Lubricant Additives

This application is a national phase application of PCT/US2023/021412 filed May 8, 2023, which claims the benefit of U.S. Provisional Patent Application No. 63/339,576, filed May 9, 2022, which is incorporated by reference herein in its entirety.

This disclosure relates to lubricant additive compositions and lubricating oil compositions containing the same. More particularly, the compositions improve oxidative stability and/or deposit control in an engine environment.

While all engines put stress on lubricating oils, some engines run continuously at near full load and high temperature conditions which place greater thermal stress on the lubricants. Under such conditions, engines are particularly susceptible to oxidation and deposit formation which can lead to significant degradation of engine performance. Moreover, some of these engines require lubricating oils to be within a specified viscosity range necessitating the use of components such as thickeners.

In one aspect, there is provided a gaseous-fueled engine lubricating oil composition comprising: a major amount of base oil; and a lubricant additive having the following structure:

wherein each Ris independently a hydrocarbyl group having 10 to 400 carbons; X is an alkyl, aryl, or heteroaromatic group having 1 to 10 carbons; Y is nitrogen, oxygen, or sulfur; each Ris independently a hydrocarbyl group having 1 to 9 carbons; Z is nitrogen, oxygen, or sulfur; and each Ris independently a hydrogen or hydrocarbyl group having 1 to 9 carbons with one or more nitrogen, oxygen, or sulfur functionalization, wherein p is 1 to 3, n is 1 to 20 and m is 0 to 3.

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

wherein each Ris independently a hydrocarbyl group having 10 to 400 carbons; X is an alkyl, aryl, or heteroaromatic group having 1 to 10 carbons; Y is nitrogen, oxygen, or sulfur; each Ris independently a hydrocarbyl group having 1 to 9 carbons; Z is nitrogen, oxygen, or sulfur; and each Ris independently a hydrogen or hydrocarbyl group having 1 to 9 carbons with one or more nitrogen, oxygen, or sulfur functionalization, wherein p is 1 to 3, n is 1 to 20 and m is 0 to 3.

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

wherein each Ris independently a hydrocarbyl group having 10 to 400 carbons; X is an alkyl, aryl, or heteroaromatic group having 1 to 10 carbons; Y is nitrogen, oxygen, or sulfur; each Ris independently a hydrocarbyl group having 1 to 9 carbons; Z is nitrogen, oxygen, or sulfur; and each Ris independently a hydrogen or hydrocarbyl group having 1 to 9 carbons with one or more nitrogen, oxygen, or sulfur functionalization, wherein p is 1 to 3, n is 1 to 20 and m is 0 to 3.

In still yet another aspect, there is provided 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 of base oil; and a lubricant additive having the following structure:

wherein each Ris independently a hydrocarbyl group having 10 to 400 carbons; X is an alkyl, aryl, or heteroaromatic group having 1 to 10 carbons; Y is nitrogen, oxygen, or sulfur; each Ris independently a hydrocarbyl group having 1 to 9 carbons; Z is nitrogen, oxygen, or sulfur; and each Ris independently a hydrogen or hydrocarbyl group having 1 to 9 carbons with one or more nitrogen, oxygen, or sulfur functionalization, wherein p is 1 to 3, n is 1 to 20 and m is 0 to 3.

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

wherein each Ris independently a hydrocarbyl group having 10 to 400 carbons; X is an alkyl, aryl, or heteroaromatic group having 1 to 10 carbons; Y is nitrogen, oxygen, or sulfur; each Ris independently a hydrocarbyl group having 1 to 9 carbons; Z is nitrogen, oxygen, or sulfur; and each Ris independently a hydrogen or hydrocarbyl group having 1 to 9 carbons with one or more nitrogen, oxygen, or sulfur functionalization, wherein p is 1 to 3, n is 1 to 20 and m is 0 to 3.

In yet still another further aspect, there is provided a method of removing existing deposits from the crankcase, rocker cover, camshaft region, timing gear cover, cylinder head, combustion chamber, piston rings and/or ring grooves in an internal combustion engine, the method comprising lubricating or rapid cleaning the engine with a composition comprising: a base oil; and an additive having the following structure:

wherein each Ris independently a hydrocarbyl group having 10 to 400 carbons; X is an alkyl, aryl, or heteroaromatic group having 1 to 10 carbons; Y is nitrogen, oxygen, or sulfur; each Ris independently a hydrocarbyl group having 1 to 9 carbons; Z is nitrogen, oxygen, or sulfur; and each Ris independently a hydrogen or hydrocarbyl group having 1 to 9 carbons with one or more nitrogen, oxygen, or sulfur functionalization, wherein p is 1 to 3, n is 1 to 20 and m is 0 to 3.

It is understood that when combinations, subsets, groups, etc. of elements are disclosed (e.g., combinations of components in a composition, or combinations of steps in a method), that while specific reference of each of the various individual and collective combinations and permutations of these elements may not be explicitly disclosed, each is specifically contemplated and described herein.

The present disclosure relates to lubricant additive compositions with enhanced oxidative stability, thickening ability, and/or deposit control capability (i.e., preventing deposit formation and/or removal of existing deposits), lubricating oil compositions containing the lubricant additive, and methods of using the compositions.

When used during regular maintenance such as scheduled oil change recommend by OEM, the lubricating oil composition works primarily (not necessarily exclusively) to prevent deposit formation. When used on as needed basis such as a rapid cleaning service, the lubricating oil composition works primarily (not necessarily exclusively) to remove existing deposits.

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

The gaseous-fueled engine may be a stationary natural gas engine, a stationary biogas engine, a stationary landfill gas engine, a stationary unconventional gaseous-fueled engine, or a dual-fuel engine. Dual-fuel engines can operate using a mixture of two different fuels. Frequently, diesel and natural gas fuels are used together within dual fuel engines. Beyond natural gas and diesel, some dual-fuel engines can also use varying mixtures of biodiesel, landfill gas, bio-gas and other fuels.

The fuel which is used to operate the gaseous-fueled engine may include carbon-based gaseous fuels (e.g., natural gas, biogas, landfill gas, wood gas, methane, propane, butane, etc.) and non-carbon based gaseous fuels (e.g. ammonia, hydrogen).

Diesel engines may generally be classified as low-speed, medium-speed or high-speed engines. Herein, a “low-speed” engine means a compression-ignition internal combustion engine that is driven at a rotational speed that is less than 500 revolutions per minute (rpm), such as marine crosshead diesel engines; a “medium-speed” engine means a compression-ignition internal combustion engine that is driven at a rotational speed of 500 to 1800 rpm, such as locomotive (“railroad”) diesel engines, marine trunk piston diesel engines, or land-based stationary power diesel engines; and a “high-speed” engine means a compression-ignition internal combustion engine that is driven at a rotational speed that is higher than 1800 rpm, such as diesel engines for highway vehicles.

In some embodiments, the lubricating oil composition disclosed herein may be utilized in controlling 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), of at least 12 bar (1.2 MPa), of at least 14 bar (1.4 MPa), of at least 16 bar (1.6 MPa), of at least 18 bar (1.8 MPa), of at least 20 bar (2.0 MPa), e.g., at least 22 bar (2.2 MPa), at least 24 bar (2.4 MPa), at least 26 bar (2.6 MPa), 10 to 30 bar (1.0 to 3.0 MPa), 20 to 30 bar (2.0 to 3.0 MPa), 22 to 30 bar (2.2 to 3.0 MPa), 22 to 28 bar (2.2 to 2.8 MPa), or 24 to 30 bar (2.4 to 3.0 MPa).

The lubricant additive disclosed herein and compositions containing the same can be used in a number of lubricant applications such as a railroad engine oil (RREO), marine system oil (SO), marine cylinder lubricant (MCL), trunk piston engine oil (TPEO), natural gas engine oil (NGEO), or dual-fuel (DF) engine oil.

In some embodiments, the lubricating oil composition disclosed herein has a total base number (TBN) of 2 to 200 mgKOH/g 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.

In some embodiments, the lubricating oil composition disclosed herein is suitable for use as a marine cylinder lubricant used to lubricate a low-speed crosshead engine. Marine cylinder lubricants are typically made to the SAE 30, SAE 40, SAE 50, or SAE 60 monograde specification in order to provide a sufficiently thick lubricant film at the high temperatures on the cylinder liner wall. Typically, marine diesel cylinder lubricants have a TBN of up to 200 mg KOH/g, or ranging from 2 to 200 mg KOH/g (e.g., from 2 to 200 mg KOH/g, from 5 to 200 mg KOH/g, from 10 to 200 mg KOH/g, from 15 to 150 mg KOH/g, from 15 to 60 mg KOH/g, from 20 to 200 mg KOH/g, from 20 to 150 mg KOH/g from 20 to 120 mg KOH/g, from 20 to 80 mg KOH/g, from 30 to 200 mg KOH/g, or from 30 to 150 mg KOH/g, or from 30 to 120 mg KOH/g, from 30 to 100 mg KOH/g, from 30 to 80 mg KOH/g, from 60 to 200 mg KOH/g, from 60 to 150 mg KOH/g, from 60 to 120 mg KOH/g, from 60 to 100 mg KOH/g, from 60 to 80 mg KOH/g, from 80 to 200 mg KOH/g, from 80 to 150 mg KOH/g, from 80 to 150 mg 120 KOH/g, from 120 to 200 mg KOH/g, or from 120 to 150 mg KOH/g).

In some embodiments, the lubricating oil composition disclosed herein is suitable for use as a marine system oil used to lubricate the crankcase of a low-speed crosshead engine, Marine system oil lubricants are typically made to the SAE 20, SAE 30, or SAE 40 monograde specification. The viscosity for the marine system oil is set at relatively low level(s) in part because a system oil can increase in viscosity during use and the engine designers have set viscosity increase limits to prevent operational problems. Typically, marine system oil lubricants have a TBN of up to 12 mg KOH/g or ranging from 2 to 12 mg KOH/g (e.g., from 3 to 12 mg KOH/g, from 5 to 12 mg KOH/g, from 5 to 10 mg KOH/g, or from 5 to 9 mg KOH/g).

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 typically made to the SAE 30 or SAE 40 monograde specification. Typically, marine TPEO lubricants have a TBN of up to 60 mg KOH/g or ranging from 2 to 60 mg KOH/g (e.g., from 5 to 60 mg KOH/g, 10 to 30 mg KOH/g, from 15 to 60 mg KOH/g, from 15 to 40 mg KOH/g, from 20 to 60 mg KOH/g, 20 to 40 mg KOH/g, from 30 to 60 mg KOH/g, or from 30 to 55 mg KOH/g).

In some embodiments, the lubricating oil composition disclosed herein is suitable for use as a gaseous-fueled engine oil, such as a natural gas fueled engine oil. Gaseous-fueled engine oils typically have a TBN up to 10 mg KOH/g or ranging from 2 to 10 mg KOH/g (e.g., from 2 to 9 mg KOH/g, or 2 to 8 mg KOH/g).

In some embodiments, the lubricating oil composition disclosed herein is suitable for use as a medium speed engine oil, such as a locomotive (railroad) engine oil. Locomotive engine oil lubricants typically have a TBN up to 20 mg KOH/g, up to 15 mg KOH/g, up to 10 mg KOH/g, or ranging from 4 to 20 mg KOH/g, from 4 to 15 mg KOH/g, 4 to 10 mg KOH/g, or 5 to 9 mg KOH/g.

In some embodiments, the lubricating oil composition disclosed herein may be used during rapid cleaning service to remove accumulated deposits, sludge, and other gunk from an internal combustion engine. A rapid cleaning service can remove sludge, heavy deposits, and/or other insoluble material that may have been built up over time. The cleaning process may be comprised of using the lubricant in the engine sump or crankcase and circulating the lubricating oil without starting the engine. An additional step would include circulating the lubricating oil and allowing it to soak under a static condition 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 could include starting and operating the engine at any running condition appropriate for the engine design and fuel 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. In some embodiments, the lubricating oil composition disclosed herein may be used for removing existing deposits from the crankcase, rocker cover, camshaft region, timing gear cover, cylinder head, combustion chamber, piston rings and/or ring grooves in an internal combustion engine.

When used during a rapid cleaning service, the lubricating oil composition can require the lubricant additive at a higher concentration than is typically used during regular maintenance. This lubricating oil with higher amounts of the deposit cleaning lubricant additive is used to lubricate and clean the engine. The resulting mixed product (concentrated lubricating oil and deposits) can then be flushed. The flushing step typically occurs after completion of the cleaning step.

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

In some embodiments, the flushing takes place after 5 minutes, after 15 minutes, after 30 minutes, after 45 minutes, after 1 hour, after 2 hours, after three 3, after 4 hours, after 5 hours, after 6 hours, after 8 hours, after 12 hours, after 16 hours, after 24 hours, after 2 days, after 3 days, after 4 days, after 1 week, after 2 weeks, after 3 weeks, after 4 weeks, after 6 weeks, after 8 weeks from the cleaning step. In some embodiments, the flushing step can occur up to a period equivalent to about 25% of the OEM recommended oil change interval period.

In some embodiments, the present disclosure relates to engine flush products containing the additive, mixed products containing the additive and used lubricating oil composition, and methods of using the same.

In some embodiments, the engine flush product is an aftermarket additive package wherein the additive is dissolved in solvent. The aftermarket additive package is suitable for rapidly cleaning or removing accumulated deposits, sludge, and other gunk from an internal combustion engine.

An engine flush process can remove sludge, heavy deposits, and/or other gunk that may have been built up from engine oil. A typical engine flush process involves adding the additive as an aftermarket additive (e.g., engine flush product) to an internal combustion engine through the oil-filler port. After the engine is allowed to idle, the additive is added to mix with the existing lubricating oil composition which has “used base oil”. This mixed product can dissolve or clean sludge, heavy deposits, and/or gunk residing in the engine. The mixed product is then drained along with the dissolved sludge, deposit, and/or gunk.

In some embodiments, the lubricating oil composition disclosed herein may contain low levels of sulfated ash, as determined by ASTM D874. The compositions 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 compositions may have a sulfated ash content from 0.01 to 1.0 wt. %, from 0.1 to 1.0 wt. %, from 0.3 to 0.8 wt. %, from 0.4 to 1.0 wt. %, from 0.5 to 0.9 wt. %, or from 0.5 to 1.0 wt, %. In some embodiments the lubricating oil composition may be ashless.

The lubricating oil composition disclosed herein may provide advantaged deposit control performance in any of a number of mechanical components of an engine. The mechanical component may be a piston, a piston ring, piston ring grooves, a crankcase, a rocker cover, a camshaft region, a timing gear cover, a cylinder head, a combustion chamber, a cylinder liner, a cylinder, a cam, a tappet, a lifter, a gear, a valve, a valve guide, or a bearing including a journal, a roller, a tapered, a needle, or a ball bearing. In some cases, the mechanical component may comprise steel.

The lubricant additive composition of the present disclosure can be represented by the following generalized chemical Structure I:

wherein each Ris independently a hydrocarbyl group having 10 to 400 carbons; X is an alkyl, aryl, or heteroaromatic group having 1 to 10 carbons; Y is nitrogen, oxygen, or sulfur; each Ris independently a hydrocarbyl group having 1 to 9 carbons; Z is nitrogen, oxygen, or sulfur; and each Ris independently a hydrogen or hydrocarbyl group having 1 to 9 carbons with one or more nitrogen, oxygen, or sulfur functionalization, 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.

Each Ris independently a moiety that includes 10 to 400 carbon atoms, such as 10 to 390, 10 to 380, 10 to 370, 10 to 360, 10 to 350, 10 to 340, 10 to 330, 10 to 320, 10 to 310, 10 to 300, 10 to 290, 10 to 280, 10 to 270, 10 to 260, 10 to 250, 10 to 240, 10 to 230, 10 to 220, 10 to 210, 10 to 200, 10 to 190, 10 to 180, 10 to 170, 10 to 160, 10 to 150, 10 to 140, 10 to 130, 10 to 120, 10 to 110, 10 to 100, 10 to 90, 10 to 80, 10 to 70, 10 to 60, 10 to 50, 10 to 40, 10 to 30, 10 to 20, 20 to 400, 20 to 390, 20 to 380, 20 to 370, 20 to 360, 20 to 350, 20 to 340, 20 to 330, 20 to 320, 20 to 310, 20 to 300, 20 to 290, 20 to 280, 20 to 270, 20 to 260, 20 to 250, 20 to 240, 20 to 230, 20 to 220, 20 to 210, 20 to 200, 20 to 190, 20 to 180, 20 to 170, 20 to 160, 20 to 150, 20 to 140, 20 to 130, 20 to 120, 20 to 110, 20 to 100, 20 to 90, 20 to 80, 20 to 70, 20 to 60, 20 to 50, 20 to 40, 20 to 30, 30 to 400, 30 to 390, 30 to 380, 30 to 370, 30 to 360, 30 to 350, 30 to 340, 30 to 330, 30 to 320, 30 to 310, 30 to 300, 30 to 290, 30 to 280, 30 to 270, 30 to 260, 30 to 250, 30 to 240, 30 to 230, 30 to 220, 30 to 210, 30 to 200, 30 to 190, 30 to 180, 30 to 170, 30 to 160, 30 to 150, 30 to 140, 30 to 130, 30 to 120, 30 to 110, 30 to 100, 30 to 90, 30 to 80, 30 to 70, 30 to 60, 30 to 50, 30 to 40, 40 to 400, 40 to 390, 40 to 380, 40 to 370, 40 to 360, 40 to 350, 40 to 340, 40 to 330, 40 to 320, 40 to 310, 40 to 300, 40 to 290, 40 to 280, 40 to 270, 40 to 260, 40 to 250, 40 to 240, 40 to 230, 40 to 220, 40 to 210, 40 to 200, 40 to 190, 40 to 180, 40 to 170, 40 to 160, 40 to 150, 40 to 140, 40 to 130, 40 to 120, 40 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 330, 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, 50 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 390, 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, 70 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 250, 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, 80 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 100, 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, 100 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, 110 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 170, 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 310, 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 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, 150 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, 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 220, 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, 190 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, 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 300, 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 340, 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, 260 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, 270 to 400, 270 to 390, 270 to 380, 270 to 370, 270 to 360, 270 to 350, 270 to 340, 270 to 330, 270 to 320, 270 to 310, 270 to 300, 270 to 290, 270 to 280, 280 to 400, 280 to 390, 280 to 380, 280 to 370, 280 to 360, 280 to 350, 280 to 340, 280 to 330, 280 to 320, 280 to 310, 280 to 300, 280 to 290, 290 to 400, 290 to 390, 290 to 380, 290 to 370, 290 to 360, 290 to 350, 290 to 340, 290 to 330, 290 to 320, 290 to 310, 290 to 300, 300 to 400, 300 to 390, 300 to 380, 300 to 370, 300 to 360, 300 to 350, 300 to 340, 300 to 330, 300 to 320, 300 to 310, 310 to 400, 310 to 390, 310 to 380, 310 to 370, 310 to 360, 310 to 350, 310 to 340, 310 to 330, 310 to 320, 320 to 400, 320 to 390, 320 to 380, 320 to 370, 320 to 360, 320 to 350, 320 to 340, 320 to 330, 330 to 400, 330 to 390, 330 to 380, 330 to 370, 330 to 360, 330 to 350, 330 to 340, 340 to 400, 340 to 390, 340 to 380, 340 to 370, 340 to 360, 340 to 350, 350 to 400, 350 to 390, 350 to 380, 350 to 370, 350 to 360, 360 to 400, 360 to 390, 360 to 380, 360 to 370, 370 to 400, 370 to 390, 370 to 380, 380 to 400, 380 to 390, or 390 to 400 carbon atoms.

In some embodiments, Rmay include, for example, saturated and unsaturated hydrocarbon groups, linear and branched alkyl groups, and polyalkyl groups (e.g., polyisobutenyl group or “PIB”, polyethylene, polypropylene, etc.). The polyalkyl groups may be the obtained from a polymerization reaction using olefin monomers (e.g., isobutylene).