, a DI package, and one or more viscosity index improvers, the DI package (less viscosity index improver) being about 8 of the lubricating oil composition. ˜16 weight percent was provided. The DI package contained conventional amounts of dispersants, antiwear additives, antifoam agents, and antioxidants as described in Table 3 below. Specifically, the DI package comprises a succinimide dispersant, a boronated succinimide dispersant, a molybdenum-containing compound, a friction modifier, one or more antioxidants, and one or more antiwear agents (unless otherwise specified). ). From about 4 to about 10% by weight of one or more viscosity index improvers were included in each tested lubricating oil composition. Base oil was used as a diluent oil for the viscosity index improver. Modified ingredients are identified in the tables and discussion of the examples provided below. All of the values listed in Table 3 are stated as weight percentages of ingredients based on the total weight of the lubricating oil composition (ie, active ingredient plus diluent oil, if any), unless otherwise specified. .

Turbocharger coking test The turbocharger coking test is a 2012 1 with 3 liters of test oil charge and qualified test fuel using the 2015 version of the General Motors dexos1® turbocharger coking test (TC test). Performed using a 4L Chevy Cruze calibration engine.

  The TCO temperature was measured every 30 seconds. “100 cycle TCO temperature” is the average TCO temperature from cycle 1 to cycle 100 of the TC test. The “1800 cycle TCO temperature” is the average TCO temperature from cycle 1701 to cycle 1800 of the TC test. The test is considered acceptable if the TCO temperature rise from 100 cycle TCO temperature to 1800 cycle TCO temperature is less than 9.0%.

Invention A-Comparative Examples C-1 and C-2 and Examples I-1 and I-2 of the Invention
In the examples below, the amount of total metal and nitrogen, boron and molybdenum amounts from one or more metal-containing detergents in various ratios to TCO temperature and NOACK volatility (ASTM D-5800 at 250 ° C.). The impact was determined. The amounts of nitrogen, boron and molybdenum were determined by ICP analysis.

  Four samples (each containing a base oil with a lubricating viscosity of greater than 50% by weight) were tested and each was formulated to have a rating of 0W-20.

  Comparative Examples C-1 and C-2 are not commercially available fluids, but demonstrate the technical problems experienced by those skilled in the art when the lubricating oil composition is modified to meet performance needs. Designed.

  In Table 4, Formulations C-1, C-2, I-1, and I-2 are between the total metal: nitrogen weight ratio (“total metal: nitrogen ratio”) from the detergent and the TCO temperature rise. The relationship is demonstrated. As in Comparative Examples C-1 and C-2, when the total metal: nitrogen ratio was outside the range of less than 1.9, the lubricating oil composition failed the TC test, i.e., increased TCO temperature. It was 9.0% or more. On the other hand, each of the lubricating oil compositions of Examples I-1 and I-2 of the present invention having an all metal: nitrogen ratio in the range of less than 1.9 passed the TC test, ie, the TCO temperature rise was 9 Less than 0.0%. Thus, Examples I-1 and I-2 of the present invention showed improved resistance to turbocharger deposit formation in boosted engines.

  In Table 4, Formulations C-1, C-2, I-1 and I-2 are between the total metal: boron weight ratio (“total metal: boron ratio”) from the detergent and the TCO temperature rise. Demonstrate the relationship. As in Comparative Examples C-1 and C-2, when the total metal: boron ratio was outside the range of less than 7.5, the lubricating oil composition failed the TC test, i.e., increased TCO temperature. It was 9.0% or more. On the other hand, each of the lubricating oil compositions of Examples I-1 and I-2 of the present invention having a total metal: boron ratio in the range of less than 7.5 passed the TC test, ie, the TCO temperature rise was 9 Less than 0.0%. Thus, Examples I-1 and I-2 of the present invention showed improved resistance to turbocharger deposit formation in boosted engines.

  In Table 4, Formulations C-1, C-2, I-1 and I-2 are between the total metal: molybdenum weight ratio from detergent (“total metal: molybdenum ratio”) and the TCO temperature rise. Demonstrate the relationship. As in Comparative Examples C-1 and C-2, when the total metal: molybdenum ratio was outside the range of less than 23.8, the lubricating oil composition failed the TC test, i.e., increased TCO temperature. It was 9.0% or more. On the other hand, each of the lubricating oil compositions of Examples I-1 and I-2 of the present invention having an all metal: molybdenum ratio in the range of less than 23.8 passed the TC test, ie, the TCO temperature rise was 9 Less than 0.0%. Thus, Examples I-1 and I-2 of the present invention showed improved resistance to turbocharger deposit formation in boosted engines.

  In Table 4, Formulations C-1, C-2, I-1 and I-2 demonstrate the relationship between base oil type and NOACK volatility. When Group III base oil is used alone, as in Comparative Examples C-1 and C-2, the NOACK volatility is outside the range of less than 11.0% by weight. On the other hand, each of the lubricating oil compositions of Examples I-1 and I-2 of the present invention having a combination of Group II and Group III base oils provided NOACK volatility of less than 11.0% by weight. Thus, Examples I-1 and I-2 of the present invention showed an improvement in NOACK volatility.

Invention B-Comparative Examples C-3 to C-5 and Inventive Examples I-3 to I-7
In the following examples, the influence of several parameters on the TCO temperature rise was determined. Eight samples were tested, each containing a base oil of lubricating viscosity greater than 50% by weight and the compounds and elements listed in Table 5 below. All 8 samples were formulated to have a rating of 5W-30.

  In Table 5, Formulations C-3, I-3, I-4, I-5, I-6, and I-7 demonstrate the relationship between the amount of organomolybdenum nitrogen complex and the TCO temperature increase. According to one aspect of the present invention, the lubricating oil comprises one or more molybdenum-containing compounds in an amount sufficient to provide the lubricating oil composition with greater than about 40 ppm by weight of molybdenum, based on the total weight of the lubricating composition. Present in the composition. If the amount was outside the range of molybdenum above about 40 ppm by weight, as in Comparative Example C-3, the lubricating oil composition failed the TC test, ie, the TCO temperature increase was greater than 9.0% Met. On the other hand, each of the lubricating oil compositions of Examples I-3, I-4, I-5, I-6, and I-7 of the present invention having molybdenum in the range of greater than about 40 ppm by weight from the molybdenum-containing compound. Passed the TC test, ie the TCO temperature rise was less than 9.0%. Thus, Examples I-3, I-4, I-5, I-6, and I-7 of the present invention showed improved resistance to turbocharger deposit formation in boosted engines.

  In Table 5, Formulations C-3, C-4, I-3, I-4, I-5, I-6 and I-7 represent the presence of magnesium-containing detergent in the lubricating oil composition and the TCO temperature. Demonstrates the relationship with the rise. According to one aspect of the present invention, the lubricating oil composition has a magnesium-containing detergent. As in Comparative Example C-3, when the lubricating oil composition did not have a magnesium-containing detergent, the lubricating oil composition failed the TC test, that is, the TCO temperature increase was 9.0% or more. It was. On the other hand, each of the lubricating oil compositions of Examples I-3, I-4, I-5, I-6, and I-7 of the present invention having a magnesium-containing detergent passed the TC test, The TCO temperature rise was less than 9.0%. Thus, Examples I-3, I-4, I-5, I-6, and I-7 of the present invention showed improved resistance to turbocharger deposit formation in boosted engines.

  In Table 5, Formulations C-3, I-3, I-4, I-5, I-6, and I-7 show the relationship between the amount of one or more overbased calcium detergents and the TCO temperature increase. Has been demonstrated. In accordance with one aspect of the present invention, one or more overbased calcium-containing cleanings in an amount sufficient to provide the lubricating oil composition with less than about 1800 ppm by weight of calcium, based on the total weight of the lubricating composition. An agent is present in the lubricating oil composition. As in Comparative Example C-3, when the amount was outside the range of calcium less than about 1800 ppm by weight, the lubricating oil composition failed the TC test, i.e., the TCO temperature rise was greater than 9.0% Met. On the other hand, each of the lubricating oil compositions of Examples I-3, I-4, I-5, I-6, and I-7 of the present invention formulated within a range of calcium less than about 1800 ppm by weight The TC test was passed, i.e. the TCO temperature rise was less than 9.0%. Thus, Examples I-3, I-4, I-5, I-6, and I-7 of the present invention showed improved resistance to turbocharger deposit formation in boosted engines.

  In Table 5, Formulations C-3, C-4, C-5, I-3, I-4, I-5, I-6, and I-7 are in ppm by weight in the lubricating oil composition. It demonstrates the relationship between the ratio of total boron to total nitrogen and TCO temperature rise. According to one aspect of the invention, the lubricating oil composition can have a ratio of total boron in weight ppm to total nitrogen in weight ppm of less than about 0.29. The lubricating oil composition does not have a ratio of total boron in weight ppm to total nitrogen in weight ppm, which may be less than about 0.29, as in Comparative Examples C-3, C-4, and C-5 The lubricating oil composition failed the TC test, i.e., the TCO temperature rise was greater than 9.0%. On the other hand, each of the lubricating oil compositions of Examples I-3, I-4, I-5, I-6, and I-7 of the present invention has total nitrogen at weight ppm that can be less than about 0.29. The lubricating oil composition passed the TC test, i.e., the TCO temperature rise was less than 9.0%. Thus, Examples I-3, I-4, I-5, I-6, and I-7 of the present invention showed improved resistance to turbocharger deposit formation in boosted engines.

  In Table 5, Formulations C-3, C-4, C-5, I-3, I-4, I-5, I-6 and I-7 are all in weight ppm in the lubricating oil composition. It demonstrates the relationship between the ratio of calcium to total nitrogen and TCO temperature rise. According to one aspect of the invention, the lubricating oil composition has a ratio of total calcium in weight ppm to total boron in weight ppm that can be greater than about 4.9 and less than about 9.7. The lubricating oil composition has a total weight in ppm relative to total boron in weight ppm that can be greater than about 4.9 and less than about 9.7, as in Comparative Examples C-3, C-4, and C-5. Without the calcium ratio, the lubricating oil composition failed the TC test, i.e., the TCO temperature rise was greater than 9.0%. On the other hand, each of the lubricating oil compositions of Examples I-3, I-4, I-5, I-6, and I-7 of the present invention can be greater than about 4.9 and less than about 9.7. Having a ratio of total calcium at weight ppm to total boron at weight ppm, the lubricating oil composition passed the TC test, ie, the TCO temperature rise was less than 9.0%. Thus, Examples I-3, I-4, I-5, I-6, and I-7 of the present invention showed improved resistance to turbocharger deposit formation in boosted engines.

  At numerous places throughout this specification, reference is made to a number of US patents and other references. All such cited references are fully expressly incorporated into this disclosure as if fully set forth herein and for the specific purpose for which they are cited.

  Other embodiments of the disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the embodiments disclosed herein. As used throughout this specification and the claims, “a” and / or “an” may refer to one or more. Unless otherwise indicated, all numbers representing characteristics, percentages, ratios, reaction conditions, etc. of the amount of raw material, molecular weight, etc. used in the specification and claims are present in the term “about”. In all cases, whether or not, should be understood as being modified by the term “about”. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and claims are approximations that may vary depending on the desired properties sought to be obtained by the present disclosure. While not attempting to limit the application of the minimal and equivalent doctrine to the claims, each numerical parameter is at least in light of the number of significant digits reported and the usual rounding Should be interpreted by applying technology. Although the numerical ranges and parameters describing the broad scope of this disclosure are approximate, the numerical values set forth in the specific examples are reported as accurately as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. It is intended that the specification and examples be illustrative only and that the true scope of the disclosure be considered as indicated by the following claims.

  The aforementioned embodiments are actually subject to significant fluctuations. Accordingly, the embodiments are not intended to be limited to the specific illustrations described hereinabove. Rather, the above-described embodiments are within the scope of the appended claims, including their legally available equivalents.

  The patent owner does not intend to abandon any disclosed embodiments to the public, and to the extent that any disclosed modifications or changes cannot be documented within the scope of the claims. Are considered part of this specification, under an equivalent doctrine.

  Each component, compound, substituent, or parameter disclosed herein is independent or one of each and every other component, compound, substituent, or parameter disclosed herein. It should be construed as being disclosed for use in combination with one or more.

  Also, each amount / value or range of amounts / values for each component, compound, substituent, or parameter disclosed herein is the same as any other component, compound, substitution, etc. disclosed herein. It should also be construed as being disclosed in combination with each amount / value or range of amounts / values of groups or parameters, and more than one of the components, compounds, substitutions disclosed herein. It should be understood that any combination of amounts / values or ranges of amounts / values for groups, or parameters, is therefore also disclosed in combination with each other for purposes herein.

  It is further understood that each range disclosed herein is to be interpreted as a disclosure of each specific value within the disclosed range having the same significant digit. Therefore, the range of 1-4 should be construed as a clear disclosure of the values 1, 2, 3, and 4.

  Each lower limit of each range disclosed herein is disclosed in combination with each upper limit and each specific value within each range disclosed herein for the same component, compound, substituent, or parameter. It is further understood that it should be construed as being. Therefore, the present disclosure provides for the combination of each lower limit value of each range with each upper limit value of each range, or each specific value within each range, or each upper limit value of each range with each specific value within each range. Should be construed as disclosure of the full range derived from the combination.

  Furthermore, specific amounts / values of ingredients, compounds, substituents, or parameters disclosed in this specification or examples are to be construed as disclosure of either the lower or upper limit of the range. Any other upper or lower limit of a range for the same component, compound, substituent, or parameter disclosed elsewhere in this application, or that component, compound, substitution, in combination with a specified amount / value Ranges for groups or parameters can be formed.

Claims (22)

A lubricating oil composition comprising a base oil having a lubricating viscosity of greater than 50% by weight and one or more metal-containing detergents,
The ratio of total metal in ppm from the one or more metal-containing detergents in the lubricating oil composition to total nitrogen in ppm in the lubricating oil composition is less than 1.9;
The ratio of total metal in ppm from the one or more metal-containing detergents in the lubricating oil composition to total boron in ppm in the lubricating oil composition is less than 7.5;
The ratio of total metal in ppm from the one or more metal-containing detergents in the lubricating oil composition to total molybdenum in ppm in the lubricating oil composition is less than 23.8;
The lubricating oil composition has a NOACK volatility of less than 11.0% by weight as measured by the ASTM D-5800 method at 250 ° C. and the lubricating oil composition is a General Motors dexos1® turbocharger. A lubricating oil composition that is effective to ensure a TCO temperature rise of less than 9.0% as measured using the 2015 edition of the coking test.   The ratio of total metals in ppm from the one or more metal-containing detergents in the lubricating oil composition to the total nitrogen in ppm in the lubricating oil composition is less than 1.8. Item 4. The lubricating oil composition according to Item 1.   The ratio of total metals in ppm from the one or more metal-containing detergents in the lubricating oil composition to total boron in ppm in the lubricating oil composition is less than 7.3. Item 4. The lubricating oil composition according to Item 1.   The ratio of total metals in ppm from the one or more metal-containing detergents in the lubricating oil composition to total molybdenum in ppm in the lubricating oil composition is less than 20.0. Item 4. The lubricating oil composition according to Item 1.   The lubricating oil composition of claim 1, wherein the lubricating oil composition has a NOACK volatility of at least 2.0 wt% and less than 11.0 wt%, as measured by ASTM D-5800 method at 250 ° C.   The lubricating oil composition is effective to ensure a TCO temperature rise of less than 8.0% as measured using the 2015 edition of the General Motors dexos1® turbocharger coking test. The lubricating oil composition described.   The lubricating oil composition of claim 1, wherein the lubricating oil composition has a rating of 0W-20. A method for reducing or preventing deposit formation in a boosted internal combustion engine comprising:
Lubricating the boosted internal combustion engine with the lubricating oil composition of claim 1;
Operating the engine lubricated with the lubricating oil composition.   9. The lubricating oil composition is effective to ensure a TCO temperature rise of less than 9.0% as measured using the 2015 edition of the General Motors dexos1® turbocharger coking test. The method described. A lubricating oil composition comprising:
A base oil having a lubricating viscosity of more than 50% by weight;
One or more boronated compounds;
One or more molybdenum-containing compounds in an amount sufficient to provide greater than about 40 ppm by weight of molybdenum to the lubricating oil composition, based on the total weight of the lubricating oil composition;
One or more magnesium-containing detergents;
One or more overbased calcium-containing detergents in an amount sufficient to provide less than about 1800 ppm by weight of calcium to the lubricating oil composition, based on the total weight of the lubricating oil composition. Lubricating oil composition.   11. The one or more molybdenum-containing compounds are present in an amount sufficient to provide the lubricating oil composition with at least about 50 ppm by weight of molybdenum, based on the total weight of the lubricating oil composition. The lubricating oil composition described in 1.   11. The one or more calcium-containing overbased detergents are selected from overbased calcium sulfonate detergents, overbased calcium phenate detergents, and overbased calcium salicylate detergents. The lubricating oil composition described.   The one or more magnesium-containing detergents are overbased, and the one or more overbased calcium-containing detergents and the one or more overbased magnesium-containing detergents are each a method of ASTM D-2896. The lubricating oil composition of claim 10, having a total base number greater than 225 mg KOH / g as measured by   The lubricating oil composition of claim 10, wherein the one or more overbased magnesium-containing detergent is an overbased magnesium sulfonate.   The lubrication of claim 10, wherein the one or more magnesium-containing compounds is an amount sufficient to provide 20 to 1800 ppm of magnesium to the lubricating oil composition, based on the total weight of the lubricating composition. Oil composition.   The lubricating oil composition of claim 10, wherein the ratio of total boron in ppm in the lubricating oil composition to total nitrogen in ppm in the lubricating oil composition is less than about 0.29.   The lubrication of claim 10, wherein the ratio of total calcium in ppm in the lubricating oil composition to total boron in ppm in the lubricating oil composition is greater than about 4.9 and less than about 9.7. Oil composition.   From the one or more overbased calcium-containing detergents and the one or more overbased calcium-containing detergents based on the total weight of calcium and magnesium from the one or more overbased magnesium-containing detergents. The lubricating oil composition according to claim 10, wherein the calcium weight percent of said is greater than 50 wt%.   11. The lubricating oil composition is effective to ensure a TCO temperature increase of less than 9.0% as measured using the 2015 edition of the General Motors dexos1® turbocharger coking test. The lubricating oil composition described.   The lubricating oil composition of claim 10, wherein the lubricating oil composition has a rating of 5W-30. A method for reducing or preventing deposit formation in a boosted internal combustion engine comprising:
Lubricating the boosted internal combustion engine with the lubricating oil composition of claim 8;
Operating the engine lubricated with the lubricating oil composition.   23. The lubricating oil composition is effective to ensure a TCO temperature rise of less than 9.0% as measured using the 2015 edition of the General Motors dexos1® turbocharger coking test. The method described.