JP6682004B2 - Lubricants for use in boosted engines - Google Patents

Description

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

  Turbocharged or supercharged engines (ie boost or forced induction internal combustion engines) experience very high operating temperatures. Lubricants used in these engines are exposed to extreme conditions when the engine is stopped and the lubricant remains in the high temperature turbocharger as it cools. Lubricants in this environment tend to form hard deposits in the turbocharger. This phenomenon can cause a significant reduction in turbocharger efficiency and can result in poor performance and / or severe damage to the engine.

  Some published studies may contribute to the use of turbochargers, engine design, engine coatings, piston geometry, fuel selection, and / or the formation of these deposits in engines turbocharged with engine oil additives. I have proved 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 (R) specification, require a turbocharger coking test to pass. One parameter that determines the passing result in the General Motors dexos1® turbocharger coking test is the percentage of less than 13% rise in turbo coolant external (TCO) temperature from 100 cycle TCO temperature to 1800 cycle TCO temperature. To keep rising.

  In order to provide a lubricating oil composition capable of recording a pass rating of less than 9.0% rise in turbo-coolant external (TCO) temperature from 100 cycle TCO temperature to 1800 cycle TCO temperature, General Motors dexos1® is provided. There is a need for improvements to the mere passing of the 2015 version of the Turbocharger Caulking Test. As used herein, "TCO temperature rise" refers to the percentage increase in TCO temperature from 100 cycle TCO temperature to 1800 cycle TCO temperature, as defined by the formula below.

SUMMARY AND TERMS The present disclosure relates to a first lubricating oil composition, and a method of operating an internal combustion engine boosted with the first lubricating oil composition (hereinafter referred to as invention A), and a second lubricating composition. A method of operating an internal combustion engine 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. The ratio of total metals 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. Ratio of total metals in ppm from total molybdenum to one or more metal-containing detergents in the lubricating oil composition of less than 23.8. The lubricating oil composition also has a NOACK volatility of less than 11.0 wt% as measured by the method of ASTM D-5800 at 250 ° C. and the lubricating oil composition has a General Motors dexos 1® turbocharger. It is effective in ensuring a TCO temperature rise of less than 9.0% measured using the 2015 version of the Caulking 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 comprises 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 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. The ratio of total metals 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. Ratio of total metals in ppm from total molybdenum to one or more metal-containing detergents in the lubricating oil composition of less than 23.8. The lubricating oil composition also has a NOACK volatility of less than 11.0 wt% as measured by the method of ASTM D-5800 at 250 ° C. By lubricating a boosted internal combustion engine with this lubricating oil composition, a TCO temperature rise 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 metals 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 1.8. It can be, or can be from 0.1 to less than 1.9, or from 0.1 to less than 1.8, or from 0.1 to 1.7.

  In each of the foregoing embodiments, the ratio of total metals 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 can be 0.1 or more and less than 7.5, or 0.1 or more and less than 7.3, or 0.1 to 7.0.

  In each of the foregoing embodiments, 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, 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 comprises 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. %, Or may have a NOACK volatility of 5.0% to 10.9% by weight.

  In each of the foregoing embodiments, the lubricating oil composition has less than 8.0%, or less than 7.0%, or 0, measured using the 2015 version of the General Motors dexos1® turbocharger coking test. 0.01% or more and less than 9.0%, 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% TCO temperature increase. Can be effective in securing.

Invention B
In one embodiment of Invention B, the lubricating oil composition comprises a base oil having a lubricating viscosity of greater than 50 wt% 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 molybdenum, based on the total weight of the lubricating composition. The lubricating oil composition also includes one or more magnesium-containing detergents. The lubricating oil composition also includes one or more calcium-based overbased 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 comprises lubricating a boosted internal combustion engine with a lubricating oil composition comprising a base oil having a lubricating viscosity of greater than 50 wt% and one or more borated compounds. The lubricating oil composition comprises one or more molybdenum-containing compounds in an amount sufficient to provide greater than about 40 ppm by weight molybdenum to the lubricating oil composition, based on the total weight of the lubricating composition. The lubricating oil composition also includes one or more magnesium-containing detergents. The lubricating oil composition also includes one or more calcium-based overbased 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 a boosted internal combustion engine with this lubricating oil composition, a TCO temperature rise 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 comprises at least about 50 ppm by weight molybdenum in the lubricating oil composition, or at least about 80 ppm by weight, or at least 40 ppm by weight, 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 1200 ppm by weight of ppm by weight or greater than 40 ppm by weight and less than 900 ppm by weight of ppm, or at least about 80 ppm by weight to 800 ppm by weight of 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 calcium-based overbased detergents comprises from about 1000 to about 1750 ppm by weight, or from 1100 to 1700 ppm by weight of calcium lubricating oil, based on the total weight of the lubricating oil composition. The composition may be provided.

  In each of the foregoing embodiments, the one or more magnesium-containing detergents may be overbased, and the one or more overbased calcium-containing detergents and the one or more overbased magnesium-containing detergents, respectively, A total base number (TBN) of greater than 225 mg KOH / g measured by the method of ASTM D-2896, or a TBN of about 250 mg KOH / gram or greater measured by the method of ASTM D-2896, or a TBN of about 300 mg KOH / gram or greater; 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 225 mg KOH / g to 425 mg KOH / gram or less TBN, or about 250 mg KOH / gram to 425 mg KOH / Grams of 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. It may have a TBN.

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

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

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

  In each of the foregoing embodiments, the one or more borated compounds comprises greater than 50 ppm boron in the lubricating oil composition, or greater than 100 ppm boron, greater than 50 ppm and less than 1000 ppm boron, or greater 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 less than 8.0% as measured using the 2015 version of the General Motors dexos1® turbocharger coking test. Effective to secure a TCO temperature rise of less than 5%, 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 otherwise stated.

  In each of the foregoing embodiments, the lubricating oil composition may also optionally contain one or more low basic / neutral detergents, the low basic / neutral detergents according to ASTM D-2896. Having a TBN of at most 175 mg KOH / g, or at most 150 mg KOH / g as measured by. 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 calcium sulfonate detergents, calcium phenate detergents, calcium salicylate detergents, or mixtures thereof. In each of the foregoing embodiments, the low basic / neutral detergent can be a calcium sulfonate detergent or a calcium phenate detergent. In some cases, "overbased" may be abbreviated as "OB" and in some cases "low basic / neutral" may be abbreviated as "LB / N".

  In each of the foregoing embodiments, the low base / neutral detergent may include 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%, Or it may comprise 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 about 10 to about 1000 ppm by weight calcium to the lubricating oil composition, based on the total weight of the lubricating oil composition. You can In each of the foregoing embodiments, the one or more low basic / neutral calcium-containing detergents comprises 25 to less than 800 ppm by weight, or 50 to 600 ppm by weight, or 100 ppm by weight based on the total weight of the lubricating oil composition. ˜500 ppm by weight of calcium may be provided in 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 at least 6.0 mg KOH / g of the lubricating oil composition measured by the method of ASTM D-2896, or the method of ASTM D-2896. It can be from 6.4 to 12.0 mgKOH / g of the lubricating oil composition or from 6.5 to 12.0 mgKOH / 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 1.0-10% 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 1.0-8.5 wt%, based on the total weight of the lubricating oil composition.

  In each of the foregoing embodiments, the lubricating oil composition is 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, all based on the total weight of the lubricating oil composition. It may 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 of metal in the lubricating oil composition, or about 1100 to about 3000 ppm of metal, or about 1150. To about 2500 ppm metal, or about 1200 to about 2400 ppm metal, or less than 1800 ppm metal may be present in an amount to provide the lubricating oil composition.

  In each of the foregoing embodiments, the lubricating oil may further comprise 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, which base oil is 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, which may be selected from the group consisting of more than 50% by weight, may be other than the diluent oil resulting from the provision of additive components or viscosity index improvers to the composition. In each of the foregoing embodiments, the lubricating oil composition comprises greater than 50 wt% Group II base oil, Group III base oil, or combinations thereof, or greater than 70 wt%, or greater than 75 wt%, Or greater than 80 wt%, or greater than 85 wt%, or greater than 90 wt% Group II base oil, Group III base oil, or combinations thereof, or greater than 97 wt% Group II base oil and III. It may include a combination with a group of base oils.

  In each of the foregoing embodiments of the method, the step of lubricating comprises a turbocharger or supercharger component and a spark ignition direct injection engine or spark ignition port fuel injection internal combustion engine combustion chamber or cylinder wall 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 the overbased calcium salicylate detergent.

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

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

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

  "Oil composition", "lubricating composition", "lubricating oil composition", "lubricating oil", "lubricant composition", "lubricating composition", "completely blended lubricant" The terms "composition," "lubricant," "crankcase oil," "crankcase lubricant," "engine oil," "engine lubricant," "motor oil," and "motor lubricant" refer to 50 weight parts. It is considered to be synonymous, fully compatible terminology, which refers to the final lubrication product containing greater than% base oil plus minor amounts of the additive composition.

  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" refer to a portion of a lubricating oil composition excluding more than 50% by weight base oil stock mixture. Are considered to be synonymous, fully compatible 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 the metal salts of sulfonates, carboxylates, salicylates, and / or phenates, the amount of metal present being in excess of the stoichiometric amount. Such salts may have conversion levels in excess of 100% (ie, they are 100 the theoretical amount of metal required to convert the acid to its "normal", "neutral" salt. % Can be included). The expression "metal ratio", often abbreviated MR, refers to the ratio of the total chemical equivalent of a metal in an overbased salt to the chemical equivalent of a metal in a neutral salt according to known chemical reactivity and stoichiometry. Used for. In normal or neutral salts, the metal ratio is 1, and in overbased salts, the MR is greater than 1. They are commonly referred to as overbased salts, overbased salts, or overbased 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 may 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 of 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 meaning well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and 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 Groups, as well as cyclic substituents 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 radicals that do not predominantly alter the hydrocarbon substituents in the context of the present disclosure, such as halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, Nitro, nitroso, amino, alkylamino, and sulfoxy) -containing substituents, and (c) hetero-substituents, ie, having predominantly hydrocarbon character, while in the context of the present disclosure otherwise at a carbon atom. Substituents containing other than carbon in the constituted ring or chain are included. Heteroatoms include sulfur, oxygen, and nitrogen and may encompass substituents such as pyridyl, furyl, thienyl, and imidazolyl. Generally, for every 10 carbon atoms in the hydrocarbyl group, there will be no more than two, eg, no more than one, non-hydrocarbon substituents, and typically there will be no non-hydrocarbon substituents in the hydrocarbyl group. do not do.

  As used herein, unless otherwise stated, the term "weight percent" refers to the percentage of the described ingredients that represents the weight of the total composition. Also, all values reported using "ppm" herein refer to ppm by weight of the total weight of the lubricating oil composition, unless expressly stated otherwise.

  As used herein, the term "soluble," "oil soluble," or "dispersible" means that the compound or additive is soluble, soluble, miscible, or suspended in the oil in all proportions. It may, but not necessarily, be shown to be turbid. However, the above terms are used to the extent that they are soluble, suspendable, soluble, or stable in oils, such as in oils, to the extent that they exert their intended effect. Means dispersible. Furthermore, the additional incorporation of other additives may also allow higher levels of the incorporation of particular additives if desired.

  The transitional phrase "consisting essentially of" as used herein substantially affects the scope of the embodiments of the invention to a particular material or process and to the basic and novel features of the invention. Limit to those that do not. As used herein, the basic and novel feature 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 describe the total base number at mgKOH / g composition as measured by the method of ASTM D-2896.

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

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

  As used herein, the term "aryl" refers to alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy, halo, and / or nitrogen, oxygen substituents. And mono- and polycyclic aromatic compounds that may include heteroatoms, including, but not limited to, and sulfur.

  The lubricants, combinations of components, or individual components herein may be suitable for use in various types of internal combustion engines. Suitable engine types may include, but are not limited to, large diesel vehicles, passenger vehicles, small diesel vehicles, medium speed diesel vehicles, marine engines, or motorcycle engines. Internal combustion engine includes diesel fuel engine, gasoline fuel engine, natural gas fuel engine, biofuel engine, mixed diesel / biofuel engine, mixed gasoline / biofuel 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 can be a compression ignition engine. The diesel engine can be a compression ignition engine with spark ignition assist. The gasoline engine may 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 commonly 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 car and truck engines.

  Internal combustion engines may contain components of one or more of aluminum alloys, lead, tin, copper, cast iron, magnesium, ceramics, stainless steel, composites 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. Aluminum alloys may include aluminum silicate, aluminum oxide, or other ceramic materials. In one embodiment, the aluminum alloy is an aluminum silicate surface. As used herein, the term "aluminum alloy" is synonymous with "aluminum composite material" and regardless of its detailed structure, aluminum and other materials mixed or reacted at the microscopic or near microscopic level. It is intended to describe components or surfaces that include the components of. This includes any conventional alloy with metals other than aluminum, as well as composite materials or alloy-like structures with 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 sulphated ash (ASTM D-874) content. The engine oil lubricant has a sulfur content of 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%. Can be: In one embodiment, the sulfur content can be in the range of about 0.001 wt% to about 0.5 wt%, or about 0.01 wt% to about 0.3 wt%. The phosphorus content is about 0.2 wt% or less, or about 0.1 wt% or less, or about 0.085 wt% or less, or about 0.08 wt% or less, or about 0.06 wt% 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 about 50 ppm to about 1000 ppm or 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%. It can be up to 0.5% by weight. In one embodiment, the sulphated ash content may be from about 0.05% to about 0.9% by weight, or about 0.1% or about 0.2% to about 0.45% by weight. 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 sulphated ash content is about 1 wt% or less. In yet another embodiment, the sulfur content may be about 0.3 wt% or less, the phosphorus content may be about 0.05 wt% or less, and the sulphated ash content may be about 0.8 wt% or less. ASTM D4951 is a test method that can cover eight elements and 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 used oil screen for signs of wear.

  In some embodiments, the total TBN of the lubricating oil composition is at least 6.0 mg KOH / g measured by the method of ASTM D-2896, or 6.4-12.m 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, (ii) a phosphorus content of about 0.1 wt% or less. And (iii) a sulfated ash content of less than or equal to about 1.5% by weight.

  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 are 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 Dexos (TM) 1, Dexos (TM) 2, MB-Approval229.51 / 229.31, 229.71, 229.3 / 229.5, VW502.00, 503.00 / 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-M2C153-H, WSS-A2C, WSS-A2C, WSS-A2C9W. Third party proprietary 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 hydraulic fluid for tractor; power transmission fluid (including automatic transmission fluid, continuously variable transmission fluid, and manual transmission fluid); hydraulic fluid (including hydraulic fluid for tractor) ); Some gear oils; power steering fluids; fluids used in wind turbines, compressors; some industrial fluids; as well as a variety of fluids related to components of powertrains, including but not limited to It is a term that covers fluids. For example, in each of these fluids, such as automatic transmission fluids, the existence of different types of fluids because different transmissions have different designs that have created a need for fluids of significantly different functional characteristics. Please note. This is contrasted by the term "lubricating fluid" which is not used to generate or transfer power.

  For example, with respect to tractor hydraulic fluids, these fluids are versatile products used for all lubricant applications within the tractor other than engine lubrication. These lubrication applications may include lubrication of gearboxes, power takeoffs and clutches, rear axles, reduction gears, wet brakes, and hydraulic fluid accessories.

  If the functional fluid is an automatic transmission fluid, then the automatic transmission fluid must have sufficient friction for the clutch plates to transmit power. However, the coefficient of friction of a fluid tends to decrease under the influence of temperature as the fluid heats up during operation. It is important for tractor hydraulic fluids or automatic transmission fluids to maintain their high coefficient of friction at high temperatures, otherwise braking systems or automatic transmissions 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 transmissions, differentials, final drive planetary gears, wet brakes, 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 components in hydraulic pumps. Detergents and dispersants used for gasoline or diesel engine performance can be detrimental to wet brake performance. Friction modifiers that are characteristic of quiet wet brake noise may lack the thermal stability required for engine oil performance. Each of these fluids, whether functional, tractor, or lubricious, is designed to meet specific stringent manufacturer requirements.

  The present disclosure provides novel lubricating oil blends formulated for use as automotive crankcase lubricants. Embodiments of the present disclosure are suitable for crankcase applications and have the following attributes: aeration, alcohol fuel compatibility, antioxidant performance, antiwear performance, biofuel compatibility, foam reduction properties, friction reduction, fuel economy. A lubricating oil may be provided that has improved properties, anti-preignition, rust control, sludge and / or soot 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 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 disclosure may be set forth in part in the description below and / or may be understood by practice of the disclosure. Additional details and advantages of the disclosure can be realized and achieved by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are merely exemplary and explanatory and are not limiting 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 engines of the present disclosure include 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 can 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, a lubricating oil composition surprisingly includes a boosted internal combustion engine that includes carbonaceous deposits in the components of a turbocharger or supercharger lubricated with the lubricating oil composition. Can be used to reduce or prevent the formation of carbonaceous deposits in. Since 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 deposits, the greater the temperature rise outside the turbocharger coolant (TCO temperature) during engine use. 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 version 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 comprises 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 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 the one or more metal-containing detergents of less than 1.9 and total boron in ppm in the lubricating oil composition The ratio of total metals in ppm from the contained detergent is less than 7.5 and in ppm from one or more metal-containing detergents in the lubricating oil composition to total molybdenum in ppm in the lubricating oil composition Of less than 23.8 and the lubricating oil composition has a NOACK volatility of less than 11.0 wt% at 250 ° C. as measured by the method of ASTM D-5800. By lubricating a boosted internal combustion engine with this lubricating oil composition, a TCO temperature rise 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 that include turbocharger or supercharger components, as demonstrated by its ability to ensure Internal combustion engines that are boosted are operated and lubricated with a lubricating oil composition to reduce or prevent the amount of deposits in the engine, including 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 a lubricating oil composition with a base oil having a lubricating viscosity of greater than 50 wt%, one or more borated compounds, and greater than about 40 ppm by weight molybdenum, based on the total weight of the lubricating composition. Sufficient to provide one or more molybdenum-containing compounds, one or more magnesium-containing detergents, and less than about 1800 ppm by weight of calcium to the lubricating oil composition, based on the total weight of the lubricating composition. Lubricating the boosted internal combustion engine with a lubricating oil composition comprising a sufficient amount of one or more calcium-based overbased detergents. By lubricating a boosted internal combustion engine with this lubricating oil composition, a TCO temperature rise 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 Internal combustion engines that are boosted are operated and lubricated with a lubricating oil composition to reduce or prevent the amount of deposits in the engine, including 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 otherwise stated.

  In some embodiments of the method, a spark ignition direct injection engine or spark ignition port fuel injection internal combustion engine combustion chamber or cylinder wall with a turbocharger or supercharger, and a turbocharger or supercharger passage, bushing, and others. Parts are lubricated with a lubricating oil composition and the 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.

  The calcium in the lubricating oil composition can be provided by various 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 as measured by the method of ASTM D-2896, and optionally ASTM D-. 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 method of 2896.

  The lubricating oil composition contains both boron and nitrogen. One source for providing boron and / or nitrogen to lubricating oil compositions is a boron-containing dispersant. In some embodiments, the lubricating oil composition can include a dispersant, which 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 a lubricating oil. It can be in an amount of 1.0 to 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, the nitrogen present in the lubricating oil composition can be added as part of one or more of dispersants, antioxidants, and friction modifiers.

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

  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, but vegetable oils. It can also be a naturally occurring oil such as. Note that although Group III base oils are derived from mineral oils, the severe processing that these fluids undergo makes their physical properties very similar to some pure compounds such as PAO. I want to be done. As such, oils derived from Group III base oils may be referred to in the industry as synthetic fluids.

  The base oil used in the disclosed lubricating oil composition can be a mineral oil, an animal oil, a vegetable oil, a synthetic oil, or a mixture thereof. Suitable oils may be derived from hydrocracking, hydrotreating, 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. Refined oils are similar to unrefined oils, except that they have been treated in one or more refining steps that can result in one or more improved 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 similarly to 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 by 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-naphthene-mixing types. Mineral lubricating oils such as solvent-treated or acid-treated mineral lubricating oils can be mentioned, but are not limited thereto. 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 tetrahydrofurans. Synthetic oils can be produced by the 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 of greater than 50 wt% included 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, with 50% by weight being The base oil exceeded is other than the base oil resulting from the provision of the additive component or viscosity index improver in the composition. In another embodiment, greater than 50 wt% base oil included in the lubricating composition may be selected from the group consisting of Group II, Group III, Group IV, Group V, and combinations of two or more of the foregoing, 50 More than wt% base oil is other than diluent oil due to 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 100% by weight is subtracted from the sum of the amount of performance additives including viscosity index improvers and / or pour point depressants and / or other surface treatment additives. 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% by weight, or greater than about 90% by weight.

  The lubricating oil composition may include 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 include less than 5 wt% Group V base oil. 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.

Detergents The lubricating oil composition may include 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, calixareates, salixates, salicylates, carboxylic acids, phosphoric acids, monothiophosphoric and / or dithiophosphoric acids, alkylphenols, sulfur-bonded alkylphenol compounds, or methylene-bridged phenols. To be Suitable detergents and their method of preparation are described in detail in numerous patent publications, including US 7,732,390 and the references cited therein. The detergent base 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, as well as alkali metal or alkaline earth metal salts of long chain mono- or dialkylaryl sulfonic acids in which the aryl groups are 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 phosphoric acid, calcium monothiophosphoric acid and / Or dithiophosphoric acid, calcium alkylphenol, calcium sulfur-bonded alkylphenol compound, calcium methylene cross-linked phenol, magnesium phenate, magnesium sulfur-containing phenate, magnesium sulfonate, magnesium calixarate, magnesium salixarate, magnesium salicylate, magnesium carboxylic acid, Magnesium phosphoric acid, magnesium monothiophosphoric acid and / or dithiophosphoric acid, magnesium alkyl fluoride Nole, magnesium sulfur-bonded alkylphenol compound, magnesium methylene cross-linked phenol, sodium phenate, sodium sulfur-containing phenate, sodium sulfonate, sodium calixarate, sodium salixarate, sodium salicylate, sodium carboxylic acid, sodium phosphate, sodium mono Examples include, but are not limited to, thiophosphoric acid and / or dithiophosphoric acid, sodium alkylphenols, sodium sulfur-bonded alkylphenol compounds, or sodium methylene bridged phenols.

  Overbased detergents are well known in the art and can be alkali metal or alkaline earth metal overbased detergents. Such detergents can be prepared by reacting a metal oxide or hydroxide with a substrate and carbon dioxide gas. The substrate is typically 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 the metal salts of sulfonates, carboxylates, and phenates, the amount of metal present being in excess of the stoichiometric amount. Such salts may have conversion levels in excess of 100% (ie, they are 100 the theoretical amount of metal required to convert the acid to its "normal", "neutral" salt. % Can be included). The expression "metal ratio", often abbreviated MR, refers to the ratio of the total chemical equivalent of a metal in an overbased salt to the chemical equivalent of a metal in a neutral salt according to known chemical reactivity and stoichiometry. Used for. In normal or neutral salts, the metal ratio is 1, and in overbased salts, the MR is greater than 1. They are commonly referred to as overbased salts, overbased salts, or overbased salts and can be salts of organic sulfur acids, carboxylic acids, or phenols.

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

  Examples of suitable overbased detergents include overbased calcium phenate, overbased calcium sulfur-containing phenate, overbased calcium sulfonate, overbased calcium calixarate, overbased calcium salixarate, and overbased calcium salixarate. 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, overbased Basic calcium methylene cross-linked phenol, overbased magnesium phenate, overbased magnesium sulfur-containing phenate, overbased magnesium sulfonate, overbased magnesium calixarate, overbased magnesium salixarate, 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 bridged phenols.

  The overbased detergent may have a metal to substrate ratio 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 entire detergent, based on the total weight of the lubricating oil composition, is at most 10% by weight, or at most about 8% by weight, or at most about 4% by weight, or more than about 1% by weight and up to about 8% by weight. Or greater than about 1% by weight and up to about 4% by weight.

  In each of the foregoing embodiments, "total metal from one or more metal-containing detergents" may be present in an amount to provide about 100 ppm to about 3500 ppm of metal in 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 can 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 from 20 ppm to 1500 ppm by weight of the lubricating oil composition, based on the total weight of the lubricating composition. Magnesium, or 100 to 800 weight ppm magnesium, or greater than about 140 weight ppm and less than or equal to about 550 weight ppm magnesium, based on the total weight of the lubricating composition. In each of the foregoing embodiments, the overbased magnesium detergent can have a TBN of 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 higher, or a TBN of about 300 mg KOH / gram or higher, or a TBN of about 350 mg KOH / gram or higher, or a TBN of about 400 mg KOH / gram or higher, or a TBN of about 425 mg KOH / gram or higher.

  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 Includes 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 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 a method or by lubricating an engine with a lubricating oil composition and operating the engine.

  The lubricating oil composition of the present disclosure has an overbased calcium-containing detergent selected from overbased calcium sulfonate detergents, overbased calcium phenate detergents, and overbased calcium salicylate detergents. 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 detergent. Preferably the overbased detergent is a calcium sulfonate detergent.

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

  The lubricating oil composition of the present invention may also optionally contain one or more low base / neutral detergents. The low basic / neutral detergent has a TBN of at most 175 mgKOH / g, or at most 150 mgKOH / g. The low basic / neutral detergent may include 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 can be a calcium-containing detergent or a mixture of calcium-containing detergents. In some embodiments, the low basic / neutral detergent can 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, if present, may comprise at least 0.1% by weight of the lubricating oil composition. In some embodiments, the low base / 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 wt%. 0.1% to 1.0% by weight of the lubricating oil composition may be included. 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 from about 0 to about 1000 ppm by weight calcium, based on the total weight of the lubricating oil composition. In some embodiments, the one or more low basic / neutral calcium-containing detergents are 25 to less than 800 ppm by weight, or 50 to 600 ppm by weight, or 100 to 100 ppm by weight, based on the total weight of the lubricating oil composition. 500 ppm by weight of calcium may be provided in the lubricating oil composition.

  In some embodiments, the ratio of ppm by weight of calcium provided to the lubricating oil composition by the low basic / neutral detergent to ppm by weight of calcium provided by the overbased calcium detergent to the lubricating oil composition. 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 composition herein contains molybdenum, which may 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 antiwear agents, antioxidants, friction modifiers, or mixtures thereof. The oil-soluble molybdenum compound is 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 dialkyldithiophosphates, 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.V. under the trade names such as Molyvan822 (trademark), Molyvan (trademark) A, Molyvan2000 (trademark), and Molyvan855 (trademark). T. Vanderbilt Co. , Ltd. , And products such as Sakura-Lube ™ 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 under the name as well as mixtures thereof are mentioned. Suitable molybdenum components are described in US 5,650,381, USRE 37,363E1, USRE 38,929E1, and USRE 40,595E1.

Also, the molybdenum compound can 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. Patent Nos. 4,263,152, 4,285,822, 4,283,295, 4,272,387, 4,265,773, Molybdenum with the molybdenum / sulfur complexes of basic nitrogen compounds described in US Pat. Nos. 4,261,843, 4,259,195, and 4,259,194, and US Patent Publication No. 2002/0038525. May be provided.

Another class of suitable organomolybdenum compounds are trinuclear molybdenum compounds, such as those of formula Mo ₃ S _k L _n Q _z , and mixtures thereof, wherein S represents sulfur and L represents a compound. Represents an independently selected ligand having an organic group having a sufficient number of carbon atoms to render it oil-soluble or oil-dispersible, n is 1 to 4 and k is 4 to 7 Varying, Q is selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers, z ranges from 0 to 5 and includes non-stoichiometric values. There can 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 ligand's organic groups. Further suitable molybdenum compounds are described in US Pat. No. 6,723,685.

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

Boron-Containing Compounds The lubricating oil compositions herein comprise one or more boron-containing compounds (also referred to herein as one or more borated compounds), such as boron-containing dispersants, as discussed above. Includes boron that may be provided to the lubricating oil composition in the form.

  Examples of boron-containing compounds include borated esters, borated fatty amines, borated epoxides, borated detergents, and borated 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. Can be used in an amount sufficient to do so. The boron-containing compound is greater than 50 ppm boron in the lubricating oil composition, or greater than 100 ppm boron, greater than 50 ppm and less than 1000 ppm boron, or greater than 100 ppm and less than 800 ppm boron, or boron, based on the total weight of the lubricating composition, or The lubricating oil composition may be included in an amount sufficient to provide 110 ppm to 600 ppm of boron, or 120 ppm to 500 ppm of boron in the lubricating oil composition.

  The lubricating oil composition may also include one or more optional components 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 and include, for example, 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 secondary butyl groups and / or tertiary butyl groups as sterically hindering groups. The phenolic group may be further substituted with a bridging group attached to the hydrocarbyl group and / or the second aromatic group. Examples of suitable hindered phenol antioxidants are 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 may be mentioned. In one embodiment, the hindered phenol antioxidant may be an ester, for example, addition products derived from IRGANOX ™ L-135 or 2,6-di-tert-butylphenol and alkyl acrylates available from BASF. The alkyl group can include, and 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 may 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, such that each antioxidant may comprise up to about 5 weight percent based on the total weight of the lubricating oil composition. May be present in an amount sufficient to provide the%. In one embodiment, the antioxidant is from about 0.3 to about 1.5% by weight diarylamine and about 0.4 to about 2.5% by weight based on the total weight of the lubricating oil composition. It can be a mixture with molecular weight phenols.

  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 may be a Diels-Alder adduct of a diene such as 1,3-butadiene and an unsaturated ester such as butyl acrylate.

  Another class of sulfurized olefin includes sulfurized fatty acids and their esters. Fatty acids are often obtained from vegetable and animal oils and typically contain 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 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% by weight of the lubricating oil composition, or from about 0.1% to about 4.0% by weight, based on the total weight of the lubricating composition. Or in the range of about 0.5% to about 3% by weight.

Antiwear Agents The lubricating oil compositions herein may also optionally contain one or more antiwear agents. Examples of suitable antiwear agents are metal thiophosphates, metal dialkyldithiophosphates, their phosphoric acid esters or salts, phosphate esters, phosphites, phosphorus-containing carboxylic acid esters, ethers or amides, sulfurized olefins, thiocarbamate esters. , Alkylene-bonded thiocarbamates, and thiocarbamate-containing compounds including bis (S-alkyldithiocarbamyl) disulfide, and mixtures thereof, but are not limited thereto. A suitable antiwear agent may be molybdenum dithiocarbamate. Phosphorus-containing antiwear agents are more fully described in EP 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 may be zinc dialkyl thiophosphate.

  Further examples of suitable antiwear agents include titanium compounds, tartrates, tartarimides, oil-soluble amine salts of phosphorus compounds, sulfurized olefins, phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate-containing compounds (thiocarbamate). Esters, thiocarbamate amides, carbamine ethers, alkylene linked thiocarbamates, and bis (S-alkyldithiocarbamyl) disulfides). The tartrate salt or tartarimide may contain an alkyl-ester group, where the total number of carbon atoms on the alkyl group may be at least 8. The antiwear agent may include citrate in one embodiment.

  The antiwear agent is from 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. To about 5% by weight, or about 0.1% by weight to about 3% by weight, or less than 2% by weight.

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

Dispersants 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 any ash when added to the lubricant. Ashless dispersants feature polar groups attached to a relatively high molecular weight hydrocarbon chain. Typical ashless dispersants include N-substituted long chain alkenyl succinimides. Examples of N-substituted long chain alkenyl succinimides include polyisobutylene having a number average molecular weight of polyisobutylene substituent in the range of from about 350 to about 50,000, or up to about 5,000, or up to about 3,000. Examples include succinimide. 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 (ethylene amine).

  In one embodiment, the present disclosure provides at least one polyisobutylene succinimide dispersion derived from polyisobutylene having a number average molecular weight in the range of from about 350 to about 50,000, or up to about 5000, or up to about 3000. The 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%. You can Such PIBs are also referred to as highly reactive PIBs (“HR-PIBs”). HR-PIB having a number average molecular weight in the range of about 800 to about 5000 is suitable for use in the 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 or such as boron trifluoride, such as those described in Boerzel et al., US Pat. No. 4,152,499 and Gateau et al., US Pat. No. 5,739,355. It can be synthesized by polymerizing isobutene in the presence of a non-chlorinated catalyst. When used in the hot ene reaction described above, HR-PIB may lead to higher conversion in the reaction and lesser amount of precipitate formation due to the increased reactivity. Suitable methods are 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”). PIBSA can have an average of between about 1.0 and about 2.0 succinic moieties per polymer.

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

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

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

  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 onto the ethylene-propylene copolymer.

  One class of suitable dispersants may 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.

  A suitable class of dispersants 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, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, carbonates, cyclic carbonates, 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 may be post-treated or further post-treated with various post-treatments designed to improve or impart different properties. Such post-treatments include those summarized in columns 27-29 of US Pat. No. 5,241,003. As such processing,
Inorganic phosphoric acid or anhydride (eg, US Pat. Nos. 3,403,102 and 4,648,980),
An organic phosphorus compound (for example, US Pat. No. 3,502,677),
Phosphorus pentasulfide,
Boron compounds as already mentioned 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 GB 1,065,595),
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),
Alkanesultone (eg, US Pat. No. 3,749,695),
1,3-dicarbonyl compounds (eg, US Pat. No. 4,579,675),
Sulfates of alkoxylated alcohols or phenols (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),
A hydroxy protected chlorodicarbonyloxy compound (eg, US Pat. No. 4,614,522),
Lactams, thiolactams, thiolactones, or ditolactones (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). And No. 4,670,170),
Nitrogen-containing carboxylic acids (eg, US Pat. No. 4,971,598 and British Patent GB 2,440,811),
A hydroxy protected chlorodicarbonyloxy compound (eg, US Pat. No. 4,614,522),
Lactams, thiolactams, thiolactones, or dithiolactones (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),
Hydroxyaliphatic carboxylic acids (eg, US Pat. Nos. 4,482,464, 4,521,318, 4,713,189),
An oxidizer (eg, US Pat. No. 4,379,064),
A combination of phosphorus pentasulfide and a polyalkylene polyamine (eg, US Pat. No. 3,185,647),
A combination of a carboxylic acid or aldehyde or ketone 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),
A combination of aldehydes and phenols (eg US Pat. Nos. 3,649,229, 5,030,249, 5,039,307),
A combination of aldehydes and O-diesters of dithiophosphoric acid (eg US Pat. No. 3,865,740),
A combination of hydroxyaliphatic carboxylic acid and boric acid (eg, US Pat. No. 4,554,086),
A hydroxyaliphatic carboxylic acid, followed by a combination of formaldehyde and phenol (eg, US Pat. No. 4,636,322),
A combination of hydroxyaliphatic carboxylic acid and subsequent aliphatic dicarboxylic acid (eg, US Pat. No. 4,663,064),
A combination of formaldehyde and phenol, followed by glycolic acid (eg, US Pat. No. 4,699,724),
A combination of a hydroxyaliphatic carboxylic acid or oxalic acid and a subsequent diisocyanate (eg, US Pat. No. 4,713,191),
A combination of an inorganic acid or anhydride of phosphorus or a partial or total sulfur analogue thereof and a boron compound (eg US Pat. No. 4,857,214),
A combination of an organic diacid, then an unsaturated fatty acid, and then a nitroso aromatic amine, optionally a boron compound, and then a glycolating agent (eg, US Pat. No. 4,973,412),
A combination of an aldehyde and a triazole (eg, US Pat. No. 4,963,278),
A combination of aldehyde and 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).

  The TBN of suitable dispersants may be from about 10 to about 65 without oil, which is from about 5 to about 30 when measured on a dispersant sample containing about 50% diluent oil. It is 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 from about 0.1% to about 10%, or from about 1% to about 9%, or about 2% by weight, based on the total weight of the lubricating oil composition. Can be from about 8.5% by weight, or from about 2.75% by weight to about 6.5% by weight. 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 can be used.

  When the dispersant contains nitrogen, the amount of dispersant used in the lubricating oil composition at that time depends on the ratio of total metal from the 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 can include metal-containing and metal-free friction modifiers, which include 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 and Mention may be made of, but 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 may 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 amide, a long chain fatty ester, a long chain fatty epoxide derivative, or a long chain imidazoline.

  Other suitable friction modifiers may include organic, ashless (metal-free), nitrogen-free organic friction modifiers. Such friction modifiers may include esters formed by reacting carboxylic acids and anhydrides with alkanols, generally with polar end groups (eg, carboxyl or hydroxyl) covalently attached to the lipophilic hydrocarbon chain. Including. One example of an organic ashless 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.

  Amine based friction modifiers may include amines or polyamines. Such compounds may be linear and have hydrocarbyl groups that are either saturated or unsaturated, or mixtures thereof, and may contain from about 12 to about 25 carbon atoms. Further examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. Such compounds may be linear and have hydrocarbyl groups that are either saturated or unsaturated, or mixtures thereof. They can contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.

  Amines and amides, even when used by themselves, are adducts with boron compounds such as boron oxide, boron halides, metaborate salts, boric acid, or 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.

  Friction modifiers are from about 0% to about 10% by weight, or from about 0.01% to about 8% by weight, or from 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.

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

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

  Among the titanium-containing compounds that can be used in the disclosed technology or used to prepare oil-soluble materials of the disclosed technology are various Ti (IV) compounds such as titanium (IV) oxide, titanium. (IV) sulfide, titanium (IV) nitrate, titanium (IV) 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, as well as 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 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, in general, titanium compounds and oils. Included are reaction products with various acid materials that form salts such as soluble salts. Therefore, titanium compounds may be derived from organic acids, alcohols, and glycols, among others. The Ti compound may also be present in the form of a dimer or oligomer containing a Ti-O-Ti structure. Such titanium materials are either commercially available or can be readily prepared by appropriate synthetic techniques apparent to those skilled in the art. They may 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) polyamines having free condensable -NH functional groups. -Based succinimide / amide dispersant, (b) polyamine-based succinimide / amide dispersant components, namely alkenyl- (or alkyl-) succinic anhydrides and polyamines, (c) substituted succinic anhydrides, polyols, amino alcohols, polyamines , 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 which are used directly for application or which are further reacted with the abovementioned succinic dispersants. 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 give a titanium-modified dispersant or intermediate. May be provided. The resulting material (30 g) was further reacted at 150 ° C. for 1.5 hours with a succinimide dispersant from a polyisobutene-substituted succinic anhydride and polyethylene polyamine mixture (127 grams + diluent oil) to give a titanium-modified succinimide dispersant. 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 1 to 3, R ₄ is an alkyl moiety having a carbon atom in the range 1 to 8 and R ₁ is about 6 to 25 carbons. Selected from hydrocarbyl groups containing atoms, R ₂ and R ₃ are the same or different and are selected from hydrocarbyl groups containing from 1 to 6 carbon atoms), or a formula:

Where x ranges from 0 to 3, R ₁ is selected from hydrocarbyl groups containing about 6 to 25 carbon atoms, and R ₂ and R ₃ are the same or different and are from about 1 to Selected from hydrocarbyl groups containing 6 carbon atoms and R ₄ is selected from the group consisting of H, any of the C _{6 to} 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, Examples include, but are not limited to, neodecanoic acid.

  In one embodiment, the oil soluble titanium compound is 0 to 3000 ppm titanium, or 25 to about 1500 ppm titanium, or about 35 ppm to 500 ppm titanium, or about 50 ppm to about 300 ppm based on the total weight of the lubricating composition. Titanium may be present in the lubricating oil composition in an amount to provide it.

Viscosity Index Improver The lubricating oil compositions herein may also optionally contain one or more viscosity index improvers. Suitable viscosity index improvers include polyolefins, olefin copolymers, ethylene / propylene copolymers, polyisobutene, hydrogenated styrene-isoprene polymers, styrene / maleic acid ester copolymers, hydrogenated styrene / butadiene copolymers, hydrogenated isoprene polymers, alpha-olefins. Mention may be made of maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrogenated alkenylaryl conjugated copolymers, or mixtures thereof. Viscosity index improvers may include star polymers, suitable examples of which are described in US Pat. No. 8,999,905B2.

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

  Viscosity index improver and / or dispersant The total amount of viscosity index improver is from about 0% to about 20%, about 0.1% to about 15%, about 0.1% by weight of the lubricating oil composition. Can be from about 13 wt%, or from 0.25 wt% to about 12 wt%, or from about 0.5 wt% to about 11 wt%, or from 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. Moreover, one or more of the additives mentioned may be multi-functional and may provide additional or additional functionality to those 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 those specified in this disclosure and / or metal deactivators, viscosity index improvers, ashless TBN boosters, friction modifiers, antiwear agents, corrosion inhibitors. Agent, rust inhibitor, dispersant, dispersant viscosity index improver, extreme pressure agent, antioxidant, foam inhibitor, demulsifier, emulsifier, pour point depressant, seal swelling agent, and mixtures thereof It may include more than one species. Fully formulated lubricating oils typically 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-alkyldithiobenzimidazoles, or 2-alkyldithiobenzazoles. Thiazoles; suds suppressors including copolymers of ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides, and (ethylene oxide-propylene oxide) polymers; anhydrous Pour point depressants may be included, including maleic acid-styrene esters, polymethacrylates, polyacrylates, or polyacrylamides.

  Suitable suds suppressors include silicon-based compounds such as siloxanes.

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

  A suitable rust inhibitor may be a single compound or a mixture of compounds having the property of inhibiting corrosion of ferrous iron metal surfaces. 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 cerotic acid. Included are oil soluble high molecular weight organic acids and oil soluble polycarboxylic acids including dimer and trimer acids such as those produced from tall oil fatty acids, oleic acid, and linoleic acid. Other suitable corrosion inhibitors include long chain alpha in the molecular weight range of about 600 to about 3000, omega-dicarboxylic acids, and tetrapropenyl succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid. Alkenyl succinic acid in which the alkenyl group of contains about 10 or more carbon atoms. Another useful class of acidic corrosion inhibitors are half-esters of alkenyl succinic acids having about 8 to about 24 carbon atoms in the alkenyl group with alcohols such as polyglycol. 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 5% by weight, based on the total weight of the lubricating oil composition. It may 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 above percentages of each component 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 subcombinations. However, it may be preferable to use an additive concentrate (ie, an additive plus a diluent such as a hydrocarbon solvent) to blend all of the ingredients simultaneously. The additives used in formulating the compositions described herein can be blended into the base oil individually or in various subcombinations. However, it may be preferable to use an additive concentrate (ie, an additive plus a diluent such as a hydrocarbon solvent) to blend all of the ingredients simultaneously.

  The present disclosure provides novel lubricating oil blends specifically formulated for use as automotive engine lubricants. Embodiments of the present disclosure may provide a suitable lubricating oil for engine applications, the lubricating oil having the following attributes: antioxidation, antiwear performance, rust control, fuel economy, water resistance, aeration, sealing. It provides protection and one or more improvements in 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 contained 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 of ordinary skill in the art and are generally used in conventional amounts with the additives and compositions described herein.

  The following examples are illustrative, but non-limiting, of the methods and compositions of the present disclosure. Other suitable modifications and adaptations of the various conditions and parameters commonly encountered in the art will be apparent to those skilled in the art and are within the scope of the present disclosure.

  Fully formulated lubricating oil compositions containing additives were made and tested to determine their effect on turbocharger deposit formation by determining the TCO temperature rise in boosted internal combustion engines. . The elevated TCO temperature provides an indication that the turbocharger deposits in the engine are creating an adiabatic effect. Therefore, increasing the TCO temperature of a 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 parts of the lubricating oil composition. ˜16 weight percent. The DI package contained conventional amounts of dispersant, antiwear additives, defoamers, and antioxidants, as described in Table 3 below. Specifically, DI packages include succinimide dispersants, borated succinimide dispersants, molybdenum-containing compounds, friction modifiers, one or more antioxidants, and one or more antiwear agents (unless otherwise specified. ) Was included. About 4 to about 10 weight percent of one or more viscosity index improvers was included in each tested lubricating oil composition. Base oil was used as a diluent oil for the viscosity index improver. The modified ingredients are identified in the example tables and discussion provided below. All of the values listed in Table 3 are stated as weight percentages of the components based on the total weight of the lubricating oil composition (ie, active feed plus diluent oil, if any), unless otherwise specified. .

Turbocharger Caulking Test The Turbocharger Caulking Test uses the 2015 version of the General Motors dexos1® Turbocharger Caulking Test (TC Test) to obtain a 2012 1 with a 3 liter test oil charge and a qualified test fuel. Performed using a 4L Chevy Cruz 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. "1800 cycle TCO temperature" is the average TCO temperature from cycle 1701 to cycle 1800 of the TC test. The test is considered to be passed 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 Invention Examples I-1 and I-2
In the following examples, the amounts of total metals and the amounts of nitrogen, boron and molybdenum from various ratios of one or more metal-containing detergents to TCO temperature and NOACK volatility (ASTM D-5800 at 250 ° C.) are given. The impact has been determined. The amounts of nitrogen, boron and molybdenum were determined by ICP analysis.

  Four samples were tested, each containing more than 50 wt% base oil of lubricating viscosity, and each was formulated to have a rating of 0W-20.

  Comparative Examples C-1 and C-2 are not commercially available fluids, but do demonstrate the technical problems experienced by those skilled in the art when the lubricating oil composition is modified to meet performance needs. Is 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. Have demonstrated a relationship. When the total metal: nitrogen ratio was outside the range of less than 1.9, as in Comparative Examples C-1 and C-2, the lubricating oil composition failed the TC test, that is, the TCO temperature rise. 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: nitrogen ratio within the range of less than 1.9 passed the TC test, i.e., the TCO temperature rise was 9. It was 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. Demonstrating the relationship. When the total metal: boron ratio is outside the range of less than 7.5, as in Comparative Examples C-1 and C-2, the lubricating oil composition fails the TC test, i.e., the TCO temperature rise is high. 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 each passed the TC test, i.e., the TCO temperature rise was 9%. It was 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 the detergent ("total metal: molybdenum ratio") and the TCO temperature rise. Demonstrating the relationship. When the total metal: molybdenum ratio is outside the range of less than 23.8, as in Comparative Examples C-1 and C-2, the lubricating oil composition failed the TC test, i.e., the TCO temperature rise. 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: molybdenum ratio within the range of less than 23.8 passed the TC test, i.e., the TCO temperature rise was 9%. It was 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 a relationship between base oil type and NOACK volatility. When Group III base oils are used alone, the NOACK volatility is outside the range of less than 11.0 wt% as in Comparative Examples C-1 and C-2. 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 less than 11.0 wt% NOACK volatility. Therefore, Examples I-1 and I-2 of the present invention showed improved NOACK volatility.

Invention B-Comparative Examples C-3 to C-5 and Examples I-3 to I-7 of the present invention.
In the examples below, the effect of some parameters on TCO temperature rise was determined. Eight samples were tested, each containing more than 50 wt% base oil of lubricating viscosity and the compounds and elements listed in Table 5 below. All eight 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 a relationship between the amount of organomolybdenum nitrogen complex and TCO temperature rise. In accordance with one aspect of the present invention, one or more molybdenum-containing compounds are provided in an amount sufficient to provide the lubricating oil composition with greater than about 40 ppm by weight molybdenum, based on the total weight of the lubricating composition. Present in the composition. When 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, i.e., the TCO temperature rise was 9.0% or more. 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, that is, 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 indicate the presence of the magnesium-containing detergent in the lubricating oil composition and the TCO temperature. Demonstrate the relationship with the rise. According to one aspect of the invention, the lubricating oil composition has a magnesium-containing detergent. When the lubricating oil composition did not have the magnesium-containing detergent as in Comparative Example C-3, the lubricating oil composition failed the TC test, that is, the TCO temperature rise 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, 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, 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 increase in TCO temperature. Has demonstrated. In accordance with one aspect of the invention, one or more calcium-based overbased cleanings 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 composition. An agent is present in the lubricating oil composition. When the amount was outside the range of less than about 1800 ppm by weight calcium, as in Comparative Example C-3, the lubricating oil composition failed the TC test, i.e., the TCO temperature rise was 9.0% or more. 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 in the range of less than about 1800 ppm by weight calcium, It 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 in ppm by weight in the lubricating oil composition. The relationship between total boron to total nitrogen ratio and TCO temperature rise is demonstrated. According to one aspect of the invention, the lubricating oil composition may have a ratio of total boron in ppm by weight to total nitrogen in ppm by weight 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 that can be less than about 0.29, as in Comparative Examples C-3, C-4, and C-5. In this case, the lubricating oil composition failed the TC test, that is, the TCO temperature rise was 9.0% or more. 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 a total nitrogen content of ppm by weight that may be less than about 0.29. Having a ratio of total boron in ppm by weight to the, 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 ppm by weight in the lubricating oil composition. It demonstrates the relationship between the ratio of calcium to total nitrogen and the increase in TCO temperature. According to one aspect of the invention, the lubricating oil composition has a ratio of total calcium in ppm by weight to total boron in ppm by weight that can be greater than about 4.9 and less than about 9.7. The lubricating oil composition may be greater than about 4.9 and less than about 9.7, such as Comparative Examples C-3, C-4, and C-5. Without the ratio of calcium, the lubricating oil composition failed the TC test, ie, the TCO temperature rise was 9.0% or more. 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 may be greater than about 4.9 and less than about 9.7. Having a ratio of total calcium in ppm by weight to total boron in ppm by weight, 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.

  In many places throughout this specification, numerous U.S. patents and other references are referenced. All such cited documents are fully expressly incorporated into this disclosure as if fully set forth herein, and for the particular purpose for which they are cited.

  Other embodiments of this disclosure will be apparent to those skilled in the art from consideration of this specification and practice of the embodiments disclosed herein. As used throughout the specification and claims, "a" and / or "an" may refer to one or more than one. Unless otherwise indicated, all numbers used in the specification and claims to describe characteristics such as amount of materials, molecular weight, etc., percentages, ratios, reaction conditions, etc., shall be in the presence of the term "about". It should be understood that, in all cases, whether modified by the term "about" or not. Accordingly, unless indicated to the contrary, the numerical parameters described in this specification and claims are approximations that may vary depending on the desired properties sought to be obtained by this disclosure. While not attempting to limit the application of minimal and equivalent doctrine to the scope of the present claims, each numerical parameter is at least in the light of the number of significant digits reported and normal rounding. It should be interpreted by applying the technique. Despite the approximate numerical ranges and parameters that explain the broad scope of this disclosure, the numerical values set forth in particular examples are reported as accurately as possible. However, any numerical value inherently contains certain errors necessarily resulting from the standard deviation found in their respective test measurements. It is intended that the specification and examples be illustrative only and the true scope of the disclosure to be considered as set forth by the following claims.

  The embodiments described above are in fact subject to significant variations. Therefore, the embodiments are not intended to be limited to the particular illustrations described herein above. Rather, the embodiments described above are within the scope of the following claims, including their legally available equivalents.

  The patentee does not intend to give away any disclosed embodiment to the public, and to the extent that any disclosed modification or alteration would not be literally within the scope of the present claims. , Under equivalent doctrine, are considered part of this specification.

  Each component, compound, substituent, or parameter disclosed herein is alone or one of each and every other component, compound, substituent, or parameter disclosed herein. It should be construed as 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 refers to any other component, compound, substitution, etc. disclosed herein. It should also be construed as disclosed in combination with each amount / value or amount / value range of groups, or parameters, and also two or more components, compounds, substitutions disclosed herein. It should be understood that any combination of amounts / values or ranges of amounts / values for a group or parameter is also disclosed in combination with each other for the purposes of this specification.

  It is further understood that each range disclosed herein is to be construed as a disclosure of each particular value in the range disclosed that has the same significant digit. Therefore, the range of 1-4 should be construed as an explicit disclosure of values of 1, 2, 3, and 4.

  Each lower limit of each range disclosed herein is disclosed in combination with each upper limit of each range and each specific value within each range disclosed herein for the same component, compound, substituent, or parameter. It is further understood that this should be construed as Therefore, the present disclosure provides that each lower limit value of each range is combined with each upper limit value of each range, or each specific value in each range, or each upper limit value of each range is each specific value in each range. It should be construed as a disclosure of all ranges derived by combining with.

  Further, the particular amounts / values of the components, compounds, substituents, or parameters disclosed herein or in the examples should be construed as disclosure of either the lower or upper limit of the range, and , Any other upper or lower limit of a range for the same ingredient, compound, substituent, or parameter disclosed elsewhere in this application, or in combination with the specified amount / value, that ingredient, compound, substitution Groups, or ranges for parameters can be formed.

Claims (16)

A lubricating oil composition,
A base oil having a lubricating viscosity of more than 50% by weight,
One or more borated compound (s) in an amount sufficient to provide 240 ppm to 300 ppm by weight of boron to the lubricating oil composition;
An organic molybdenum nitrogen complex in an amount sufficient to provide 80 ppm to 730 ppm by weight molybdenum to the lubricating oil composition, based on the total weight of the lubricating oil composition;
One or more overbased magnesium sulphonate detergent (s) in an amount sufficient to provide 140 ppm to 550 ppm by weight of magnesium to the lubricating oil composition;
Based on the total weight of the lubricating oil composition, in an amount sufficient to provide a calcium 1340 weight ppm~1500 wt ppm in the lubricating oil composition, as measured by the method of ASTM D-2896 225mgKOH / one or more overbased calcium sulfonate detergent (s) having a total base number greater than g;
It includes the following 1340 wt ppm to 1500 wt ppm, and the total amount of calcium from the calcium-containing detergent, and
The total base number of the lubricating oil composition is 6.0 mg KOH / g to 12.0 mg KOH / g measured by the method of ASTM D-2896,
The ratio of total calcium in ppm by weight in the lubricating oil composition to total boron in ppm by weight in the lubricating oil composition is 5.0 to 6.0;
A lubricating oil composition, wherein the lubricating oil composition comprises 10 wt% or less of a Group IV base oil, a Group V base oil, or a combination thereof. The lubricating oil composition of claim 1, wherein the one or more overbased magnesium sulfonate detergent (s) has a total base number greater than 225 mg KOH / g as measured by the method of ASTM D-2896. The lubricating oil composition of claim 1, wherein the ratio of total boron in ppm by weight in the lubricating oil composition to total nitrogen in ppm by weight in the lubricating oil composition is less than 0.29 .   The lubricating oil composition is effective in ensuring a TCO temperature rise of less than 9.0% as measured using the 2015 version 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 5W-30. A method for reducing or preventing the formation of deposits in a boosted internal combustion engine, comprising:
Lubricating a boosted internal combustion engine with the lubricating oil composition of claim 1.
Operating the engine lubricated with the lubricating oil composition.   7. The lubricating oil composition of claim 6, wherein the lubricating oil composition is effective to ensure a TCO temperature rise of less than 9.0% as measured using the 2015 version of the General Motors dexos1® turbocharger coking test. The method described. The lubricating oil composition of claim 1, wherein the overbased calcium sulfonate detergent has a TBN of 250 mg KOH / g to 425 mg KOH / g as measured by the method of ASTM D-2896.   The lubricating oil composition of claim 1, wherein the lubricating oil composition further comprises a low basic calcium-containing detergent having a TBN of at most 175 mg KOH / g as measured by the method of ASTM D-2896. The lubricating oil composition according to claim 9, wherein the low-basic calcium-containing detergent is a calcium sulfonate detergent.   The lubricating oil composition of claim 1, wherein the one or more borated compounds is a borated succinimide dispersant. The lubricating oil composition of claim 11, wherein the borated succinimide dispersant provides 240-300 ppm by weight of boron to the lubricating oil composition. 3. The method of claim 2, wherein the one or more overbased magnesium sulfonate detergent (s) has a total base number of 250 mgKOH / g to 425 mgKOH / g as measured by the method of ASTM D-2896. Lubricating oil composition.   The lubricating oil composition according to claim 1, further comprising one or more components selected from the group consisting of friction modifiers, antiwear agents, dispersants, antioxidants, and viscosity index improvers.   The lubricating oil composition of claim 2, wherein the lubricating oil composition does not contain any Group IV base oil.   The lubricating oil composition of claim 2, wherein the lubricating oil composition does not contain any Group V base oil.