Lubricant additive

Abstract

The present disclosure describes a gaseous fuel, a low or medium speed engine lubricating oil composition. The composition comprises a major amount of a base oil; and a lubricant additive having the following structure: (I) # imgabs0 # wherein each R1 is independently a hydrocarbyl group having from 10 to 400 carbons; x is an alkyl, aryl or heteroaromatic group having 1 to 10 carbons; y is nitrogen, oxygen or sulfur; each R2 is independently a hydrocarbyl group having 1 to 9 carbons; z is nitrogen, oxygen or sulfur; and each R3 is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons with one or more nitrogen, oxygen or sulfur functionalizations wherein p is 1 to 3, n is 1 to 20 and m is 0 to 3.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 339,576, filed on May 9, 2022, which is incorporated herein by reference in its entirety. Technical Field

[0003] The present disclosure relates to lubricant additive compositions and lubricating oil compositions containing the lubricant additive compositions. More specifically, these compositions improve oxidation stability and / or deposit control in an engine environment. Background Art

[0004] While all engines place stress on the lubricant, some engines operate continuously at near full load and high temperature conditions, which place greater thermal stress on the lubricant. Under such conditions, the engine is particularly susceptible to oxidation and deposit formation, which can result in a significant reduction in engine performance. In addition, some of these engines require the lubricant to be within a specified viscosity range, thus requiring the use of components such as thickeners. Summary of the invention

[0005] In one aspect, a gaseous fuel engine lubricating oil composition is provided, the composition comprising: a major amount of a base oil; and a lubricant additive having the following structure:

[0006]

[0007] Each R 1 is independently a hydrocarbon group having 10 to 400 carbon atoms; X is an alkyl, aryl or heteroaromatic group having 1 to 10 carbon atoms; 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; and each R 3 is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons with one or more nitrogen, oxygen or sulfur functionalizations, wherein p is 1 to 3, n is 1 to 20 and m is 0 to 3.

[0008] In another aspect, a lubricating oil composition for a low-speed or medium-speed diesel engine is provided, the composition comprising: a major amount of a base oil; and a lubricant additive having the following structure:

[0009]

[0010] Each R 1 is independently a hydrocarbon group having 10 to 400 carbon atoms; X is an alkyl, aryl or heteroaromatic group having 1 to 10 carbon atoms; Y is nitrogen, oxygen or sulfur; each R 2is 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 with one or more nitrogen, oxygen or sulfur functionalizations, wherein p is 1 to 3, n is 1 to 20 and m is 0 to 3.

[0011] In yet another aspect, there is provided a method of thickening a lubricating oil composition in a gaseous fuel, slow or medium speed engine, the method comprising adding to the engine a lubricating oil composition comprising: a major amount of a base oil; and a lubricant additive having the following structure:

[0012]

[0013] Each R 1 is independently a hydrocarbon group having 10 to 400 carbon atoms; X is an alkyl, aryl or heteroaromatic group having 1 to 10 carbon atoms; 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; and each R 3 is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons with one or more nitrogen, oxygen or sulfur functionalizations, wherein p is 1 to 3, n is 1 to 20 and m is 0 to 3.

[0014] 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 comprising: a base oil; and a lubricant additive having the following structure:

[0015]

[0016] Each R 1 is independently a hydrocarbon group having 10 to 400 carbon atoms; X is an alkyl, aryl or heteroaromatic group having 1 to 10 carbon atoms; 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; and each R 3 is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons with one or more nitrogen, oxygen or sulfur functionalizations, wherein p is 1 to 3, n is 1 to 20 and m is 0 to 3.

[0017] In yet another aspect, a method of removing existing deposits in an internal combustion engine is provided, the method comprising lubricating the engine with a composition comprising: a base oil; and an additive having the following structure:

[0018]

[0019] Each R 1is independently a hydrocarbon group having 10 to 400 carbon atoms; X is an alkyl, aryl or heteroaromatic group having 1 to 10 carbon atoms; 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; and each R 3 is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons with one or more nitrogen, oxygen or sulfur functionalizations, wherein p is 1 to 3, n is 1 to 20 and m is 0 to 3.

[0020] In yet another aspect, a method for removing existing deposits from a crankcase, rocker cover, camshaft area, timing cover, cylinder head, combustion chamber, piston ring and / or annular groove in an internal combustion engine is provided, the method comprising lubricating or flash cleaning the engine with a composition comprising: a base oil; and an additive having the following structure:

[0021]

[0022] Each R 1 is independently a hydrocarbon group having 10 to 400 carbon atoms; X is an alkyl, aryl or heteroaromatic group having 1 to 10 carbon atoms; 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; and each R 3 is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons with one or more nitrogen, oxygen or sulfur functionalizations, wherein p is 1 to 3, n is 1 to 20 and m is 0 to 3. DETAILED DESCRIPTION

[0023] It should be understood that when combinations, subsets, groups, etc. of elements are disclosed (e.g., combinations of components in compositions, or combinations of steps in methods), while specific reference to each of the various individual and collective combinations and arrangements of these elements may not be explicitly disclosed, each is specifically contemplated and described herein.

[0024] The present disclosure relates to lubricant additive compositions having enhanced oxidation stability, thickening ability, and / or deposit control ability (ie, preventing deposit formation and / or removing existing deposits), lubricating oil compositions containing the lubricant additives, and methods of using the compositions.

[0025] When used during routine maintenance, such as OEM recommended scheduled oil changes, the lubricating oil composition is primarily (not necessarily exclusively) used to prevent deposit formation. When used as needed, such as for a quick cleaning service, the lubricating oil composition is primarily (not necessarily exclusively) used to remove existing deposits.

[0026] Composition disclosed herein is particularly suitable for engines operated under continuous high load conditions, such as gaseous fuel engines, dual fuel engines and low or medium speed engines. The engine can be a two-stroke engine or a four-stroke engine. The engine can also include any number (e.g., 1-24) of combustion chambers, pistons and associated cylinders. For example, in certain embodiments, the engine can be a large-scale industrial reciprocating engine with 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 16, 18, 20, 24 or more pistons that reciprocate in the cylinder. In certain embodiments, the piston can be an aluminum piston or a steel piston (e.g., any one of steel alloys in steel or a variety of steel alloys, such as 42CrMo4V or 38MnVS6).

[0027] A gas fuel engine can be a stationary natural gas engine, a stationary biogas engine, a stationary landfill gas engine, a stationary unconventional gas fuel engine, or a dual fuel engine. A dual fuel engine can operate using a mixture of two different fuels. Typically, diesel fuel and natural gas fuel are used together in a dual fuel engine. In addition to natural gas and diesel, some dual fuel engines can also use different mixtures of biodiesel, landfill gas, biogas, and other fuels.

[0028] Fuels used to operate gaseous fuel engines may include carbon-based gaseous fuels (eg, natural gas, biogas, landfill gas, wood gas, methane, propane, butane, etc.) and non-carbon-based gaseous fuels (eg, ammonia, hydrogen).

[0029] Diesel engines can generally be classified as low-speed, medium-speed or high-speed engines. Herein, a "low-speed" engine means a compression-ignition internal combustion engine 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 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; a "high-speed" engine means a compression-ignition internal combustion engine driven at a rotational speed of more than 1800 rpm, such as a diesel engine for road vehicles.

[0030] 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 bar to 30 bar (1.0 to 3.0 MPa), 20 bar to 30 bar (2.0 to 3.0 MPa), 22 bar to 30 bar (2.2 to 3.0 MPa), 22 bar to 28 bar (2.2 to 2.8 MPa), or 24 bar to 30 bar (2.4 to 3.0 MPa).

[0031] The lubricant additives disclosed herein and compositions comprising the lubricant additives can be used in many lubricant applications, such as railway engine oils (RREOs), marine system oils (SOs), marine cylinder lubricants (MCLs), trunk piston engine oils (TPEOs), natural gas engine oils (NGEOs), or dual fuel (DF) engine oils.

[0032] In some embodiments, the lubricating oil compositions disclosed herein have a total base number (TBN) of 2 to 200, such as 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 mgKOH / g.

[0033] In some embodiments, the lubricating oil composition disclosed herein is suitable for use as a marine cylinder lubricant for lubricating a low-speed crosshead engine. Marine cylinder lubricants are typically manufactured according to SAE 30, SAE 40, SAE 50 or SAE 60 single-grade specifications to provide a sufficiently thick lubricant film on the cylinder liner wall at high temperatures. Typically, the marine diesel engine cylinder lubricant has up to 200 mg KOH / g or 2 to 200 mg KOH / g (e.g., 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). KOH / g, 60 to 80 mg KOH / g, 80 to 200 mg KOH / g, 80 to 150 mg KOH / g, 80 to 150 mg 120 KOH / g, 120 to 200 mg KOH / g, or 120 to 150 mg KOH / g).

[0034] In some embodiments, the lubricating oil composition disclosed herein is suitable for use as a marine system oil for lubricating the crankcase of a low-speed crosshead engine. Marine system oil lubricants are generally prepared according to SAE 20, SAE 30 or SAE 40 single-grade specifications. The viscosity of the marine system oil is set at a relatively low level, in part because the viscosity of the system oil may increase during use and the engine designer has set a viscosity increase limit to prevent operational problems. Typically, the marine system oil lubricant has a TBN in the range of up to 12 mg KOH / g or 2 to 12 mg KOH / g (e.g., 3 to 12 mg KOH / g, 5 to 12 mg KOH / g, 5 to 10 mg KOH / g or 5 to 9 mg KOH / g).

[0035] In some embodiments, the lubricating oil composition disclosed herein is suitable for use as a marine trunk piston engine oil (TPEO). Marine TPEO lubricants are generally prepared according to SAE 30 or SAE 40 single-grade specifications. Typically, marine TPEO lubricants have a TBN in the range of up to 60 mg KOH / g or 2 to 60 mg KOH / g (e.g., 5 to 60 mg KOH / g, 10 to 30 mg KOH / g, 15 to 60 mg KOH / g, 15 to 40 mg KOH / g, 20 to 60 mg KOH / g, 20 to 40 mg KOH / g, 30 to 60 mg KOH / g, or 30 to 55 mg KOH / g).

[0036] In some embodiments, the lubricating oil compositions disclosed herein are suitable for use as gaseous fuel engine oils, such as natural gas fuel engine oils. Gaseous fuel engine oils typically have a TBN in the range of up to 10 mg KOH / g or 2 to 10 mg KOH / g (e.g., 2 to 9 mg KOH / g or 2 to 8 mg KOH / g).

[0037] 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 to 20 mg KOH / g, 4 to 15 mg KOH / g, 4 to 10 mg KOH / g, or 5 to 9 mg KOH / g.

[0038] In some embodiments, the lubricating oil composition disclosed herein can be used during a quick cleaning service to remove deposits, sludge and other muddy materials accumulated in an internal combustion engine. The quick cleaning service can remove sludge, heavy sediments and / or other insoluble materials that may accumulate over time. The cleaning process may include using a lubricant in an engine oil tank or crankcase and circulating the lubricating oil without starting the engine. Additional steps include circulating the lubricating oil and soaking it under static conditions 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 a week. Another cleaning step may include starting the engine and operating the engine 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 one week under any operating conditions suitable for the engine design and fuel. In some embodiments, the lubricating oil compositions disclosed herein can be used to remove existing deposits in the crankcase, rocker cover, camshaft area, timing gear cover, cylinder head, combustion chamber, piston ring and / or annular grooves of an internal combustion engine.

[0039] When used during a quick cleaning service, the lubricating oil composition may require a higher concentration of lubricant additives than is typically used during regular maintenance. This lubricating oil with a higher amount of sediment cleaning lubricant additives is used to lubricate and clean the engine. The resulting mixed product (concentrated lubricating oil and sediment) can then be flushed. The flushing step typically occurs after the cleaning step is completed.

[0040] In some embodiments, the cleaning step of the express 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 one week. The exact amount of 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, the desired cleanliness level, etc.

[0041] In some embodiments, the flushing is performed after 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 may be performed for a period of time up to about 25% of the OEM recommended oil change interval.

[0042] In some embodiments, the present disclosure is directed to engine flush products containing additives, mixed products containing additives and used lubricating oil compositions, and methods of using the products.

[0043] In some embodiments, the engine flush product is an aftermarket additive package in which the additives are dissolved in a solvent. The aftermarket additive package is suitable for quickly cleaning or removing deposits, sludge and other gunk that accumulates in an internal combustion engine.

[0044] The engine flushing process can remove sludge, heavy deposits and / or other gunk that may have accumulated in the engine oil. A typical engine flushing process involves adding additives as aftermarket additives (e.g., engine flushing products) to an internal combustion engine through the filler port. After the engine is allowed to idle, the additives are added to mix with the existing lubricating oil composition with the "used base oil." The mixed product can dissolve or clean the sludge, heavy deposits and / or gunk that remains in the engine. The mixed product is then discharged along with the dissolved sludge, deposits and / or gunk.

[0045] In some embodiments, the lubricating oil compositions disclosed herein may contain low levels of sulfated ash, as determined by ASTM D874. The composition may have a sulfated ash content of less than 1.5 wt % (e.g., less than 0.6 wt % or even less than 0.06 wt %) based on the total weight of the composition. The composition may have a sulfated ash content of 0.01 to 1.0 wt %, 0.1 to 1.0 wt %, 0.3 to 0.8 wt %, 0.4 to 1.0 wt %, 0.5 to 0.9 wt %, or 0.5 to 1.0 wt %. In some embodiments, the lubricating oil composition may be ashless.

[0046] The lubricating oil compositions disclosed herein can provide favorable deposit control performance in any of a number of mechanical parts of an engine. The mechanical part can be a piston, a piston ring, a piston ring groove, a crankcase, a rocker cover, a camshaft area, a timing gear cover, a cylinder head, a combustion chamber, a cylinder liner, a cylinder, a cam, a tappet, a tappet, a gear, a valve, a valve guide, or a bearing (including a journal, a roller, a tapered bearing, a needle bearing, or a ball bearing). In some cases, the mechanical part may contain steel.

[0047] Lubricant Additives

[0048] The lubricant additive composition of the present disclosure can be represented by the following general chemical structure I:

[0049]

[0050] Each R 1 is independently a hydrocarbon group having 10 to 400 carbon atoms; X is an alkyl, aryl or heteroaromatic group having 1 to 10 carbon atoms; 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; and each R 3 is independently hydrogen or a hydrocarbon group with 1 to 9 carbons functionalized with one or more nitrogen, oxygen or sulfur, wherein p is 1 to 3, n is 1 to 20 and m is 0 to 3. In some embodiments, X is a cyclic or acyclic alkyl group. In some embodiments, Y may include one or more hydrogens. In some preferred embodiments, Z is nitrogen.

[0051] Each R 110 to 300, 10 to 290, 10 to 280, 10 to 270, 10 to 280, 10 to 290, 10 to 300, 10 to 310, 10 to 320, 10 to 330, 10 to 340, 10 to 350, 10 to 360, 10 to 370, 10 to 380, 10 to 390, 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 0 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 1 30, 40 to 120, 40 to 110, 40 to 100, 40 to 90, 40 to 80, 40 to 70, 40 to 60, 40 to 50, 50 to 400, 50 to 390, 50 to 380, 50 to 370, 50 to 360, 50 to 350, 50 to 340, 50 to 33 0, 50 to 320, 50 to 310, 50 to 300, 50 to 290, 50 to 280, 50 to 270, 50 to 260, 50 to 250, 50 to 240, 50 to 230, 50 to 220, 50 to 210, 50 to 200, 50 to 190, 50 to 180, 5 0 to 170, 50 to 160, 50 to 150, 50 to 140, 50 to 130, 50 to 120, 50 to 110, 50 to 100, 50 to 90, 50 to 80, 50 to 70, 50 to 60, 60 to 400, 60 to 390, 60 to 380, 60 to 370, 60 to 360, 60 to 350, 60 to 340, 60 to 330, 60 to 320, 60 to 310, 60 to 300, 60 to 290, 60 to 280, 60 to 270, 60 to 260, 60 to 250, 60 to 240, 60 to 230, 60 to 220, 60 to 210 , 60 to 200, 60 to 190, 60 to 180, 60 to 170, 60 to 160, 60 to 150, 60 to 140, 60 to 130, 60 to 120, 60 to 110, 60 to 100, 60 to 90, 60 to 80, 60 to 70, 70 to 400, 70 to 39 0, 70 to 380, 70 to 370, 70 to 360, 70 to 350, 70 to 340, 70 to 330, 70 to 320, 70 to 310, 70 to 300, 70 to 290, 70 to 280, 70 to 270, 70 to 260, 70 to 250, 70 to 240, 7 0 to 230, 70 to 220, 70 to 210, 70 to 200, 70 to 190, 70 to 180, 70 to 170, 70 to 160, 70 to 150, 70 to 140, 70 to 130, 70 to 120, 70 to 110, 70 to 100, 70 to 90, 70 to 80,80 to 400, 80 to 390, 80 to 380, 80 to 370, 80 to 360, 80 to 350, 80 to 340, 80 to 330, 80 to 320, 80 to 310, 80 to 300, 80 to 290, 80 to 280, 80 to 270, 80 to 260, 80 to 2 50, 80 to 240, 80 to 230, 80 to 220, 80 to 210, 80 to 200, 80 to 190, 80 to 180, 80 to 170, 80 to 160, 80 to 150, 80 to 140, 80 to 130, 80 to 120, 80 to 110, 80 to 100, 8 0 to 90, 90 to 400, 90 to 390, 90 to 380, 90 to 370, 90 to 360, 90 to 350, 90 to 340, 90 to 330, 90 to 320, 90 to 310, 90 to 300, 90 to 290, 90 to 280, 90 to 270, 90 to 260 , 90 to 250, 90 to 240, 90 to 230, 90 to 220, 90 to 210, 90 to 200, 90 to 190, 90 to 180, 90 to 170, 90 to 160, 90 to 150, 90 to 140, 90 to 130, 90 to 120, 90 to 110, 90 to 1 100 to 400, 100 to 390, 100 to 380, 100 to 370, 100 to 360, 100 to 350, 100 to 340, 100 to 330, 100 to 320, 100 to 310, 100 to 300, 100 to 290, 100 to 280, 100 to 270, 100 to 260, 100 to 250, 100 to 240, 100 to 230, 100 to 220, 100 to 210, 100 to 200, 100 to 190, 100 to 180, 100 to 170, 100 to 160, 100 to 150, 100 to 140, 10 0 to 130, 100 to 120, 100 to 110, 110 to 400, 110 to 390, 110 to 380, 110 to 370, 110 to 360, 110 to 350, 110 to 340, 110 to 330, 110 to 320, 110 to 310, 110 to 300, 1 10 to 290, 110 to 280, 110 to 270, 110 to 260, 110 to 250, 110 to 240, 110 to 230, 110 to 220, 110 to 210, 110 to 200, 110 to 190, 110 to 180, 110 to 170, 110 to 160,110 to 150, 110 to 140, 110 to 130, 110 to 120, 120 to 400, 120 to 390, 120 to 380, 120 to 370, 120 to 360, 120 to 350, 120 to 340, 120 to 330, 120 to 320, 120 to 310 , 120 to 300, 120 to 290, 120 to 280, 120 to 270, 120 to 260, 120 to 250, 120 to 240, 120 to 230, 120 to 220, 120 to 210, 120 to 200, 120 to 190, 120 to 180, 120 to 17 0, 120 to 160, 120 to 150, 120 to 140, 120 to 130, 130 to 400, 130 to 390, 130 to 380, 130 to 370, 130 to 360, 130 to 350, 130 to 340, 130 to 330, 130 to 320, 130 to 3 10, 130 to 300, 130 to 290, 130 to 280, 130 to 270, 130 to 260, 130 to 250, 130 to 240, 130 to 230, 130 to 220, 130 to 210, 130 to 200, 130 to 190, 130 to 180, 130 to 170, 130 to 160, 130 to 150, 130 to 140, 140 to 400, 140 to 390, 140 to 380, 140 to 370, 140 to 360, 140 to 350, 140 to 340, 140 to 330, 140 to 320, 140 to 310, 140 to 300, 140 to 290, 140 to 280, 140 to 270, 140 to 260, 140 to 250, 140 to 240, 140 to 230, 140 to 220, 140 to 210, 140 to 200, 140 to 190, 140 to 180, 140 to 170, 140 to 180 0 to 160, 140 to 150, 150 to 400, 150 to 390, 150 to 380, 150 to 370, 150 to 360, 150 to 350, 150 to 340, 150 to 330, 150 to 320, 150 to 310, 150 to 300, 150 to 290, 1 50 to 280, 150 to 270, 150 to 260, 150 to 250, 150 to 240, 150 to 230, 150 to 220, 150 to 210, 150 to 200, 150 to 190, 150 to 180, 150 to 170, 150 to 160, 160 to 400,160 to 390, 160 to 380, 160 to 370, 160 to 360, 160 to 350, 160 to 340, 160 to 330, 160 to 320, 160 to 310, 160 to 300, 160 to 290, 160 to 280, 160 to 270, 160 to 260 , 160 to 250, 160 to 240, 160 to 230, 160 to 220, 160 to 210, 160 to 200, 160 to 190, 160 to 180, 160 to 170, 170 to 400, 170 to 390, 170 to 380, 170 to 370, 170 to 360 0, 170 to 350, 170 to 340, 170 to 330, 170 to 320, 170 to 310, 170 to 300, 170 to 290, 170 to 280, 170 to 270, 170 to 260, 170 to 250, 170 to 240, 170 to 230, 170 to 2 20, 170 to 210, 170 to 200, 170 to 190, 170 to 180, 180 to 400, 180 to 390, 180 to 380, 180 to 370, 180 to 360, 180 to 350, 180 to 340, 180 to 330, 180 to 320, 180 to 310, 180 to 300, 180 to 290, 180 to 280, 180 to 270, 180 to 260, 180 to 250, 180 to 240, 180 to 230, 180 to 220, 180 to 210, 180 to 200, 180 to 190, 190 to 400, 190 to 390, 190 to 380, 190 to 370, 190 to 360, 190 to 350, 190 to 340, 190 to 330, 190 to 320, 190 to 310, 190 to 300, 190 to 290, 190 to 280, 190 to 270, 190 to 260, 19 0 to 250, 190 to 240, 190 to 230, 190 to 220, 190 to 210, 190 to 200, 200 to 400, 200 to 390, 200 to 380, 200 to 370, 200 to 360, 200 to 350, 200 to 340, 200 to 330, 2 200 to 320, 200 to 310, 200 to 300, 200 to 290, 200 to 280, 200 to 270, 200 to 260, 200 to 250, 200 to 240, 200 to 230, 200 to 220, 200 to 210, 210 to 400, 210 to 390,210 to 380, 210 to 370, 210 to 360, 210 to 350, 210 to 340, 210 to 330, 210 to 320, 210 to 310, 210 to 300, 210 to 290, 210 to 280, 210 to 270, 210 to 260, 210 to 250 , 210 to 240, 210 to 230, 210 to 220, 220 to 400, 220 to 390, 220 to 380, 220 to 370, 220 to 360, 220 to 350, 220 to 340, 220 to 330, 220 to 320, 220 to 310, 220 to 30 0, 220 to 290, 220 to 280, 220 to 270, 220 to 260, 220 to 250, 220 to 240, 220 to 230, 230 to 400, 230 to 390, 230 to 380, 230 to 370, 230 to 360, 230 to 350, 230 to 3 40, 230 to 330, 230 to 320, 230 to 310, 230 to 300, 230 to 290, 230 to 280, 230 to 270, 230 to 260, 230 to 250, 230 to 240, 240 to 400, 240 to 390, 240 to 380, 240 to 370, 240 to 360, 240 to 350, 240 to 340, 240 to 330, 240 to 320, 240 to 310, 240 to 300, 240 to 290, 240 to 280, 240 to 270, 240 to 260, 240 to 250, 250 to 400, 250 to 390, 250 to 380, 250 to 370, 250 to 360, 250 to 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, 26 0 to 400, 260 to 390, 260 to 380, 260 to 370, 260 to 360, 260 to 350, 260 to 340, 260 to 330, 260 to 320, 260 to 310, 260 to 300, 260 to 290, 260 to 280, 260 to 270, 2 70 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 from 370 to 400, 370 to 390, 370 to 380, 380 to 400, 380 to 390, 390 to 400, 380 to 390, 380 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 390 to 400 carbon atoms.

[0052] In some embodiments, R 1 For example, saturated and unsaturated hydrocarbon groups, linear and branched alkyl groups, and polyalkyl groups (such as polyisobutylene groups or "PIB", polyethylene, polypropylene, etc.) may be included. Polyalkyl groups can be obtained by polymerization using olefin monomers (such as isobutylene).

[0053] In some preferred embodiments, R 1In some preferred embodiments, the polyisobutylene group has an average molecular weight of about 350 to about 5000. In some preferred embodiments, the polyisobutylene 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 polyisobutylene 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.

[0054] In some preferred embodiments, the polyisobutylenyl group has a molecular weight of about 500 to about 4000, such as about 600 to about 5000, about 700 to about 5000, about 800 to about 5000, about 900 to about 5000, about 1000 to about 5000, about 500 to about 4000, such as about 600 to about 4000, about 700 to about 4000, about 800 to about 4000, about 900 to about 4000, about 1000 to about 4000, about 1100 to about 4000, about 1200 to about 4000, about 1300 to about 4000, about 1400 to about 4000, about 1500 to about 4000, about 1600 to about 4000, about 1700 to about 4000, about 1800 to about 4000, about 1900 to about 4000, about 2000 to about 2500, about 2600 to about 2700, about 2800 to about 2900, about 3000 to about 3000, about 3100 to about 3100, about 3200 to about 3300, about 3400 to about 3500 00, about 1800 to about 4000, about 1900 to about 4000, about 2000 to about 4000, about 2100 to about 4000, about 2200 to about 4000, about 2300 to about 4000, about 2400 to about 4000, about 2500 to about 4000, about 2600 to about 4000, about 2700 to about 4000, about 2800 to about 4000, about 2900 to about 4000, about 3000 to about 4000, about 500 to about 3500, such as about 600 to about 3500, about 700 to about 3500, about 800 to about 3500, about 900 to about 3500, about 1000 to about 3500, about 1100 to about 3500, about 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 about The average molecular weight of the present invention is 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.

[0055] R 1Specific examples include the following:

[0056]

[0057] wherein x is an integer such that the total number of carbons is from 10 to 400 as described herein.

[0058] X is a moiety comprising 1 to 10 carbon atoms, such as 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.

[0059] Specific examples of X include the following:

[0060]

[0061] Examples of Y include, for example, the following:

[0062]

[0063] Each R 2 In some embodiments, the present invention relates to a moiety comprising 1 to 9 carbon atoms, such as 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.

[0064] R 2 Suitable examples of include, for example, saturated and unsaturated hydrocarbon groups and straight-chain and branched alkyl groups.

[0065] R 2 Specific examples include the following:

[0066]

[0067] Z is a nitrogen, oxygen or sulfur atom.

[0068] Each R3 is independently a hydrogen atom or a moiety comprising 1 to 9 carbon atoms, such as 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 The moieties include one or more nitrogen, oxygen or sulfur functionalizations.

[0069] R 3 Specific examples include the following:

[0070]

[0071] In some preferred embodiments, the lubricant additive may have the following general structure 2:

[0072]

[0073] Each R 1 is independently a hydrocarbon group having 10 to 400 carbon atoms; 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; and each R 3 is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons with one or more nitrogen, oxygen or sulfur functionalizations, wherein p is 1 to 3, n is 1 to 20 and m is 0 to 3.

[0074] In some embodiments, Y may contain one or more hydrogens.

[0075] In some preferred embodiments, the lubricant additive may have the following general structure 3:

[0076]

[0077] Each R 1 is independently a hydrocarbon group having 10 to 400 carbon atoms; 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 with one or more nitrogen, oxygen or sulfur functionalizations, wherein p is 1 to 3, n is 1 to 20 and m is 0 to 3.

[0078] In some preferred embodiments, the lubricant additive may have the following general structure 4:

[0079]

[0080] Each R 1 is a hydrocarbon group having 10 to 400 carbon atoms; each R 2 is independently a hydrocarbyl group having 1 to 9 carbon atoms; and each R 3 is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons with one or more nitrogen, oxygen or sulfur functionalizations, wherein p is 1 to 3 and n is 1 to 20.

[0081] When formulated in an engine oil (i.e., a lubricating oil composition), used as part of an aftermarket additive package during an engine flush, or used during a quick clean service, the lubricant additive composition is typically present in an amount ranging from about 0.1 to about 50.0 weight percent, such as from about 1 weight percent to about 50 weight percent, from about 5 weight percent to about 50 weight percent, from about 10 weight percent to about 50 weight percent, from about 15 weight percent to about 50 weight percent, from about 20 weight percent to about 50 weight percent, from about 25 weight percent to about 50 weight percent, from about 30 weight percent to about 50 weight percent, from about 35 weight percent to about 50 weight percent, from about 40 weight percent to about 50 weight percent, from about 45 weight percent to about 50 weight percent, based on the total weight of the lubricating oil composition (which may be a blended product). %, about 0.1 wt % to about 45 wt %, about 1 wt % to about 45 wt %, about 5 wt % to about 45 wt %, about 10 wt % to about 45 wt %, about 15 wt % to about 45 wt %, about 20 wt % to about 45 wt %, about 25 wt % to about 45 wt %, about 30 wt % to about 45 wt %, about 35 wt % to about 45 wt %, about 40 wt % to about 45 wt %, about 0.1 wt % to about 40 wt %, about 1 wt % to about 40 wt %, about 5 wt % to about 40 wt %, about 10 wt % to about 40 wt %, about 15 wt % to about 40 wt %, about 20 wt % to about 40 wt %, about 25 wt % to about 40 wt %, about 30 wt % to about 45 wt %, about 35 wt % to about 45 wt %, about 40 wt % to about 45 wt %, %, about 35 wt % to about 40 wt %, about 0.1 wt % to about 35 wt %, about 1 wt % to about 35 wt %, about 5 wt % to about 35 wt %, about 10 wt % to about 35 wt %, about 15 wt % to about 35 wt %, about 20 wt % to about 35 wt %, about 25 wt % to about 35 wt %, about 30 wt % to about 35 wt %, about 0.1 wt % to about 30 wt %, about 1 wt % to about 30 wt %, about 5 wt % to about 30 wt %, about 10 wt % to about 30 wt %, about 15 wt % to about 30 wt %, about 20 wt % to about 30 wt %, about 25 wt % to about 30 wt %, about 0.1 wt % to about 25 %, about 5 wt % to about 25 wt %, about 10 wt % to about 25 wt %, about 15 wt % to about 25 wt %, and about 20 wt % to about 25 wt %, about 0.1 wt % to about 20.0 wt %, about 0.1 wt % to about 19.0 wt %, about 0.1 wt % to about 18.0 wt %, about 0.1 wt % to about 17.0 wt %, about 0.1 wt % to about 16.0 wt %, about 0.1 wt % to about 15.0 wt %, about 0.1 wt % to about 14.0 wt %, about 0.1 wt % to about 13.0 wt %, about 0.1 wt % to about 12.0 wt %, about 0.1 wt % to about 11.0 wt %, about 0.1 wt % to about 10.0 wt %, about 0.1 wt % to about 9.0 wt %, about 0.1 wt % to about 8.0 wt %, about 0.1 wt % to about 7.0 wt %, about 0.1 wt % to about 6.0 wt %, about 0.1 wt % to about 5.0 wt %, about 0.1 wt % to about 4.0 wt %, about 0.1 wt % to about 3.0 wt %, about 0.1 wt % to about 2.0 wt %, about 0.1 wt % to about 1.0 wt %, about 1.0 wt % to about 20.0 wt %, about 1.0 wt % to about 19.0 wt %, about 1.0 wt % to about 18.0 wt %, about 1.0 wt % to about 17.0 wt %, about 1.0 wt % to about 16.0 wt %, about 1.0 wt % to about 15.0 wt %, about 1.0 wt % %, about 1.0 wt % to about 14.0 wt %, about 1.0 wt % to about 13.0 wt %, about 1.0 wt % to about 12.0 wt %, about 1.0 wt % to about 11.0 wt %, about 1.0 wt % to about 10.0 wt %, about 1.0 wt % to about 9.0 wt %, about 1.0 wt % to about 8.0 wt %, about 1.0 wt % to about 7.0 wt %, about 1.0 wt % to about 6.0 wt %, about 1.0 wt % to about 5.0 wt %, about 1.0 wt % to about 4.0 wt %, about 1.0 wt % to about 3.0 wt %, about 1.0 wt % to about 2.0 wt %, about 2.0 wt % to about 20.0 wt %, about 2.0 wt % to about 19.0 wt %, about 2.0 wt % to about 1 8.0 wt %, about 2.0 wt % to about 17.0 wt %, about 2.0 wt % to about 16.0 wt %, about 2.0 wt % to about 15.0 wt %, about 2.0 wt % to about 14.0 wt %, about 2.0 wt % to about 13.0 wt %, about 2.0 wt % to about 12.0 wt %, about 2.0 wt % to about 11.0 wt %, about 2.0 wt % to about 10.0 wt %, about 2.0 wt % to about 9.0 wt %, about 2.0 wt % to about 8.0 wt %, about 2.0 wt % to about 7.0 wt %, about 2.0 wt % to about 6.0 wt %, about 2.0 wt % to about 5.0 wt %, about 2.0 wt % to about 4.0 wt %, about 2.0 wt % to about 3. 0 wt %, about 3.0 wt % to about 20.0 wt %, about 3.0 wt % to about 19.0 wt %, about 3.0 wt % to about 18.0 wt %, about 3.0 wt % to about 17.0 wt %, about 3.0 wt % to about 16.0 wt %, about 3.0 wt % to about 15.0 wt %, about 3.0 wt % to about 14.0 wt %, about 3.0 wt % to about 13.0 wt %, about 3.0 wt % to about 12.0 wt %, about 3.0 wt % to about 11.0 wt %, about 3.0 wt % to about 10.0 wt %, about 3.0 wt % to about 9.0 wt %, about 3.0 wt % to about 8.0 wt %, about 3.0 wt % to about 7.0 wt %, about 3.0 wt % to about 6.%, about 5.0 wt % to about 15.0 wt %, about 5.0 wt % to about 14.0 wt %, about 5.0 wt % to about 15.0 wt %, about 5.0 wt % to about 16.0 wt %, about 5.0 wt % to about 17.0 wt %, about 5.0 wt % to about 18.0 wt %, about 5.0 wt % to about 19.0 wt %, about 5.0 wt % to about 19.0 wt %, about 5.0 wt % to about 18.0 wt %, about 5.0 wt % to about 19.0 wt %, about 5.0 wt % to about 19.0 wt %, about 5.0 wt % to about 19.0 wt %, about 5.0 wt % to about 19.0 wt %, about 5.0 wt % to about 19.0 wt %, about 5.0 wt % to about 19.0 wt %, about 5.0 wt % to about 19.0 wt %, about 9.0 wt %, about 5.0 wt % to about 8.0 wt %, about 5.0 wt % to about 7.0 wt %, about 5.0 wt % to about 6.0 wt %, about 6.0 wt % to about 20.0 wt %, about 6.0 wt % to about 19.0 wt %, about 6.0 wt % to about 18.0 wt %, about 6.0 wt % to about 17.0 wt %, about 6.0 wt % to about 16.0 wt %, about 6.0 wt % to about 15.0 wt %, about 6.0 wt % to about 14.0 wt %, about 6.0 wt % to about 13.0 wt %, about 6.0 wt % to about 12.0 wt %, about 6.0 wt % to about 11.0 wt %, about 6.0 wt % to about 10.0 wt %, about 6.0 wt % %, about 7.0 wt % to about 15.0 wt %, about 7.0 wt % to about 14.0 wt %, about 7.0 wt % to about 13.0 wt %, about 7.0 wt % to about 12.0 wt %, about 7.0 wt % to about 11.0 wt %, about 7.0 wt % to about 10.0 wt %, about 7.0 wt % to about 9.0 wt %, about 7.0 wt % to about 18.0 wt %, about 7.0 wt % to about 17.0 wt %, about 7.0 wt % to about 16.0 wt %, about 7.0 wt % to about 15.0 wt %, about 7.0 wt % to about 14.0 wt %, about 7.0 wt % to about 13.0 wt %, about 7.0 wt % to about 12.0 wt %, about 7.0 wt % to about 11.0 wt %, about 7.0 wt % to about 10.0 wt %, about 7.0 wt % to about 9.0 wt %, about 7.0 wt % to about % to about 8.0 wt %, about 8.0 wt % to about 20.0 wt %, about 8.0 wt % to about 19.0 wt %, about 8.0 wt % to about 18.0 wt %, about 8.0 wt % to about 17.0 wt %, about 8.0 wt % to about 16.0 wt %, about 8.0 wt % to about 15.0 wt %, about 8.0 wt % to about 14.0 wt %, about 8.0 wt % to about 13.0 wt %, about 8.0 wt % to about 12.0 wt %, about 8.0 wt % to about 11.0 wt %, about 8.0 wt % to about 10.0 wt %, 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.% 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 %, 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 %, % 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 15.0 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 15.0 wt % to about 17.0 wt %, about 15.0 wt % to 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 %.

[0082] Specific non-limiting examples of lubricant additive compositions include the following: 1 As defined above):

[0083]

[0084]

[0085]

[0086] The lubricant additive composition can be synthesized by any compatible method. For example, the general synthesis of compound 1 is described in detail in U.S. Patent No. 5,669,939, which is incorporated herein by reference. Such a reaction generally produces a product comprising compound 1 dissolved in an organic solvent. In some embodiments, it may be desirable to evaporate the organic solvent before utilizing compound 1.

[0087] In some embodiments, compound 1 can be used as a starting material for synthesizing other lubricant additive compounds (e.g., compounds 4, 5, 6). An overview of how compounds 4, 5, and 6 can be derived by reactions between compound 1 and reagents (glycidol) is shown below. The starting materials in each reaction are the same. Only the feed molar ratio (compound 1 to glycidol molar ratio) is changed. Other reagents other than glycidol may also be considered. In addition, the lubricant additive is not necessarily a reaction product of glycidol or derived from glycidol.

[0088]

[0089] Base oil

[0090] The lubricating oil composition of the present invention comprises one or more base oils (e.g., Group I, Group II, Group III, Group IV, or Group V). In addition, the one or more base oils may include base oils from the same class (e.g., Group II Chevron Neutral Oil Group II Chevron Neutral Oil and Group II Chevron Neutral Oil ). The amount of base oil is about 40 wt % or greater ("major amount"), such as about 45 wt % or greater, 50 wt % or greater, 55 wt % or greater, 60 wt % or greater, etc., based on the total weight of the lubricating oil composition.

[0091] Group I, Group II, Group III, Group IV, and Group V are broad categories of base oil stocks developed and defined by the American Petroleum Institute (API Publication 1509-Appendix E) to establish guidelines for lubricant base oils. Group I base stocks contain less than 90% saturates and / or greater than 0.03% sulfur and have a viscosity index greater than or equal to 80 and less than 120. Group II base stocks contain greater than or equal to 90% saturates and less than or equal to 0.03% sulfur and have a viscosity index greater than or equal to 80 and less than 120. Group III base stocks contain greater than or equal to 90% saturates and less than or equal to 0.03% sulfur and have a viscosity index greater than or equal to 120. Group IV base stocks are polyalphaolefins. Group V base stocks include all other base stocks not included in Group I, Group II, Group III, or Group IV. Table 1 summarizes the characteristics of each of the five categories.

[0092] Table 1

[0093] Base oil characteristics

[0094]

[0095] (1) ASTM D2007

[0096] (2)ASTM D2622, ASTM D3120, ASTM D4294 or ASTM D4927

[0097] (3) ASTM D2270

[0098] Lubricating oil composition

[0099] The lubricating oil compositions of the present disclosure can be identified by the Society of Automotive Engineers (SAE) viscosity standard for engine oils, namely the SAE J300 standard. The SAE J300 viscosity grades are summarized in Table 2.

[0100] Table 2

[0101]

[0102] (1) ASTM D5293

[0103] (2) ASTM D4684

[0104] (3) ASTM D445

[0105] (4) ASTM D4683, ASTM D4741, ASTM D5481 or CEC L-36-90

[0106] (5) For 0W-40, 5W-40 and 10W-40 grades

[0107] (6) For 15W-40, 20W-40, 25W-40 and 40 grades

[0108] The lubricating oil composition of the present disclosure may be a monograde engine oil, such as a SAE 20, SAE 30, SAE 40, SAE 50 or SAE 60 viscosity grade engine oil.

[0109] The lubricating oil composition of the present disclosure may be a multi-grade engine oil, such as an engine oil having a SAE viscosity grade of 15W-X, 20W-X or 25W-X, wherein X may be selected from 30, 40, 50 or 60.

[0110] Additional additives

[0111] The lubricating oil composition of the present disclosure may contain one or more performance additives that can impart or improve any desired properties of the lubricating oil composition. Any additive known to those skilled in the art can be used in the lubricating oil composition disclosed herein. Some suitable additives are described in RM Mortier et al., "Chemistry and Technology of Lubricants", 3rd edition, Springer (2010) and LR Rudnik, "Lubricant Additives: Chemistry and Applications", 2nd edition, CRC Press (2009).

[0112] Generally speaking, when used, the concentration of each additive in the lubricating oil composition may be in the range of 0.001 to 60 wt % (e.g., 0.01 to 50 wt % or 0.05 to 40 wt %) of the lubricating oil composition. In addition, the total amount of additives in the lubricating oil composition may be in the range of 0.001 to 70 wt % (e.g., 0.01 to 50 wt % or 0.1 to 40 wt %) of the lubricating oil composition.

[0113] The lubricating oil composition may additionally contain one or more of other commonly used lubricating oil performance additives, including antioxidants, antiwear agents, metal detergents, dispersants, friction modifiers, corrosion inhibitors, demulsifiers, viscosity modifiers, pour point depressants, foam inhibitors, and the like.

[0114] Antioxidants

[0115] Antioxidants retard the oxidative degradation of the base oil during use. Such degradation can lead to deposits on metal surfaces, the presence of sludge, or an increase in the viscosity of the lubricant. Useful antioxidants include hindered phenols, aromatic amines, and sulfurized alkylphenols and their alkali metal and alkaline earth metal salts.

[0116] Hindered phenol antioxidants may contain sec-butyl and / or tert-butyl groups as sterically hindered groups. The phenolic group may be further substituted with a hydrocarbyl group and / or a bridging group connected to a second 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). Hindered phenol antioxidants may be esters or addition products derived from 2,6-di-tert-butylphenol and alkyl acrylates, wherein the alkyl group may contain 1 to 18 carbon atoms.

[0117] Suitable aromatic amine antioxidants include diarylamines, such as alkylated diphenylamines (eg, dioctyldiphenylamine, dinonyldiphenylamine), phenyl-α-naphthalene, and alkylated phenyl-α-naphthalene.

[0118] Antiwear Agents

[0119] Antiwear agents reduce the wear of metal parts. Examples of antiwear agents include phosphorus-containing antiwear / extreme pressure agents (e.g., metal thiophosphates, phosphates and salts thereof), phosphorus-containing carboxylic acids, esters, ethers and amides, and phosphites. The antiwear agent can be zinc dialkyl dithiophosphates. Phosphorus-free antiwear agents include boric acid esters (including borated epoxides), dithiocarbamate compounds, molybdenum-containing compounds, and sulfided olefins.

[0120] Metal Cleaners

[0121] Typical detergents are anionic materials containing a long-chain hydrophobic portion of the molecule and a smaller anionic or oleophobic hydrophilic portion of the molecule. The anionic portion of the detergent is usually derived from an organic acid, such as sulfuric acid, carboxylic acid, phosphorous acid, phenol, or a mixture thereof. The counter ion is usually an alkaline earth metal or an alkali metal.

[0122] In some embodiments, the lubricating oil composition provided herein comprises at least a neutral or overbased metal detergent as an additive or additive component. In certain embodiments, the metal detergent in the lubricating oil composition acts as a neutralizer for the acidic products in the oil. In certain embodiments, the metal detergent prevents the formation of deposits on the engine surface. 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, which comprises an overbased detergent or a mixture of neutral and overbased detergents. The term "overbased" is intended to define an additive containing a metal content that exceeds the metal content required for the stoichiometry of the specific metal and specific organic acid used. Excess metal exists in the form of inorganic base (e.g., hydroxide or carbonate) particles surrounded by a metal salt sheath. The sheath is used to keep the particles dispersed in a liquid oily carrier. The amount of excess metal is generally expressed as the ratio of the total equivalent of the excess metal to the equivalent of the organic acid, and is generally in the range of 0.1 to 30.

[0123] Some examples of suitable metal detergents include sulfurized or unsulfurized alkyl or alkenyl phenolates, alkyl or alkenyl aromatic sulfonates, borated sulfonates, sulfurized or unsulfurized metal salts of polyhydroxy alkyl or alkenyl aromatic compounds, alkyl or alkenyl hydroxy aromatic sulfonates, sulfurized or unsulfurized alkyl or alkenyl cycloalkanoates, metal salts of alkanoic acids, metal salts of alkyl or alkenyl polyacids, and chemical and physical mixtures thereof. Other examples of suitable metal detergents include metal sulfonates, phenates, salicylates (i.e., carboxylates, hydroxybenzoates), phosphonates, thiophosphonates, and combinations thereof. The metal may be any metal suitable for preparing sulfonate, phenate, salicylate, or phosphonate cleaning agents. Non-limiting examples of suitable metals include alkali metals, basic metals, and transition metals. In some embodiments, the metal is Ca, Mg, Ba, K, Na, Li, etc. Exemplary metal detergents that can be used in lubricating oil compositions include overbased sulfurized calcium phenate.

[0124] Ashless dispersant

[0125] Dispersants are additives whose primary function is to keep solid and liquid contaminants in suspension, thereby passivating them and reducing engine deposits while reducing sludge deposition. For example, dispersants keep oil-insoluble materials produced by oxidation during the use of the lubricant in suspension, thereby preventing sludge from flocculating and settling or depositing on metal parts of the engine.

[0126] Dispersants are generally "ashless", being non-metallic organic materials that do not form substantially ash when burned, as opposed to materials that contain metals and therefore form ash. They contain long hydrocarbon chains with a polar head, the polarity resulting from the inclusion of at least one nitrogen, oxygen or phosphorus atom. The hydrocarbon is the oleophilic group that imparts oil solubility, having, for example, 40 to 500 carbon atoms. Thus, ashless dispersants may include an oil-soluble polymer backbone.

[0127] One preferred class of olefin polymers consists of polybutenes, particularly polyisobutylene (PIB) or poly-n-butenes, such as may be prepared by polymerization of C4 refinery streams.

[0128] Dispersants include, for example, derivatives of long chain hydrocarbon-substituted carboxylic acids, exemplified by derivatives of high molecular weight hydrocarbon-substituted succinic acid. One notable group of dispersants consists of hydrocarbon-substituted succinimides, such as those prepared by reacting the above acids (or derivatives) with nitrogen-containing compounds, advantageously polyalkylene polyamines, such as polyethylene polyamines. Typical commercially available polyisobutenyl succinimide dispersants comprise polyisobutylene polymers having a number average molecular weight in the range of 900 to 2500, functionalized with maleic anhydride and derivatized with polyamines having a molecular weight in the range of 100 to 350.

[0129] Other suitable dispersants include succinic acid esters and ester-amides, Mannich bases, polyisobutylene succinic acid (PIBSA), and other related components.

[0130] Succinates are formed by the condensation reaction between a hydrocarbon-substituted succinic anhydride and an alcohol or polyol. For example, the condensation product of a hydrocarbon-substituted succinic anhydride and pentaerythritol is a useful dispersant.

[0131] Succinate-amides are formed by the condensation reaction between hydrocarbon-substituted succinic anhydride and alkanolamine. For example, suitable alkanolamines include ethoxylated polyalkyl polyamines, propoxylated polyalkyl polyamines and polyalkenyl polyamines, such as polyethylene polyamines. An example is propoxylated hexamethylene diamine.

[0132] Mannich bases are prepared by the reaction of alkylphenols, formaldehyde and polyalkylene polyamines. The molecular weight of the alkylphenols may be between 800 and 2500.

[0133] The nitrogen-containing dispersant may be post-treated by conventional methods to improve its properties by reaction with any of a variety of agents, among which are boron compounds (eg, boric acid) and cyclic carbonates (eg, ethylene carbonate).

[0134] Friction modifiers

[0135] Friction modifiers are any such material that is capable of changing the coefficient of friction of a surface lubricated by any lubricant or liquid containing one or more materials. Friction modifiers include alkoxylated fatty amines, borated fatty epoxides, fatty phosphites, fatty epoxides, fatty amines, borated alkoxylated fatty amines, metal salts of fatty acids, fatty acid amides, glycerides, borated glycerides, and fatty imidazolines. As used herein, the term "fat" refers to a hydrocarbon chain having 10 to 22 carbon atoms, typically a straight hydrocarbon chain.

[0136] Other known friction modifiers include oil-soluble organic molybdenum compounds. Such organic molybdenum friction modifiers also provide antioxidant and anti-wear properties to the lubricating oil composition. Suitable oil-soluble organic molybdenum compounds have a molybdenum-sulfur core. As examples, dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, sulfides and mixtures thereof may be mentioned. The molybdenum compound may be binuclear or trinuclear.

[0137] Corrosion Inhibitors

[0138] Corrosion inhibitors protect lubricated metal surfaces 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.

[0139] Viscosity Modifiers

[0140] Viscosity modifiers provide both high and low temperature operability to lubricants. These additives increase the viscosity of the oil composition at high temperatures, which increases film thickness, while having limited effect on viscosity at low temperatures.

[0141] Suitable viscosity improvers include high molecular weight hydrocarbons, polyesters, and viscosity index improver dispersants that act as both viscosity index improvers and dispersants. Typical molecular weights for these polymers range from 1000 to 1,000,000 (eg, 2000 to 500,000 or 25,000 to 100,000).

[0142] Examples of suitable viscosity modifiers are polymers and copolymers of methacrylates, butadiene, olefins or alkylated styrenes. Polyisobutylene is a commonly used viscosity modifier. Another suitable viscosity modifier is polymethacrylate (e.g., copolymers of various chain length alkyl methacrylates), some of whose formulations are also used as pour point depressants. Other suitable viscosity modifiers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (e.g., copolymers of various chain length acrylates). Specific examples include styrene-isoprene or styrene-butadiene based polymers of 50,000 to 200,000 molecular weight.

[0143] Pour Point Depressants

[0144] Pour point depressants lower the minimum temperature at which a fluid will flow or be pourable. Suitable pour point depressants include C8 to C18 dialkyl fumarate / vinyl acetate copolymers, polyalkyl methacrylates, and the like.

[0145] Foam Inhibitor

[0146] Foam suppressors retard the formation of stable foam. Examples of suitable foam suppressors include silicones, polyacrylates, and the like.

[0147] Thickener

[0148] Thickeners can increase the viscosity of the lubricating oil composition in order to achieve the desired viscosity grade. Any suitable thickener such as polyisobutylene (PIB) can be used. PIB is a commercially available material from several manufacturers. Polyisobutylene is typically a polymer having a number average molecular weight of 800 to 5000 (e.g., 1000 to 2500) and a viscosity of 200 to 5000 mm at 100°C. 2 / s (e.g., 200 to 1000 mm 2 The amount of PIB added to the lubricating oil composition is generally 1 to 20 wt % (eg, 2 to 15 wt % or 4 to 12 wt %) of the finished oil.

[0149] Example

[0150] The following non-limiting examples are illustrative of the present invention. A brief description of how the examples were prepared and the test methods used to evaluate the lubricants of the present invention are provided.

[0151] Black sludge sediment test

[0152] This test is used to evaluate the ability of a lubricant to handle unstable unburned asphaltenes in residual fuel oil. The test measures the tendency of a lubricant to produce deposits on a test strip by applying an oxidative thermal strain to a mixture of heavy fuel oil and lubricant.

[0153] During this test, a sample of the lubricating oil composition is mixed with a specific amount of residual fuel to form a test mixture. The test mixture is injected as a thin film on a metal test strip at a certain time period (12 hours) and temperature (200°C). Next, the test strip is cooled, washed, dried, and then weighed. In this way, the weight of the deposit is measured (expressed in mg) and recorded as the weight change of the test strip.

[0154] DSC oxidation test

[0155] The thin film oxidation stability of the test oils was evaluated using DSC testing according to ASTM D-6186. During the test, the heat flow into and out of the test oil in the sample cup was compared to a reference cup.

[0156] The Oxidation Onset Temperature is the temperature at which the test oil begins to oxidize. The Oxidation Induction Time (OIT) is the time at which the test oil begins to oxidize. Longer OITs indicate better performance. The oxidation reaction is exothermic, as shown by the heat flow. The OIT evaluates the film oxidation stability of the test oil.

[0157] Pressure Differential Scanning Calorimetry (PDSC) Test (ASTM D-6186)

[0158] Using the PDSC test, the oxidative stability of a test oil (at 180°C and 500 psi oxygen pressure) can be measured by detecting the exothermic release of energy that occurs when the oil is subjected to auto-oxidation. The length of time required to achieve auto-oxidation is a measure of oxidation resistance and is known as the oxidation induction time.

[0159] During this test, a small amount of the test oil is weighed into a sample pan and placed in a test cell. The cell is heated to a specific temperature and then pressurized with oxygen. The cell is maintained at the regulated temperature and pressure until an exothermic reaction occurs. The extrapolated onset time is measured and reported as the oxidation induction time of the lubricating oil at the specified test temperature.

[0160] TEOST MHT4 Test

[0161] ASTM D-7097 is designed to predict the deposit forming tendency of engine oils in the piston ring land and upper piston crown area. The test measures the mass of deposits formed as a thin film on a specially constructed test rod exposed to repeated passes of 8.5 g of engine oil over the rod under oxidizing and catalytic conditions at 285°C.

[0162] The deposit formation tendency of engine oil under oxidative conditions was determined by circulating an oil-catalyst mixture containing a small amount (8.4 g) of oil sample and a very small amount (0.1 g) of an organometallic catalyst. The mixture was circulated in a TEOST MHT instrument on a special wound deposition rod heated to a controlled temperature of 285° C. by an electric current at the hottest position of the rod for 24 hours. The rod was weighed before and after the test. The deposits that fell off the deposition rod into the oil were filtered and weighed. The total deposit was calculated as the sum of the weight of the deposits on the deposition rod and on the filter.

[0163] Base oil

[0164] The base oil components used in the formulations of the examples include the following:

[0165] 1) 600N: ExxonMobil 600N Class I Lubricant, K at 100°C v 12.4cSt

[0166] 2) 2500BS ExxonMobil 2500BS Class I Lubricant, K at 100°C v It is 30.6cSt.

[0167] 3) 600R: Chevron 600R Class II lubricant, Kv at 100°C is 11.9 cSt

[0168] 4) 220R: Chevron 220R Class II lubricant, Kv at 100°C is 6.45 cSt

[0169] 5) 150N: ExxonMobil 150N Class I lubricant, Kv at 100°C is 5.3 cSt

[0170] 6) OCP VII: 35 SSI ethylene propylene olefin copolymer oil concentrate with about 60% ethylene and Mn of 80,000

[0171] Examples 1-3 and Comparative Example A

[0172] Examples 1-3 and Comparative Example A were formulated to provide marine cylinder lubricating (MCL) oils having the following specifications: 40 BN, SAE 50 viscosity grade (K at 100°C). v 18.5mm 2 / s).

[0173] The following components were used in Examples 1-3:

[0174] a) 18.3 to 19.1 wt % detergent additive package

[0175] b) 1.5 wt% antioxidant

[0176] c) 0.11 wt% foam inhibitor

[0177] d) Compound 1 (diluted in 30 wt% C9 aromatic solvent):

[0178]

[0179] The amount of Compound 1 varied in Examples 1-3 (see Table 3).

[0180] The formulation of Comparative Example A is similar to Examples 1-3. However, Comparative Example A does not include Compound 1. Succinimide dispersant is added to Comparative Example A instead of Compound 1.

[0181] The DSC oxidation test was used to evaluate the oxidation stability of each finished oil lubricant. The results are listed in Table 3 below.

[0182] Table 3

[0183]

[0184]

[0185] The results listed in Table 3 show that the marine cylinder lubricating oil compositions containing lubricant additive Compound 1 exhibit surprisingly superior oxidation performance than Comparative Example A, as evidenced by the longer oxidation induction time of the inventive examples compared to Comparative Example A. In addition to the improved oxidation performance, the marine diesel engine cylinder lubricating oil compositions of Examples 1-3 each achieve the desired viscosity using less bright stock than the Comparative Example, demonstrating the thickening ability of lubricant additive Compound 1.

[0186] Examples 4 to 5

[0187] Examples 4-5 were formulated to provide marine cylinder lubricating (MCL) oils having the following specifications: SAE 50 viscosity grade (K at 100°C) v 18.5 and 20.44 mm respectively 2 / s).

[0188] The following components were used in Example 4:

[0189] a) 4.0 wt% 17BN low overbased calcium sulfonate detergent

[0190] b) 14.0 wt% 95BN low overbased sulfurized calcium phenate detergent derived from C20-24 isomerized alpha olefins

[0191] c) 0.2 wt% bis-succinimide dispersant derived from 1000 MW PIB

[0192] d) 0.75 wt% phenolic antioxidant

[0193] e) 0.75 wt% amine antioxidant

[0194] f) 1.0 wt% of compound 2

[0195] g) 0.1 wt% foam inhibitor

[0196] The following components were used in Example 5:

[0197] a) 19.8 wt% 410BN highly overbased calcium sulfonate detergent

[0198] b) 0.1 wt% 17BN low overbased calcium sulfonate detergent

[0199] c) 14.0 wt% 95BN low overbased sulfurized calcium phenate detergent derived from C20-24 isomerized alpha olefins

[0200] d) 6.0 wt% bis-succinimide dispersant derived from 1000 MW PIB

[0201] e) 1.0 wt% zinc dithiophosphate from a C8 primary alcohol

[0202] f) 10.0 wt% of compound 2

[0203] g) 0.1 wt% foam inhibitor

[0204] The DSC oxidation test was used to evaluate the oxidation stability of each finished oil lubricant of Examples 4-5. The results are listed in Table 4 below.

[0205] Table 4

[0206]

[0207] The results listed in Table 4 show that the marine cylinder lubricating oil composition containing lubricating additive Compound 2 exhibits desirable oxidation performance.

[0208] Example 6 and Comparative Example B

[0209] Example 6 and Comparative Example B were formulated to provide a marine cylinder lubricant (MCL) oil having the following specifications: 40 BN, SAE 50 viscosity grade (K at 100°C) v 18.5mm 2 / s).

[0210] The following components were used in Example 6:

[0211] a) 8.5 wt% 410BN highly overbased calcium sulfonate

[0212] b) 2.6 wt% 95BN low overbased sulfurized calcium phenate derived from C20-24 isomerized alpha olefins

[0213] c) 0.2 wt% bis-succinimide dispersant derived from 1000 MW PIB

[0214] d) 1.0 wt% amine antioxidant

[0215] e) 0.1 wt% foam inhibitor

[0216] f) 6.0 wt% Compound 2

[0217] The formulation of Comparative Example B is similar to Example 6. However, Comparative Example B does not include lubricant additive Compound 2.

[0218] The black sludge deposit test was used to evaluate the deposit performance of each finished oil lubricant. The results are listed in Table 5 below.

[0219] Table 5

[0220]

[0221] The results listed in Table 5 show that the marine cylinder lubricating oil composition containing lubricant additive compound 2 exhibits surprisingly superior deposit performance to that of comparative example B, as example 6 exhibits significantly less black sludge deposit formation than comparative example B. In addition to improved deposit control performance, the marine diesel engine cylinder lubricating oil composition of example 6 achieves the desired viscosity using less thickener (2300 MW PIB) than the comparative example, demonstrating the thickening ability of lubricant additive compound 2.

[0222] Example 7 and Comparative Example C

[0223] Example 7 and Comparative Example C were formulated to provide a marine trunk piston engine oil (TPEO) having the following specifications: 12BN, SAE 40 viscosity grade (K at 100°C). v 14.5mm 2 / s).

[0224] The following components were used in Example 7:

[0225] a) 0.85 wt% 420BN highly overbased calcium hydroxybenzoate detergent derived from C20-24 isomerized alpha olefins

[0226] b) 4.0 wt% 180BN medium overbased calcium hydroxybenzoate detergent derived from C20-24 isomerized alpha olefins

[0227] c) 5.0 wt% bis-succinimide dispersant derived from ethylene carbonate post-treated 2300 MW PIB

[0228] d) 0.5 wt% amine antioxidant

[0229] e) 0.7 wt.% zinc dithiophosphate from C8 primary alcohol

[0230] f) 3.0 wt% of compound 2

[0231] g) 0.1 wt% foam inhibitor

[0232] The formulation of Comparative Example C is similar to Example 7. However, Comparative Example C does not include lubricant additive Compound 2.

[0233] The black sludge deposit test was used to evaluate the deposit performance of each finished oil lubricant. The results are listed in Table 6 below.

[0234] Table 6

[0235]

[0236] The results listed in Table 6 show that the marine trunk piston engine lubricating oil composition containing lubricant additive compound 2 exhibits surprisingly superior deposit performance to that of comparative example C, as example 7 exhibits significantly less black sludge deposit formation than comparative example C. In addition to improved deposit control performance, the marine trunk piston engine lubricating oil composition of example 7 achieves a desired viscosity without the use of a thickener, demonstrating the thickening ability of lubricant additive compound 2.

[0237] Fast cleaning deposit removal

[0238] Examples 8-10 and Comparative Example D were formulated to provide railroad engine oil lubricating compositions meeting the following specifications: SAE 30 viscosity grade (K at 100°C) v About 15.0mm 2 / s).

[0239] Examples 8-10 were blended with the following components:

[0240] a) Group II base oil

[0241] b) 9.7 wt% railway engine oil additive package

[0242] c) Compound 2 at various treatment rates (solvent was distilled) (Table 7):

[0243]

[0244] The additive package mentioned in Table 7 is a representative railroad engine oil package including the following additives:

[0245] a) Ethylene carbonate post-treated succinimide dispersant

[0246] b) Molybdate succinimide

[0247] c) Calcium phenate sulfide and calcium salicylate detergents

[0248] d) Mannich base detergent

[0249] e) Amine antioxidants

[0250] f) Borated monoolein

[0251] The formulation examples in Table 7 do not contain zinc-based additives that are typically used as anti-wear agents. Comparative Example D is similar to the inventive examples, but does not contain Compound 2.

[0252] Experimental Procedure I

[0253] Compound 2 was added in different amounts to finished oil containing an engine oil additive package to observe its solvency and tendency to dissolve carbocyclic deposits. Blending was performed at ambient temperature for 20 minutes.

[0254] Ring sections from an internal combustion engine containing high concentrations of carbon deposits were used for the experiment. The rings were pre-washed with hexane, dried, and then weighed to 4 decimal places. Next, the ring sections were carefully placed in a beaker containing the finished oil (i.e., Examples 8-10 and Comparative Example D). The samples were allowed to stand in the finished oil for 4, 6, and 24 hours without stirring. The approximate temperature of the finished oil was ~22°C. A turbidity formed around the segmented ring pieces, indicating that the deposits were partially removed. The ring segments were removed, rinsed with hexane, allowed to air dry, and then weighed again.

[0255] Table 7

[0256]

[0257] The concentration of Compound 2 in the finished oil correlated strongly with deposit removal, as did the soak / residence time, as shown in Table 7. The cumulative ring weight loss corresponding to deposit removal is reported in mg (higher mg values ​​indicate better deposit removal performance).

[0258] Examples 11-12 and Comparative Example E

[0259] Examples 11-12 and Comparative Example E were formulated to provide natural gas engine oil (NGEO) compositions having the following specifications: 3BN, SAE 40 viscosity grade, 0.32 percent sulfated ash.

[0260] Examples 11-12 were blended with the following components:

[0261] a) 0.75 wt% succinimide dispersant derived from 1000 MW PIB

[0262] b) 0.75 wt% succinimide dispersant derived from 1300 MW PIB

[0263] c) 1.9 wt% 114BN low overbased sulfurized calcium phenate detergent

[0264] d) 0.3 wt% zinc dithiophosphate derived from a C8 primary alcohol

[0265] e) 0.2 wt% 17BN calcium sulfonate

[0266] f) 0.25 wt% phenolic antioxidant

[0267] g) 50ppm foam inhibitor

[0268] h) Compound 2 at various treatment rates (solvent distilled) (Table 8)

[0269] The formulation of Comparative Example E was similar to Examples 11-12. However, Comparative Example E did not include lubricant additive Compound 2. A natural gas engine oil was formulated using Chevron RLOP 600R Group II base oil.

[0270] The PDSC test was used to evaluate the oxidation stability of each finished oil lubricant and the TEOST MHT test was used to evaluate the deposit performance. The results for each sample are listed in Table 8 below.

[0271] Table 8

[0272]

[0273] The results listed in Table 8 show that the natural gas engine lubricating oil composition containing lubricity additive Compound 2 exhibits surprisingly superior oxidation stability performance over Comparative Example E, as evident by the longer oxidation induction time. Examples 11-12 also exhibit superior deposit performance over the Comparative Examples in the TEOST MHT deposit test, as evidenced by less total deposits at the end of the test.

[0274] Examples 13-14 and Comparative Example F

[0275] Examples 13-14 and Comparative Example F were formulated to provide ashless natural gas engine oil (NGEO) compositions having the following specifications: 1 BN, SAE 40 viscosity grade, 0.06 percent sulfated ash.

[0276] Examples 13-14 were blended with the following components:

[0277] a) 0.75 wt% succinimide dispersant derived from 1000 MW PIB

[0278] b) 0.75 wt% succinimide dispersant derived from 1300 MW PIB

[0279] c) 0.3 wt% zinc dithiophosphate derived from a C8 primary alcohol

[0280] d) 0.25 wt% phenolic antioxidant

[0281] e) 50ppm foam inhibitor

[0282] f) Compound 2 at various treatment rates (solvent distilled) (Table 9)

[0283] The formulation of Comparative Example F was similar to Examples 13-14. However, Comparative Example F did not include lubricant additive Compound 2. A natural gas engine oil formulation was formulated using Chevron RLOP 600R Group II base oil.

[0284] The PDSC test was used to evaluate the oxidation stability of each finished oil lubricant. The results for each sample are listed in Table 9 below.

[0285] Table 9

[0286]

[0287] The results listed in Table 9 show that the ashless natural gas engine lubricating oil composition containing lubricious additive Compound 2 exhibits surprisingly superior oxidation stability performance over Comparative Example F, as evidenced by the longer oxidation induction time.

[0288] Examples 15-16 and Comparative Example G

[0289] Examples 15-16 and Comparative Example G were formulated to provide natural gas engine oil (NGEO) compositions having the following specifications: 3BN, SAE 40 viscosity grade, 0.3 percent sulfated ash.

[0290] Examples 15-16 were blended with the following components:

[0291] a) 0.75 wt% succinimide dispersant derived from 1000 MW PIB

[0292] b) 0.75 wt% succinimide dispersant derived from 1300 MW PIB

[0293] c) 0.47 wt% 114BN low overbased calcium sulphurized phenate

[0294] d) 0.2 wt% 260BN highly overbased calcium sulfide phenate

[0295] e) 0.85 wt% 17BN calcium sulfonate

[0296] f) 0.31 wt% 180BN moderately overbased calcium hydroxybenzoate derived from isomerized C20-24 olefins

[0297] g) 0.3 wt% zinc dithiophosphate derived from a C8 primary alcohol

[0298] h) 0.25 wt% phenolic antioxidant

[0299] i) 50ppm foam inhibitor

[0300] j) Compound 2 at various treatment rates (solvent distilled) (Table 10)

[0301] The formulation of Comparative Example G was similar to Examples 15-16. However, Comparative Example G did not include lubricant additive Compound 2. A natural gas engine oil was formulated using Chevron RLOP 600R Group II base oil.

[0302] The PDSC test was used to evaluate the oxidation stability of each finished oil lubricant. The results for each sample are listed in Table 10 below.

[0303] Table 10

[0304]

[0305] The results listed in Table 10 show that the natural gas engine lubricating oil composition containing lubricious additive Compound 2 exhibits surprisingly superior oxidation stability performance over Comparative Example G, as evidenced by the longer oxidation induction time.

[0306] Examples 17-18 and Comparative Example H

[0307] Examples 17-18 and Comparative Example H were formulated to provide natural gas engine oil (NGEO) compositions having the following specifications: 4BN, SAE 40 viscosity grade, 0.58 percent sulfated ash.

[0308] Examples 17-18 were blended with the following components:

[0309] a) 0.75 wt% succinimide dispersant derived from 1000 MW PIB

[0310] b) 0.75 wt% succinimide dispersant derived from 1300 MW PIB

[0311] c) 0.94 wt% 114BN low overbased calcium sulphurized phenate

[0312] d) 0.42 wt% 260BN highly overbased calcium sulfide phenate

[0313] e) 1.71 wt% 17BN calcium sulfonate

[0314] f) 0.63 wt% 180BN moderately overbased calcium hydroxybenzoate derived from isomerized C20-24 olefins

[0315] g) 0.3 wt% zinc dithiophosphate derived from a C8 primary alcohol

[0316] h) 0.25 wt% phenolic antioxidant

[0317] i) 50ppm foam inhibitor

[0318] j) Compound 2 at various treatment rates (solvent distilled) (Table 11)

[0319] The formulation of Comparative Example H was similar to Examples 17-18. However, Comparative Example H did not include lubricant additive Compound 2. A natural gas engine oil composition was formulated using Chevron RLOP 600R Group II base oil.

[0320] The PDSC test was used to evaluate the oxidation stability of each finished oil lubricant. The results for each sample are listed in Table 11 below.

[0321] Table 11

[0322]

[0323] The results listed in Table 11 show that the natural gas engine lubricating oil composition containing lubricious additive Compound 2 exhibits surprisingly superior oxidation stability performance over Comparative Example H, as evidenced by the longer oxidation induction time.

[0324] Examples 19-20 and Comparative Example 1

[0325] 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 having the following specifications: 3BN, SAE 40 viscosity grade lubricant.

[0326] Examples 19-20 were blended with the following components:

[0327] a) 1.0 wt% succinimide dispersant derived from 1300 MW PIB

[0328] b) 1.0 wt% succinimide dispersant derived from ethylene carbonate post-treatment of 2300 MW PIB

[0329] c) 1.1 wt% 114BN low overbased calcium sulphurized phenate

[0330] d) 0.5 wt% 260BN highly overbased calcium sulfide phenate

[0331] e) 0.7 wt% 17BN calcium sulfonate

[0332] f) 0.1 wt% 180BN moderately overbased calcium hydroxybenzoate derived from isomerized C20-24 olefins

[0333] g) 0.3 wt% zinc dithiophosphate derived from a C8 primary alcohol

[0334] h) 0.35 wt% phenolic antioxidant

[0335] i) 50ppm foam inhibitor

[0336] j) Compound 2 at various treatment rates (solvent distilled) (Table 12)

[0337] The formulation of Comparative Example 1 is similar to Examples 19-20. However, Comparative Example 1 does not include lubricant additive Compound 2.

[0338] The DSC test was used to evaluate the oxidation stability of each finished oil lubricant. The results for each sample are listed in Table 12 below.

[0339] Table 12

[0340]

[0341] The results listed in Table 12 show that the dual fuel engine lubricating oil composition containing lubricating additive Compound 2 exhibits surprisingly better oxidation stability performance than Comparative Example 1, as evidenced by the longer oxidation induction time.

[0342] Examples 21-22 and Comparative Example J

[0343] Examples 21-22 and Comparative Example J were formulated to provide railroad engine oil compositions having the following specifications: 15BN, SAE 20W-40 viscosity grade lubricant.

[0344] Examples 21-22 were blended with the following components:

[0345] a) 1.0 wt% succinimide dispersant derived from 1300 MW PIB

[0346] b) 1.0 wt% succinimide dispersant derived from ethylene carbonate post-treatment of 2300 MW PIB

[0347] c) 1.9 wt% 114BN low overbased calcium sulphurized phenate

[0348] d) 4.6 wt% 260BN highly overbased calcium sulfide phenate

[0349] e) 0.9 wt% 17BN calcium sulfonate

[0350] f) 0.1 wt% amine antioxidant

[0351] g) 50ppm foam inhibitor

[0352] h) Compound 2 at various treatment rates (solvent distilled) (Table 13)

[0353] The formulation of Comparative Example J is similar to Examples 21-22. However, Comparative Example J does not include lubricant additive Compound 2.

[0354] The DSC test was used to evaluate the oxidation stability of each finished oil lubricant. The results for each sample are listed in Table 13 below.

[0355] Table 13

[0356]

[0357] The results listed in Table 13 show that the railroad engine lubricating oil compositions containing lubricant additive Compound 2 exhibit surprisingly superior oxidation stability performance, as evidenced by the longer oxidation induction time, than Comparative Example J. In addition to the improved oxidation stability performance, the railroad engine oil lubricating oil compositions of Examples 21-22 achieve the desired viscosity grade at a lower amount of high viscosity base oil (600R), demonstrating the thickening ability of Lubricant Additive Compound 2.

[0358] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, the range from any lower limit can be combined with any upper limit to list a range that is not explicitly listed, and the range from any lower limit can be combined with any other lower limit to list a range that is not explicitly listed, and in the same manner, the range from any upper limit can be combined with any other upper limit to list a range that is not explicitly listed. In addition, each point or single value between the endpoints of the range is included in the range, even if it is not explicitly listed. Therefore, each point or single value can serve as its own lower limit or upper limit to be combined with any other point or single value or any other lower limit or upper limit to list a range that is not explicitly listed.

[0359] Likewise, the term "comprising" is considered synonymous with the term "including." Likewise, whenever a composition, an element, or a group of elements is preceded by the transitional phrase "comprising," it should be understood that we also contemplate the same composition or group of elements having the transitional phrases "consisting essentially of," "consisting of," "selected from the group consisting of," or "being" preceding the recitation of the composition, an element, or a plurality of elements, and vice versa.

[0360] As used herein, the terms "a", "an" and "the" should be construed to cover the plural as well as the singular.

[0361] Various terms have been defined above. If a term used in a claim is not defined above, it should be given the broadest definition that persons in the relevant art have given that term as reflected in at least one printed publication or issued patent. In addition, all patents, test procedures, and other documents cited in this application are fully incorporated by reference to the extent such disclosure is not inconsistent with this application and for all jurisdictions in which such incorporation is permitted.

[0362] The foregoing description of the present disclosure illustrates and describes the present disclosure. In addition, the present disclosure shows and describes only preferred embodiments, but as mentioned above, it should be understood that the present disclosure can be used in various other combinations, modifications and environments, and can be changed or modified within the scope of the concepts expressed herein commensurate with the above teachings and / or the technology or knowledge of the relevant field. Although the foregoing is directed to embodiments of the present disclosure, other and further embodiments of the present disclosure can be designed without departing from the basic scope of the present disclosure, and the scope of the present disclosure is determined by the appended claims.

[0363] It should be understood that when combinations, subsets, groups, etc. of elements are disclosed (e.g., combinations of components in compositions, or combinations of steps in methods), while specific reference to each of the various individual and collective combinations and arrangements of these elements may not be explicitly disclosed, each is specifically contemplated and described herein.

[0364] The embodiments described above are further intended to explain the best known modes of practicing it and to enable others skilled in the art to utilize the present disclosure in such or other embodiments and with various modifications required for a particular application or use. Therefore, this specification is not intended to be limited to the forms disclosed herein. In addition, the appended claims are intended to be interpreted as including alternative embodiments.

Claims

1. A gas fuel engine lubricating oil composition, comprising: a major amount of base oil; and Lubricant additives having the following structure: Each R 1 is independently a hydrocarbon group having 10 to 400 carbon atoms; X is an alkyl, aryl or heteroaromatic group having 1 to 10 carbon atoms; 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; and each R 3 is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons with one or more nitrogen, oxygen or sulfur functionalizations, wherein p is 1 to 3, n is 1 to 20 and m is 0 to 3.

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

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

4. The gaseous fuel engine lubricating oil composition of claim 1, wherein the lubricant additive has the following general structure: Each R 1 is independently a hydrocarbon group having 10 to 400 carbon atoms; 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; and each R 3 is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons with one or more nitrogen, oxygen or sulfur functionalizations, wherein p is 1 to 3, n is 1 to 20 and m is 0 to 3.

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

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

7. The gaseous fuel engine lubricating oil composition of claim 1, wherein the gaseous fuel engine lubricating oil composition is a SAE 15W-X, 20W-X or 25W-X viscosity grade engine oil, 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 Lubricant additives having the following structure: Each R 1 is independently a hydrocarbon group having 10 to 400 carbon atoms; X is an alkyl, aryl or heteroaromatic group having 1 to 10 carbon atoms; 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; and each R 3 is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons with one or more nitrogen, oxygen or sulfur functionalizations, wherein p is 1 to 3, n is 1 to 20 and m is 0 to 3.

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

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

11. The lubricating oil composition of claim 8, wherein the lubricant additive has the following general structure: Each R 1 is independently a hydrocarbon group having 10 to 400 carbon atoms; 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; and each R 3 is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons with one or more nitrogen, oxygen or sulfur functionalizations, wherein p is 1 to 3, n is 1 to 20 and m is 0 to 3.

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

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

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

15. A method of thickening a lubricating oil composition in a gaseous fuel, slow speed or medium speed engine, the method comprising adding to the engine a lubricating oil composition comprising: a major amount of base oil; and Lubricant additives having the following structure: Each R 1 is independently a hydrocarbon group having 10 to 400 carbon atoms; X is an alkyl, aryl or heteroaromatic group having 1 to 10 carbon atoms; 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; and each R 3 is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons with one or more nitrogen, oxygen or sulfur functionalizations, wherein p is 1 to 3, n is 1 to 20 and m is 0 to 3.

16. The method of claim 15, wherein the lubricant additive is present at about 0.1 to about 50 weight percent based on the total weight of the lubricating oil composition.

17. The method of claim 15, wherein R 1 It is a polyisobutylene group.

18. The method of claim 15, wherein the lubricant additive has the following general structure: Each R 1 is independently a hydrocarbon group having 10 to 400 carbon atoms; 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; and each R 3 is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons with one or more nitrogen, oxygen or sulfur functionalizations, wherein p is 1 to 3, n is 1 to 20 and m is 0 to 3.

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

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

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

22. The method of claim 15, wherein the engine is a stationary natural gas engine, a stationary biogas engine, a stationary landfill gas engine, a stationary unconventional natural gas fuel engine, or a dual fuel engine.

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

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

25. The method of 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 of improving piston cleanliness or oxidation inhibition in an engine, the method comprising lubricating the engine with a lubricating oil composition comprising: a major amount of base oil; and Lubricant additives having the following structure: Each R 1 is independently a hydrocarbon group having 10 to 400 carbon atoms; X is an alkyl, aryl or heteroaromatic group having 1 to 10 carbon atoms; 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; and each R 3 is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons with one or more nitrogen, oxygen or sulfur functionalizations, wherein p is 1 to 3, n is 1 to 20 and m is 0 to 3.

27. The method of claim 26, wherein the lubricant additive has the following general structure: Where R 1 is a hydrocarbon group having 10 to 400 carbon atoms, Y is nitrogen, oxygen or sulfur, and each R 2 is independently a hydrocarbon group having 1 to 9 carbon atoms, Z is nitrogen, oxygen or sulfur, and each R 3 is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons with one or more nitrogen, oxygen or sulfur functionalizations, wherein n is 1 to 20 and m is 1 to 3.

28. A method of removing existing deposits in an internal combustion engine, the method comprising lubricating the engine with a composition comprising: Base oil; and An additive having the following structure: Each R 1 is independently a hydrocarbon group having 10 to 400 carbon atoms; X is an alkyl, aryl or heteroaromatic group having 1 to 10 carbon atoms; 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; and each R 3 is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons with one or more nitrogen, oxygen or sulfur functionalizations, wherein p is 1 to 3, n is 1 to 20 and m is 0 to 3.

29. The method of claim 28, wherein the additive is present in about 0.1 to about 50 weight percent based on the total weight of the composition.

30. The method of claim 28, wherein R 1 It is a polyisobutylene group.

31. The method of claim 28, wherein the additive has the following general structure: Each R 1 is independently a hydrocarbon group having 10 to 400 carbon atoms; 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; and each R 3 is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons with one or more nitrogen, oxygen or sulfur functionalizations, wherein p is 1 to 3, n is 1 to 20 and m is 0 to 3.

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

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

34. A method of removing existing deposits from a crankcase, rocker cover, camshaft area, timing cover, cylinder head, combustion chamber, piston rings and / or grooves in an internal combustion engine, the method comprising lubricating the engine with a composition comprising: Base oil; and An additive having the following structure: Each R 1 is independently a hydrocarbon group having 10 to 400 carbon atoms; X is an alkyl, aryl or heteroaromatic group having 1 to 10 carbon atoms; 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; and each R 3 is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons with one or more nitrogen, oxygen or sulfur functionalizations, wherein p is 1 to 3, n is 1 to 20 and m is 0 to 3.

35. The method of claim 34, wherein the additive is present in about 0.1 to about 50 weight percent based on the total weight of the composition.

36. The method of claim 34, wherein R 1 It is a polyisobutylene group.

37. The method of claim 34, wherein the additive has the following general structure: Each R 1 is independently a hydrocarbon group having 10 to 400 carbon atoms; 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; and each R 3 is independently hydrogen or a hydrocarbyl group having 1 to 9 carbons with one or more nitrogen, oxygen or sulfur functionalizations, wherein p is 1 to 3, n is 1 to 20 and m is 0 to 3.

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

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

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