Lubricant additive

Abstract

The present disclosure describes a gas fuel, low-speed, or medium-speed engine lubricating oil composition. The composition comprises a major amount of a base oil and a lubricating additive having the following structure: [Chemical 1] TIFF2025516657000073.tif42165 (wherein each R 1 is independently a hydrocarbyl group having 10 to 400 carbons, X is an alkyl, aryl, or aromatic heterocyclic group having 1 to 10 carbons, Y is nitrogen, oxygen, or sulfur, each R 2 is independently a hydrocarbyl group having 1 to 9 carbons, Z is nitrogen, oxygen, or sulfur, each R 3 is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons containing one or more nitrogen, oxygen, or sulfur functionalizations, p is 1 to 3, n is 1 to 20, and m is 0 to 3).

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims the benefit of U.S. Provisional Patent Application No. 63 / 339,576, filed May 9, 2022, which is hereby incorporated by reference in its entirety.

[0002] Technical Field The present disclosure relates to lubricant additive compositions and lubricating oil compositions containing the same. More specifically, the compositions improve oxidation stability and / or deposit control in engine environments.

Background Art

[0003] All engines stress lubricating oils, and some engines operate continuously under near full - load and high - temperature conditions, subjecting the lubricant to thermal stress. Under such conditions, engines are particularly susceptible to oxidation and form deposits, which can lead to a significant decrease in engine performance. Further, some of these engines require the lubricating oil to be within a specified viscosity range and require the use of components such as thickeners.

Summary of the Invention

[0004] In one aspect, there is provided a gaseous fuel engine lubricating oil composition comprising a major amount of base oil and a lubricant additive having the following structure:

Chemical Formula

[0005] In another aspect, a lubricating oil composition for a low- or medium-speed diesel engine is provided, the composition comprising a major amount of a base oil and a lubricating additive having the following structure:

Chemical formula

[0006] In yet another aspect, a method of thickening a lubricating oil composition in a gas fuel, low-, or medium-speed engine is provided, the method comprising adding to the engine a lubricating oil composition comprising a major amount of a base oil and a lubricating additive having the following structure:

Chemical formula

[0007] In yet another aspect, a method of improving piston cleanliness or oxidation inhibition in an engine is provided, the method comprising lubricating the engine with a lubricating oil composition, the composition comprising a base oil and a lubricating additive having the following structure:

Chemical formula

[0008] In yet another further aspect, a method of removing existing deposits in an internal combustion engine is provided, the method comprising lubricating the engine with a composition, the composition comprising a base oil and an additive having the following structure:

Chemical formula

[0009] In yet another further aspect, a method is provided for removing existing deposits from within an internal combustion engine, in a crankcase, rocker cover, camshaft region, timing gear cover, cylinder head, combustion chamber, piston rings, and / or ring grooves, the method including lubricating or rapidly cleaning the engine with a composition, the composition including a base oil and an additive having the following structure: [Chemical formula] wherein each R 1 is, independently, a hydrocarbyl group having from 10 to 400 carbons, X is an alkyl, aryl, or aromatic heterocyclic group having from 1 to 10 carbons, Y is nitrogen, oxygen, or sulfur, each R 2 is, independently, a hydrocarbyl group having from 1 to 9 carbons, Z is nitrogen, oxygen, or sulfur, each R 3 is, independently, hydrogen or a hydrocarbyl group having from 1 to 9 carbons and including functionalization with one or more nitrogen, oxygen, or sulfur atoms, p is from 1 to 3, n is from 1 to 20, and m is from 0 to 3. DETAILED DESCRIPTION

[0010] When combinations of elements, subsets, groups, etc. (e.g., combinations of components in a composition or combinations of steps in a method) are disclosed, each specific reference to each individual and collective combination and permutation of these elements may not be explicitly disclosed, but each is specifically contemplated and understood to be described herein.

[0011] The present disclosure relates to lubricant additive compositions having improved oxidation stability, thickening ability, and / or deposit control ability (i.e., preventing the formation of deposits and / or removing existing deposits), lubricating oil compositions containing such lubricant additives, and methods of using such compositions.

[0012] When used during regular maintenance such as the scheduled oil change recommended by the OEM, the lubricating oil composition functions primarily (but not exclusively) to prevent deposit formation. When used as needed such as for a rapid cleaning service, the lubricating oil composition functions primarily (but not exclusively) to remove existing deposits.

[0013] The compositions disclosed herein are particularly suitable for engines operating under sustained high load conditions such as gas fuel engines, dual fuel engines, and low or medium speed engines. The engine can be a two-stroke or four-stroke engine. The engine can also include any number of combustion chambers, pistons, and associated cylinders (e.g., 1 to 24). For example, in certain embodiments, the engine can be a large industrial reciprocating engine having 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 16, 18, 20, 24 or more reciprocating pistons within the cylinders. In certain embodiments, the pistons can be aluminum pistons or steel pistons (e.g., steel, or any of various steel alloys such as 42CrMo4V or 38MnVS6).

[0014] The gas fuel engine can be a stationary natural gas engine, a stationary biogas engine, a stationary landfill gas engine, a stationary non-conventional gas fuel engine, or a dual fuel engine. A dual fuel engine can be operated using a mixture of two different fuels. Frequently, diesel and natural gas fuels are used together within a dual fuel engine. In addition to natural gas and diesel, some dual fuel engines can also use various mixtures of biodiesel, landfill gas, biogas, and other fuels.

[0015] Fuels used to operate a gas fuel engine may include carbon-based gas fuels (e.g., natural gas, biogas, landfill gas, wood gas, methane, propane, butane, etc.) and non-carbon-based gas fuels (e.g., ammonia, hydrogen).

[0016] Diesel engines can generally be classified as low-speed, medium-speed, or high-speed engines. As used herein, a "low-speed" engine means a compression ignition internal combustion engine that is driven at a rotational speed of less than 500 revolutions per minute (rpm), such as a marine crosshead diesel engine; a "medium-speed" engine means a compression ignition internal combustion engine that is driven at a rotational speed of 500 to 1800 rpm, such as a locomotive ("railway") diesel engine, a marine trunk piston diesel engine, or a land-based stationary power diesel engine; and a "high-speed" engine means a compression ignition internal combustion engine that is driven at a rotational speed higher than 1800 rpm, such as a diesel engine for high-speed vehicles.

[0017] In some embodiments, the lubricating oil compositions disclosed herein can be used to control deposits in engines operating under high sustained load conditions, such as a brake mean effective pressure (BMEP) of at least 10 bar (1.0 MPa), at least 12 bar (1.2 MPa), at least 14 bar (1.4 MPa), at least 16 bar (1.6 MPa), at least 18 bar (1.8 MPa), at least 20 bar (2.0 MPa), for example, at least 22 bar (2.2 MPa), at least 24 bar (2.4 MPa), at least 26 bar (2.6 MPa), 10 to 30 bar (1.0 to 3.0 MPa), 20 to 30 bar (2.0 to 3.0 MPa), 22 to 30 bar (2.2 to 3.0 MPa), 22 to 28 bar (2.2 to 2.8 MPa), or 24 to 30 bar (2.4 to 3.0 MPa).

[0018] The lubricant additives and compositions containing them disclosed herein can be used in several lubricant applications such as railway engine oil (RREO), marine system oil (SO), marine cylinder lubricant (MCL), trunk piston engine oil (TPEO), natural gas engine oil (NGEO), or dual fuel (DF) engine oil.

[0019] In some embodiments, the lubricating oil compositions disclosed herein have a total base number (TBN) of from 2 to 200 mg KOH / g, such as, for example, 2 to 175, 2 to 150, 2 to 100, 5 to 200, 5 to 175, 5 to 150, 5 to 100, 10 to 200, 10 to 175, 10 to 150, 10 to 100, 50 to 200, 50 to 175, 50 to 150, and 50 to 100.

[0020] In some embodiments, the lubricating oil compositions disclosed herein are suitable for use as a marine cylinder lubricant for lubricating a slow speed crosshead engine. Marine cylinder lubricants are typically made to SAE30, SAE40, SAE50, or SAE60 monograde specifications in order to provide a sufficiently thick lubricating film at high temperatures on the cylinder liner wall. Typically, marine diesel cylinder lubricants have a TBN in the range of up to 200 mg KOH / g, or 2 to 200 mg KOH / g (such as, for example, 2 to 200 mg KOH / g, 5 to 200 mg KOH / g, 10 to 200 mg KOH / g, 15 to 150 mg KOH / g, 15 to 60 mg KOH / g, 20 to 200 mg KOH / g, 20 to 150 mg KOH / g, 20 to 120 mg KOH / g, 20 to 80 mg KOH / g, 30 to 200 mg KOH / g, or 30 to 150 mg KOH / g, or 30 to 120 mg KOH / g, 30 to 100 mg KOH / g, 30 to 80 mg KOH / g, 60 to 200 mg KOH / g, 60 to 150 mg KOH / g, 60 to 120 mg KOH / g, 60 to 100 mg KOH / g, 60 to 80 mg KOH / g, 80 to 200 mg KOH / g, 80 to 150 mg KOH / g, 80 to 150 mg 120KOH / g, 120 to 200 mg KOH / g, or 120 to 150 mg KOH / g).

[0021] In some embodiments, the lubricating oil compositions disclosed herein are suitable for use as marine system oils for lubricating the crankcases of slow-speed crosshead engines. Marine system oils are typically made to meet the monograde specifications of SAE20, SAE30, or SAE40. The viscosity of the marine system oil is set to a relatively low level(s) in part because the system oil can increase in viscosity during use, and engine designers have set a limit on the increase in viscosity to prevent operating problems. Typically, marine system oil lubricants have a TBN in the range of up to 12 mg KOH / g, or 2 - 12 mg KOH / g (e.g., 3 - 12 mg KOH / g, 5 - 12 mg KOH / g, 5 - 10 mg KOH / g, or 5 - 9 mg KOH / g).

[0022] In some embodiments, the lubricating oil compositions disclosed herein are suitable for use as marine trunk piston engine oils (TPEO). Marine TPEO oils are typically made to meet the monograde specifications of SAE30 or SAE40. Typically, marine TPEO lubricants have a TBN in the range of up to 60 mg KOH / g, or 2 - 60 mg KOH / g (e.g., 5 - 60 mg KOH / g, 10 - 30 mg KOH / g, 15 - 60 mg KOH / g, 15 - 40 mg KOH / g, 20 - 60 mg KOH / g, 20 - 40 mg KOH / g, 30 - 60 mg KOH / g, or 30 - 55 mg KOH / g).

[0023] In some embodiments, the lubricating oil compositions disclosed herein are suitable for use as gas fuel engine oils, such as natural gas fuel engine oils. Gas fuel engine oils typically have a TBN in the range of up to 10 mg KOH / g, or 2 - 10 mg KOH / g (e.g., 2 - 9 mg KOH / g, or 2 - 8 mg KOH / g).

[0024] In some embodiments, the lubricating oil compositions disclosed herein are suitable for use as medium-speed engine oils such as locomotive (railway) engine oils. Locomotive engine oil lubricants typically have a TBN in the range of up to 20 mg KOH / g, up to 15 mg KOH / g, up to 10 mg KOH / g, or 4 - 20 mg KOH / g, 4 - 15 mg KOH / g, 4 - 10 mg KOH / g, or 5 - 9 mg KOH / g.

[0025] In some embodiments, the lubricating oil compositions disclosed herein can be used during rapid cleaning services to remove deposits, sludge, and other dirt accumulated from internal combustion engines. Rapid cleaning services can remove sludge, heavy deposits, and / or other insoluble substances that may have accumulated over time. The cleaning process can consist of using the lubricant in the engine's drain or crankcase and circulating the lubricating oil without starting the engine. Additional steps may include circulating the lubricating oil and allowing it to soak for 15 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 16 hours, 20 hours, 24 hours, 2 days, 3 days, 4 days, 5 days, 6 days, or 1 week under static conditions. Another cleaning step may include starting the engine and operating it for 15 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 16 hours, 20 hours, 24 hours, 2 days, 3 days, 4 days, 5 days, 6 days, or 1 week under any operating conditions appropriate for the engine design and fuel. In some embodiments, the lubricating oil compositions disclosed herein can be used to remove existing deposits from within an internal combustion engine, such as in the crankcase, rocker cover, camshaft area, timing gear cover, cylinder head, combustion chamber, piston rings, and / or ring grooves.

[0026] When used during a rapid cleaning service, the lubricating oil composition may require a higher concentration of lubricating additives than those normally used during regular maintenance. This lubricating oil with a high amount of deposit cleaning lubricating additives is used to lubricate and clean the engine. The resulting mixed product (concentrated lubricating oil and deposits) can then be flushed. The flushing step is typically performed after completion of the cleaning step.

[0027] In some embodiments, the flushing step of the rapid cleaning service involves lubricating the engine with the lubricating oil composition for 15 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 16 hours, 20 hours, 24 hours, 2 days, 3 days, 4 days, 5 days, 6 days, or 1 week. The exact time can vary depending on many factors, such as but not limited to the size of the engine, the amount of deposits in the engine, and the desired level of cleaning.

[0028] In some embodiments, flushing is performed 5 minutes, 15 minutes, 30 minutes, 45 minutes, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 8 hours, 12 hours, 16 hours, 24 hours, 2 days, 3 days, 4 days, 1 week, 2 weeks, 3 weeks, 4 weeks, 6 weeks, 8 weeks after the cleaning step. In some embodiments, the flushing step can be performed for a period corresponding to up to about 25% of the period of the OEM-recommended oil change interval.

[0029] In some embodiments, the present disclosure relates to engine flushing products containing additives, mixed products containing additives and used lubricating oil compositions, and methods of using them.

[0030] In some embodiments, the engine flushing product is an aftermarket additive package in which the additive is dissolved in a solvent. The aftermarket additive package is suitable for rapidly cleaning or removing deposits, sludge, and other dirt accumulated from an internal combustion engine.

[0031] The engine flush process can remove sludge, heavy deposits, and / or other dirt that may have accumulated from the engine oil. A typical engine flush process involves adding an additive as an aftermarket additive (e.g., an engine flush product) to the internal combustion engine through the oil filler port. After idling the engine, the additive is added and mixed with the existing lubricating oil composition having "used base oil". This mixed product can dissolve or remove sludge, heavy deposits, and / or dirt remaining in the engine. The mixed product is then drained along with the dissolved sludge, deposits, and / or dirt.

[0032] In some embodiments, the lubricating oil compositions disclosed herein may contain low levels of sulfuric acid ash as determined by ASTM D874. The composition may have less than 1.5 wt% (e.g., less than 0.6 wt%, or even less than 0.06 wt%) sulfuric acid ash based on the total weight of the composition. The composition may have a sulfuric acid ash content of 0.01 - 1.0 wt%, 0.1 - 1.0 wt%, 0.3 - 0.8 wt%, 0.4 - 1.0 wt%, 0.5 - 0.9 wt%, or 0.5 - 1.0 wt%. In some embodiments, the lubricating oil composition may be ashless.

[0033] The lubricating oil compositions disclosed herein can provide advantageous deposit control performance in any of many mechanical parts of an engine. The mechanical components can be pistons, piston rings, piston ring grooves, crankcases, rocker covers, camshaft regions, timing gear covers, cylinder heads, combustion chambers, cylinder liners, cylinders, cams, tappets, lifters, gears, valves, valve guides, or bearings including journal, roller, taper, needle, or ball bearings. In some cases, the mechanical components can include steel.

[0034] Lubricating Additive The lubricating additive composition of the present disclosure is represented by the following generalized chemical structure I: [Chem.] In the formula, each R 1 is independently a hydrocarbyl group having 10 to 400 carbons, X is an alkyl, aryl, or aromatic heterocyclic group having 1 to 10 carbons, Y is nitrogen, oxygen, or sulfur, and each R 2 is independently a hydrocarbyl group having 1 to 9 carbons, Z is nitrogen, oxygen, or sulfur, and each R 3 is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons containing one or more nitrogen, oxygen, or sulfur functionalizations, p is from 1 to 3, n is from 1 to 20, and m is from 0 to 3. In some embodiments, X is a cyclic or acyclic alkyl group. In some embodiments, Y may contain one or more hydrogens. In some preferred embodiments, Z is nitrogen.

[0035] Each R 1independently has from 10 to 400 carbon atoms, such as 10 to 390, 10 to 380, 10 to 370, 10 to 360, 10 to 350, 10 to 340, 10 to 330, 10 to 320, 10 to 310, 10 to 300, 10 to 290, 10 to 280, 10 to 270, 10 to 260, 10 to 250, 10 to 240, 10 to 230, 10 to 220, 10 to 210, 10 to 200, 10 to 190, 10 to 180, 10 to 170, 10 to 160, 10 to 150, 10 to 140, 10 to 130, 10 to 120, 10 to 110, 10 to 100, 10 to 90, 10 to 80, 10 to 70, 10 to 60, 10 to 50, 10 to 40, 10 to 30, 10 to 20, 20 to 400, 20 to 390, 20 to 380, 20 to 370, 20 to 360, 20 to 350, 20 to 340, 20 to 330, 20 to 320, 20 to 310, 20 to 300, 20 to 290, 20 to 280, 20 to 270, 20 to 260, 20 to 250, 20 to 240, 20 to 230, 20 to 220, 20 to 210, 20 to 200, 20 to 190, 20 to 180, 20 to 170, 20 to 160, 20 to 150, 20 to 140, 20 to 130, 20 to 120, 20 to 110, 20 to 100, 20 to 90, 20 to 80, 20 to 70, 20 to 60, 20 to 50, 20 to 40, 20 to 30, 30 to 400, 30 to 390, 30 to 380, 30 to 370, 30 to 360, 30 to 350, 30 to 340, 30 to 330, 30 to 320, 30 to 310, 30 to 300, 30 to 290, 30 to 280, 30 to 270, 30 to 260, 30 to 250, 30 to 240, 30 to 230, 30 to 220, 30 to 210, 30 to 200, 30 to 190, 30 to 180, 30 to 170, 30 to 160, 30 to 150, 30 to 140, 30 to 130, 30 to 120, 30 to 110, 30 to 100, 30 to 90, 30 to 80, 30 to 70, 30 to 60, 30 to 50, 30 to 40, 40 to 400, 40 to 390, 40 to 380, 40 to 370, 40 to 360, 40 to 350, 40 to 340, 40 to 330, 40 to 320, 40 to 310, 40 to 300, 40 to 290, 40 to 280, 40 to 270, 40 to 260, 40 to 250, 40 to 240, 40 to 230, 40 to 220, 40 to 210, 40 to 200, 40 to 190, 40 to 180, 40 to 170, 40 to 160, 40 to 150, 40 to 140, 40 to 130, 40 to 120,40~110、40~100、40~90、40~80、40~70、40~60、40~50、50~400、50~390、50~380、50~370、50~360、50~350、50~340、50~330、50~320、50~310、50~300、50~290、50~280、50~270、50~260、50~250、50~240、50~230、50~220、50~210、50~200、50~190、50~180、50~170、50~160、50~150、50~140、50~130、50~120、50~110、50~100、50~90、50~80、50~70、50~60、60~400、60~390、60~380、60~370、60~360、60~350、60~340、60~330、60~320、60~310、60~300、60~290、60~280、60~270、60~260、60~250、60~240、60~230、60~220、60~210、60~200、60~190、60~180、60~170、60~160、60~150、60~140、60~130、60~120、60~110、60~100、60~90、60~80、60~70、70~400、70~390、70~380、70~370、70~360、70~350、70~340、70~330、70~320、70~310、70~300、70~290、70~280、70~270、70~260、70~250、70~240、70~230、70~220、70~210、70~200、70~190、70~180、70~170、70~160、70~150、70~140、70~130、70~120、70~110、70~100、70~90、70~80、80~400、80~390、80~380、80~370、80~360、80~350、80~340、80~330、80~320、80~310、80~300、80~290、80~280、80~270、80~260、80~250、80~240、80~230、80~220、80~210、80~200、80~190、80~180、80~170、80~160、80~150、80~140、80~130、80~120、80~110、80~100、80~90、90~400、90~390、90~380、90~370、90~360、90~350、90~340、90~330、90~320、90~310、90~300、90~290、90~280、90~270、90~260、90~250、90~240、90~230、90~220、90~210、90~200、90~190、90~180、90~170、90~160、90~150、90~140、90~130、90~120、90~110、90~100、100~400、100~390、100~380、100~370、100~360、100~350、100~340、100~330、100~320、100~310、100~300、100~290、100~280、100~270、100~260、100~250、100~240、100~230、100~220、100~210、100~200、100~190、100~180、100~170、100~160、100~150、100~140、100~130、100~120、100~110、110~400、110~390、110~380、110~370、110~360、110~350、110~340、110~330、110~320、110~310、110~300、110~290、110~280、110~270、110~260、110~250、110~240、110~230、110~220、110~210、110~200、110~190、110~180、110~170、110~160、110~150、110~140、110~130、110~120、120~400、120~390、120~380、120~370、120~360、120~350、120~340、120~330、120~320、120~310、120~300、120~290、120~280、120~270、120~260、120~250、120~240、120~230、120~220、120~210、120~200、120~190、120~180、120~170、120~160、120~150、120~140、120~130、130~400、130~390、130~380、130~370、130~360、130~350、130~340、130~330、130~320、130~310、130~300、130~290、130~280、130~270、130~260、130~250、130~240、130~230、130~220、130~210、130~200、130~190、130~180、130~170、130~160、130~150、130~140、140~400、140~390、140~380、140~370、140~360、140~350、140~340、140~330、140~320、140~310、140~300、140~290、140~280、140~270、140~260、140~250、140~240、140~230、140~220、140~210、140~200、140~190、140~180、140~170、140~160、140~150、150~400、150~390、150~380、150~370、150~360、150~350、150~340、150~330、150~320、150~310、150~300、150~290、150~280、150~270、150~260、150~250、150~240、150~230、150~220、150~210、150~200、150~190、150~180、150~170、150~160、160~400、160~390、160~380、160~370、160~360、160~350、160~340、160~330、160~320、160~310、160~300、160~290、160~280、160~270、160~260、160~250、160~240、160~230、160~220、160~210、160~200、160~190、160~180、160~170、170~400、170~390、170~380、170~370、170~360、170~350、170~340、170~330、170~320、170~310、170~300、170~290、170~280、170~270、170~260、170~250、170~240、170~230、170~220、170~210、170~200、170~190、170~180、180~400、180~390、180~380、180~370、180~360、180~350、180~340、180~330、180~320、180~310、180~300、180~290、180~280、180~270、180~260、180~250、180~240、180~230、180~220、180~210、180~200、180~190、190~400、190~390、190~380、190~370、190~360、190~350、190~340、190~330、190~320、190~310、190~300、190~290、190~280、190~270、190~260、190~250、190~240、190~230、190~220、190~210、190~200、200~400、200~390、200~380、200~370、200~360、200~350、200~340、200~330、200~320、200~310、200~300、200~290、200~280、200~270、200~260、200~250、200~240、200~230、200~220、200~210、210~400、210~390、210~380、210~370、210~360、210~350、210~340、210~330、210~320、210~310、210~300、210~290、210~280、210~270、210~260、210~250、210~240、210~230、210~220、220~400、220~390、220~380、220~370、220~360、220~350、220~340、220~330、220~320、220~310、220~300、220~290、220~280、220~270、220~260、220~250、220~240、220~230、230~400、230~390、230~380、230~370、230~360、230~350、230~340、230~330、230~320、230~310、230~300、230~290、230~280、230~270、230~260、230~250、230~240、240~400、240~390、240~380、240~370、240~360、240~350、240~340、240~330、240~320、240~310、240~300、240~290、240~280、240~270、240~260、240~250、250~400、250~390、250~380、250~370、250~360、250~350、250 to 340, 250 to 330, 250 to 320, 250 to 310, 250 to 300, 250 to 290, 250 to 280, 250 to 270, 250 to 260, 260 to 400, 260 to 390, 260 to 380, 260 to 370, 260 to 360, 260 to 3 50, 260 to 340, 260 to 330, 260 to 320, 260 to 310, 260 to 300, 260 to 290, 260 to 280, 260 to 270, 270 to 400, 270 to 390, 270 to 380, 270 to 370, 270 to 360, 270 to 350, 270 to 340, 270 to 330, 270 to 320, 270 to 310, 270 to 300, 270 to 290, 270 to 280, 280 to 400, 280 to 390, 280 to 380, 280 to 370, 280 to 360, 280 to 350, 280 to 340, 280 to 330, 280 to 320, 280 to 310, 280 to 300, 280 to 290, 290 to 400, 290 to 390, 290 to 380, 290 to 370, 290 to 360, 290 to 350, 290 to 340, 290 to 330, 290 to 320, 290 to 310, 290 to 300, 300 to 400, 300 to 390, 300 to 380, 300 to 370, 300 to 360, 300 to 350, 300 to 340, 300 to 330, 300 to 320, 300 to 310, 310 to 400, 310 to 390, 310 to 380, 310 to 370, 310 to 360, 310 to 350, 310 to 340, 310 to 330, 310 to 320, 320 to 400, 320 to 390, 320 to 380, 320 to 370, 320 to 360, 320 to 350, 320 to 340, 320 to 330, 330 to 400, 330 to 390, 330 to 380, 330 to 370, 330 to 360, 330 to 350, 330 to 340, 340 to 400, 340 to 390, 340 to 380, 340 to 370, 340 to 360, 340 to 350, 350 to 400, 350 to 390, 350 to 380, 350 to 370, 350 to 360, 360 to 400, 360 to 390, 360 to 380, 360 to 370, 370 to 400, 370 to 390, 370 to 380, 380 to 400, 380 to 390, or a moiety containing 390 to 400 carbon atoms.

[0036] In some embodiments, R1 may include, for example, saturated and unsaturated hydrocarbon groups, linear and branched alkyl groups, and polyalkyl groups (e.g., polyisobutenyl group or "PIB", polyethylene, polypropylene, etc.). The polyalkyl group may be obtained from a polymerization reaction using an olefin monomer (e.g., isobutylene).

[0037] In some preferred embodiments, R 1 is a polyisobutenyl group. In some preferred embodiments, the polyisobutenyl group has an average molecular weight of about 350 to about 5000. In some preferred embodiments, the polyisobutenyl group has an average molecular weight of about 150 to about 1250, such as about 200 to about 1200, about 300 to about 1100, about 400 to about 1000, about 500 to about 900, and about 600 to about 800. In some preferred embodiments, the polyisobutenyl group has an average molecular weight of about 250 to about 1000, such as about 300 to about 900, about 400 to about 800, and about 500 to about 700.

[0038] In some preferred embodiments, the polyisobutenyl group has an average molecular weight of from about 500 to about 4000, such as from about 600 to about 5000, from about 700 to about 5000, from about 800 to about 5000, from about 900 to about 5000, from about 1000 to about 5000, from about 500 to about 4000, such as from about 600 to about 4000, from about 700 to about 4000, from about 800 to about 4000, from about 900 to about 4000, from about 1000 to about 4000, from about 1100 to about 4000, from about 1200 to about 4000, from about 1300 to about 4000, from about 1400 to about 4000, from about 1500 to about 4000, from about 1600 to about 4000, from about 1700 to about 4000, from about 1800 to about 4000, from about 1900 to about 4000, from about 2000 to about 4000, from about 2100 to about 4000, from about 2200 to about 4000, from about 2300 to about 4000, from about 2400 to about 4000, from about 2500 to about 4000, from about 2600 to about 4000, from about 2700 to about 4000, from about 2800 to about 4000, from about 2900 to about 4000, from about 3000 to about 4000, from about 500 to about 3500, such as from about 600 to about 3500, from about 700 to about 3500, from about 800 to about 3500, from about 900 to about 3500, from about 1000 to about 3500, from about 1100 to about 3500, from about 1200 to about 3500, from about 1300 to about 3500, from about 1400 to about 3500, from about 1500 to about 3500, from about 1600 to about 3500, from about 1700 to about 3500, from about 1800 to about 3500, from about 1900 to about 3500, from about 2000 to about 3500, from about 2100 to about 3500, from about 2200 to about 3500, from about 2300 to about 3500, from about 2400 to about 3500, from about 2500 to about 3500, from about 2600 to about 3500, from about 2700 to about 3500, from about 2800 to about 3500, from about 2900 to about 3500, from about 3000 to about 3500, from about 500 to about 3000, such as from about 600 to about 3000, from about 700 to about 3000, from about 800 to about 3000, from about 900 to about 3000, from about 1000 to about 3000, from about 1100 to about 3000, from about 1200 to about 3000, from about 1300 to about 3000, from about 1400 to about 3000, from about 1500 to about 3000, from about 1600 to about 3000, from about 1700 to about 3000, from about 1800 to about 3000, from about 1900 to about 3000, from about 2000 to about 3000, from about 2100 to about 3000, from about 2200 to about 3000, from about 2300 to about 3000, from about 2400 to about 3000, and from about 2500 to about 3000.

[0039] R 1 Specific examples of [R] include the following: [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] In the formula, x is an integer such that the total number of carbon atoms is 10 to 400 as described in this specification.

[0040] X is a moiety containing 1 to 10 carbon atoms, for example, 1 to 9, 1 to 8, 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3, 1 to 2, 2 to 10, 2 to 9, 2 to 8, 2 to 7, 2 to 6, 2 to 5, 2 to 4, 2 to 3, 3 to 10, 3 to 9, 3 to 8, 3 to 7, 3 to 6, 3 to 5, 3 to 4, 4 to 10, 4 to 9, 4 to 8, 4 to 7, 4 to 6, 4 to 5, 5 to 10, 5 to 9, 5 to 8, 5 to 7, 5 to 6, 6 to 10, 6 to 9, 6 to 8, 6 to 7, 7 to 10, 7 to 9, 7 to 8, 8 to 10, 8 to 9, or 9 to 10 carbon atoms.

[0041] Specific examples of x include the following: [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chem.] [Chem.] [Chem.] [Chem.]

[0042] Examples of Y include, for example, the following: [Chem.] [Chem.] [Chem.]

[0043] Each R 2 is, independently, a moiety containing 1 to 9 carbon atoms, for example, 1 to 8, 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3, 1 to 2, 2 to 9, 2 to 8, 2 to 7, 2 to 6, 2 to 5, 2 to 4, 2 to 3, 3 to 9, 3 to 7, 3 to 6, 3 to 5, 3 to 4, 4 to 9, 4 to 8, 4 to 7, 4 to 6, 4 to 5, 5 to 9, 5 to 8, 5 to 7, 5 to 6, 6 to 9, 6 to 8, 6 to 7, 7 to 9, 7 to 8, or 8 to 9 carbon atoms.

[0044] R 2 Suitable examples of R include, for example, saturated and unsaturated hydrocarbon groups, and linear and branched alkyl groups.

[0045] R 2 Specific examples of R include the following. [Chem.] [Chemical] [Chemical] [Chemical] [Chemical]

[0046] In the formula, Z is an oxygen, nitrogen, or sulfur atom.

[0047] Each R 3 is independently a hydrogen atom or a moiety containing 1 to 9 carbon atoms, for example, 1 to 8, 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3, 1 to 2, 2 to 9, 2 to 8, 2 to 7, 2 to 6, 2 to 5, 2 to 4, 2 to 3, 3 to 9, 3 to 7, 3 to 6, 3 to 5, 3 to 4, 4 to 9, 4 to 8, 4 to 7, 4 to 6, 4 to 5, 5 to 9, 5 to 8, 5 to 7, 5 to 6, 6 to 9, 6 to 8, 6 to 7, 7 to 9, 7 to 8, or 8 to 9 carbon atoms. Each R 3 moiety contains one or more nitrogen, oxygen, or sulfur functionalizations.

[0048] R 3 Specific examples of which are as follows: [Chemical] [Chemical] [Chemical] [Chemical]

[0049] In some preferred embodiments, the lubricant additive comprises the following generalized structure 2,

Chemical formula

[0050] In some embodiments, Y may include one or more hydrogens.

[0051] In some preferred embodiments, the lubricant additive comprises the following generalized structure 3,

Chemical formula

[0052] In some preferred embodiments, the lubricant additive comprises the following generalized structure 4,

Chemical formula

[0053] When formulated in engine oil (i.e., lubricating oil composition) and used in an engine flushing process as part of an aftermarket additive package or during a rapid cleaning service, the lubricating additive composition is typically in the range of about 0.1 to about 50.0 weight percent, based on the total weight of the lubricating oil composition (which may be a blended product), for example, about 1 weight percent to about 50 weight percent, about 5 weight percent to about 50 weight percent, about 10 weight percent to about 50 weight percent, about 15 weight percent to about 50 weight percent, about 20 weight percent to about 50 weight percent, about 25 weight percent to about 50 weight percent, about 30 weight percent to about 50 weight percent, about 35 weight percent to about 50 weight percent, about 40 weight percent to about 50 weight percent, about 45 weight percent to about 50 weight percent, about 0.1 weight percent to about 45 weight percent, about 1 weight percent to about 45 weight percent, about 5 weight percent to about 45 weight percent, about 10 weight percent to about 45 weight percent, about 15 weight percent to about 45 weight percent, about 20 weight percent to about 45 weight percent, about 25 weight percent to about 45 weight percent, about 30 weight percent to about 45 weight percent, about 35 weight percent to about 45 weight percent, about 40 weight percent to about 45 weight percent, about 0.1 weight percent to about 40 weight percent, about 1 weight percent to about 40 weight percent, about 5 weight percent to about 40 weight percent, about 10 weight percent to about 40 weight percent, about 15 weight percent to about 40 weight percent, about 20 weight percent to about 40 weight percent, about 25 weight percent to about 40 weight percent, about 30 weight percent to about 40 weight percent, about 35 weight percent to about 40 weight percent, about 0.1 weight percent to about 35 weight percent, about 1 weight percent to about 35 weight percent, about 5 weight percent to about 35 weight percent, about 10 weight percent to about 35 weight percent, about 15 weight percent to about 35 weight percent, about 20 weight percent to about 35 weight percent, about 25 weight percent to about 35 weight percent, about 30 weight percent to about 35 weight percent, about 0.1 weight percent to about 30 weight percent, about 1 weight percent to about 30 weight percent, about 5 weight percent to about 30 weight percent, about 10 weight percent to about 30 weight percent, about 15 weight percent to about 30 weight percent, about 20 weight percent to about 30 weight percent, about 25 weight percent to about 30 weight percent, about 0.1 weight percent to about 25 weight percent, about 1 weight percent to about 25 weight percent, about 5 weight percent to about 25 weight percent, about 10 weight percent to about 25 weight percent, about 15 weight percent to about 25 weight percent, and about 20 weight percent to about 25 weight percent, about 0.1 weight percent to about 20.0 weight percent, about 0.1 weight percent to about 19.0 weight percent, about 0.1 weight percent to about 18.0 weight percent, about 0.1 weight percent to about 17.0 weight percent, about 0.1 weight percent to about 16.0 weight percent, about 0.1 weight percent to about 15.0 weight percent, about 0.1 weight percent to about 14.0 weight percent, about 0.1 weight percent to about 13.0 weight percent, about 0.1 weight percent to about 12.0 wt%, from about 0.1 wt% to about 11.0 wt%, from about 0.1 wt% to about 10.0 wt%, %, from about 0.1 wt% to about 9.0 wt%, from about 0.1 wt% to about 8.0 wt%, from about 0.1 wt% to about 7.0 wt%, from about 0.1 wt% to about 6.0 wt%, from about 0.1 wt% to about 5.0 wt%, from about 0.1 wt% to about 4.0 wt%, from about 0.1 wt% to about 3.0 wt%, from about 0.1 wt% to about 2.0 wt%, from about 0.1 wt% to about 1.0 wt%, from about 1.0 wt% to about 20.0 wt%, from about 1.0 wt% to about 19.0 wt%, from about 1.0 wt% to about 18.0 wt%, from about 1.0 wt% to about 17.0 wt%, from about 1.0 wt% to about 16.0 wt%, from about 1.0 wt% to about 15.0 wt%, from about 1.0 wt% to about 14.0 wt%, from about 1.0 wt% to about 13.0 wt%, from about 1.0 wt% to about 12.0 wt%, from about 1.0 wt% to about 11.0 wt%, from about 1.0 wt% to about 10.0 wt%, from about 1.0 wt% to about 9.0 wt%, from about 1.0 wt% to about 8.0 wt%, from about 1.0 wt% to about 7.0 wt%, from about 1.0 wt% to about 6.0 wt%, from about 1.0 wt% to about 5.0 wt%, from about 1.0 wt% to about 4.0 wt%, from about 1.0 wt% to about 3.0 wt%, from about 1.0 wt% to about 2.0 wt%, from about 2.0 wt% to about 20.0 wt%, from about 2.0 wt% to about 19.0 wt%, from about 2.0 wt% to about 18.0 wt%, from about 2.0 wt% to about 17.0 wt%, from about 2.0 wt% to about 16.0 wt%, from about 2.0 wt% to about 15.0 wt%, from about 2.0 wt% to about 14.0 wt%, from about 2.0 wt% to about 13.0 wt%, from about 2.0 wt% to about 12.0 wt%, from about 2.0 wt% to about 11.0 wt%, from about 2.0 wt% to about 10.0 wt%, from about 2.0 wt% to about 9.0 wt%, from about 2.0 wt% to about 8.0 wt%, from about 2.0 wt% to about 7.0 wt%, from about 2.0 wt% to about 6.0 wt%, from about 2.0 wt% to about 5.0 wt%, from about 2.0 wt% to about 4.0 wt%, from about 2.0 wt% to about 3.0 wt%, from about 3.0 wt% to about 20.0 wt%, from about 3.0 wt% to about 19.0 wt%, from about 3.0 wt% to about 18.0 wt%, from about 3.0 wt% to about 17.0 wt%, from about 3.0 wt% to about 16.0 wt%, from about 3.0 wt% to about 15.0 wt%, from about 3.0 wt% to about 14.0 wt%, from about 3.0 wt% to about 13.0 wt%, from about 3.0 wt% to about 12.0 wt%, from about 3.0 wt% to about 11.0 wt%, from about 3.0 wt% to about 10.0 wt%, from about 3.0 wt% to about 9.0 wt%, from about 3.0 wt% to about 8.0 wt%, from about 3.0 wt% to about 7.0 wt%, from about 3.0 wt% to about 6.0 wt%, from about 3.0 wt% to about 5.0 wt%, from about 3.0 wt% to about 4.0 wt%, from about 4.0 wt% to about 20.0 wt%, from about 5.0 wt% to about 20.0 wt%, from about 5.0 wt% to about 19.0 wt%, from about 5.0 wt% to about 18.0 wt%, from about 5.0 wt% to about 17.0 wt%, from about 5.0 wt% to about 16.0 wt%, from about 5.0 wt% to about 15.0 wt%, from about 5.0 wt% to about 14.0 wt%, from about 5.0 wt% to about 13.0 wt%, from about 5.0 wt% to about 12.0 wt%, from about 5.0 wt% to about 11.0 wt%, from about 5.0 wt% to about 10.0 wt%, from about 5.0 wt% to about 9.0 wt%, from about 5.0 wt% to about 8.0 wt%, from about 5.0 wt% to about 7.0 wt%, from about 5.0 wt% to about 6.0 wt%, from about 6.0 wt% to about 20.0 wt%, from about 6.0 wt% to about 19.0 wt%, from about 6.0 wt% to about 18.0 wt%, from about 6.0 wt% to about 17.0 wt%, from about 6.0 wt% to about 16.0 wt%, from about 6.0 wt% to about 15.0 wt%, from about 6.0 wt% to about 14.0 wt%, from about 6.0 wt% to about 13.0 wt%, from about 6.0 wt% to about 12.0 wt%, from about 6.0 wt% to about 11.0 wt%, from about 6.0 wt% to about 10.0 wt%, from about 6.0 wt% to about 9.0 wt%, from about 6.0 wt% to about 8.0 wt%, from about 6.0 wt% to about 7.0 wt%, from about 7.0 wt% to about 20.0 wt%, from about 7.0 wt% to about 19.0 wt%, from about 7.0 wt% to about 18.0 wt%, from about 7.0 wt% to about 17.0 wt%, from about 7.0 wt% to about 16.0 wt%, from about 7.0 wt%, to about 15.0 wt%, from about 7.0 wt% to about 14.0 wt%, from about 7.0 wt% to about 13.0 wt%, from about 7.0 wt% to about 12.0 wt%, from about 7.0 wt% to about 11.0 wt%, from about 7.0 wt% to about 10.0 wt%, from about 7.0 wt% to about 9.0 wt%, from about 7.0 wt% to about 8.0 wt%, from about 8.0 wt% to about 20.0 wt%, from about 8.0 wt% to about 19.0 wt%, from about 8.0 wt% to about 18.0 wt%, from about 8.0 wt% to about 17.0 wt%, from about 8.0 wt% to about 16.0 wt%, from about 8.0 wt% to about 15.0 wt%, from about 8.0 wt% to about 14.0 wt%, from about 8.0 wt% to about 13.0 wt%, from about 8.0 wt% to about 12.0 wt%, from about 8.0 wt% to about 11.0 wt%, from about 8.0 wt% to about 10.0 wt%, from about 8.0 wt% to about 9.0 wt%, about 9.0 wt% to about 20.0 wt%, about 9.0 wt% to about 19.0 wt%, about 9.0 wt% to about 18.0 wt%, about 9.0 wt% to about 17.0 wt%, about 9.0 wt% to about 16.0 wt%, about 9.0 wt% to about 15.0 wt%, about 9.0 wt% to about 14.0 wt%, about 9.0 wt% to about 13.0 wt%, about 9.0 wt% to about 12.0 wt%, about 9.0 wt% to about 11.0 wt%, about 9.0 wt% to about 10.0 wt%, about 10.0 wt% to about 20.0 wt%, about 10.0 wt% to about 19.0 wt%, about 10.0 wt% to about 18.0 wt%, about 10.0 wt% to about 17.0 wt%, about 10.0 wt% to about 16.0 wt%, about 10.0 wt% to about 15.0 wt%, about 10.0 wt% to about 14.0 wt%, about 10.0 wt% to about 13.0 wt%, about 10.0 wt% to about 12.0 wt%, about 10.0 wt% to about 11.0 wt%, about 11.0 wt% to about 20.0 wt%, about 11.0 wt% to about 19.0 wt%, about 11.0 wt% to about 18.0 wt%, about 11.0 wt% to about 17.0 wt%, about 11.0 wt% to about 16.0 wt%, about 11.0 wt% to about 15.0 wt%, about 11.0 wt% to about 14.0 wt%, about 11.0 wt% to about 13.0 wt%, about 11.0 wt% to about 12.0 wt%, about 12.0 wt% to about 20.0 wt%, about 12.0 wt% to about 19.0 wt%, about 12.0 wt% to about 18.0 wt%, about 12.0 wt% to about 17.0 wt%, about 12.0 wt% to about 16.0 wt%, about 12.0 wt% to about 15.0 wt%, about 12.0 wt% to about 14.0 wt%, about 12.0 wt% to about 13.0 wt%, about 13.0 wt% to about 20.0 wt%, about 13.0 wt% to about 19.0 wt%, about 13.0 wt% to about 18.0 wt%, about 13.0 wt% to about 17.0 wt%, about 13.0 wt% to about 16.0 wt%, about 13.0 wt% to about 15.0 wt%, about 13.0 wt% to about 14.0 wt%, about 14.0 wt% to about 20.0 wt%, about 14.0 wt% to about 19.0 wt%, about 14.0 wt% to about 18.0 wt%, about 14.0 wt% to about 17.0 wt%, about 14.0 wt% to about 16.0 wt%, about 14.0 wt% to about 15.0 wt%, about 15.0 wt% to about 20.0 wt%, about 15.0 wt% to about 19.0 wt%, about 15.0 wt% to about 18.0 wt%, about 15.0 wt% to about 17.0 wt%, about 15.It is present at a concentration of 0 wt% to about 16.0 wt%, about 16.0 wt% to about 20.0 wt%, about 16.0 wt% to about 19.0 wt%, about 16.0 wt% to about 18.0 wt%, about 16.0 wt% to about 17.0 wt%, about 17.0 wt% to about 20.0 wt%, about 17.0 wt% to about 19.0 wt%, about 17.0 wt% to about 18.0 wt%, about 18.0 wt% to about 20.0 wt%, about 18.0 wt% to about 19.0 wt%, or about 19.0 wt% to about 20.0 wt%.

[0054] Specific non-limiting examples of the lubricant additive composition include the following (R 1 is defined above):

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0055] The lubricant additive composition can be synthesized by any suitable method. For example, the general synthesis of Compound 1 is described in U.S. Patent No. 5,669,939 (incorporated herein by reference). Such reactions typically result in a product containing Compound 1 dissolved in an organic solvent. In some embodiments, it may be desirable to evaporate the organic solvent before using Compound 1.

[0056] In some embodiments, Compound 1 can be used as a starting material for synthesizing other lubricant additive compounds (e.g., Compounds 4, 5, 6). A summary of how Compounds 4, 5, and 6 can be derivatized by the reaction of Compound 1 with a reagent (glycidol) is shown below. The starting material is the same for each reaction. Only the charge molar ratio (Compound 1 to glycidol) is different. Other reagents besides glycidol can be contemplated. Further, the lubricant additive is not necessarily the reaction product of glycidol or derivatized by glycidol.

Chemical formula

Chemical formula

Chemical formula

[0057] Base oil The lubricating oil composition of the present invention includes one or more base oils (e.g., Group I, II, III, IV, or V). Further, the one or more base oils can include base oils from the same group (e.g., Group II Chevron Neutral Oil 600R (registered trademark), Group II Chevron Neutral Oil 220R (registered trademark), and Group II Chevron Neutral Oil 100R (registered trademark)). The amount of the base oil(s) is about 40 wt% or more (a "major amount"), e.g., about 45 wt% or more, 50 wt% or more, 55 wt% or more, 60 wt% or more, etc., based on the total weight of the lubricating oil composition.

[0058] Groups I, II, III, IV, and V are broad classifications of base oils developed and defined by the American Petroleum Institute (API Publication 1509 - Appendix E) for creating guidelines for lubricant base oils. The base materials of Group I contain less than 90% saturation and / or more than 0.03% sulfur, and have a viscosity index of 80 or more and less than 120. The base materials of Group II contain 90% or more saturation and 0.03% or less sulfur, and have a viscosity index of 80 or more and less than 120. The base materials of Group III contain 90% or more saturation and 0.03% or less sulfur, and have a viscosity index of 120 or more. The base materials of Group IV are polyalphaolefins. The base materials of Group V include all other base materials not included in Groups I, II, III, or IV. Table 1 summarizes the characteristics of each of these five groups. [Table 1]

[0059] Lubricating oil composition The lubricating oil compositions of the present disclosure can be identified by the viscosity specifications of the Society of Automotive Engineers (SAE) for engine oils (i.e., SAE J300 specification). The SAE J300 viscosity grades are summarized in Table 2. [Table 2]

[0060] The lubricating oil compositions of the present disclosure can be monograde engine oils, for example, engine oils of SAE20, SAE30, SAE40, SAE50, or SAE60 viscosity grades.

[0061] The lubricating oil compositions of the present disclosure can be multigrade engine oils, for example, engine oils having SAE viscosity grades of 15W-X, 20W-X, or 25W-X (X can be selected from 30, 40, 50, or 60).

[0062] Additional additives The lubricating oil composition of the present invention may contain one or more performance additives that can impart or improve any desired properties of the lubricating oil composition. Any additives known to those skilled in the art can be used in the lubricating oil composition disclosed herein. Some suitable additives are described in R.M. Mortier et al. “Chemistry and Technology of Lubricants,” 3 rd Edition, Springer (2010) and L.R. Rudnik “Lubricant Additives: Chemistry and Applications,” Second Edition, CRC Press (2009).

[0063] Generally, the concentration of each additive in the lubricating oil composition, when used, can be in the range of 0.001 to 60% by weight (e.g., 0.01 to 50% by weight, or 0.05 to 40% by weight) of the lubricating oil composition. Further, the total amount of additives in the lubricating oil composition can be in the range of 0.001 to 70% by weight (e.g., 0.01 to 50% by weight, or 0.1 to 40% by weight) of the lubricating oil composition.

[0064] The present lubricating oil composition may further contain one or more of other commonly used lubricating oil performance additives including antioxidants, antiwear agents, metal detergents, dispersants, friction modifiers, rust inhibitors, fluidizers, viscosity modifiers, pour point depressants, defoamers, and others.

[0065] Antioxidants Antioxidants retard the decomposition of the base oil during use due to oxidation. Such decomposition can lead to deposition on metal surfaces, the presence of sludge, or an increase in the viscosity of the lubricant. Useful antioxidants include hindered phenols, aromatic amines, sulfurized alkylphenols and alkalis, and their alkaline earth metal salts.

[0066] The hindered phenol antioxidant may contain a secondary butyl group and / or a tertiary butyl group as a steric hindrance group. The phenol group may be further substituted with a crosslinking group bonded to a hydrocarbyl group and / or a secondary aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 4,4'-bis(2,6-di-tert-butylphenol), and 4,4'-methylenebis(2,6-di-tert-butylphenol). The hindered phenol antioxidant may be an ester or an addition product derived from 2,6-di-tert-butylphenol and an alkyl acrylate, and the alkyl group may contain 1 to 18 carbon atoms.

[0067] Suitable aromatic amine antioxidants include diarylamines such as alkylated diphenylamines (e.g., dioctyldiphenylamine, dinonyldiphenylamine), phenyl-alpha-naphthalene, and alkylated phenyl-alpha-naphthalene.

[0068] Antiwear agent The antiwear agent reduces the wear of metal parts. Examples of antiwear agents include phosphorus-containing antiwear agents / extreme pressure agents such as metal thiophosphates, phosphate esters and their salts, phosphorus-containing carboxylic acids, esters, ethers, and amides, and phosphite esters. The antiwear agent may be zinc dialkyldithiophosphate. Phosphorus-free antiwear agents include boric acid esters (including boronated epoxides), dithiocarbamate compounds, molybdenum-containing compounds, and sulfurized olefins.

[0069] Metal detergent Typical detergents are anionic materials that contain a long-chain hydrophobic portion of the molecule and a smaller anionic or lipophobic hydrophilic portion of the molecule. The anionic portion of the detergent typically derives from an organic acid (such as sulfuric acid, carboxylic acid, phosphorous acid, phenol, or mixtures thereof). The counterion is typically an alkaline earth or alkali metal.

[0070] In some embodiments, the lubricating oil compositions provided herein include, as an additive or additive component, at least a neutral or overbased metal detergent. In certain embodiments, the metal detergent in the lubricating oil composition acts as a neutralizer for acidic products in the oil. In certain embodiments, the metal detergent prevents the formation of deposits on the surfaces of the engine. Depending on the nature of the acid used, the detergent may have additional functions, such as antioxidant properties. In certain aspects, the lubricating oil composition contains a metal detergent that includes either an overbased detergent or a mixture of a neutral detergent and an overbased detergent. The term "overbased" is intended to define an additive that contains a metal content in excess of that required by the stoichiometry of the particular metal and particular organic acid used. The excess metal is present in the form of particles of an inorganic base (such as a hydroxide or carbonate) surrounded by a sheath of the metal salt. The sheath serves to maintain the particles in a dispersed state in the liquid oily vehicle. The amount of excess metal is generally expressed as the ratio of the total equivalents of excess metal to the equivalents of organic acid and typically ranges from 0.1 to 30.

[0071] Some examples of suitable metal detergents include sulfided or non-sulfided alkyl or alkenyl phenates, alkyl or alkenyl aromatic sulfonates, borated sulfonates, sulfided or non-sulfided metal salts of multi-hydroxyalkyl or alkenyl aromatic compounds, alkyl or alkenyl hydroxyaromatic sulfonates, sulfided or non-sulfided alkyl or alkenyl naphthenates, metal salts of alkanoic acids, metal salts of alkyl or alkenyl polyacids, and their chemical and physical mixtures. Other examples of suitable metal detergents include metal sulfonates, phenates, salicylates (i.e., carboxylates, hydroxybenzoates) phosphonates, thiophosphonates and combinations thereof. The metal can be any metal suitable for the production of sulfonate, phenate, salicylate or phosphonate detergents. Non-limiting examples of suitable metals include alkali metals, alkaline metals and transition metals. In some embodiments, the metal is Ca, Mg, Ba, K, Na, Li, etc. An exemplary metal detergent that can be used in a lubricating oil composition includes overbased calcium sulfonate phenate.

[0072] Ashless dispersant A dispersant is an additive whose main function is to immobilize solid and liquid contaminants by keeping them in suspension, reducing sludge deposition and at the same time reducing engine deposits. For example, a dispersant keeps insoluble substances in the oil, which are formed by oxidation during the use of the lubricant, in suspension, thus preventing sludge aggregation and precipitation or deposition on the metal parts of the engine.

[0073] Dispersants are usually "ashless", i.e., non-metallic organic materials that do not substantially form ash upon combustion, as opposed to metal-containing materials and thus ash-forming materials. They contain long hydrocarbon chains with polar heads, the polarity being derived from the inclusion of at least one nitrogen, oxygen, or phosphorus atom. The hydrocarbon is, for example, a lipophilic group that imparts oil solubility and has 40 to 500 carbon atoms. Thus, ashless dispersants can include an oil-soluble polymer backbone.

[0074] Preferred classes of olefin polymers are constituted by polybutylenes, specifically polyisobutylene (PIB) or poly-n-butylene, such as can be prepared by polymerization of a C4 purification stream.

[0075] Examples of dispersants include derivatives of long-chain hydrocarbon-substituted carboxylic acids, such as derivatives of high molecular weight hydrocarbyl-substituted succinic acids. A group of dispersants of note is constituted by hydrocarbon-substituted succinimides, which are made, for example, by reacting the above acids (or derivatives) with nitrogen-containing compounds, preferably polyalkylene polyamines such as polyethylene polyamine. A typical commercially available polyisobutylene-based succinimide dispersant contains a polyisobutylene polymer having a number average molecular weight in the range of 900 to 2500, functionalized with maleic anhydride and derivatized with a polyamine having a molecular weight of 100 to 350.

[0076] Other suitable dispersants include succinic esters and ester-amides, Mannich bases, polyisobutylene succinic acid (PIBSA), and other related components.

[0077] Succinic esters are formed by the condensation reaction of a hydrocarbon-substituted succinic anhydride with an alcohol or polyol. For example, the condensation product of a hydrocarbon-substituted succinic anhydride and pentaerythritol is a useful dispersant.

[0078] Succinic ester-amides are formed by the condensation reaction of a hydrocarbon-substituted succinic anhydride with an alkanolamine. Examples of suitable alkanolamines include polyalkenyl polyamines such as ethoxylated polyalkyl polyamine, propoxylated polyalkyl polyamine, and polyethylene polyamine. One example is propoxylated hexamethylenediamine.

[0079] Mannich bases are produced from the reaction of alkylphenols, formaldehyde, and polyalkylene polyamines. The molecular weight of the alkylphenol can range from 800 to 2500.

[0080] The nitrogen-containing dispersant can be post-treated by conventional methods to improve the properties of any of various agents by reacting with any of them. Among these are boron compounds (e.g., boric acid) and cyclic carbonates (e.g., ethylene carbonate).

[0081] Friction modifier A friction modifier is any material(s) that can change the coefficient of friction of a surface lubricated by any lubricant or fluid containing such material(s). Friction modifiers include alkoxylated fatty amines, boricated fatty epoxides, fatty phosphates, fatty epoxides, fatty amines, boricated alkoxylated fatty amines, fatty acid metal salts, fatty acid amides, glycerol esters, boricated glycerol esters, and fatty imidazolines. The term "fatty" means a carbon chain having 10 to 22 carbon atoms, typically a straight carbon chain.

[0082] Other known friction modifiers include oil-soluble organomolybdenum compounds. Such organomolybdenum friction modifiers also provide antioxidant and antiwear benefits to lubricating oil compositions. Suitable oil-soluble organomolybdenum compounds have a molybdenum sulfur core. Examples can include dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, sulfides, and mixtures thereof. The molybdenum compounds can be dinuclear or trinuclear.

[0083] Corrosion inhibitor A corrosion inhibitor protects a lubricated metal surface from chemical attack by water or other contaminants. Suitable corrosion inhibitors include polyoxyalkylene polyols and their esters, polyoxyalkylene phenols, thiadiazoles, and anionic alkyl sulfonic acids.

[0084] Viscosity modifier The viscosity modifier provides a lubricant with operability at high and low temperatures. These additives increase the viscosity of the oil composition at high temperatures, thereby increasing the film thickness, but have a limited effect on the viscosity at low temperatures.

[0085] Suitable viscosity improvers include high molecular weight hydrocarbons, polyesters, and viscosity index improver-dispersants that function as both a viscosity index improver and a dispersant. The typical molecular weight of these polymers is in the range of 1,000 to 1,000,000 (for example, 2,000 to 500,000 or 25,000 to 100,000).

[0086] Examples of suitable viscosity improvers are polymers and copolymers of methacrylate, butadiene, olefin, or alkylated styrene. Polyisobutylene is a commonly used viscosity modifier. Another suitable viscosity modifier is polymethacrylate (for example, a copolymer of alkyl methacrylates of various chain lengths), which also functions as a pour point depressant depending on its formulation. Other suitable viscosity modifiers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (for example, copolymers of acrylates of various chain lengths). Specific examples include styrene-isoprene or styrene-butadiene-based polymers with a molecular weight of 50,000 to 200,000.

[0087] Pour point depressant The pour point depressant lowers the lowest temperature at which a fluid can flow or be poured. Suitable pour point depressants include C8-C18 dialkyl fumarate / vinyl acetate copolymers, polyalkyl methacrylates, and the like.

[0088] Foam inhibitor The foam inhibitor delays the formation of stable bubbles. Examples of suitable foam inhibitors include polysiloxanes, polyacrylates, and the like.

[0089] Thickener Viscosity modifiers can increase the viscosity of lubricant compositions to achieve the desired viscosity grade. Any suitable viscosity modifier such as polyisobutylene (PIB) can be used. PIB is a commercially available material from several manufacturers. Polyisobutylene typically has a number average molecular weight of 800 to 5000 (e.g., 1000 to 2500) and a kinematic viscosity of 200 to 5000 mm 2 / s (e.g., 200 to 1000 mm 2 / s) of a viscous oil-miscible liquid. The amount of PIB added to the lubricant composition can typically be 1 to 20 wt% (e.g., 2 to 15 wt% or 4 to 12 wt%) of the finished oil.

Examples

[0090] The following non-limiting examples are illustrative of the present invention. A brief description of the methods by which the examples were prepared and the test methods used to evaluate the lubricants of the present invention is provided.

[0091] Black sludge deposition test This test was used to evaluate the ability of lubricants to cope with unstable unburned asphaltenes in residual fuel oil. In this test, oxidative thermal stress is applied to a mixture of heavy fuel oil and lubricant to measure the tendency of the lubricant to produce deposits on the test strip.

[0092] During this test, a sample of the lubricant composition is mixed with a specific amount of residual fuel to form a test mixture. The test mixture is injected as a thin film onto a metal test strip for a certain period (12 hours) and at a temperature (200 °C). The test strip is then cooled, washed, dried, and then weighed. In this way, the weight (mg) of the deposit is measured and recorded as the change in the weight of the test strip.

[0093] DSC oxidation test The DSC test was used to evaluate the thin-film oxidation stability of the test oil in accordance with ASTM D-6186. During the test, the heat flow to and from the test oil in the sample cup was compared to a reference cup.

[0094] The oxidation start temperature is the temperature at which the oxidation of the test oil begins. The oxidation induction time (OIT) is the time at which the oxidation of the test oil begins. The longer the oxidation induction time, the better the performance. The oxidation reaction is exothermic as indicated by the heat flow. The oxidation induction time evaluates the thin-film oxidation stability of the test oil.

[0095] Pressure Differential Scanning Calorimetry (PDSC) Test (ASTM D-6186) Using the PDSC test, the oxidation stability of the test oil (at 180 °C and an oxygen pressure of 500 psi) can be measured by detecting the heat release of the energy that occurs when the oil auto-oxidizes. The length of time required to reach auto-oxidation is a measure of oxidation resistance and is known as the oxidation induction time.

[0096] During this test, a small amount of the test oil was weighed into a sample pan and placed in the test cell. The cell was heated to the specified temperature and then pressurized with oxygen. The cell was held at the regulated temperature and pressure until an exothermic reaction occurred. The extrapolated start time was measured and reported as the oxidation induction time of the lubricating oil at the specified test temperature.

[0097] TEOST MHT4 Test ASTM D-7097 is designed to predict the tendency of engine oil to form deposits in the piston ring belt and upper piston crown regions. In this test, the mass of the deposits formed on a specially constructed test rod exposed to repeated passes of 8.5 g of engine oil on the rod was determined at 285 °C under oxidation and catalytic conditions.

[0098] The tendency of engine oil to form deposits under acidic conditions is determined by circulating an oil-catalyst mixture containing a small amount (8.4 g) of oil and a very small amount (0.1 g) of an organometallic catalyst. This mixture was circulated for 24 hours on a deposition rod wrapped with a special wire heated by an electric current to a controlled temperature of 285 °C at the hottest position on the rod within a TEOST MHT apparatus. The weight of the rod was measured before and after the test. The deposits that fell from the rod into the oil were filtered and weighed. The total deposits were calculated as the sum of the weights of the deposits on the depositor rod and on the filter.

[0099] Base oil The base oil components used in the formulations of the examples include the following. 1) 600N: ExxonMobil CORE® 600N Group I lubricating oil (K v @100 °C 12.4 cSt) 2) 2500BS ExxonMobil CORE® 2500BS Group I lubricating oil (K v @100 °C 30.6 cSt.) 3) 600R: Chevron RLOP® 600R Group II lubricating oil (Kv @100 °C 11.9 cSt) 4) 220R: Chevron RLOP® 220R Group II lubricating oil (Kv @100 °C 6.45 cSt) 5) 150N: ExxonMobil CORE® 150N Group I lubricating oil (Kv @100 °C 5.3 cSt) 6) OCP VII: Oil concentrate of a 35 SSI ethylene-propylene olefin copolymer having about 60% ethylene and 80,000 Mn

[0100] Examples 1 to 3 and Comparative Example A The following specifications: 40 BN, SAE 50 viscosity grade (K v @100 °C 18.5 mm 2 / s) were formulated for Examples 1 to 3 and Comparative Example A to provide a marine cylinder lubricant (MCL) oil.

[0101] The following components were used in Examples 1 to 3. a) 18.3 to 19.1 wt% detergent additive package b) 1.5 wt% antioxidant c) 0.11 wt% anti-foaming agent d) Compound 1 (diluted with 30 wt% C9 aromatic solvent):

Chemical formula

[0102] Examples 1 to 3 differed in the amount of Compound 1 (see Table 3).

[0103] The formulation of Comparative Example A was the same as that of Examples 1 to 3. However, Comparative Example A did not contain Compound 1. Instead of Compound 1, a succinimide dispersant was added to Comparative Example A.

[0104] The completed lubricating oils were each evaluated for oxidation stability using a DSC oxidation test. The results are shown in Table 3 below.

Table 3

[0105] As demonstrated by the higher oxidation induction times of the Examples of the invention compared to Comparative Example A, the results shown in Table 3 indicate that the cylinder lubricating oil composition for ships containing the lubricating additive Compound 1 exhibits surprisingly superior oxidation performance compared to Comparative Example A. In addition to the improvement in oxidation performance, the marine diesel cylinder lubricating oil compositions of Examples 1 to 3 each achieved the desired viscosity using less bright stock than the Comparative Examples, demonstrating the thickening ability of the lubricating additive Compound 1. Examples 4 to 5 The following specifications: SAE 50 viscosity grade (each, K v @ 100 °C 18.5 and 20.44 mm 2 / s) were formulated for Examples 4 to 5 to provide a cylinder lubricant (MCL) oil for ships. The following components were used in Example 4. a) 4.0 wt% of 17BN low overbased calcium sulfonate detergent b) 14.0 wt% of 95BN low overbased calcium sulfonate phenate detergent derived from C20 - 24 isomerized alpha olefin c) 0.2 wt% of bis(succinimide) dispersant derived from 1000MW of PIB d) 0.75 wt% of phenolic antioxidant e) 0.75 wt% of amine antioxidant f) 1.0 wt% of Compound 2 g) 0.1 wt% of foam inhibitor The following components were used in Example 5. a) 19.8 wt% of 410BN high overbased calcium sulfonate detergent b) 0.1 wt% of 17BN low overbased calcium sulfonate detergent c) 14.0 wt% of 95BN low overbased calcium sulfonate phenate detergent derived from C20 - 24 isomerized alpha olefin c) 6.0 wt% of bis(succinimide) dispersant derived from 1000MW of PIB e) 1.0 wt% of zinc dithiophosphate derived from primary C8 alcohol f) 10.0 wt% of Compound 2 g) 0.1 wt% of foam inhibitor

[0106] The finished lubricating oils of Examples 4 - 5 were evaluated for oxidation stability using the DSC oxidation test. The results are shown in Table 4 below.

Table 4

[0107] The results shown in Table 4 illustrate that the cylinder lubricating oil composition for ships containing the lubricating additive Compound 2 exhibited the desired oxidation performance.

[0108] Example 6 and Comparative Example B The following specifications: 40BN, SAE50 viscosity grade (K v@100 °C 18.5 mm 2 Examples 6 and Comparative Example B were formulated to provide a marine cylinder lubricant (MCL) oil having ( / second).

[0109] The following components were used in Example 6. a) 8.5 wt% calcium 410BN overbased sulfonate b) 2.6 wt% calcium 95BN underbased sulfide phenate derived from C20-24 isomerized alpha olefin c) 0.2 wt% succinimide dispersant derived from 1000 MW of PIB d) 1.0 wt% amine antioxidant e) 0.1 wt% anti-foaming agent f) 6.0 wt% of Compound 2

[0110] The formulation of Comparative Example B was similar to that of Example 6. However, Comparative Example B did not contain the lubricant additive Compound 2.

[0111] Each of the finished oil lubricants was evaluated for deposition performance using the black sludge deposition test. The results are shown in Table 5 below.

Table 5

[0112] The results shown in Table 5 indicate that the marine cylinder lubricating oil composition containing the lubricant additive Compound 2 exhibited surprisingly better deposition performance than Comparative Example B, as Example 6 showed significantly less formation of black sludge deposits compared to Comparative Example B. In addition to the improved deposition control performance, the marine diesel cylinder lubricating oil composition of Example 6 achieved the desired viscosity using less thickener (2300 MW of PIB) than the comparative example, demonstrating the thickening ability of the lubricant additive Compound 2.

[0113] Example 7 and Comparative Example C The following specifications: 12 BN, SAE 40 viscosity grade (K v @100 °C 14.5 mm 2Examples 7 and Comparative Example C were formulated to provide trunk piston engine oil (TPEO) for ships having (××× / second).

[0114] The following components were used in Example 7. a) 0.85 wt% of 420BN overbased calcium hydroxybenzoate detergent derived from C20-24 isomerized alpha olefin b) 4.0 wt% of 180BN medium overbased calcium hydroxybenzoate detergent derived from C20-24 isomerized alpha olefin c) 5.0 wt% of ethylene carbonate post-treated succinimide dispersant derived from 2300 MW of PIB d) 0.5 wt% of amine-based antioxidant e) 0.7 wt% of zinc dithiophosphate derived from primary C8 alcohol f) 3.0 wt% of Compound 2 g) 0.1 wt% of anti-foaming agent

[0115] The formulation of Comparative Example C was similar to that of Example 7. However, Comparative Example C did not contain the lubricant additive Compound 2.

[0116] Each of the finished lubricants was evaluated for deposition performance using a black sludge deposition test. The results are shown in Table 6 below.

Table 6

[0117] The results shown in Table 6 indicate that the trunk piston engine lubricating oil composition containing the lubricant additive Compound 2 exhibited surprisingly better deposition performance than Comparative Example C, as Example 7 showed significantly less formation of black sludge deposits compared to Comparative Example C. In addition to the improved deposition control performance, the trunk piston engine lubricating oil composition of Example 7 achieved the desired viscosity without using a thickener, demonstrating the thickening ability of the lubricant additive Compound 2.

[0118] Rapid clean deposit removal The following specifications: SAE 30 viscosity grade (K v @100 °C approximately 15.0 mm 2 / s) were formulated in Examples 8 to 10 and Comparative Example D to provide a railway engine oil lubricating composition that meets these requirements.

[0119] Examples 8 to 10 were mixed with the following components: a) Group II base oil b) 9.7 wt% railway engine oil additive package c) Compound 2 (solvent distillation) at different treatment rates (Table 7):

Chemical formula

[0120] The additive package referred to in Table 7 is a representative railway engine oil package containing the following additives. a) Ethylene carbonate post-treated succinimide dispersant b) Molybdenum succinimide c) Calcium sulfonate phenate and calcium salicylate detergents d) Mannich base detergent e) Amine antioxidant f) Glycerol monooleate borate

[0121] The formulation examples in Table 7 do not contain zinc-based additives that are commonly used as anti-wear agents. Comparative Example D was similar to an example of the invention that did not contain Compound 2.

[0122] Experimental procedure 1 Compound 2 was added in different amounts to the finished oil containing the engine oil additive package, and its solubility and tendency to solubilize the deposition of carbonaceous rings were observed. It was mixed for 20 minutes at ambient temperature.

[0123] A ring section containing high-concentration carbonaceous deposits from an internal combustion engine was used in the experiment. The ring was pre-washed with hexane, dried, and then weighed to four decimal places. Next, the ring section was carefully placed into a beaker containing the finished oil (i.e., Examples 8-10 and Comparative Example D). The sample was left standing for 4, 6, and 24 hours without stirring in the finished oil. The approximate temperature of the finished oil was about 22 °C. Turbidity was formed around the sliced ring pieces, indicating that some of the deposits were removed. The ring segment was removed, rinsed with hexane, air-dried, and then reweighed.

Table 7

[0124] As shown in Table 7, the concentration of Compound 2 in the finished oil correlates well with deposit removal, similar to the soaking / residence time associated with deposit removal. The cumulative ring weight loss corresponding to deposit removal is reported in mg units (a higher mg value indicates better deposit removal performance).

[0125] Examples 11-12 and Comparative Example E Examples 11-12 and Comparative Example E were formulated to provide a natural gas engine oil (NGEO) composition having the following specifications: 3BN, SAE 40 viscosity grade, and 0.32% sulfuric acid ash. Examples 11-12 were mixed with the following components: a) 0.75 wt% succinimide dispersant derived from 1000 MW PIB b) 0.75 wt% succinimide dispersant derived from 1300 MW PIB c) 1.9 wt% 114BN overbased calcium sulfonate detergent d) 0.3 wt% zinc dithiophosphate derived from primary C8 alcohol e) 0.2 wt% 17BN calcium sulfonate f) 0.25 wt% phenolic antioxidant g) 50 ppm anti-foaming agent h) Compound 2 (solvent distillation) at different treatment rates (Table 8)

[0126] The formulation of Comparative Example E was the same as that of Examples 11 to 12. However, Comparative Example E did not contain the lubricating additive compound 2. The natural gas engine oil was formulated using Chevron RLOP 600R Group II base oil.

[0127] The completed lubricants were evaluated for oxidation stability using the PDSC test and for deposit performance using the TEOST MHT test, respectively. The results of each example are shown in Table 8 below.

Table 8

[0128] As is clear from the longer oxidation induction time, the results shown in Table 8 indicate that the natural gas engine lubricant compositions containing the lubricating additive compound 2 exhibited surprisingly superior oxidation stability performance compared to Comparative Example E. Examples 11 to 12 also showed better deposit performance in the TEOST MHT deposit test, as is clear from the low total deposit amount at the end of the test.

[0129] Examples 13 - 14 and Comparative Example F Examples 13 - 14 and Comparative Example F were formulated to provide an ashless natural gas engine oil (NGEO) composition having the following specifications: 1BN, SAE 40 viscosity grade, and 0.06% sulfuric acid ash. Examples 13 - 14 were mixed with the following components: a) 0.75 wt% succinimide dispersant derived from 1000 MW PIB b) 0.75 wt% succinimide dispersant derived from 1300 MW PIB c) 0.3 wt% zinc dithiophosphate derived from primary C8 alcohol d) 0.25 wt% phenolic antioxidant e) 50 ppm foam inhibitor f) Compound 2 (solvent distillation) at different treatment rates (Table 9)

[0130] The formulation of Comparative Example F was the same as that of Examples 13 to 14. However, Comparative Example F did not contain the lubricating additive compound 2. The natural gas engine oil component was formulated using Chevron RLOP 600R Group II base oil.

[0131] The completed lubricating oils were each evaluated for oxidation stability using the PDSC test. The results of each example are shown in Table 9 below.

Table 9

[0132] As is apparent from the longer oxidation induction times, the results shown in Table 9 indicate that the ashless natural gas engine lubricating oil composition containing the lubricating additive compound 2 exhibited surprisingly superior oxidation stability performance compared to Comparative Example F.

[0133] Examples 15 - 16 and Comparative Example G Examples 15 - 16 and Comparative Example G were formulated to provide a natural gas engine oil (NGEO) composition having the following specifications: 3BN, SAE 40 viscosity grade, and 0.3% sulfuric acid ash. Examples 15 - 16 were mixed with the following components: a) 0.75 wt% succinimide dispersant derived from 1000 MW PIB b) 0.75 wt% succinimide dispersant derived from 1300 MW PIB c) 0.47 wt% 114BN low overbased calcium sulfonate phenate d) 0.2 wt% 260BN high overbased calcium sulfonate phenate e) 0.85 wt% 17BN calcium sulfonate f) 0.31 wt% 180BN medium overbased calcium hydroxybenzoate derived from isomerized C20 - 24 olefins g) 0.3 wt% zinc dithiophosphate derived from primary C8 alcohol h) 0.25 wt% phenolic antioxidant i) 50 ppm anti - foaming agent j) Compound 2 (solvent distillation) at different processing speeds (Table 10)

[0134] The formulation of Comparative Example G was the same as in Examples 15 to 16. However, Comparative Example G did not contain the lubricating additive compound 2. The natural gas engine oil was formulated using Chevron RLOP 600R Group II base oil.

[0135] The completed lubricating oils were each evaluated for oxidation stability using the PDSC test. The results of each example are shown in Table 10 below.

Table 10

[0136] Examples 17 - 18 and Comparative Example H Examples 17 - 18 and Comparative Example H were formulated to provide a natural gas engine oil (NGEO) composition having the following specifications: 4BN, SAE 40 viscosity grade, and 0.58% sulfuric acid ash. Examples 17 - 18 were mixed with the following components: a) 0.75 wt% succinimide dispersant derived from 1000 MW PIB b) 0.75 wt% succinimide dispersant derived from 1300 MW PIB c) 0.94 wt% 114BN low overbased calcium sulfonate phenate d) 0.42 wt% 260BN high overbased calcium sulfonate phenate e) 1.71 wt% 17BN calcium sulfonate f) 0.63 wt% 180BN medium overbased calcium hydroxybenzoate derived from isomerized C20 - 24 olefins g) 0.3 wt% zinc dithiophosphate derived from primary C8 alcohol h) 0.25 wt% phenolic antioxidant i) 50 ppm anti-foaming agent j) Compound 2 (solvent distillation) at different processing speeds (Table 11)

[0137] The formulation of Comparative Example H was the same as that of Examples 17 - 18. However, Comparative Example H did not contain the lubricant additive Compound 2. The natural gas engine oil composition was formulated using Chevron RLOP 600R Group II base oil.

[0138] The completed lubricants were each evaluated for oxidation stability using the PDSC test. The results of each example are shown in Table 11 below.

Table 11

[0139] The results shown in Table 11 indicate that the natural gas engine lubricant composition containing the lubricant additive Compound 2 exhibited surprisingly superior oxidation stability performance compared to Comparative Example H, as evidenced by a longer oxidation induction time.

[0140] Examples 19 - 20 and Comparative Example I Examples 19 - 20 and Comparative Example I were formulated using Chevron RLOP 600R Group II base oil to provide a low - ash dual - fuel engine oil composition with the following specifications: 3BN, SAE 40 viscosity grade lubricant. Examples 19 - 20 were mixed with the following components: a) 1.0 wt% succinimide dispersant derived from 1300 MW PIB b) 1.0 wt% ethylene carbonate post - treated succinimide dispersant derived from 2300 MW PIB c) 1.1 wt% 114BN low - overbased calcium sulfonate phenate d) 0.5 wt% 260BN high - overbased calcium sulfonate phenate e) 0.7 wt% 17BN calcium sulfonate f) 0.1 wt% of medium overbased calcium hydroxybenzoate 180BN derived from isomerized C20 - 24 olefins g) 0.3 wt% of zinc dithiophosphate derived from primary C8 alcohol h) 0.35 wt% of phenolic antioxidant i) 50 ppm of anti - foaming agent j) Compound 2 (solvent distillation) at different treatment rates (Table 12)

[0141] The formulation of Comparative Example I was the same as that of Examples 19 - 20. However, Comparative Example I did not contain the lubricating additive Compound 2.

[0142] The completed oil lubricants were each evaluated for oxidation stability using a DSC test. The results of each example are shown in Table 12 below.

Table 12

[0143] The results shown in Table 12 indicate that, as revealed by a longer oxidation induction time, the dual - fuel engine lubricating oil composition containing the lubricating additive Compound 2 exhibited surprisingly excellent oxidation stability performance compared to Comparative Example I.

[0144] Examples 21 - 22 and Comparative Example J Examples 21 - 22 and Comparative Example J were formulated to provide a railway engine oil composition with the following specifications: a lubricant with 15BN, SAE 20W - 40 viscosity grade. Examples 21 - 22 were mixed with the following components: a) 1.0 wt% of succinimide dispersant derived from 1300MW PIB b) 1.0 wt% of ethylene carbonate post - treated succinimide dispersant derived from 2300MW PIB c) 1.9 wt% of 114BN low overbased calcium sulfonate phenate d) 4.6 wt% of 260BN high overbased calcium sulfonate phenate e) 0.9 wt% calcium 17BN sulfonate f) 0.1 wt% amine antioxidant g) 50 ppm anti-foaming agent h) Compound 2 (solvent distillation) at different processing speeds (Table 13)

[0145] The formulation of Comparative Example J was the same as that of Examples 21-22. However, Comparative Example J did not contain the lubricating additive Compound 2.

[0146] The completed lubricating oils were each evaluated for oxidation stability using a DSC test. The results of each example are shown in Table 13 below.

Table 13

[0147] As is clear from the longer oxidation induction times, the results listed in Table 13 show that the railway engine lubricating oil compositions containing the lubricating additive Compound 2 exhibited surprisingly superior oxidation stability performance compared to Comparative Example J. In addition to the improvement in oxidation stability performance, the railway engine oil lubricating oil compositions of Examples 21-22 achieved the desired viscosity grade with a smaller amount of high-viscosity base oil (600R), demonstrating the thickening ability of the lubricating additive Compound 2.

[0148] For the sake of brevity, only specific ranges are explicitly disclosed in this specification. However, ranges from any lower limit may be combined with any upper limit to enumerate ranges not explicitly described, and similarly, ranges from any lower limit may be combined with other arbitrary lower limits to enumerate ranges not explicitly described, and similarly, ranges from any upper limit may be combined with other arbitrary upper limits to enumerate ranges not explicitly described. Furthermore, within a range, all points or individual values between its endpoints are included even if not explicitly listed. Thus, all points or individual values may be combined with other points or individual values, or other lower or upper limits, to function as their own lower or upper limits and enumerate ranges not explicitly described.

[0149] Similarly, the term "comprising" is considered to be synonymous with the term "including". Similarly, whenever there is a transitional phrase "comprising" before a composition, element, or group of elements, it is always understood to also contemplate the same composition or group of elements with a transitional phrase "consisting essentially of", "consisting of", "selected from the group consisting of", or "being" before the description of the composition, element, or group of elements, and vice versa.

[0150] As used herein, the terms "a" and "the" are understood to encompass not only the singular but also the plural forms.

[0151] Various terms are defined above. To the extent that a term used in a claim is not defined above, the broadest definition given to that term by an expert in the relevant technical field, as reflected in at least one printed publication or issued patent, shall be given. Further, all patents, test methods, and other documents cited in this application are hereby incorporated by reference in their entirety to the extent such disclosure is not inconsistent with this application and in all jurisdictions in which such incorporation is permitted.

[0152] The above description of the present disclosure is illustrative and explanatory thereof. Further, while the present disclosure shows and describes only preferred embodiments, as described above, the present disclosure is capable of being used in other various combinations, modifications, and environments, and within the scope of the concepts expressed herein, changes or modifications commensurate with the above teachings and / or the skill or knowledge of the relevant art are possible. It is to be understood that the above is directed to embodiments of the present disclosure, but other additional embodiments of the present disclosure can be devised without departing from the basic scope thereof, which is determined by the claims that follow.

[0153] When combinations, subsets, groups, etc. of elements (e.g., combinations of components in a composition, or combinations of steps in a method) are disclosed, specific references to each of the various individual and collective combinations and permutations of these elements may not be explicitly disclosed, but each is specifically contemplated and understood to be described herein.

[0154] The embodiments described herein are further intended to explain the best mode known for carrying out the invention and to enable other persons skilled in the art to utilize the disclosure with various modifications required for a particular application or use in such or other embodiments. Accordingly, the description is not intended to be limited to the forms disclosed herein. Also, the appended claims are intended to be construed to include alternative embodiments.

Claims

1. A gas fuel engine lubricating oil composition comprising a major amount of base oil, and a lubricating additive having the following structure 【Chemical 1】 (wherein each R １ is independently a hydrocarbyl group having 10 to 400 carbons, X is an alkyl, aryl, or aromatic heterocyclic group having 1 to 10 carbons, Y is nitrogen, oxygen, or sulfur, and each R ２ is independently a hydrocarbyl group having 1 to 9 carbons, Z is nitrogen, oxygen, or sulfur, and each R ３ is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons containing functionalization with one or more nitrogen, oxygen, or sulfur functional groups, p is 1 to 3, n is 1 to 20, and m is 0 to 3), the gas fuel engine lubricating oil composition comprising

2. The gas fuel engine lubricating oil composition according to claim 1, wherein the lubricating additive is present in an amount of about 0.1 to about 50% by weight based on the total weight of the lubricating oil composition.

3. R １ The gas fuel engine lubricating oil composition according to claim 1, wherein R is a polyisobutenyl group.

4. The lubricating additive has the following general structure: [Chemical 2] (wherein each R １ is independently a hydrocarbyl group having 10 to 400 carbons, Y is nitrogen, oxygen, or sulfur, each R ２ is independently a hydrocarbyl group having 1 to 9 carbons, Z is nitrogen, oxygen, or sulfur, each R ３ is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons including functionalization with one or more nitrogen, oxygen, or sulfur functional groups, p is 1 to 3, n is 1 to 20, and m is 0 to 3), the gas fuel engine lubricating oil composition according to claim 1.

5. The gas fuel engine lubricating oil composition according to claim 1, wherein the gas fuel engine lubricating oil composition has a total base number of 2 to 10 mg KOH / g.

6. The gas fuel engine lubricating oil composition according to claim 1, wherein the gas fuel engine lubricating oil composition is an engine oil of SAE 20, SAE 30, SAE 40, SAE 50 or SAE 60 viscosity grade.

7. The gas fuel engine lubricating oil composition according to claim 1, wherein the gas fuel engine lubricating oil composition is an engine oil of SAE 15W-X, 20W-X, or 25W-X viscosity grade, wherein X is 30, 40, 50, or 60.

8. A lubricating oil composition for a low-speed or medium-speed diesel engine, the composition comprising a major amount of base oil, and a lubricating additive having the following structure 【Chemical Formula 3】 (wherein each R １ is independently a hydrocarbyl group having 10 to 400 carbons, X is an alkyl, aryl, or aromatic heterocyclic group having 1 to 10 carbons, Y is nitrogen, oxygen, or sulfur, each R ２ is independently a hydrocarbyl group having 1 to 9 carbons, Z is nitrogen, oxygen, or sulfur, each R ３ is independently hydrogen, or a hydrocarbyl group having 1 to 9 carbons including functionalization with one or more nitrogen, oxygen, or sulfur functional groups, p is 1 to 3, n is 1 to 20, and m is 0 to 3), the lubricating oil composition comprising.

9. The lubricating oil composition according to claim 8, wherein the lubricating additive is present in an amount of about 0.1 to about 50% by weight based on the total weight of the lubricating oil composition.

10. R １ The lubricating oil composition according to claim 8, wherein R is a polyisobutenyl group.

11. The lubricating additive has the following general structure: 【Chemical Formula 4】 (wherein each R １ is independently a hydrocarbyl group having 10 to 400 carbons, Y is nitrogen, oxygen, or sulfur, each R ２ is independently a hydrocarbyl group having 1 to 9 carbons, Z is nitrogen, oxygen, or sulfur, each R ３ is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons and containing one or more nitrogen, oxygen, or sulfur functionalizations, p is 1 to 3, n is 1 to 20, and m is 0 to 3), the lubricating oil composition according to claim 8.

12. The lubricating oil composition according to claim 8, wherein the lubricating oil composition has a total base number of 5 to 200 mg KOH / g.

13. The lubricating composition according to claim 8, wherein the lubricating oil composition is a marine diesel engine monograde composition meeting the viscosity specifications of an engine oil of SAE 20, SAE 30, SAE 40, SAE 50, or SAE 60 viscosity grade.

14. The lubricating oil composition according to claim 8, wherein the lubricating oil composition is an engine oil of SAE 15W-X, 20W-X, or 25W-X viscosity grade, wherein X is 30, 40, 50, or 60.

15. A method of thickening a lubricating oil composition in a gas fuel, low-speed, or medium-speed engine, the method comprising adding a lubricating oil composition to the engine, the lubricating oil composition comprising a major amount of base oil, and a lubricating additive having the following structure: 【Chemical Formula 5】 (wherein each R １ is independently a hydrocarbyl group having 10 to 400 carbons, X is an alkyl, aryl, or aromatic heterocyclic group having 1 to 10 carbons, Y is nitrogen, oxygen, or sulfur, each R ２ is independently a hydrocarbyl group having 1 to 9 carbons, Z is nitrogen, oxygen, or sulfur, each R ３ is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons including functionalization with one or more nitrogen, oxygen, or sulfur functional groups, p is 1 to 3, n is 1 to 20, and m is 0 to 3) comprising said method.

16. The method according to claim 15, wherein the lubricating additive is present in an amount of about 0.1 to about 50% by weight based on the total weight of the lubricating oil composition.

17. R １ The method according to claim 15, wherein R is a polyisobutenyl group.

18. The lubricating additive has the following general structure: ​ (wherein each R １ is independently a hydrocarbyl group having 10 to 400 carbons, Y is nitrogen, oxygen, or sulfur, each R ２ is independently a hydrocarbyl group having 1 to 9 carbons, Z is nitrogen, oxygen, or sulfur, each R ３ is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons containing one or more nitrogen, oxygen, or sulfur functionalizations, p is 1 to 3, n is 1 to 20, and m is 0 to 3), the method according to claim 15.

19. The method according to claim 15, wherein the lubricating oil composition has a total base number of 5 to 200 mg KOH / g.

20. The method according to claim 15, wherein the lubricating oil composition is an engine oil having a viscosity grade of SAE 20, SAE 30, SAE 40, SAE 50, or SAE 60.

21. The method according to claim 15, wherein the lubricating oil composition is an engine oil having a viscosity grade of SAE 15W-X, 20W-X, or 25W-X, wherein X is 30, 40, 50, or 60.

22. The method according to claim 15, wherein the engine is a stationary natural gas engine, a stationary biogas engine, a stationary landfill gas engine, a stationary non-conventional gas fuel engine, or a dual fuel engine.

23. The method according to claim 15, wherein the engine is a low-speed diesel engine or a medium-speed diesel engine.

24. The method according to claim 23, wherein the low-speed diesel engine is a marine crosshead diesel engine.

25. The method according to claim 23, wherein the medium-speed diesel engine is a locomotive diesel engine, a marine trunk piston diesel engine, or a land-based stationary power diesel engine.

26. A method for improving the cleanliness or oxidation inhibition of pistons in an engine, the method comprising lubricating the engine with a lubricating oil composition, the lubricating oil composition comprising a major amount of base oil, and a lubricating additive having the following structure: 【Chemical Formula 7】 (wherein each R １ is independently a hydrocarbyl group having 10 to 400 carbons, X is an alkyl, aryl, or aromatic heterocyclic group having 1 to 10 carbons, Y is nitrogen, oxygen, or sulfur, each R ２ is independently a hydrocarbyl group having 1 to 9 carbons, Z is nitrogen, oxygen, or sulfur, each R ３ is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons containing functionalization with one or more nitrogen, oxygen, or sulfur functional groups, p is 1 to 3, n is 1 to 20, and m is 0 to 3).

27. The lubricating additive has the following general structure: 【Chemical Formula 8】 (wherein each R １ is a hydrocarbyl group having 10 to 400 carbons, Y is nitrogen, oxygen, or sulfur, each R ２ is independently a hydrocarbyl group having 1 to 9 carbons, Z is nitrogen, oxygen, or sulfur, each R ３ is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons including functionalization with one or more nitrogen, oxygen, or sulfur functional groups, n is from 1 to 20, and m is from 1 to 3), the method according to claim 26.

28. A method for removing existing deposits in an internal combustion engine, the method comprising lubricating the engine with a composition, the composition comprising base oil, and an additive having the following structure: 【Chemical Formula 9】 (wherein each R １ is independently a hydrocarbyl group having 10 to 400 carbons, X is an alkyl, aryl, or aromatic heterocyclic group having 1 to 10 carbons, Y is nitrogen, oxygen, or sulfur, each R ２ is independently a hydrocarbyl group having 1 to 9 carbons, Z is nitrogen, oxygen, or sulfur, each R ３ is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons including functionalization with one or more nitrogen, oxygen, or sulfur functional groups, p is 1 to 3, n is 1 to 20, and m is 0 to 3).

29. The method according to claim 28, wherein the additive is present in an amount of about 0.1 to about 50% by weight based on the total weight of the composition.

30. R １ The method according to claim 28, wherein R is a polyisobutenyl group.

31. The additive has the following general structure: 【Chemical Formula 10】 (wherein each R １ is independently a hydrocarbyl group having 10 to 400 carbons, Y is nitrogen, oxygen, or sulfur, each R ２ is independently a hydrocarbyl group having 1 to 9 carbons, Z is nitrogen, oxygen, or sulfur, each R ３ is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons containing one or more nitrogen, oxygen, or sulfur functionalizations, p is 1 to 3, n is 1 to 20, and m is 0 to 3), the method according to claim 28.

32. R １ The method according to claim 28, wherein R is independently a hydrocarbyl group having 75 to 400 carbons.

33. The method according to claim 30, wherein the polyisobutenyl group has an average molecular weight of 800 to 5000.

34. A method for removing existing deposits from a crankcase, rocker cover, camshaft region, timing gear cover, cylinder head, combustion chamber, piston ring, and / or groove within an internal combustion engine, the method comprising lubricating the engine with a composition, the composition comprising: a base oil, and an additive having the following structure: 【Chemical Formula 11】 (In the formula, each R １ is independently a hydrocarbyl group having 10 to 400 carbons, X is an alkyl, aryl, or aromatic heterocyclic group having 1 to 10 carbons, Y is nitrogen, oxygen, or sulfur, each R ２ is independently a hydrocarbyl group having 1 to 9 carbons, Z is nitrogen, oxygen, or sulfur, each R ３ is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons including functionalization with one or more nitrogen, oxygen, or sulfur functional groups, p is 1 to 3, n is 1 to 20, and m is 0 to 3).

35. The method according to claim 34, wherein the additive is present in an amount of about 0.1 to about 50% by weight based on the total weight of the composition.

36. R １ The method according to claim 34, wherein R is a polyisobutenyl group.

37. The additive has the following general structure: 【Chemical Formula 12】 (wherein each R １ is independently a hydrocarbyl group having 10 to 400 carbons, Y is nitrogen, oxygen, or sulfur, each R ２ is independently a hydrocarbyl group having 1 to 9 carbons, Z is nitrogen, oxygen, or sulfur, each R ３ is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons containing one or more nitrogen, oxygen, or sulfur functionalizations, p is 1 to 3, n is 1 to 20, and m is 0 to 3), the method according to claim 34.

38. R １ The method according to claim 34, wherein R is independently a hydrocarbyl group having 75 to 400 carbons.

39. The method according to claim 36, wherein the polyisobutenyl group has an average molecular weight of 800 to 5000.

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