Lubricant composition containing detergent for reducing abnormal combustion events in hydrogen-fueled engines

Abstract

This invention relates to a method for reducing abnormal combustion events during engine operation of a hydrogen-fired internal combustion engine (HICE). The method includes the steps of: a) providing the HICE with a lubricating oil composition comprising or a mixture of the following components: i) a base oil having a KV100 of less than or equal to 12 cSt and an amount greater than 50% by weight of the composition, and containing Group I, Group II, Group III, Group IV base oils, or combinations thereof; ii) a super-alkaline metal-containing detergent comprising a super-alkaline metal salicylate detergent, a super-alkaline metal phenolate detergent, or a combination thereof, having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500, and being contained at a treatment level providing the composition with a total metal content between 100 and 5000 ppm by weight and a total soap content between 0.15% by weight and 8.0% by weight; and iii) The lubricating oil composition has a total sulfate ash content of less than or equal to 2.0% by weight, a total phosphorus level of less than or equal to 0.120% by weight, and an SAE viscosity grade of 25W-X, 20W-X, 15W-X, 10W-X, 5W-X, or 0W-X, where X represents any one of 8, 12, 16, 20, 30, 40, 50, or 60; b) supplying hydrogen-containing fuel to the HICE; and c) burning the fuel in the HICE. Lubricating oil compositions and concentrates for reducing the tendency for abnormal combustion events in HICE are also provided.

Description

[0001] Inventor

[0002] Tom Featherstone, Ellis Mutter, Roxana Chirita and Andrew Ritchie Technical Field

[0003] This disclosure relates to the use of a lubricating oil composition having an overly alkaline metallic detergent in a hydrogen-fired engine to reduce abnormal combustion events, for example in compression-ignition and / or spark-ignition internal combustion engines. Background Technology

[0004] This invention relates to lubricating oil compositions for internal combustion engines (such as hydrogen-fired engines using spark ignition, compression ignition, or spark-assisted compression ignition) that exhibit improved ACE ("ACE") characteristics (e.g., backfire, various types of knock, including super-knock and severe knock events, and pre-ignition events). The invention further relates to lubricating oil compositions for compression-ignition or spark-assisted compression-ignition internal combustion engines, such compositions being commonly referred to as crankcase lubricants; and to the use of additives in such lubricating oil compositions to reduce ACE events in the use of such engines and / or to improve the performance of engines lubricated with said lubricating oil compositions, particularly by promoting the use of hydrogen-fired internal combustion engines where ACE events (such as pre-ignition) are a problem.

[0005] Several terms exist for various forms of abnormal combustion in internal combustion engines, including knock, extreme knock (sometimes called super-knock, mega-knock, or severe knock), surface ignition, and pre-ignition (ignition occurring before spark ignition or the desired compression ignition point). Extreme knock occurs in the same manner as conventional knock, but with increased amplitude, and can usually be mitigated using conventional knock control methods. Pre-ignition can occur at high or low speeds and is a prominent feature of hydrogen internal combustion engines.

[0006] Pre-ignition is a form of abnormal combustion event in which the air / fuel mixture ignites before it is expected to be ignited by the spark plug, such as before spark plug firing or before the desired ignition point in a compression ignition engine. There are many types of pre-ignition, and methods used to address one type of pre-ignition do not necessarily address another. Similarly, many factors combine to influence pre-ignition, making it a complex problem.

[0007] In the past, pre-ignition in hydrogen fuel systems has often been a challenge. Compared to gasoline, hydrogen as a fuel for internal combustion engines exhibits a lower minimum ignition energy, a wider flammability range, and faster flame propagation. A Study of Abnormal Ignition in a Hydrogen Combustion Engine, Naoyoshi Matsubara, YoshinoriMiyamoto, Shiro Tanno, Carbon Neutral Development Div. Toyota MotorCorporation, Yuua Abe Denso Corporation, 10 th International Engine Congress, Baden-Baden, Germany, February 28 – March 1, 2023, ATZ Live Springer Fachmedien Weisbaden GmbH, Wiesbaden, Germany. These combustion properties increase the likelihood of anomalous combustion of the air-fuel mixture. Early anomalous combustion events are often triggered by energy sources other than the designed spark event in spark-ignition engines, or by compressed-heated air in compression-ignition engines. Sources of anomalous combustion ignition can include combustion chamber hot spots (hot air pockets, hot surfaces, or combustion chamber deposits), or energy contained within fuel droplets injected into the combustion chamber. FEV's Pathway to an ICE Powertrain Powered by Future Fuels Achieving the Maximum Efficiency , Dieter Van DerPut, FEV Eurpoe GmbH, 10 th International Engine Congress, Baden-Baden, Germany, February 28 to March 1, 2023, ATZ Live Springer Fachmedien Weisbaden GmbH, Wiesbaden, Germany).

[0008] Abnormal combustion events can occur in both spark-ignition and compression-ignition internal combustion engines (see...). Hydrogen Combustion in a Compression Ignition Diesel EngineStanislaw Szwaja & KarolGrab-Rogalinski, International Journal of Hydrogen Energy, Vol. 34, No. 10, May 2009, pp. 4413-4421, and combustion cycles with early and / or high-pressure events relative to the average combustion pressure trace are typically identified by examining crankangle-resolved cylinder pressure traces, or by counting and characterizing the combustion mass fraction at a specific crank angle. These high-pressure events can potentially cause engine damage, including but not limited to damage to the piston or piston rings, or damage to the cylinder head gasket, cylinder head bolts, or cylinder head. Such damage adversely affects expected engine life (see Xu H, Ni X, Su X, Xiao B, Luo Y, Zhang F, Weng C, and Yao C, Experimental and numerical investigation on effects of pre-ignition positions on knock intensity of hydrogen fuel Int. J. Hydrogen Energy 46 26631–45, 2021, and Yang Luo, ChuanhaoZhao, Na Overview of Pre-ignition of Hydrogen Engine, J. Scientific Research and Reports. 26(10): 1-7, 2020). Milder pre-ignition events may not cause significant engine damage, but they can adversely affect fuel economy, engine performance, exhaust emissions, and engine noise, vibration, and harshness (NVH).

[0009] Hydrogen ignition failure from lubricating oil differs from low-speed pre-ignition in gasoline. Trace amounts of base oil appear to reduce the auto-ignition delay of the hydrogen-air mixture, effectively making early ignition failure more likely (see [link to relevant documentation]). Hydrogen Combustion in a Compression Ignition Diesel Engine Stanislaw Szwaja & Karol Grab-Rogalinski, International Journal of Hydrogen Energy, Vol. 34, No. 10, May 2009, pp. 4413-4421, and Aggarwal SK, Awomolo O and Akber K, Ignition characteristics of heptane-hydrogen and heptanemethane fuel blends at elevated pressures Int. J. Hydrogen Energy 36 15392–402, 2011).

[0010] As hydrogen internal combustion engines continue to evolve, the causes and effects of pre-ignition are also expected to evolve. First-generation hydrogen internal combustion engines were typically port fuel injection or low-pressure direct injection. This was driven by available hardware technology (high-pressure direct injection injectors generally did not have the required level of durability and required complex fuel tank management to provide competitive vehicle range). Limited achievable fuel pressures, combined with the tendency for pre-ignition in the air-fuel mixture, prompted engine manufacturers to develop very lean-burn engines, where the air-fuel ratio (AFR) is typically between 2 and 2.5 (compared to gasoline engines tending to operate around 1).

[0011] The consequence of very lean combustion is additional air handling costs, as more air needs to be delivered to the combustion chamber (compared to lean-burn engines), and this requires a higher air charge. In practice, this is delivered using variable geometry turbochargers, two-stage turbochargers, or superchargers. Air pressure cooling is also required to ensure sufficient air density and prevent aberrant combustion of the heated air charge. Operators also find that lean-burn engines have poorer throttle response, increasing the time between input and desired output. This is a consequence of the greater inertia of the air charge system and the desire to prevent pre-ignition caused by fuel enrichment.

[0012] While not wanting to be bound by theory, the inventors anticipate that engine designers will want to increase the engine's mean effective braking pressure (BMEP) to narrow the performance gap between hydrogen internal combustion engines and diesel or gasoline internal combustion engines. This requires finding solutions to limit or mitigate pre-ignition at high BMEP, where higher-energy combustion and larger air / fuel charges increase the likelihood of pre-ignition. Furthermore, the inventors expect that engine designers will both want to improve engine throttle performance and reduce air charge handling costs by shifting to lower lean-burn engine operation (preferably an air-fuel ratio of 1).

[0013] It is also recognized that, in some aspects of abnormal combustion, certain components in the lubricating oil may have different effects on increasing or decreasing abnormal combustion, and may have an effect on other components when they affect abnormal combustion events.

[0014] Many different lubricant additive chemistry systems have been proposed to control or influence the occurrence of abnormal combustion events (i.e., pre-ignition, knocking, and severe knocking events) in modern internal combustion engines, such as turbocharged gasoline direct injection engines. However, these chemistry systems are not easily adapted to hydrogen-fired engines, which have significantly different combustion environments.

[0015] U.S. Patent Application USSN 18 / 475,174, filed on September 26, 2023, discusses preventing low-speed pre-ignition in hydrogen engines and proposes that lubricants formulated with high amounts of pre-ignition event inhibitory compounds (such as phosphorus compounds) can significantly reduce or eliminate pre-ignition events, providing opportunities to increase the power density of internal combustion engines and use a wider range of fuels (such as e-fuels, blended fuels, fuels containing pre-ignition event promoters (such as ethanol), and / or lower octane / cetane fuels).

[0016] U.S. Patent No. 8,163,681 discloses a lubricant composition comprising a synthetic oil having a lubricating viscosity, 3 to 6 wt% of a nitrogen-containing dispersant, 1 to 2.5 wt% of a superalkaline magnesium detergent, 1 to 5 wt% of an antioxidant, and 0.25 to 1.5 wt% of a friction modifier, which can be used to lubricate hydrogen-fired engines. This composition typically contains less than 0.01 wt% Ca, less than 0.01 wt% Zn, less than 0.06 wt% P, and has a sulfate ash level of less than 1.2%. In column 14, lines 48-66 of USP 8,163,681, a zinc-free, low-corrosion / low-rust lubricant for hydrogen fuel cell bus fleets is disclosed, which specifically comprises Group IV base oils (synthetic polyalphaolefins), polyol esters, succinimide dispersants, magnesium alkylbenzene sulfonate detergents, an antioxidant mixture (ester-substituted hindered phenols, alkyl aromatic amines, and phosphorus-sulfurized olefins), linear fatty acid monoesters and oleamides, and defoamers, wherein the calculated KV100 of the combined PAO base oils is likely to be approximately 12 cSt (based on a weighted average of the two PAO base oils), and the lubricant may have a 60 wt (60) SAE viscosity descriptor.

[0017] USP 11,034,912 discloses a method for preventing or reducing low-speed pre-ignition in a direct-injection, turbocharged, spark-ignition gasoline internal combustion engine by lubricating the crankcase with a lubricating oil composition, the lubricating oil composition having a total sulfate ash content of no more than about 1.2% by mass, a zinc-phosphorus compound providing the composition with a phosphorus content of about 0.05 to about 0.08% by mass, a magnesium detergent providing the composition with an amount of at least about 0.3% by mass magnesium sulfate ash, and a calcium detergent or calcium and sodium detergent providing the composition with an amount of about 0.3 to about 0.4% by mass calcium sulfate ash or calcium and sodium sulfate ash, wherein the total sulfate ash provided to the composition by the detergent is no more than 1.0% by mass, and at least 40% by mass of the total metal introduced into the lubricating oil composition by the metal detergent is magnesium, and wherein the zinc-phosphorus compound is zinc dialkyl dithiophosphate derived from secondary alcohols or primary and secondary alcohols.

[0018] Other relevant literature includes: CN11512503A; WO2023057581; WO 2017 / 011633; WO 2018 / 036285; EP 3 366 755; EP 2940110; US 11,214,756; US 11,034,910; US 11,142,719; US10,604,720; US 10,214,703; US 10,519,394; US 10,584,300; US 10,669,505; US 11,155,764; US 10,604,720; Leach et al., SAE Int. J. Fuels Lubr. / Volume 15, Issue 1, 2022, SAE 04-15-01-001.

[0019] The inventors’ research on hydrogen pre-ignition has determined that the effect of lubricant compositions in hydrogen-fired internal combustion engines differs from that of gasoline LSPI, thus presenting different and unique challenges.

[0020] This invention relates to lubricating oil compositions for internal combustion engines using fuel compositions containing up to and including 100% hydrogen as fuel (spark ignition) and (compression ignition, or spark-assisted compression ignition); and to the use of additives in such lubricating oil compositions for reducing abnormal combustion events during the use of such engines and / or improving the performance of hydrogen-fired engines lubricated with said lubricating oil compositions, such as mean effective braking pressure (BMEP) and / or durability effects.

[0021] The inventors have now surprisingly discovered that certain overly alkaline metal-based detergents, such as overly alkaline metal-containing salicylate detergents, overly alkaline metal-containing phenolate detergents, and combinations thereof, can be used in lubricant compositions (such as in lubricant compositions for hydrogen-fired internal combustion engines) to provide very low rates of abnormal combustion events, such as pre-ignition. Summary of the Invention

[0022] This invention relates to a method for reducing abnormal combustion events during engine operation of a hydrogen-fired internal combustion engine (HICE), comprising: a) providing the hydrogen-fired internal combustion engine with a lubricating oil composition comprising or a mixture of the following components: i) a base oil having a viscosity KV100 of less than or equal to 12 cSt and an amount greater than 50% by weight of the composition, and comprising Group I, Group II, Group III, Group IV base oils or combinations thereof; ii) an over-alkaline metal-containing detergent comprising an over-alkaline metal salicylate detergent, an over-alkaline metal phenolate detergent or a combination thereof, having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500 and being contained at a treatment level providing the composition with a total metal content between 100 and 5000 ppm by weight and a total soap content between 0.15% by weight and 8.0% by weight; and iii) The lubricating oil composition has a total sulfate ash content of less than or equal to 2.0% by weight, a total phosphorus level of less than or equal to 0.120% by weight, and an SAE viscosity grade of 25W-X, 20W-X, 15W-X, 10W-X, 5W-X, or 0W-X, wherein X represents any one of 8, 12, 16, 20, 30, 40, 50, or 60; b) supplying hydrogen-containing fuel to the hydrogen-fired internal combustion engine; and c) burning the fuel in the hydrogen-fired internal combustion engine.

[0023] The present invention further relates to a lubricating oil composition for hydrogen-fired internal combustion engines (HICE), comprising or being a mixture of the following components: i) a base oil having a KV100 of less than or equal to 12 cSt and comprising more than 50% by weight of the composition, and comprising Group I base oil, Group II base oil, Group III base oil, Group IV base oil, or a combination thereof; ii) The super-alkaline metal-containing detergent comprises a super-alkaline metal salicylate detergent, a super-alkaline metal phenolate detergent, or a combination thereof, having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500 and being contained at a treatment level providing the composition with a total metal content between 100 and 5000 ppm by weight and a total soap content between 0.15% by weight and 8.0% by weight; and wherein the lubricating oil composition has a total sulfate ash content less than or equal to 2.0% by weight, a total phosphorus level less than or equal to 0.120% by weight, and an SAE viscosity grade of 25W-X, 20W-X, 15W-X, 10W-X, 5W-X, or 0W-X, wherein X represents any one of 8, 12, 16, 20, 30, 40, 50, or 60.

[0024] The present invention further relates to a concentrate comprising or a mixture thereof: 1% to 95% by weight of one or more base oils having a KV100 of 12 cSt or less and comprising Group I, Group II, Group III, Group IV base oils or combinations thereof; and 5% to 99% by weight of a super-alkaline metal-containing detergent based on the weight of the concentrate, comprising a super-alkaline metal salicylate detergent, a super-alkaline metal phenolate detergent or combinations thereof, having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500.

[0025] In another embodiment, the method for reducing abnormal combustion events during engine operation of a hydrogen-fired internal combustion engine (HICE) further includes measuring the number of abnormal pre-ignition events during combustion (1000 rpm, 12 bar BMEP and 1.85 air-fuel ratio (AFR)), wherein the number of pre-ignition events per 1,000 engine cycles is less than or equal to 10.

[0026] In another embodiment, the method for reducing abnormal combustion events during engine operation of a hydrogen-fired internal combustion engine (HICE) further includes measuring the number of abnormal pre-ignition events during combustion (1200 rpm, 18 bar BMEP and 2.05 air-fuel ratio (AFR)), wherein the number of pre-ignition events per 1,000 engine cycles is less than or equal to 5.

[0027] In yet another embodiment, the method for reducing abnormal combustion events in a hydrogen-fired internal combustion engine (HICE) during engine operation at 100% load is provided to reduce the frequency of abnormal pre-ignition events during combustion by at least 20% compared to comparable lubricating oil compositions that do not include the overly alkaline metal-containing detergent.

[0028] The present invention further relates to embodiments in which the lubricating oil composition for a hydrogen-fired engine comprises an overly alkaline metal-containing salicylate detergent.

[0029] The present invention further relates to embodiments in which a lubricating oil composition for a hydrogen-fired engine comprises an overly alkaline metal-containing phenolic detergent.

[0030] The present invention further relates to embodiments in which the lubricating oil composition for a hydrogen-fired engine comprises a combination of a superalkaline metal-containing salicylate detergent and a superalkaline metal-containing phenolate detergent. Attached Figure Description

[0031] Figure 1This is a prior art bar chart of low-speed pre-ignition (LSPI) events versus detergent types in lubricating oil compositions, taken from SAE 2016-01-0717. No statistical sensitivity to detergent soap type was shown in gasoline-fueled internal combustion engines.

[0032] Figure 2 This is a bar chart showing the number of pre-ignition events per 1000 cycles (measured at 1000 rpm, 12 bar BMEP and 1.85 air-fuel ratio (AFR)) of the lubricating oil compositions of the present invention disclosed herein and comparative lubricating oil compositions in hydrogen-fired internal combustion engines (HICE) versus the detergent soap type of the lubricating oil compositions, which shows a clear gain (credit) of salicylate detergents.

[0033] Figure 3 This is a bar chart showing the number of pre-ignition events per 1000 cycles (measured at 1200 rpm, 18 bar BMEP and 2.05 air-fuel ratio (AFR)) of the lubricating oil compositions of the present invention disclosed herein and comparative lubricating oil compositions in hydrogen-fired internal combustion engines (HICE), versus the detergent soap type of the lubricating oil compositions, which shows a clear gain (credit) of salicylate detergents.

[0034] Figure 4 This is a bar graph of oxidation induction time at 200°C for lubricating oil compositions with different soap types, measured by differential pressure scanning calorimetry (PDSC), showing a clear gain (credit) of salicylate detergents and phenolate detergents (in this invention) relative to sulfonate detergents (comparative).

[0035] definition

[0036] For the purposes of this specification and all claims, the following words and expressions have the meanings given below.

[0037] For the purposes of this paper, as described in CHEMICAL AND ENGINEERING NEWS, 63(5), 27 (1985), the new numbering scheme of the periodic table is used, in which alkali metals are group 1 metals (e.g., Li, Na, K, etc.) and alkaline earth metals are group 2 metals (e.g., Mg, Ca, Ba, etc.).

[0038] The term "about" means approximate, including values ​​obtained through rounding. As used herein, the term "about," modifying the amount of an ingredient, component, or reactant of the invention, refers to a numerical quantity that can vary, for example, through typical measurement and liquid handling procedures used to manufacture concentrates or lubricating oil compositions. Furthermore, variations can occur due to unintentional errors in the measurement procedures, differences in the manufacture, source, or purity of the ingredients used to manufacture the composition or to carry out the method, etc. In one aspect, the term "about" means within 10% of a reported value. In another aspect, the term "about" means within 5% of a reported value. In yet another aspect, the term "about" means within 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1% of a reported value.

[0039] The term "LOC" refers to a lubricating oil composition.

[0040] The term "major quantity" refers to the quantity of the composition based on the mass of the composition, such as greater than 50% by mass, greater than 60% by mass, greater than 70% by mass, 80 to 99.009% by mass, or 80 to 99.9% by mass.

[0041] Unless otherwise specified, the term "mass%" refers to the percentage of a component by mass based on the mass of the composition measured in grams, and is alternatively referred to as weight percentage ("weight%", "wt%", "wt.%" or "%w / w").

[0042] The term “minor amount” refers to 50% or less of the composition by mass, 40% or less of the composition by mass, 30% or less of the composition by mass, 20 to 0.001% by mass, or 20 to 0.1% by mass, based on the mass of the composition.

[0043] The term "active ingredient" (also known as "ai" or "AI") refers to an additive material that is neither a diluent nor a solvent. Unless otherwise specified, the amounts described herein are as active ingredients.

[0044] The terms “oil-soluble” and “oil-dispersible” or related terms used herein do not necessarily mean that the compound or additive is soluble, miscible, or able to suspend in the oil in all proportions. However, they mean that they are soluble or stably dispersed in the oil, for example, to a degree sufficient to achieve their intended effect in the environment in which the oil is used. Furthermore, the additional blending of other additives may allow for the addition of higher amounts of a particular additive if desired.

[0045] The term "hydrocarbon" refers to a compound containing hydrogen and carbon atoms. A "heteroatom" is an atom that is neither carbon nor hydrogen. When referred to as a "hydrocarbon," especially as a "refined hydrocarbon," the hydrocarbon may also contain one or more heteroatoms or heteroatom-containing groups (such as halogens, especially chlorine and fluorine, amino, alkoxy, mercapto, alkyl mercapto, nitro, nitroso, sulfoxy, etc.) in minor amounts (e.g., where the heteroatoms do not substantially alter the hydrocarbon properties of the hydrocarbon compound).

[0046] The terms “group” and “radical” are used interchangeably in this document.

[0047] The term "hydrocarbon group" refers to a group containing hydrogen and carbon atoms. Preferably, unless otherwise specified, the group consists essentially of hydrogen and carbon atoms, more preferably only of hydrogen and carbon atoms. Preferably, the hydrocarbon group comprises an aliphatic hydrocarbon group. The term "hydrocarbon group" includes "alkyl," "alkenyl," "alkynyl," and "aryl" as defined herein. A hydrocarbon group may contain one or more atoms / groups that are not carbon and hydrogen, as long as they do not affect the fundamental hydrocarbon group properties of the hydrocarbon group. Those skilled in the art are aware of such atoms / groups (e.g., halogens, especially chlorine and fluorine, amino, alkoxy, mercapto, alkyl mercapto, nitro, nitroso, sulfoxy, etc.).

[0048] The term "alkyl" refers to a carbon and hydrogen group (such as C1 to C2). 30 , such as C1 to C 12 Alkyl groups are typically directly bonded to the compound via carbon atoms. Unless otherwise specified, alkyl groups can be straight-chain (i.e., unbranched) or branched, cyclic, acyclic, or partially cyclic / acyclic. Preferably, the alkyl group comprises a straight-chain or branched acyclic alkyl group. Representative examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, dimethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, and triacontyl.

[0049] The term "alkenyl" refers to a group having at least one double bond between carbon and hydrogen (such as C2 to C3). 30 Groups, such as C2 to C 12 Alkenes are typically bonded directly to a carbon atom in a compound. Unless otherwise specified, alkenes can be straight (i.e., unbranched) or branched, cyclic, acyclic, or partially cyclic / acyclic.

[0050] The term "alkylene" refers to C1 to C2. 20 C1 to C are preferred 10Divalent saturated aliphatic groups, which can be straight-chain or branched. Representative examples of alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, 1-methylethylene, 1-ethylethylene, 1-ethyl-2-methylethylene, 1,1-dimethylethylene, and 1-ethylpropylene.

[0051] "Olefin," also known as "olefin," is a straight-chain, branched, or cyclic hydrocarbon having at least one double bond. For the purposes of this specification and the appended claims, when a polymer or copolymer is referred to as containing an olefin, the olefin present in such a polymer or copolymer is a polymeric form of an olefin. For example, when a copolymer is said to have an "isoprene" content of 55% to 95% by mass, it is to be understood that the monomer units in the copolymer are derived from isoprene in the polymerization reaction, and said derived units are present in 55% to 95% by mass based on the weight of the copolymer. A "polymer" has two or more identical or different monomer units. A "homopolymer" is a polymer having identical monomer units. A "copolymer" is a polymer having two or more monomer units that are different from each other. The term "different" to refer to monomer units means that the monomer units are at least one atom different or isomerically different from each other. "Isoprene polymer" or "isoprene copolymer" is a polymer or copolymer containing at least 50 mol% isoprene-derived units, "butadiene polymer" or "butadiene copolymer" is a polymer or copolymer containing at least 50 mol% butadiene-derived units, and so on. Similarly, when a polymer is referred to as "partially or fully saturated with C..." 4-5 When referring to "polymers of olefins", the C present in such polymers or copolymers... 4-5 An olefin is the polymeric form of the olefin, and the polymer is partially or completely saturated after monomer polymerization (e.g., by hydrogenation).

[0052] The term "alkynyl" refers to a C2 to C3 group that includes at least one carbon-carbon triple bond. 30 (e.g., C2 to C) 12 ) group.

[0053] The term "aryl" refers to a group containing at least one aromatic ring, such as cyclopentadiene, phenyl, naphthyl, anthracene, etc. Aryl groups are typically C5 to C6. 40 (e.g., C5 to C) 18 , such as C6 to C 14 The aryl group may be optionally substituted with one or more hydrocarbon groups, heteroatoms, or heteroatom-containing groups (such as halogens, hydroxyl groups, alkoxy groups, and amino groups). Preferred aryl groups include phenyl and naphthyl groups and their substituted derivatives, especially phenyl and alkyl-substituted derivatives of phenyl.

[0054] The term "substitution" refers to the replacement of a hydrogen atom with a hydrocarbon group, heteroatom, or heteroatom-containing group. Alkyl-substituted derivatives mean that the hydrogen atom has been replaced by an alkyl group. "Alkyl-substituted phenyl" is one in which the hydrogen atom has been replaced by an alkyl group, such as C1 to C2. 20 Alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, dimethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, and / or triacontyl substituted phenyl groups.

[0055] The term "halogen" or "halogen group" refers to a group of Group 17 atoms or a group of Group 17 atoms, such as fluorine, chlorine, bromine, and iodine.

[0056] The term "ashless" for additives means that the composition does not contain metals. The term "ash-containing" for additives means that the composition contains metals.

[0057] The term "effective amount" in relation to additives refers to the amount of such additive in a lubricating oil composition that enables the additive to provide the desired technical effect.

[0058] The term "effective minor amount" for additives refers to the amount of such additive, less than 50% by mass of the lubricating oil composition, that enables the additive to provide the desired technical effect. The term "effective major amount" for additives refers to the amount of such additive, 50% by mass or more of the lubricating oil composition, that enables the additive to provide the desired technical effect.

[0059] Unless otherwise specified, the term "ppm" refers to parts per million based on the total mass of the lubricating oil composition.

[0060] The term "metal content," such as magnesium content, molybdenum content, or total metal content (i.e., the sum of all individual metal contents), for lubricant compositions or additive components is determined by ASTM D5185.

[0061] The terms “absent” or “substantially absent” when referring to components included in the lubricating oil compositions described herein and in its claims mean that the particular component is present at 0% by weight based on the weight of the lubricating oil composition, or if present in the lubricating oil composition, at a level that does not affect the properties of the lubricating oil composition, such as less than 10 ppm, less than 1 ppm, or less than 0.001 ppm. When the term “absent” is used with respect to monomer reactants and / or repeating units in the (co)polymer described herein, it means that all (copolymer)monomers are present at 0% by weight based on the weight of the (co)polymer, or if present, at a level so low that they substantially do not affect the physical properties of the (co)polymer, such as 0.2% by weight or less, or 0.1% by weight or less.

[0062] As used herein, Mn is the number-average molecular weight, Mw is the weight-average molecular weight, and Mz is the z-average molecular weight. Molecular weight distribution (MWD), also known as polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise stated, all molecular weight units (e.g., Mw, Mn, Mz) are reported in g / mol. When used in the context of functionalized polymers (e.g., dispersants, functionalized styrene polymers, etc.), the molecular weight is typically reported against the unmodified base polymer. For example, the molecular weight of the PIBSA-PAM dispersant is typically reported against the base polyisobutylene polymer before functionalization with an acylating agent (maleic acid or anhydride) and functional groups (e.g., polyamines).

[0063] Regarding additive components or lubricating oil compositions (i.e., unused lubricating oil compositions), the total base number, also known as "TBN," refers to the total base number measured by ASTM D2896 and reported in mgKOH / g. "High TBN" is considered to be greater than or equal to 200 KOH / g, or 300 to 500 mgKOH / g. "Low TBN" is considered to be less than 200 KOH / g, or less than 100 KOH / g.

[0064] Total acid number (“TAN”) is determined according to ASTM D664.

[0065] The contents of phosphorus, boron, calcium, zinc, molybdenum, sodium, silicon, and magnesium were measured according to ASTM D5185.

[0066] The sulfur content in the oil formulation was measured according to ASTM D5185.

[0067] The sulfate ash (“SASH”) content was measured according to ASTM D874.

[0068] Unless otherwise specified, kinematic viscosity (KV100, KV40) is determined according to ASTM D445-19a and reported in cSt.

[0069] Viscosity index was determined according to ASTM D2270.

[0070] The saponification value was determined by ASTM D94 and reported in mgKOH / g.

[0071] A hydrogen-fired internal combustion engine (HICE) is an internal combustion engine (mobile or stationary) that uses hydrogen fuel as the combustion source in a spark-ignition, compression-ignition, or combination thereof engine. Based on the total mass of the fuel, it can be up to essentially 100% hydrogen by mass (meaning there may be levels of other components, such as 1 to 100% hydrogen by mass, 25 to 100% hydrogen by mass, 50 to 100% hydrogen by mass, or 77 to 100% hydrogen by mass. Common hydrogen fuels include compressed hydrogen and hydrogen-compressed hydrocarbon combinations (such as hydrogen / compressed natural gas).

[0072] For the purposes of this specification and all claims, an abnormal combustion event (“ACE”) is defined as an event in which combustion in a spark-ignition internal combustion engine (SI engine) occurs outside the flame front propagating from the spark plug, or in a compression-ignition internal combustion engine (“CI engine”), combustion occurs outside the piston compression cycle or at an incorrect position or time during the piston compression cycle. Spark-assisted compression-ignition engines may have any one or both of the abnormal combustion events defined above. Spontaneous combustion and pre-ignition are both abnormal combustion events. Spontaneous combustion (also known as detonation) is the spontaneous combustion of the fuel / air mixture in the combustion chamber after normal combustion has been initiated by the spark plug or by compression (e.g., by the compression piston). Pre-ignition is defined as the ignition of the air / fuel mixture before spark plug ignition in a spark-ignition (SI) engine or before the correct time / pressure during the compression ignition cycle in a compression-ignition (CI) engine. Low-speed pre-ignition (LSPI) is a specific type of pre-ignition that occurs at low engine speeds and relatively high engine loads. Knocking in an internal combustion engine (also known as knock, detonation, spark knock, pinging, or pinking) typically occurs when the combustion of the air / fuel mixture in the cylinder does not originate from the propagation of the flame front ignited by the spark plug, but rather when one or more pockets of the air / fuel mixture explode outside the envelope of the normal combustion front. The fuel-air charge should be ignited solely by the spark plug and at a precise point during the piston stroke. Knocking occurs when the peak of the combustion process no longer occurs at the optimal moment in the engine stroke cycle (such as a four-stroke cycle). The shock wave from the spontaneous combustion produces a characteristic metallic "pinging" or "knocking" sound. The effects of engine knock range from insignificant to completely destructive to the engine. Knocking should not be confused with pre-ignition, as they are two separate events. However, knocking can occur after pre-ignition. Abnormal combustion events (such as spontaneous combustion) are affected by a variety of factors, including but not limited to engine design (shape, size, geometry, spark plug position), spark plug performance / timing, compression ratio, engine timing, air / fuel mixture temperature, cylinder pressure, fuel octane rating, lubricant composition, and fuel additive composition.

[0073] Octane rating is defined as the sum of the Research Octane Rating (RON) and the Motor Octane Rating (MON) divided by 2 (i.e., (RON + MON) / 2). RON is determined by ASTM D2699-21. MON is determined by ASTM D2700-21. Cetane rating for diesel gasoline is determined by ASTM D613.

[0074] Unless otherwise specified, all percentages reported are based on the active ingredient by mass, i.e., without regard to carriers or diluent oils.

[0075] It should also be understood that the various components used (basic, optimal and conventional) may react under the conditions of formulation, storage or use, and this disclosure also provides products that are available or have been obtained due to any such reaction.

[0076] Furthermore, it should be understood that any upper and lower limits of the quantities, ranges, and ratios listed in this article can be combined independently.

[0077] It should also be understood that preferred features of each aspect of this disclosure are considered preferred features of every other aspect of this disclosure. Accordingly, preferred and more preferred features of one aspect of this disclosure may be independently combined with other preferred and / or more preferred features of the same or different aspects of this disclosure. Detailed Implementation

[0078] The features of this disclosure will now be described in more detail below, which, where appropriate, relates to all and all aspects of this disclosure.

[0079] It is generally believed that the type of detergent soap included in lubricating oils for gasoline internal combustion engines has no effect on the tendency for low-speed pre-ignition (LSPI) events. The inventors have unexpectedly and surprisingly discovered that the type of soap of the over-basic metal-based detergent used in lubricating oil compositions for hydrogen-fired internal combustion engines (HICE) has a significant effect on the tendency for abnormal combustion events (ACE) to occur during the combustion of hydrogen-containing fuels in HICE. In particular, the inventors have found that, when used in lubricating oil compositions, over-basic metal-based salicylates, over-basic metal-based phenolate detergents, or combinations thereof act as quenchers and reduce the tendency for ACE (particularly abnormal pre-ignition events) compared to comparable lubricating oil compositions that do not include said over-basic metal-based salicylates, over-basic metal-based phenolate detergents, or combinations thereof, which is unexpected based on the effect of detergent soap type on low-speed pre-ignition (LSPI) in spark-ignition gasoline-fueled internal combustion engines. The inventors have also discovered that, when used in lubricating oil compositions, over-basic metal-based salicylate detergents, over-basic metal-based phenolic detergents, or combinations thereof, reduce the tendency for ACE (particularly anomalous pre-ignition events) relative to comparable lubricating oil compositions including different soap types (i.e., sulfonates, thiophosphonates, naphthenates), based on the unexpected effect of detergent soap type on low-speed pre-ignition (LSPI) in spark-ignition gasoline-fueled internal combustion engines.

[0080] Aberrant combustion in hydrogen engines is independent of and distinct from low-speed pre-ignition (LSPI) in gasoline internal combustion engines. Specifically, the minimum ignition energy required for a hydrogen-air mixture is significantly lower than that for a gasoline-air mixture, approximately 0.02 mJ compared to 0.25 mJ for the latter. Furthermore, at higher combustion temperatures and lower cylinder pressures, the hydrogen-air mixture exhibits a shorter ignition delay than the gasoline-air mixture (see http: / / teams / sites / il / Conferences / Baden%20Baden%20-%20International%20Engine%20Congress / 2023%2010th%20International%20Engine%20Congress / 13p_Matsubara_Toyota.pdf). These factors are expected to increase the tendency for aberrant combustion in hydrogen compared to gasoline pre-ignition under equivalent combustion conditions. Furthermore, hydrogen internal combustion engines (ICEs) exhibit a high tendency for aberrant combustion, requiring lean-burn operation, typically with an air-fuel ratio of 1.5 to 2.5. In contrast, gasoline combustion engines operate close to stoichiometry with an air-fuel ratio of approximately or near 1.0. It is well known that fuel enrichment in gasoline engines undergoing LSPI mitigates pre-ignition (see https: / / cris.brighton.ac.uk / ws / portalfiles / portal / 31594156 / Harvey_Thesis.pdf). However, in hydrogen ICE applications, the inventors have demonstrated that, contrary to the typical situation in gasoline ICEs, aberrant combustion, particularly pre-ignition, unexpectedly and surprisingly increases with fuel enrichment (refer to Table 1 of this paper).

[0081] Lubricating oil compositions and methods for reducing pre-ignition using such compositions

[0082] This invention relates to a method for reducing abnormal combustion events during the operation of a hydrogen-fired internal combustion engine (HICE), comprising: a) Providing the hydrogen-fired internal combustion engine with a lubricating oil composition comprising or a mixture of the following components: i) A base oil having a viscosity KV100 of less than or equal to 12 cSt and an amount of more than 50% by weight of the composition, and comprising Group I base oil, Group II base oil, Group III base oil, Group IV base oil or a combination thereof. ii) An overly alkaline metal-containing detergent comprising an overly alkaline metal salicylate detergent, an overly alkaline metal phenolate detergent, or a combination thereof, having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500 and being contained at a treatment level providing the composition with a total metal content between 100 and 5000 ppm by weight and a total soap content between 0.15% by weight and 8.0% by weight; and iii) The lubricating oil composition has a total sulfate ash content of less than or equal to 2.0% by weight, a total phosphorus level of less than or equal to 0.120% by weight, and an SAE viscosity grade of 25W-X, 20W-X, 15W-X, 10W-X, 5W-X, or 0W-X, wherein X represents any one of 8, 12, 16, 20, 30, 40, 50, or 60; b) To supply hydrogen-containing fuel to the hydrogen-fired internal combustion engine; and c) Combust the fuel in the hydrogen-fired internal combustion engine.

[0083] The present invention also relates to a lubricating oil composition for hydrogen-fired internal combustion engines (HICE), comprising or being a mixture of the following components: i) A base oil having a KV100 of less than or equal to 12 cSt and an amount of more than 50% by weight of the composition, and comprising Group I base oil, Group II base oil, Group III base oil, Group IV base oil or a combination thereof. ii) An overly alkaline metal-containing detergent comprising an overly alkaline metal salicylate detergent, an overly alkaline metal phenolate detergent, or a combination thereof, having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500 and being contained at a treatment level providing the composition with a total metal content between 100 and 5000 ppm by weight and a total soap content between 0.15% by weight and 8.0% by weight; and The lubricating oil composition has a total sulfate ash content of less than or equal to 2.0% by weight, a total phosphorus level of less than or equal to 0.120% by weight, and an SAE viscosity grade of 25W-X, 20W-X, 15W-X, 10W-X, 5W-X, or 0W-X, wherein X represents any one of 8, 12, 16, 20, 30, 40, 50, or 60.

[0084] The method for reducing abnormal combustion events during engine operation of a hydrogen-fired internal combustion engine (HICE) may further include measuring the number of abnormal pre-ignition events during combustion at 1000 rpm, 12 bar BMEP, and 1.85 air-fuel ratio (AFR), which yields a pre-ignition event count of less than or equal to 10, or less than or equal to 8, or less than or equal to 6, or less than or equal to 4 per 1000 engine cycles.

[0085] The method for reducing abnormal combustion events during engine operation of a hydrogen-fired internal combustion engine (HICE) may further include measuring the number of abnormal pre-ignition events during combustion at 1000 rpm, 18 bar BMEP, and 2.05 air-fuel ratio (AFR), which yields a pre-ignition event count of less than or equal to 5, or less than or equal to 4, or less than or equal to 3, or less than or equal to 2, or less than or equal to 1 per 1000 engine cycles.

[0086] The method for reducing abnormal combustion events during engine operation of a hydrogen-fired internal combustion engine (HICE) may further include measuring the number of abnormal pre-ignition events during combustion at 1000 rpm to 1200 rpm, 12 to 18 bar BMEP, and 1.5 to 2.5 air-fuel ratio (AFR), which yields a reduction of at least 20%, or at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90% in the number of pre-ignition events per 1000 engine cycles during combustion in a HICE operating at full (100%) load compared to a comparable lubricating oil composition excluding the over-alkaline metal-containing detergent.

[0087] The method for reducing abnormal combustion events during engine operation of hydrogen-fired internal combustion engines (HICE) and the base oil used in the lubricating oil composition of this disclosure for HICE may have a KV100 viscosity of less than or equal to 12 cSt, or less than 10 cSt, or less than 9 cSt, or less than 8 cSt, or less than 7 cSt, or less than 6 cSt, or less than 5 cSt, or less than 5 cSt; and the content may be greater than 50% by weight, or greater than 60% by weight, or greater than 70% by weight, or greater than 80% by weight, or greater than 90% by weight, or greater than 95% by weight of the composition.

[0088] The method for reducing abnormal combustion events during engine operation of hydrogen-fired internal combustion engines (HICE) and the over-alkaline metal-containing detergents used in the lubricating oil compositions of this disclosure for HICE may have a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500, or 50 to 450, or 100 to 400, or 150 to 400, or 200 to 350, or 250 to 300 (KOH / g). In another form, overly alkaline metal-containing detergents may have a TBN of 100 mg KOH / g or greater (e.g., 200 mg KOH / g or greater), and typically have a TBN of 250 mg KOH / g or greater, such as 300 mg KOH / g or greater, such as 200 to 500 mg KOH / g, 225 to 450 mg KOH / g, 250 to 400 mg KOH / g, or 300 to 350 mg KOH / g.

[0089] The method for reducing abnormal combustion events during engine operation of a hydrogen-fired internal combustion engine (HICE) and the use of over-alkaline metal-containing detergents, over-alkaline metal phenolate detergents, or combinations thereof in the lubricating oil compositions of this disclosure for HICE may be included at a treatment level providing the lubricating oil composition with a total metal content of 100 to 5000 ppm, or 500 to 4500 ppm, or 1000 to 4000 ppm, or 1500 to 3500 ppm, or 2000 to 3000 ppm by weight. The metal in the over-alkaline metal salicylate or metal phenolate detergent may be calcium, magnesium, sodium, potassium, or lithium. In one embodiment, the metal in the over-alkaline detergent is calcium.

[0090] The method for reducing abnormal combustion events during engine operation of hydrogen-fired internal combustion engines (HICE) and the use of over-alkaline metal-containing detergents, including over-alkaline metal phenolate detergents or combinations thereof, in the lubricating oil compositions of this disclosure for HICE may be included at a treatment level providing the lubricating oil composition with 0.15 to 8.0 wt%, or 0.2 to 7.5 wt%, or 0.3 to 7.0 wt%, or 0.4 to 6.5 wt%, or 0.5 to 6.0 wt%, or 0.6 to 5.0 wt%, or 0.8 to 4.0 wt%, or 1.0 to 3.0 wt%, or 1.5 to 2.5 wt%, or 2.0 to 2.3 wt% of total soap. Alternatively, an over-alkaline metal-containing detergent comprising an over-alkaline metal salicylate detergent, an over-alkaline metal phenolate detergent, or a combination thereof may be included at a treatment level providing the lubricating oil composition with 1.0 to 100 mmol, or 2.0 to 50 mmol, or 3.0 to 30 mmol, or 4.0 to 20 mmol, or 5.0 to 15 mmol, or 7.0 to 12 mmol of total soap.

[0091] The method for reducing abnormal combustion events during engine operation of a hydrogen-fired internal combustion engine (HICE) and the lubricating oil composition of this disclosure for HICE may have a total sulfate ash content of less than or equal to 2.0 wt%, or less than or equal to 1.8 wt%, or less than or equal to 1.6 wt%, or less than or equal to 1.4 wt%, or less than or equal to 1.2 wt%, or less than or equal to 1.0 wt%, or less than or equal to 0.8 wt%, or less than or equal to 0.6 wt%, or less than or equal to 0.4 wt%. The lubricating oil composition of this disclosure for HICE may have a total phosphorus level of less than or equal to 0.120 wt%, or less than or equal to 0.100 wt%, or less than or equal to 0.090 wt%, or less than or equal to 0.080 wt%, or less than or equal to 0.070 wt%, or less than or equal to 0.060 wt%, or less than or equal to 0.050 wt%, or less than or equal to 0.040 wt%, or less than or equal to 0.030 wt%.

[0092] The method for reducing abnormal combustion events during engine operation of a hydrogen-fired internal combustion engine (HICE) and the lubricating oil composition of this disclosure for HICE may have various SAE viscosity grades, including but not limited to 25W-X, 20W-X, 15W-X, 10W-X, 5W-X or 0W-X, wherein X represents any one of 8, 12, 16, 20, 30, 40, 50 or 60.

[0093] In another embodiment, the method for reducing abnormal combustion events during engine operation of a hydrogen-fired internal combustion engine (HICE) and the lubricating oil composition of this disclosure for HICE may include base oils comprising Group I, Group II, Group III, Group IV, Group V, or combinations thereof, wherein the content of the base oil is greater than 60% by weight, or greater than 70% by weight, or greater than 80% by weight, or greater than 90% by weight, or greater than 95% by weight of the composition.

[0094] In another embodiment, the method for reducing abnormal combustion events during engine operation of a hydrogen-fired internal combustion engine (HICE) and the lubricating oil composition of this disclosure for HICE may include a base oil comprising Group I, Group II, Group III, Group IV, or a combination thereof, wherein the base oil content is greater than 60%, or greater than 70%, or greater than 80%, or greater than 90%, or greater than 95% by weight of the composition. That is, the base oil is substantially free of Group V base oil.

[0095] In another embodiment, the method for reducing abnormal combustion events during engine operation of a hydrogen-fired internal combustion engine (HICE) and the lubricating oil composition of this disclosure for HICE may include a base oil comprising Group I, Group II, Group III, or a combination thereof, wherein the content of the base oil is greater than 60% by weight, or greater than 70% by weight, or greater than 80% by weight, or greater than 90% by weight, or greater than 95% by weight of the composition. That is, the base oil is substantially free of Group V and Group IV base oils.

[0096] In yet another embodiment, the method for reducing abnormal combustion events during engine operation of a hydrogen-fired internal combustion engine (HICE) and the lubricating oil composition of this disclosure for HICE may include a base oil comprising Group I base oil, Group II base oil, or a combination thereof, wherein the base oil content is greater than 60% by weight, or greater than 70% by weight, or greater than 80% by weight, or greater than 90% by weight, or greater than 95% by weight of the composition. That is, the base oil is substantially free of Group V and Group IV base oils and Group III base oils.

[0097] In another embodiment, the method for reducing abnormal combustion events during engine operation of a hydrogen-fired internal combustion engine (HICE) and the lubricating oil composition of this disclosure for HICE may include a dispersant, a dispersant viscosity modifier, or a combination thereof. In one form, the dispersant or dispersant viscosity modifier comprises an amide, an imide, and / or an ester-functionalized, partially or fully saturated C-containing... 4-5The polymer of the olefin has: i) a Mw / Mn ratio of less than 2, ii) a functionality distribution (Fd) value of 3.5 or less, and iii) a pre-functionalized polymer Mn of 10,000 g / mol or greater. In another form, the dispersant comprises one or more optionally boronized higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersants (Mn 1600 g / mol or greater), one or more optionally boronized lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersants (Mn less than 1600 g / mol), or a combination thereof, and wherein the treatment level of the dispersant is 1.0 to 15.0% by weight of the lubricating oil composition. In another form, higher molecular weight PIBSA-PAM is boronized, lower molecular weight PIBSA-PAM is boronized, or a combination thereof, and is included in the lubricating oil composition at a treatment level providing 20 ppm to 700 ppm, or 50 to 650 ppm, or 100 to 600 ppm, or 200 to 500 ppm, or 300 to 400 ppm of boron by weight. Dispersants, dispersant viscosity modifiers, or combinations thereof may be included in the lubricating oil composition at a treatment level of 1.0 to 15.0 wt%, or 1.5 to 12.0 wt%, or 1.8 to 10.0 wt%, or 2.0 to 9.0 wt%, or 3.0 to 8.0 wt%, or 4.0 to 7.0 wt%, or 5.0 to 6.0 wt%.

[0098] In another embodiment, the method for reducing abnormal combustion events during engine operation of a hydrogen-fired internal combustion engine (HICE) and the lubricating oil composition of this disclosure for HICE may include a corrosion inhibitor. Water is a reaction product of the combustion of hydrogen-containing fuels; therefore, corrosion of various internal components of the HICE due to water exposure can be addressed by appropriately selecting the type and treatment level of the corrosion inhibitor in the lubricating oil composition. Corrosion inhibitors may include, but are not limited to, substituted thiadiazoles, substituted benzotriazoles, substituted triazoles, trisubstituted borate esters, ethoxylated lauryl alcohol, nonylphenol ethoxylates, and C6 to C6... 20 Ethoxylated straight-chain alcohols or combinations thereof. The corrosion inhibitor may be included in the lubricating oil composition at a treatment level of 0.001% to 5.0% by weight, or 0.01 to 4.8% by weight, or 0.1 to 4.5% by weight, or 0.5 to 4.0% by weight, or 1.0 to 3.5% by weight, or 1.5 to 3.0% by weight, or 2.0 to 2.5% by weight.

[0099] In another embodiment, the method for reducing abnormal combustion events during engine operation of a hydrogen-fired internal combustion engine (HICE) and the lubricating oil composition of this disclosure for HICE may include an anti-wear agent. The anti-wear agent may include, but is not limited to, one or more zinc dialkyl dithiophosphate (ZDDP) compounds. The ZDDP compound may include a hydrocarbon group derived from one or more primary alcohols, one or more secondary alcohols, or a combination of primary and secondary alcohols of alkyl zinc dithiophosphate. The one or more ZDDP compounds may be included in the lubricating oil at a treatment level of about 0.4% to about 1.5% by weight, or 0.5% to 1.3% by weight, or 0.6% to 1.1% by weight, or 0.7% to 1.0% by weight, or 0.8% to 0.9% by weight of the lubricating oil composition.

[0100] In another embodiment, the method for reducing abnormal combustion events during engine operation of a hydrogen-fired internal combustion engine (HICE) and the lubricating oil composition of this disclosure for HICE may include one or more of the following components: one or more functional polymers; one or more friction modifiers; one or more antioxidants; one or more pour point depressants; one or more defoamers; one or more viscosity modifiers; one or more other dispersants; one or more other over-alkaline metal-containing detergents; one or more inhibitors; one or more rust inhibitors; one or more sealing swelling agents; and / or one or more anti-wear agents.

[0101] The method for reducing abnormal combustion events during engine operation of hydrogen-fired internal combustion engines (HICE) and the lubricating oil compositions of this disclosure for HICE may have a kinematic viscosity at 100°C (measured by ASTM D445) of 10 cSt or less, or 2 to 9 cSt, or 3 to 8 cSt, or 4 to 7 cSt, or 5 to 6 cSt. The lubricating oil compositions of this disclosure for HICE may be used as passenger car lubricants (PVL), commercial vehicle lubricants (CVL), or marine engine lubricants.

[0102] The method for reducing abnormal combustion events during engine operation of a hydrogen-fired internal combustion engine (HICE) and the lubricating oil composition of this disclosure for HICE can be used in conjunction with various hydrogen-containing fuel sources (including, but not limited to, green hydrogen, blue hydrogen, gray hydrogen, brown hydrogen, or combinations thereof) that are burned in a hydrogen-fired internal combustion engine. The hydrogen-containing fuel sources may also include other non-hydrogen fuel sources, including but not limited to natural gas, compressed natural gas, propane, automotive gasoline (mogas, such as gasoline with an octane number of 87 or higher, such as gasoline with an octane number of 93 or higher), diesel fuel (such as diesel fuel with a cetane number of 40 or higher, such as diesel fuel with an octane number of 50 or higher), renewable fuels (such as hydrogenated vegetable oil, fatty acid methyl esters, sustainable aviation fuel (SAF)), or combinations thereof. Other non-hydrogen fuels may be included in the hydrogen-containing fuel at 1 to 75% by weight, or 5 to 70% by weight, or 10 to 65% by weight, or 15 to 60% by weight, or 20 to 55% by weight, or 25 to 50% by weight, or 30 to 45% by weight, or 35 to 40% by weight of the total fuel composition. Therefore, the fuel supplied to the hydrogen engine contains at least 5% by mass hydrogen, such as at least 10% by mass hydrogen, such as at least 15% by mass hydrogen, such as 20% by mass hydrogen, such as at least 25% by mass hydrogen, such as at least 30% by mass hydrogen, such as at least 35% by mass hydrogen, such as at least 40% by mass hydrogen, such as at least 45% by mass hydrogen, such as at least 50% by mass hydrogen, such as at least 55% by mass hydrogen, such as at least 60% by mass hydrogen, such as at least 70% by mass hydrogen, such as at least 75% by mass hydrogen, such as at least 80% by mass hydrogen, such as at least 85% by mass hydrogen, such as at least 90% by mass hydrogen, such as at least 95% by mass hydrogen, such as at least 99% by mass hydrogen, such as 100% by mass hydrogen. In a preferred embodiment, the fuel supplied to the hydrogen engine contains essentially 100% by mass hydrogen based on the fuel mass.

[0103] In other embodiments, the fuel supplied to the hydrogen-fired engine comprises at least 5% by mass hydrogen and less than 95% by mass non-hydrogen fuel (such as hydrocarbon fuel), such as at least 10% by mass hydrogen and less than 90% by mass non-hydrogen fuel, such as at least 15% by mass hydrogen and less than 85% by mass non-hydrogen fuel, such as 20% by mass hydrogen and less than 80% by mass non-hydrogen fuel, such as at least 25% by mass hydrogen and less than 75% by mass non-hydrogen fuel, such as at least 30% by mass hydrogen and less than 70% by mass non-hydrogen fuel, such as at least 35% by mass hydrogen and less than 65% by mass non-hydrogen fuel, such as at least 40% by mass hydrogen and less than 60% by mass non-hydrogen fuel, such as at least 45% by mass hydrogen and less than 55% by mass non-hydrogen fuel. Non-hydrogen fuels, such as at least 50% by mass of hydrogen and less than 50% by mass of non-hydrogen fuels, such as at least 55% by mass of hydrogen and less than 45% by mass of non-hydrogen fuels, such as at least 60% by mass of hydrogen and less than 40% by mass of non-hydrogen fuels, such as at least 70% by mass of hydrogen and less than 30% by mass of non-hydrogen fuels, such as at least 75% by mass of hydrogen and less than 25% by mass of non-hydrogen fuels, such as at least 80% by mass of hydrogen and less than 20% by mass of non-hydrogen fuels, such as at least 85% by mass of hydrogen and less than 15% by mass of non-hydrogen fuels, such as at least 90% by mass of hydrogen and less than 10% by mass of non-hydrogen fuels, such as at least 95% by mass of hydrogen and less than 5% by mass of non-hydrogen fuels, such as at least 99% by mass of hydrogen and less than 1% by mass of non-hydrogen fuels.

[0104] The method for reducing abnormal combustion events during engine operation of a hydrogen-fired internal combustion engine (HICE) and the lubricating oil composition of this disclosure for HICE can be used in such a manner that the hydrogen-containing fuel and the lubricating oil composition are combined to form a fuel composition before being injected into the combustion chamber of the hydrogen-fired internal combustion engine (HICE). Alternatively, the method for reducing abnormal combustion events during engine operation of a hydrogen-fired internal combustion engine (HICE) and the lubricating oil composition of this disclosure for HICE can be used in such a manner that the hydrogen-containing fuel and the lubricating oil composition are combined to form a fuel composition in the combustion chamber of the hydrogen-fired internal combustion engine (HICE).

[0105] The method for reducing abnormal combustion events during engine operation of a hydrogen-fired internal combustion engine (HICE) and the lubricating oil composition of this disclosure for HICE can be used in conjunction with a spark-ignition, compression-ignition, or combination thereof hydrogen-fired internal combustion engine (HICE). The hydrogen-fired internal combustion engine can be a heavy-duty or light-duty internal combustion engine. Alternatively, the hydrogen-fired internal combustion engine used in conjunction with the method for reducing abnormal combustion events during engine operation of a hydrogen-fired internal combustion engine (HICE) and the lubricating oil composition of this disclosure for HICE can be a stationary internal combustion engine. The hydrogen-fired internal combustion engine (HICE) may optionally include a turbocharger or supercharger preceding the hydrogen-fired internal combustion engine.

[0106] The method for reducing abnormal combustion events during engine operation of a hydrogen-fired internal combustion engine (HICE) and the lubricating oil composition of this disclosure for HICE can be used in hydrogen-fired internal combustion engines (HICE) operating at a BMEP of 12 to 18 bar, or 13 to 17 bar, or 14 to 16 bar, or 15 bar and an air-fuel ratio (AFR) of 1:1 to 3:1. Specifically, when the hydrogen-fired internal combustion engine operates at approximately 12 bar, the AFR can be 3:1 or less, 2.5:1 or less, or 2:1 or less, 1.85:1 or less, or 1.7:1 or less, or 1.6:1 or 1.5:1 or less, or 1.4:1 or less, such as 1:1 to 2:1. When the hydrogen-fired internal combustion engine is running at approximately 18 bar, the AFR can be 3:1, 2.5:1 or less, or 2:1 or less, 1.85:1 or less, or 1.7:1 or less, or 1.6:1 or 1.5:1 or less, or 1.4:1 or less, such as 1:1 to 2:1.

[0107] The present invention also relates to the use of the lubricating oil composition described herein for lubricating a hydrogen-fired internal combustion engine, wherein the fuel supplied to said hydrogen-fired internal combustion engine comprises: a) 1 to 100% by mass of hydrogen gas, b) 0 to 99% by mass of petroleum-derived fuels, and / or c) 0 to 99% by mass, or 0.1 to 98.9% by mass, or 1 to 75% by mass, or 5 to 50% by mass of non-hydrogen renewable fuels, based on the total mass of hydrogen fuels, renewable fuels and petroleum-derived fuels.

[0108] In one embodiment, the hydrogen-containing fuel and lubricating oil composition are combined in the combustion chamber to form a fuel composition, or the hydrogen-containing fuel and lubricating oil composition are combined to form a fuel composition before being injected into the combustion chamber.

[0109] In the embodiments, based on the mass of the hydrogen fuel and lubricating oil composition, the hydrogen fuel and lubricating oil composition comprises 0.01 to 20% by mass of the lubricating oil composition, such as 0.025 to 15% by mass, 0.05 to 10% by mass, 0.10 to 5% by mass, or 0.015 to 2.5% by mass of the lubricating oil composition.

[0110] Lambda The air-fuel ratio (AFR) is the amount of air and fuel supplied to the engine combustion chamber divided by the air-fuel ratio used for stoichiometric reactions in the same engine combustion chamber under the same pressure and temperature conditions. In a preferred embodiment, the lambda of a hydrogen-fired engine lubricated with the lubricating composition described herein is... () or AFR is 2.5 or less, such as 2 or less, such as 1.85 or less, such as 1.7 or less, such as 1.6 or less, such as 1.5:1 or less, such as 1.4 or less, such as 0.5 to 3, such as 1 to 2.1, such as 1.3 to 2, such as 1.4 to 1.9, such as 1.5 to 1.85. For a given hydrogen-fueled engine, the lower This means lower costs because less air is injected into the combustion chamber, allowing for the consumption of more fuel and the production of more power. Similarly, it results in lower costs in engine design and operation due to the more efficient lambda-D at higher pressures. Fewer specialized high-pressure devices (such as turbochargers or superchargers) are needed to inject air into the combustion chamber, etc. Therefore, the lubricant composition described herein, when used with hydrogen-fired engines built with existing engine block technology, allows for easier / more efficient retrofitting / less redesign to efficiently utilize hydrogen fuel. Furthermore, the lubricant composition described herein can provide one or more of the following benefits to HICE during operation: by reducing the amount of hydrogen typically produced by hydrogen fuel... Running (relative to 2 to 2.5) Related oil-derived abnormal combustion events can be reduced This enables better throttle response, improved power density, reduced air charge complexity and cost, or reduced engine research and development.

[0111] In the implementation scheme, the air-fuel ratio (AFR) in the combustion chamber of the hydrogen-fired internal combustion engine at 12 bar (1.2 MPa) is 2.5:1 or less, or 2:1 or less, 1.85:1 or less, or 1.7:1 or less, or 1.6:1 or 1.5:1 or less, or 1.4:1 or less, such as 1:1 to 2:1 or 1.5 to 1.9.

[0112] In other embodiments, the air-fuel ratio (AFR) in the combustion chamber of the hydrogen-fired internal combustion engine at 18 bar (1.8 MPa) is 2.5:1 or less, or 2:1 or less, 1.85:1 or less, or 1.7:1 or less, or 1.6:1 or 1.5:1 or less, or 1.4:1 or less, such as 1:1 to 2:1 or 1.5 to 1.9.

[0113] In some further embodiments, the ratio of the air-fuel ratio in the combustion chamber of a hydrogen-fired internal combustion engine at 12 bar (1.2 MPa) to that in the combustion chamber of a hydrogen-fired internal combustion engine at 18 bar (1.8 MPa) is 0.75 or greater, such as 0.8 or greater, such as 0.85 or greater, such as 0.90 or greater.

[0114] The lubricating oil compositions described herein, when used in hydrogen-fired internal combustion engines, promote higher mean effective braking pressure (BMEP) by allowing the engine to operate at greater power and torque without the tendency for abnormal combustion events. For example, hydrogen-fueled ICE engines can achieve BMEPs of 12 to 18 bar.

[0115] The hydrogen-fired internal combustion engine described in this article can be a modified engine, or an engine designed for use in mobile vehicles (such as cars, trucks, generators, ships, etc.), a stationary engine, such as a heavy-duty internal combustion engine, or a standing generator that includes an internal combustion engine.

[0116] In embodiments, the lubricating compositions disclosed herein can be used in heavy-duty engines (e.g., heavy-duty vehicles with a gross vehicle weight rating of 10,000 pounds or more).

[0117] In an embodiment, the lubricating composition disclosed herein can be used as a passenger vehicle engine oil.

[0118] In embodiments, the lubricating compositions disclosed herein can be used in passenger vehicles, wherein the hydrogen-fired internal combustion engine is a passenger vehicle internal combustion engine (optionally also using gasoline and / or diesel fuel).

[0119] In embodiments, the lubricating compositions disclosed herein can be used in heavy-duty internal combustion engines or stationary internal combustion engines.

[0120] Concentrate

[0121] Concentrates, also known as additive packages, adpak, or addpacks, are compositions containing less than 50% by weight (e.g., 1 to 40% by weight, 2 to 30% by weight, 3 to 25% by weight, 4 to 20% by weight, 5 to 15% by weight) of base oil and (as described herein) lubricant composition additives, which are typically subsequently blended with additional Group I, Group II, and / or Group III base oils to form a lubricating oil product. The concentrate typically does not contain Group IV base oils (such as polyalphaolefins) with a viscosity index of 100 or greater, such as 120 or greater, such as 140 or greater, as determined by ASTM D2270. Alternatively, the concentrate contains a Group IV base oil, such as polyalphaolefin, with a viscosity index of 100 or greater, such as 120 or greater, such as 140 or greater, as determined by ASTM D2270, such that the total PAO concentration in the final lubricating oil composition is 70% by weight or less, such as 60% by weight or less, 50% by weight or less, such as 40% by weight or less, 30% by weight or less, such as 20% by weight or less, 10% by weight or less, such as 5% by weight or less, based on the weight of the lubricating oil composition.

[0122] This disclosure relates to a concentrate composition comprising or a mixture thereof: 1% to 95% by weight of one or more base oils having a KV100 of 12 cSt or less and comprising Group I, Group II, Group III, Group IV base oils or combinations thereof; and 5% to 99% by weight of a super-alkaline metal-containing detergent based on the weight of the concentrate, comprising a super-alkaline metal salicylate detergent, a super-alkaline metal phenolate detergent or combinations thereof, having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500.

[0123] The concentrate compositions disclosed herein may further comprise combining the concentrate with a base oil to form a lubricating oil composition comprising: i) a base oil having a KV100 of less than 10 cSt and comprising more than 50% by weight of the composition, comprising Group I, Group II, Group III, Group IV base oils or combinations thereof; and ii) an over-alkaline metal-containing detergent comprising an over-alkaline metal salicylate detergent, an over-alkaline metal phenolate detergent or combinations thereof, having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500 and being contained at a treatment level providing the composition with a total metal content between 100 and 5000 ppm by weight and a total soap content between 0.15% by weight and 8.0% by weight. The resulting lubricating oil composition may have a total sulfate ash content of less than or equal to 2.0% by weight, a total phosphorus level of less than or equal to 0.120% by weight, and an SAE viscosity grade of 25W-X, 20W-X, 15W-X, 10W-X, 5W-X, or 0W-X, where X represents any one of 8, 12, 16, 20, 30, 40, 50, or 60. The resulting lubricating oil composition will reduce the number of abnormal pre-ignition events in a hydrogen-fired internal combustion engine (HICE) measured at 1000 rpm, 12 bar BMEP, and an air-fuel ratio (AFR) of 1.85 to less than or equal to 10 events per 1,000 engine cycles. Alternatively, the resulting lubricating oil composition will reduce the number of abnormal pre-ignition events in a hydrogen-fired internal combustion engine (HICE) measured at 1200 rpm, 18 bar BMEP, and an air-fuel ratio (AFR) of 2.05 to less than or equal to 5 events per 1,000 engine cycles. Alternatively, compared to comparable lubricating oil compositions that do not include the aforementioned alkaline metal-containing detergent, the resulting lubricating oil composition reduces the number of abnormal pre-ignition events during combustion in a hydrogen-fired internal combustion engine (HICE) operating at 100% load by at least 20%.

[0124] The concentrates disclosed herein may be present in the lubricating oil composition in amounts ranging from 0.5% to 35% by mass, such as 5% to 30% by mass, such as 7.5% to 25% by mass, such as 10% to 22.5% by mass, such as 15% to 20% by mass, based on the mass of the lubricating oil composition.

[0125] Optionally, the concentrate may be free of functionalized oils.

[0126] In the embodiments, the concentrate composition may optionally be free of solvents (such as aliphatic or aromatic solvents) and / or free of functionalized base oils.

[0127] Optionally, the concentrate may be free of phenolic antioxidants.

[0128] In an embodiment, the concentrate may contain less than 75 ppm of boron, or less than 60 ppm of boron, or 1 to 70 ppm of boron. Alternatively, the concentrate may be free of boron.

[0129] In one embodiment, the concentrate may contain less than or equal to 20 (e.g., 15, 10, 5, 3, 1) by mass% of functionalized (e.g., amination) polybutene (e.g., polyisobutylene), such as PIBSA-PAM. In another embodiment, the concentrate contains, substantially does not contain, or is absent from functionalized (e.g., amination) polybutene (e.g., polyisobutylene), such as PIBSA-PAM.

[0130] In an embodiment, the concentrate may further comprise one or more of the following components: one or more functionalized polymers, one or more other friction modifiers; one or more antioxidants; one or more pour point depressants; one or more defoamers; one or more viscosity modifiers; one or more dispersants; one or more inhibitors; one or more rust inhibitors; one or more sealing swelling agents; and / or one or more anti-wear agents.

[0131] In one embodiment, the concentrate may comprise an acylated polymer, such as polyisobutylene succinic acid, optionally having 500 to 50,000 g / mol, such as 600 to 5,000 g / mol, such as 700 to 3,000 g / mol of Mn. In another embodiment, the concentrate may comprise an acylated polymer, such as polyisobutylene succinic acid, having 500 to 1600 g / mol, such as 700 to 1200 g / mol of Mn.

[0132] In the implementation scheme, the concentrate may contain 20 (e.g., 15, 10, 5, 3, 1)% by mass or less of block copolymers, such as block, star, random and / or graded block copolymers.

[0133] In the implementation scheme, the concentrate may be substantially free of or absent from block copolymers, such as block, star, random and / or graded block copolymers.

[0134] In an embodiment, the concentrate may contain 20% by mass or less (e.g., 15% by mass or less, 10% by mass or less, 5% by mass or less, 3% by mass or less, 1% by mass or less, or 1% by mass or less) of styrene-based copolymers, such as block, star, random and / or graded styrene-based block copolymers.

[0135] In the implementation scheme, the concentrate may be substantially free of or absent from styrene-based copolymers, such as block, star, random and / or graded styrene-based block copolymers.

[0136] In the implementation scheme, the concentrate may contain less than 20% by mass (e.g., less than 15%, 10%, 5%, 3%, 1%) of a functionalized diluent, such as a functionalized oil.

[0137] In the implementation plan, the concentrate may be substantially free of or contain no functionalized diluents, such as functionalized oils.

[0138] In the implementation scheme, based on the weight of the concentrate, the concentrate may contain less than 0.5% by weight of secondary hydrocarbon amine compounds and tertiary hydrocarbon amine compounds (e.g., less than 0.4% by weight, less than 0.3% by weight, less than 0.2% by weight, 0.1% by weight, substantially absent, or non-existent).

[0139] In the implementation scheme, the concentrate may be substantially absent or may not contain secondary and tertiary alkyl amine compounds.

[0140] In the implementation scheme, the concentrate may have a kinematic viscosity at 100°C of less than 1000 cSt, such as less than 500 cSt, such as less than 200 cSt.

[0141] This disclosure also relates to a method of manufacturing a concentrate composition comprising: 1 to less than or equal to 50% by weight of one or more base oils; 2 to 25% by weight of a superalkaline magnesium-based detergent having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500, based on the weight of the concentrate; and 2 to 25% by weight of a superalkaline calcium-based detergent having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500.

[0142] Lubricating oil composition components and concentrate components

[0143] A. Base oil

[0144] The base oils used herein (also referred to as “base oils,” “lubricating oil base oils,” or “oils with lubricating viscosity”) may be single oils or blends of oils, and are typically the main liquid component of a lubricating composition (also referred to as a lubricant), to which additives and optional additional oils are mixed to, for example, to manufacture lubricating compositions such as final lubricant compositions, concentrates, or other lubricating compositions.

[0145] Base oils can be selected from vegetable oils, animal oils, mineral oils, and synthetic lubricants and their mixtures. Their viscosity ranges from light distillate mineral oils to heavy lubricants, such as those used in gas engine oils, mineral lubricants, motor vehicle oils, and heavy-duty diesel engine oils. Typically, the kinematic viscosity ("KV100") of base oils at 100°C is 1 to 30 cSt, such as 2 to 25 cSt, such as 5 to 20 cSt (measured according to ASTM D445-19a), particularly 1.0 to 12 cSt, 1.2 to 10 cSt, 1.5 to 8.3 cSt, 2.7 to 8.1 cSt, 3.0 to 7.2 cSt, or 2.5 to 6.5 cSt. Typically, the high-temperature high-shear (HTHS) viscosity of base oils at 150°C is 0.5 to 20 cP, such as 1 to 10 cP, such as 2 to 5 cP (measured according to ASTM D4683-20).

[0146] Typically, when lubricating oil base oils are used to manufacture concentrates, they may advantageously be present in an amount that forms a concentrate to obtain a concentrate containing 1% to 20% by weight of the concentrate, such as 5% to 80% by weight, 10% to 70% by weight, or 5% to 50% by weight of active ingredients.

[0147] Commonly used oils as base oils include animal and vegetable oils (such as castor oil and lard), liquid petroleum products, and hydrorefined and / or solvent-treated alkyl, cycloalkane, and mixed alkyl-cycloalkane mineral lubricating oils. Oils derived from coal or shale are also available as base oils. Base oils can be manufactured using a variety of different methods, including but not limited to distillation, solvent refining, hydrogen processing, oligomerization, esterification, and refining.

[0148] Synthetic lubricants that can be used as base oils include hydrocarbon oils, such as homopolymers and copolymers, referred to as polyalphaolefins (PAOs) or Group IV base oils [as defined in API EOLCS 1509 (American Petroleum Institute Publication 1509, see section E.1.3, 19th edition, January 2021, www.API.org)]. Examples of PAOs that can be used as base oils include: poly(ethylene), ethylene-propylene copolymers, polybutene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutene, poly(1-hexene), poly(1-octene), poly(1-decene), C8 to C999, and poly(ethylene-propylene-isobutylene). 20 Homopolymers or copolymers of olefins, C8 and / or C 10 and / or C 12 Homopolymers or copolymers of olefins, C8 / C 10 copolymers, C8 / C 10 / C 12 copolymers and C 10 / C 12 Copolymers, and their derivatives, analogs and homologues.

[0149] In another embodiment, the base oil may comprise a polyalphaolefin, including oligomers of linear olefins having 6 to 14 carbon atoms, more preferably 8 to 12 carbon atoms, more preferably 10 carbon atoms, having a kinematic viscosity of 10 or greater at 100°C (as determined by ASTM D445); preferably having a viscosity index ("VI") of 100 or greater, more preferably 110 or greater, more preferably 120 or greater, more preferably 130 or greater, more preferably 140 or greater, as determined by ASTM D2270; and / or having a pour point of -5°C or lower (as determined by ASTM D97), more preferably -10°C or lower, more preferably -20°C or lower.

[0150] In another embodiment, the polyalphaolefin oligomers that can be used in this disclosure may contain C 20 To C 1500 Alkanes, preferably C 40 To C 1000 Alkanes, preferably C 50 To C 750 Alkanes, preferably C 50 To C 500 Alkane. PAO oligomers are C5 to C6 in one embodiment. 14 α-olefins, in another embodiment, C6 to C 12 α-olefins, in another embodiment C8 to C 12Dimers, trimers, tetramers, pentamers, etc., of α-olefins. Suitable olefins include 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene. In one embodiment, the olefin is a combination of 1-octene, 1-decene, and 1-dodecene, or may be substantially 1-decene, and the PAO is a mixture of its dimers, trimers, tetramers, and pentamers (and more). Available PAOs are described more specifically in, for example, U.S. Patent Nos. 5,171,908 and 5,783,531 and Synthetic Lubricants and High-Performance Functional Fluids 1-52 (Leslie R. Rudnick & Ronald L. Shubkin, ed. Marcel Dekker, Inc. 1999).

[0151] The PAOs used in this disclosure typically have a number-average molecular weight of 100 to 21,000 g / mol in one embodiment, 200 to 10,000 g / mol in another embodiment, 200 to 7,000 g / mol in yet another embodiment, 200 to 2,000 g / mol in yet another embodiment, and 200 to 500 g / mol in yet another embodiment. Ideal PAOs are available as SpectraSyn™ Hi-Vis, SpectraSyn™ Low-Vis, SpectraSyn™ plus, SpectraSyn™ Elite PAO's (ExxonMobil Chemical Company, Houston, Texas), and Durasyn PAO's from Ineos OligomersUSA LLC.

[0152] Synthetic lubricants that can be used as base oils also include hydrocarbon oils, such as homopolymers and copolymers of: alkylbenzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2-ethylhexyl)benzene); polyphenols (benzenes) (e.g., biphenyl, terphenyl, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides; and their derivatives, analogs and homologues.

[0153] In an alternative embodiment, the lubricating oil composition contains less than 50% by mass of a Group IV base oil (such as PAO as described above), less than 40% by mass, less than 30% by mass, less than 20% by mass, or less than 10% by mass, based on the mass of the lubricating oil composition.

[0154] Another suitable class of synthetic lubricants that can be used as base oils comprises esters formed by the reaction of dicarboxylic acids (such as phthalic acid, succinic acid, alkyl succinic acid and alkenyl succinic acid, maleic acid, azelaic acid, octanoic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid) with various alcohols (such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicoyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, and complex esters formed by reacting 1 mole of sebacate with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid.

[0155] Esters that can be used as synthetic oils in this article also include those from C5 to C6. 12 Those made from monocarboxylic acids and polyols and polyol ethers (such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol).

[0156] Ideal ester base oils are available as Esterex™ Esters (ExxonMobil Chemical Company, Houston, Texas).

[0157] Silicone-based oils, such as polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-silicone oils and silicate ester oils, constitute another class of useful synthetic lubricants that can be used herein; such oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) silicate, tetra-(p-tert-butylphenyl) silicate, hexa-(4-methyl-2-ethylhexyl)disiloxane, poly(methyl)siloxane, and poly(methylphenyl)siloxane.

[0158] Other synthetic lubricants that may be used in this article include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl decylphosphonate) and polytetrahydrofuran.

[0159] Unrefined oils, refined oils, and re-refined oils can be used in the lubricating compositions disclosed herein. Unrefined oils are those obtained directly from natural or synthetic sources without further purification. For example, shale oils obtained directly from dry distillation operations, petroleum oils obtained directly from distillation, or ester oils obtained directly from esterification processes and used without further processing are considered unrefined oils. Refined oils are similar to unrefined oils, except that they have undergone further processing in one or more purification steps to improve one or more properties. Many such purification techniques are used by those skilled in the art, such as distillation, solvent extraction, acid or alkali extraction, filtration, and percolation. Re-refined oils are oils obtained through a process similar to that used to obtain refined oils, wherein the refining process is applied to previously used refined oils. Such re-refined oils are also referred to as recycled oils or reprocessed oils and are typically further processed to remove waste additives and oil cracking products. Re-refined base oils preferably contain substantially no materials introduced through manufacturing, contamination, or prior use.

[0160] Other examples of available base oils are gas-to-liquid (“GTL”) base oils, which are oils derived from hydrocarbons produced from syngas containing H2 and CO using a Fischer-Tropsch catalyst. These hydrocarbons typically require further processing before they can be used as base oils. For example, they can be hydroisomerized; hydrocracking and hydroisomerizing; dewaxing; or hydroisomerizing and dewaxing by methods known in the art. Further information on available GTL base oils and their blends can be found in U.S. Patent No. 10,913,916 (column 4, line 62 through column 5, line 60) and U.S. Patent No. 10,781,397 (column 14, line 54 through column 15, line 5, and column 16, line 44 through column 17, line 55).

[0161] In particular, oils derived from renewable sources, i.e., those based in part on carbon and energy captured from the environment (such as biomass), are used in this study.

[0162] Various base oils are typically classified into Group I, Group II, Group III, Group IV, or Group V according to API EOLCS 1509 (American Petroleum Institute Publication 1509, see Section E.1.3, 19th Edition, January 2021, www.API.org). Generally, Group I base oils have a viscosity index between approximately 80 and 120 and contain more than approximately 0.03% sulfur and / or less than approximately 90% saturates. Group II base oils have a viscosity index between approximately 80 and 120 and contain less than or equal to approximately 0.03% sulfur and more than or equal to approximately 90% saturates. Group III base oils have a viscosity index greater than approximately 120 and contain less than or equal to approximately 0.03% sulfur and more than approximately 90% saturates. Group IV base oils include polyalphaolefins (PAO). Group V base oils include base oils not included in Groups I-IV, such as ester base oils. (Viscosity index is measured by ASTM D 2270, saturates by ASTM D2007, and sulfur by ASTM D5185, D2622, ASTM D4294, ASTM D4927, and ASTM D3120). Group I, II, and III base oils are derived from petroleum, while Group IV and V base oils are often synthetic.

[0163] The base oils that can be used in the formulation of the lubricating compositions of this disclosure are any one, two, three, or more of the various oils described herein. In an ideal embodiment, the base oils that can be used in the formulation of the lubricating compositions of this disclosure are those described as API Group I (including Group I+), Group II (including Group II+), Group III (including Group III+), Group IV, and Group V oils and mixtures thereof, preferably those of API Group II, Group III, Group IV, and Group V oils and mixtures thereof. Similarly, in an ideal embodiment, the base oils that can be used in the formulation of the lubricating compositions of this disclosure are those described as API Group I (including Group I+), Group II (including Group II+), Group III (including Group III+), and mixtures thereof, preferably those of API Group II, Group III oils and mixtures thereof. Due to their excellent volatility, stability, viscosity, and cleaning properties, the base oils can be Group III, Group III+, Group IV, and Group V base oils. Small amounts of Group I base oils are permissible, such as for diluting additives for incorporation into formulated lubricant products, but are generally kept to a minimum, for example, only in relation to their use as a diluent / carrier oil for additives used on an as-received basis. Regarding Group II base oils, it is generally more useful to refer to Group II base oils within the higher quality range associated with that base oil, i.e., Group II base oils with a viscosity index in the range of 100 to 120.

[0164] The base oils used in this article may be selected from any synthetic, natural, or refined oils (such as those commonly used as crankcase lubricants in spark-ignition and compression-ignition engines). If desired, mixtures of synthetic base oils and / or natural base oils and / or refined base oils may be used. If desired, multimodal mixtures (such as bimodal or trimodal mixtures) of Group I, II, III, IV, and / or V base oils may be used. If desired, multimodal mixtures (such as bimodal, trimodal, or quadrumodal mixtures) of Group I, II, and / or III base oils with Group IV base oils (such as PAO) in the following amounts may be used: 70% by mass or less, such as 60% by mass or less; 50% by mass or less, such as 40% by mass or less; 30% by mass or less, such as 20% by mass or less; 10% by mass or less, such as 5% by mass or less; or, for example, not present.

[0165] The base oils or base oil blends used in this article conveniently have a kinematic viscosity (KV100, measured according to ASTM D445-19a and expressed in centistokees (cSt) or their equivalent units mm at 100°C of approximately 2 to approximately 40 cSt, or 3 to 30 cSt, or 4 to 20 cSt, or 5 to 10 cSt at 100°C. 2 (Reported in units of / s), or the base oil or base oil blend may have a kinematic viscosity at 100°C of 2 to 20 cSt, 2.5 to 2 cSt, preferably about 2.5 cSt to about 9 cSt.

[0166] The base oil or base oil blend preferably has a saturated content of at least 65% by mass, more preferably at least 75% by mass, such as at least 85% by mass, such as at least 90% by mass, as determined by ASTM D2007.

[0167] Preferably, the base oil or base oil blend has a sulfur content of less than 1% by mass, preferably less than 0.6% by mass, most preferably less than 0.4% by mass, and such as less than 0.3% by mass, based on the total mass of the lubricating composition as measured by ASTM D5185.

[0168] In the implementation scheme, the volatility of the base oil or base oil blend, as determined by the Noack test (ASTM D5800, Procedure B), is less than or equal to 30% by mass, less than or equal to 25% by mass, less than or equal to 20% by mass, less than or equal to 16% by mass, less than or equal to 12% by mass, or less than or equal to 10% by mass.

[0169] In the implementation scheme, the viscosity index (VI) of the base oil is at least 95, preferably at least 110, more preferably at least 120, even more preferably at least 125, and most preferably about 130 to 240, particularly about 105 to 140 (as determined by ASTM D2270).

[0170] The base oil may be provided in a major amount, combined with a minor amount of one or more additive components as described below, to constitute a lubricant. This preparation can be achieved by adding the additives directly to the oil or by adding the one or more additives in the form of their concentrates to disperse or dissolve the additives. The additives may be added to the oil before, simultaneously with, or after the addition of other additives by any method known to those skilled in the art.

[0171] The base oil may be provided in a minor amount, combined with one or more additive components as described below, to form an additive concentrate. This preparation can be achieved by adding the additive directly to the oil or by adding the one or more additives in the form of a solution, slurry, or suspension to disperse or dissolve the additive in the oil. The additive may be added to the oil before, simultaneously with, or after the addition of other additives by any method known to those skilled in the art.

[0172] Base oil typically constitutes the major component of the engine oil lubricant compositions disclosed herein and is generally present in an amount of about 50 to about 99% by weight, preferably about 70 to about 95% by weight, more preferably about 80 to about 95% by weight, based on the total weight of the composition.

[0173] Typically, one or more base oils are present in the lubricating composition in an amount of 32% by mass or more, or 55% by mass or more, or 60% by mass or more, or 65% by mass or more, based on the total weight of the lubricating composition. Typically, one or more base oils are present in the lubricating composition in an amount of 98% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less. Alternatively, one or more base oils are present in the lubricating composition in an amount of 1 to 99% by mass, or 50 to 97% by mass, or 60 to 95% by mass, or 70 to 95% by mass, based on the weight of the lubricating composition.

[0174] The aforementioned base oils and their blends can also be used to manufacture concentrates and lubricants.

[0175] Concentrates constitute a convenient means of handling additives before their use and of promoting the dissolution or dispersion of additives in lubricants. When preparing lubricants containing more than one type of additive (sometimes referred to as "additive components"), each additive can be incorporated separately as a concentrate. However, in many cases, it is convenient to provide so-called additive "packs" (also known as "addpacks") containing one or more of the additives / co-additives described below in a single concentrate.

[0176] Typically, one or more base oils are present in the concentrate composition in an amount of 50% or less, 40% or less, 30% or less, or 20% or less based on the total weight of the concentrate composition. Typically, one or more base oils are present in the concentrate composition in an amount of 0.1 to 49% by weight, 5 to 40% by weight, 10 to 30% by weight, or 15 to 25% by weight based on the weight of the concentrate composition.

[0177] B. Cleaning agent

[0178] In addition to the combination or mixture of the aforementioned super-alkaline calcium-based and super-alkaline magnesium-based detergents, the lubricating oil composition and concentrate composition may also contain one or more additional / other super-alkaline metal detergents (such as blends of metal detergents), also referred to as "detergent additives". The lubricating composition may contain one or more metal detergents (such as blends of metal detergents), also referred to as "detergent additives". Metal detergents typically act both as detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life. Detergents typically contain a polar head and a long hydrophobic tail, with the polar head containing a metal salt of an acidic organic compound. This salt may contain a basic stoichiometric amount of metal, in which case they are typically described as normal or neutral salts and typically have a total base number ("TBN", measured by ASTM D2896) of up to 150 mg KOH / g, such as 0 to 80 (or 5-30) mg KOH / g. Large amounts of metal alkali can be incorporated by reacting an excess of a metal compound (e.g., oxides or hydroxides) with an acidic gas (e.g., carbon dioxide). Such detergents, sometimes referred to as super-alkaline, may have TBN of 100 mg KOH / g or greater (e.g., 200 mg KOH / g or greater), and typically have TBN of 250 mg KOH / g or greater, such as 300 mg KOH / g or greater, such as 200 to 800 mg KOH / g, 225 to 700 mg KOH / g, 250 to 650 mg KOH / g, or 300 to 600 mg KOH / g, such as 150 to 650 mg KOH / g.

[0179] Other suitable detergents include metals, particularly alkali metals (Group 1 metals, such as Li, Na, K, Rb) or alkaline earth metals (Group 2 metals, such as Be, Mg, Ca, Sr, Ba), especially sodium, potassium, lithium, calcium, and magnesium, such as oil-soluble neutral and superalkaline sulfonates, phenolates, thiophosphonates, salicylates, naphthenates, and other oil-soluble carboxylates of Ca and / or Mg. Furthermore, detergents may comprise hybrid detergents containing any combination of sulfonates, phenolates, thiophosphonates, thiophosphonates, salicylates, and naphthenates of sodium, potassium, lithium, calcium, or magnesium, or other oil-soluble carboxylates of Group 1 and / or 2 metals.

[0180] Preferably, other peralkaline metal-based detergent additives that can be used in this disclosure comprise calcium and / or magnesium metal salts. The detergent may be a calcium and / or magnesium carboxylate (e.g., salicylate), sulfonate, or phenolate detergent. More preferably, the detergent additive is selected from magnesium salicylate, calcium salicylate, magnesium sulfonate, calcium sulfonate, magnesium phenolate, calcium phenolate, and hybrid detergents comprising two, three, four, or more of these detergents and / or combinations thereof.

[0181] Metal-containing detergents may also include “hybrid” detergents, as described, for example, in U.S. Patent Nos. 6,429,178; 6,429,179; 6,153,565; and 6,281,179, formed using a mixed surfactant system comprising phenolate and / or sulfonate components, such as phenolate / salicylate, sulfonate / phenolate, sulfonate / salicylate, or sulfonate / phenolate / salicylate. When, for example, a hybrid sulfonate / phenolate detergent is used, the hybrid detergent is considered equivalent to the amount of individual phenolate and sulfonate detergents, respectively, which introduce similar amounts of phenolate and sulfonate soaps.

[0182] The metal-containing detergents disclosed herein may also include polyolefin-substituted hydroxy aromatic carboxylic acids or their salts, wherein the polyolefin is derived from a branched olefin having at least 4 carbon atoms, and wherein the polyolefin has a number-average molecular weight of 150 to 800 g / mol (as disclosed in US 2022 / 0073836), such as salicylates.

[0183] Over-alkaline metal-containing detergents can be sodium, calcium, magnesium, or mixtures of phenolates, sulfur-containing phenolates, sulfonates, salixarates, and salicylates. Over-alkaline phenolates and salicylates typically have a total base value of 180 to 650 mg KOH / g, such as 200 to 450 TBN mg KOH / g. Over-alkaline sulfonates typically have a total base value of 250 to 600 mg KOH / g, or 300 to 500 mg KOH / g. In embodiments, sulfonate detergents can be primarily linear alkylbenzene sulfonate detergents having a metal ratio of at least 8, as described in paragraphs

[0026] to

[0037] of U.S. Patent Application Publication No. 2005 / 065045 (granted as U.S. Patent No. 7,407,919). Based on the lubricating composition, the overly alkaline detergent may be present in amounts of 0% to 15% by mass, or 0.1% to 10% by mass, or 0.2% to 8% by mass, or 0.2% to 3% by mass. For example, in heavy-duty diesel engines, the detergent may be present in amounts of 2% to 3% by mass of the lubricating composition. For passenger car engines, the detergent may be present in amounts of 0.2% to 1% by mass of the lubricating composition.

[0184] The detergent additive may contain one or more magnesium sulfonate detergents. The magnesium detergent may be a neutral salt or a superalkaline salt. Suitably, the magnesium detergent is a superalkaline magnesium sulfonate having 80 to 650 mgKOH / g (ASTM D2896), such as 200 to 500 mgKOH / g, such as 240 to 450 mgKOH / g.

[0185] Alternatively, the detergent additive is magnesium salicylate, optionally having 30 to 650 mgKOH / g (ASTM D2896), such as 50 to 500 mgKOH / g, such as 200 to 500 mgKOH / g, such as 240 to 450 mgKOH / g, or 150 mgKOH / g or less, such as 100 mgKOH / g or less TBN.

[0186] Magnesium detergents typically provide 200-4000 ppm of magnesium atoms to their lubricating compositions, suitably 200-2000 ppm, 300 to 1500 or 450-1200 ppm of magnesium atoms (ASTM D5185).

[0187] The detergent composition may comprise (or consist of) a combination of one or more magnesium sulfonate detergents and one or more calcium salicylate detergents. Alternatively, the detergent additive may be a combination of magnesium salicylate and magnesium sulfonate.

[0188] Optionally, a combination of one or more magnesium sulfonate detergents and one or more calcium salicylate detergents provides the lubricating composition with: 1) 200-4000 ppm magnesium atoms, suitably 200-2000 ppm, 300 to 1500 ppm or 450-1200 ppm magnesium atoms (ASTM D5185), and 2) at least 500 ppm, preferably at least 750 ppm, more preferably at least 900 ppm calcium atoms, such as 500-4000 ppm, preferably 750-3000 ppm, more preferably 900-2000 ppm calcium atoms (ASTM D5185).

[0189] Detergents may contain one or more calcium detergents, such as calcium carboxylates (e.g., salicylates), sulfonates, or phenolate detergents.

[0190] Suitable calcium detergents have a TBN of 30 to 700 mg KOH / g (ASTM D2896), such as 50 to 650 mg KOH / g, such as 200 to 500 mg KOH / g, such as 240 to 450 mg KOH / g, or 150 mg KOH / g or less, such as 100 mg KOH / g or less, or 200 mg KOH / g or more, or 300 mg KOH / g or more, or 350 mg KOH / g or more.

[0191] Suitable calcium detergents are calcium salicylate, calcium sulfonate, or calcium phenolate with TBN of 30 to 700 mg KOH / g, 30 to 650 mg KOH / g (ASTM D2896), such as 50 to 650 mg KOH / g, such as 200 to 500 mg KOH / g, such as 240 to 450 mg KOH / g, or 150 mg KOH / g or less, such as 100 mg KOH / g or less, or 200 mg KOH / g or more, or 300 mg KOH / g or more, or 350 mg KOH / g or more.

[0192] Calcium detergents are typically present in an amount sufficient to provide at least 500 ppm, preferably at least 750, more preferably at least 900 ppm of atomic calcium to the lubricating oil composition (ASTM D5185). If present, any calcium detergent is suitably present in an amount sufficient to provide no more than 4000 ppm, preferably no more than 3000 ppm, more preferably no more than 2000 ppm of atomic calcium to the lubricating oil composition (ASTM D5185). If present, any calcium detergent is suitably present in an amount sufficient to provide 500-4000 ppm, preferably 750-3000 ppm, more preferably 900-2000 ppm of atomic calcium to the lubricating oil composition (ASTM D5185).

[0193] Suitably, the total atomic weight of the detergent metals in the lubricating composition according to all aspects of this disclosure is not greater than 5000 ppm, preferably not greater than 4000 ppm, more preferably not greater than 2000 ppm (ASTM D5185). Suitably, the total atomic weight of the detergent metals in the lubricating oil composition according to all aspects of this disclosure is at least 500 ppm, preferably at least 800 ppm, more preferably at least 1000 ppm (ASTM D5185). Suitably, the total atomic weight of the detergent metals in the lubricating oil composition according to all aspects of this disclosure is from 500 to 5000 ppm, preferably from 500 to 3000 ppm, more preferably from 500 to 2000 ppm (ASTM D5185).

[0194] Sulfonate detergents can be prepared from sulfonic acids, typically obtained by sulfonation of alkyl-substituted aromatics (such as those obtained by fractionation of petroleum or by alkylation of aromatics). Examples include those obtained by alkylation of benzene, toluene, xylene, naphthalene, biphenyl, or their halogenated derivatives, such as chlorobenzene, chlorotoluene, and chloronaphthalene. Alkylation can be carried out in the presence of a catalyst with an alkylating agent having about 3 to more than 70 carbon atoms. Alkyl aryl sulfonates typically contain about 9 to about 80 or more carbon atoms per alkyl-substituted aromatic moiety, preferably about 16 to about 60 carbon atoms. The oil-soluble sulfonate or alkyl aryl sulfonic acid can be neutralized with metal oxides, hydroxides, alkoxides, carbonates, carboxylates, sulfides, hydrosulfides, nitrates, borates, and ethers. The amount of metal compound is selected with consideration of the desired TBN of the final product, but is typically about 100 to 220% by mass (preferably at least 125% by mass) of the stoichiometric amount required.

[0195] Phenols and metal salts of thiophenols are prepared by reaction with suitable metal compounds, such as oxides or hydroxides, and neutral or superbasic products can be obtained by methods known in the art. Thiophenols can be prepared by reacting phenols with sulfur or sulfur-containing compounds (such as hydrogen sulfide, sulfur monohalides, or sulfur dihalides) to form a product that is usually a mixture of compounds in which two or more phenols are bridged by sulfur-containing bridges.

[0196] Carboxylate detergents (such as salicylates) can be used to clean aromatic carboxylic acids (such as C... 5-100 C 9-30 C 14-24 Aromatic carboxylic acids are prepared by reacting alkyl-substituted hydroxybenzoic acids with suitable metal compounds, such as oxides or hydroxides, and neutral or superbasic products can be obtained by methods known in the art. The aromatic moiety of the aromatic carboxylic acid may contain heteroatoms, such as nitrogen and oxygen. Preferably, the moiety contains only carbon atoms; more preferably, the moiety contains six or more carbon atoms; for example, benzene is a preferred moiety. Aromatic carboxylic acids may contain one or more aromatic moieties, such as one or more benzene rings, fused or linked via alkylene bridges.

[0197] Preferred substituents in oil-soluble salicylic acid are alkyl substituents, which can be linear or branched. In alkyl-substituted salicylic acids, the alkyl group advantageously contains 1 to 500, such as 5 to 100, preferably 9 to 30, and especially 14 to 20 carbon atoms. If more than one alkyl group is present, the average number of carbon atoms in all alkyl groups is preferably at least 9 to ensure sufficient oil solubility.

[0198] Alternatively, the salicylate detergents used herein may be selected from those disclosed in US 2022 / 0073836. Such detergents contain a polyisobutylene (Mn 100 to 900 g / mol, such as 150 to 400 g / mol) substituted phenol as part of the salicylate alkyl ester structural moiety of the salicylate alkyl ester metal salt.

[0199] Furthermore, since the organic and inorganic alkaline salts used as detergents can contribute to the sulfate ash content of the lubricating oil composition, the amount of such additives is minimized in embodiments of this disclosure. To maintain a low sulfur content, salicylate detergents can be used, and the lubricating compositions herein may contain one or more salicylate detergents (the detergents are preferably used in an amount of 0.05 to 20.0% by mass, more preferably 1.0 to 10.0% by mass, and most preferably 2.0 to 5.0% by mass based on the total weight of the lubricating composition).

[0200] As determined by ASTM D874, the total sulfate ash content of the lubricating compositions described herein is generally no more than 2.0% by mass, or no more than 1.0% by mass, or no more than 0.8% by mass, based on the total weight of the lubricating composition.

[0201] Furthermore, it is useful that each detergent independently has a TBN (Total Base Number) measured according to ISO 3771 in the range of 10 to 700 mgKOH / g, 10 to 500 mgKOH / g, 100 to 650 mgKOH / g, 10 to 500 mgKOH / g, 30 to 350 mgKOH / g, or 50 to 300 mgKOH / g.

[0202] Sulfonate detergents (such as Ca and / or Mg sulfonate detergents) may be present in amounts of 0.1% to 1.5% by mass, or 0.15% to 1.2% by mass, or 0.2% to 0.9% by mass of sulfonate soap to the lubricant composition.

[0203] The salicylate detergent (such as Ca and / or Mg salicylate detergent) is present in an amount of 0.3% to 1.4% by mass, or 0.35% to 1.2% by mass, or 0.4% to 1.0% by mass of salicylate soap to the lubricant composition.

[0204] Sulfonate soaps may be present in an amount of 0.2% to 0.8% by mass of the lubricant composition, and salicylate soaps may be present in an amount of 0.3% to 1.0% by mass of the lubricant composition.

[0205] All alkaline earth metal detergent soaps may be present in an amount of 0.6% to 2.1% by mass, or 0.7% to 1.4% by mass, of the lubricant composition.

[0206] Typically, lubricating compositions formulated for heavy-duty diesel engines contain about 0.1 to about 10% by mass, or about 0.5 to about 7.5% by mass, or about 1 to about 6.5% by mass, of detergent based on the lubricating composition.

[0207] Typically, lubricating compositions formulated for passenger vehicle engines contain about 0.1 to about 10% by mass, or about 0.5 to about 7.5% by mass, or about 1 to about 6.5% by mass, based on the lubricating composition.

[0208] Typically, lubricating compositions formulated for transmission systems (such as gearboxes) contain about 0.1 to about 10% by mass, or about 0.5 to about 7.5% by mass, or about 2 to about 6.5% by mass, based on the lubricating composition.

[0209] Optionally, phenolic salts are essentially absent or not present in detergents in lubricating oil compositions.

[0210] C. Functional polymers or functionalized polymers

[0211] The optional functionalized polymer or functionalized polymer component of the lubricating oil compositions and concentrate compositions disclosed herein comprises a polymer having, prior to functionalization, about 10,000 g / mol or greater, such as 20,000 g / mol or greater, such as 25,000 g / mol or greater, such as 30,000 g / mol or greater, such as 35,000 g / mol or greater. Alternatively, the functionalized polymer comprises a polymer having, prior to functionalization, 10,000 to 300,000 g / mol, such as 20,000 to about 150,000 g / mol, such as 30,000 to about 125,000 g / mol, such as 35,000 to about 100,000 g / mol, such as 40,000 to 80,000 g / mol of Mn (GPC-PS). The unfunctionalized polymer may have a Mw / Mn ratio of less than 2 (e.g., less than 1.6, less than 1.5, 1.4 or less, 1 to 1.3, 1.0 to 1.25, 1.0 to 1.2, 1.0 to 1.15, 1.0 to 1.1, as determined by GPC-PS). The unfunctionalized polymer may contain one or more repeating units of an olefin (preferably a conjugated diene with 4 to 5 carbon atoms). Prior to functionalization, C... 4-5The polymer is preferably fully or partially saturated (e.g., fully or partially hydrogenated). This functionalized polymer can be achieved by making C... 4-5 The polymer is obtained by reacting it with an acylated agent to form an acylated polymer, and then reacting the acylated polymer with an amine or alcohol to form an amide, imide, ester, or a combination thereof. This functionalized polymer can also be obtained by reacting an acylated C... 4-5 Polymers (such as commercially available maleic acid-modified or partially hydrogenated C450) 4-5 It is obtained by reacting polymers with amines to form amides, imides, or combinations thereof.

[0212] This disclosure further relates to lubricating oil compositions comprising functionalized polymers, said functionalized polymers including the C described herein. 4-5 Amid, imide, and / or ester-functionalized saturated (e.g., hydrogenated) polymers of conjugated dienes, which are obtained by making Cw / Mn less than 2. 4-5 The conjugated diene is obtained by reacting a fully or partially saturated (e.g., fully or partially hydrogenated) polymer with an acylation agent, such as maleic acid or maleic anhydride, and subsequently reacting the acylated polymer with an amine (e.g., a polyamine) to form an imide, amide, or a combination thereof.

[0213] This disclosure relates to lubricating oil compositions comprising functionalized polymers containing one or more amine side groups and comprising or a mixture of the following components: at least partially (preferably fully) hydrogenated C 4-5 Olefin polymers are reacted with acylating agents, such as maleic acid or maleic anhydride, and then the acylated polymers are reacted with polyamines to form imides, amides, or combinations thereof.

[0214] In the embodiments, the functionalized polymer is not prepared in an aromatic solvent (such as benzene or toluene), or the aromatic solvent is present in 2% by weight or less (such as 1% by weight or less, such as 0.5% by weight or less) based on the weight of the solvent, diluent and polymer.

[0215] In the implementation scheme, the functionalized polymer is not prepared in an alkylnaphthylenic solvent, or the alkylnaphthylenic solvent is present in 5% by weight or less (e.g., 3% by weight or less, or 1% by weight or less) based on the weight of the solvent, diluent, and polymer.

[0216] The polymers that can be used to prepare functionalized polymers in this article are homopolymers of butadiene, isoprene, etc.

[0217] In the implementation scheme, the polymers that can be used to prepare the functionalized polymers herein may be homopolymers of isoprene, or copolymers of isoprene and less than 5 mol% (e.g., less than 3 mol%, less than 1 mol%, less than 0.1 mol%) of comonomers.

[0218] The polymers used in this article for preparing functionalized polymers can be copolymers of isoprene and one or more of the following: styrene, methyl-styrene, 2,3-dimethyl-butadiene, 2-methyl-1,3-pentadiene, myrcene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, 2-phenyl-1,3-pentadiene, 3-phenyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2-hexyl-1,3-butadiene, 3-methyl-1,3-hexadiene, 2-benzyl- 1,3-Butadiene, 2-p-Tolyl-1,3-Butadiene, 1,3-Butadiene, 1,3-Pentadiene, 1,3-Hexadiene, 1,3-Heptadiene, 2,4-Heptadiene, 1,3-Octadiene, 2,4-Octadiene, 3,5-Octadiene, 1,3-Nonadiene, 2,4-Nonadiene, 3,5-Nonadiene, 1,3-Decadiene, 2,4-Decadiene and 3,5-Decadiene, [optionally, the comonomer is present in amounts of less than 20 mol%, less than 5 mol%, such as less than 3 mol%, such as less than 1 mol%, such as less than 0.1 mol%].

[0219] Typically, the polymeric conjugated diene polymers used in this study to prepare functionalized polymers include mixtures of 1,4- and 1,2-insertions (also known as 2,1-insertions; for butadiene, 1,2-insertions are the same as 3,4-insertions). 1 According to H NMR measurements, the polymeric conjugated diene polymers used in this study for preparing functionalized polymers contain at least about 50% 1,4-intercalation, such as at least about 75% 1,4-intercalation, such as at least about 80% 1,4-intercalation, such as at least about 90% 1,4-intercalation, such as at least about 95% 1,4-intercalation, such as at least 98% 1,4-intercalation, based on isoprene-based 2,1-intercalation, 1,4-intercalation, and 3) 1,4-intercalation, such as at least 3,4-intercalation and 4,3-intercalation. For the purposes of this disclosure: 1) the phrase “1,4-intercalation” includes 1,4-intercalation and 4,1-intercalation, 2) the phrase “2,1-intercalation” includes 2,1-intercalation and 1,2-intercalation, and 3) the phrase “3,4-intercalation” includes 3,4-intercalation and 4,3-intercalation.

[0220] Optionally, styrene repeating units may be absent in the polymers that can be used herein to prepare functionalized polymers. Optionally, styrene repeating units may be absent in the functionalized hydrogenated / saturated polymers.

[0221] Optionally, butadiene repeating units may be absent in the polymers that can be used to prepare functionalized polymers described herein. Optionally, butadiene repeating units may be absent in the functionalized hydrogenated / saturated polymers.

[0222] Optionally, the polymers used in this study to prepare the functionalized polymers may not be homopolymer butene. Optionally, the functionalized hydrogenated / saturated polymers may not be homopolymer butene.

[0223] Optionally, the polymers used in this study to prepare the functionalized polymers may not be homopolymer isobutylene. Optionally, the functionalized hydrogenated / saturated polymers may not be homopolymer isobutylene.

[0224] Optionally, the polymers used in this study to prepare the functionalized polymers may not be copolymers of isoprene and butadiene. Optionally, the functionalized hydrogenated / saturated polymers may not be copolymers of isoprene and butadiene.

[0225] The polymers and / or functionalized polymers that can be used to prepare functionalized polymers described herein can be homopolymers or copolymers. The copolymers can be random copolymers, graded block copolymers, star copolymers, or block copolymers. Block copolymers are formed from a mixture of monomers comprising one or more first monomers (such as isobutylene), wherein, for example, the first monomer forms discrete blocks of the polymer that are linked to second discrete blocks of the polymer formed by a second monomer (such as butadiene). Although block copolymers have essentially discrete blocks formed by monomers, graded block copolymers can consist of a relatively pure first monomer at one end and a relatively pure second monomer at the other end. The middle of a graded block copolymer can be more of a gradient composition of these two monomers.

[0226] The polymers described herein that can be used to prepare functionalized polymers typically have Mn (GPC-PS) in the range of 20,000 to 150,000 g / mol, or 20,000 to about 150,000 g / mol, or 30,000 to about 125,000 g / mol, or 35,000 to about 100,000 g / mol, or 40,000 to 80,000 g / mol.

[0227] The polymers described herein for use in the preparation of functionalized polymers typically have a Mw / Mn ratio of 1 to 2, or greater than 1 to less than 2, or 1.1 to 1.8, or 1.2 to 1.5 (as determined by GPC-PS). Alternatively, the polymers described herein for use in the preparation of functionalized polymers typically have a Mw / Mn ratio of 1 or greater than 1 to less than 2 (e.g., less than 1.8, less than 1.7, less than 1.6, less than 1.5, less than 1.4, less than 1.3, less than 1.2, less than 1.15, less than 1.12, less than 1.10).

[0228] The polymer used to prepare the functionalized polymer may have an Mz (determined by GPC-PS) of 20,000 to 150,000 g / mol, or 20,000 to about 150,000 g / mol, or 30,000 to about 125,000 g / mol, or 35,000 to about 100,000 g / mol, or 40,000 to 80,000 g / mol, or 40,000 to 60,000 g / mol (as determined by GPC-PS).

[0229] The polymers used in this paper to prepare functionalized polymers may have a glass transition temperature (Tg) of -25°C or lower, such as -40°C or lower, such as -50°C or lower, determined by differential scanning calorimetry (DSC) using a Perkin Elmer or TA Instrument Thermal Analysis System (the sample is heated from ambient temperature to 210°C at 10°C / min and held at 210°C for 5 minutes, then cooled to -40°C at 10°C / min and held for 5 minutes).

[0230] The polymers that can be used to prepare functionalized polymers in this article typically have a residual unsaturation of less than 3%, such as less than 2%, such as less than 1%, such as less than 0.5%, such as less than 0.25%, based on the number of double bonds in the non-hydrogenated polymer.

[0231] The polymers used in this paper to prepare functionalized polymers typically have a residual metal (such as Li, Co, and Al) content of less than 100 ppm, such as less than 50 ppm, such as less than 25 ppm, such as less than 10 ppm, such as less than 5 ppm.

[0232] hydrogenation

[0233] This article can be used to prepare C of functionalized polymers. 4-5 Polymers can be partially or fully hydrogenated using any hydrogenating agent known to those skilled in the art. For example, saturated or partially saturated polymers can be prepared by: (a) providing C containing unsaturated carbon atoms (such as double or triple bonds). 4-5(a) The polymer; and (b) the unsaturated (e.g., double or triple bonds) in the polymer are hydrogenated in the presence of a hydrogenating agent. In some embodiments, the polymer is completely hydrogenated. In some embodiments, the polymer is partially hydrogenated. In some embodiments, the polymer is saturated (hydrogenated) at 50% or more, such as 60% or more, such as 70% or more, such as 80% or more, such as 90% or more, such as 95% or more, such as 98% or more, such as 99% or more, such as 50% to 100% saturated (hydrogenated), by the ozone adsorption method described in Martino N. Smits and Dirkman Hoefman, Quantative Determination of Olefinic Unsaturation by Measurement of Ozone Absorption Analytical Chemistry, Vol. 44, No. 9, p. 1688, 1972, Martino N. Smits.

[0234] In embodiments, the hydrogenating agent may be hydrogen gas in the presence of a hydrogenation catalyst. In some embodiments, the hydrogenation catalyst is Pd, Pd / C, Pt, PtO2, Ru(PPh3)2Cl2, Raney nickel, or a combination thereof. In one embodiment, the catalyst is a Pd catalyst. In another embodiment, the catalyst is 5% Pd / C. In a further embodiment, the catalyst may contain or be in a high-pressure reaction vessel containing 10% Pd / C, and the hydrogenation reaction may be allowed to proceed until completion. Typically, after completion, the reaction mixture can be washed, concentrated, and dried to obtain the corresponding hydrogenated product. Alternatively, any reducing agent that can reduce C=C bonds to C=C bonds can be used. For example, olefin polymers can be hydrogenated by treatment with hydrazine in an oxygen atmosphere in the presence of a catalyst such as 5-ethyl-3-methyllumiflavinium perchlorate to obtain the corresponding hydrogenated product. The reduction reaction using hydrazine is disclosed in Imada et al., J Am. Chem. Soc., 127, pp. 14544-14545, (2005), which is hereby cited and incorporated herein by reference.

[0235] acylation

[0236] Fully or partially saturated (hydrogenated) polymers can be chemically modified (functionalized) to provide polymers having at least one polar functional group, such as, but not limited to, halogen, epoxy, hydroxyl, amino, hyponitro, mercapto, imide, carboxyl, and sulfonic acid groups or combinations thereof. Functionalized polymers can be further modified to provide more desired functional types. In a preferred embodiment, fully or partially hydrogenated polymers are functionalized by a method comprising reacting the fully or partially hydrogenated polymer with an unsaturated carboxylic acid (or a derivative thereof, such as maleic anhydride) to provide an acylated polymer (which may subsequently be further functionalized as described below).

[0237] In some embodiments, a carboxylic acid functional or its reactive equivalent is grafted onto a polymer to form an acylated polymer. Typically, an olefinically unsaturated carboxylic acid material is grafted onto the polymer backbone. These materials attached to the polymer generally contain at least one olefinic bond (before the reaction) and at least one carboxylic acid (or its anhydride) group, or a polar group that can be converted into said carboxyl group by oxidation or hydrolysis. Maleic anhydride or its derivatives are suitable. They are grafted onto the polymer to provide two carboxylic acid functionalities. Other examples of unsaturated carboxylic acid materials include itaconic anhydride or corresponding dicarboxylic acids, such as maleic acid, fumaric acid and their esters, and cinnamic acid and its esters.

[0238] Unsaturated olefinic carboxylic acid materials can be grafted onto polymers in a variety of ways. They can be grafted onto polymers in solution or in essentially pure (molten) form, with or without a free radical initiator. Free radical-initiated grafting of olefinic carboxylic acid materials can also be carried out in solvents such as hexane or mineral oil. This can be done at elevated temperatures ranging from 100°C to 250°C, for example, 120°C to 190°C, or 150°C to 180°C, for example, above 160°C.

[0239] Suitable free radical initiators include peroxides, hydroperoxides, and azo compounds, typically those with boiling points greater than about 100°C and thermally decomposing within the grafting temperature range to provide free radicals. Representative examples of these free radical initiators include azobisisobutyronitrile (AIBN) and 2,5-dimethyl-hex-3-yne-2,5-bis-tert-butylperoxide. The initiator can be used in amounts from 0.005% to 1% by weight based on the weight of the reaction mixture solution. Grafting can be carried out under an inert atmosphere, such as under nitrogen cover. The resulting acylated polymer intermediate is characterized by having carboxylic acid acylation functionality as part of its structure.

[0240] In an embodiment, the acylated polymer may have two or more anhydride groups per polymer molecule and may exhibit less than 10% gelation. Alternatively, the acylated polymer may have less than two anhydride groups per polymer molecule and may exhibit less than 10% gelation. (See also column 17, line 14-column 18, line 11 of U.S. Patent No. 5,429,758).

[0241] Alternatively, in some embodiments, the acylated polymer may have a gel content of less than about 5% by weight, less than 3% by weight, less than 2% by weight, less than 1% by weight, less than 0.5% by weight, less than 0.1% by weight, or 0% by weight, wherein the gel content is measured by determining the amount of material extractable from the polymer using boiling xylene (or cyclohexane) as an extractant. The percentage of soluble and insoluble (gel) material in the polymer composition is determined by immersing a nominal 0.5 mm thick polymer film sample in cyclohexane at 23°C for 48 hours or by refluxing the film sample in boiling xylene for half an hour, removing the solvent, weighing the dried residue, and calculating the amounts of soluble and insoluble (gel) material. This method is generally described in U.S. Patent No. 4,311,628, which is incorporated herein by reference. For the purposes of this disclosure, boiling xylene is used to measure the gel content unless the sample is insoluble in xylene, in which case the cyclohexane method is used.

[0242] In the implementation, the acylated polymer may have a saponification value (SAP) of 5 g / KOH or greater, such as 10 g / KOH or greater, such as 20 g / KOH or greater, such as 30 g / KOH or greater, such as 50 g / KOH or greater, such as 10 to 60 g / KOH, such as 20 to 40 g / KOH, as determined by ASTM D94.

[0243] In an embodiment, the acylated polymer composition may have less than 5% by weight of unreacted acylated agent (such as maleic anhydride) based on the weight of the acylated polymer composition (i.e., polymer, acylated agent and diluent), such as less than 4% by weight, less than 3% by weight, less than 1% by weight, less than 0.5% by weight, less than 0.25% by weight, or less than 0.1% by weight.

[0244] In the implementation scheme, the acylation reaction described herein can be carried out in a base oil diluent. As a byproduct, a functionalized base oil can be produced. This oil itself may be acylated. For example, maleized base oil may be present after the acylation reaction described herein.

[0245] The functionalized base oil may contain acylated oil and / or the reaction products of acylated oil with amines, amides, imides or combinations thereof.

[0246] Preferably, based on the weight of the concentrate composition, the acylated oil and / or the reaction product of the acylated oil with an amine or alcohol to form an amide, imide, ester, or combination thereof may be present in the concentrate in an amount of 40% by weight or less, or 20% by weight or less, or 10% by weight or less, or 5% by weight or less, or 3% by mass or less, preferably 2% by mass or less, preferably 1% by mass or less, preferably 0.1% by mass or less, preferably 0% by mass (e.g., 0 to 40% by mass, or 0.01 to 40% by mass, or 0.1 to 20% by mass, or 1 to 10% by mass, or 1.5 to 5% by mass).

[0247] Preferably, based on the weight of the lubricating oil composition, one or more functionalized base oils, such as acylated oils and / or the reaction products of acylated oils with amines or alcohols to form amides, imides, esters or combinations thereof, may be present in the lubricating oil composition in an amount of 0.01 to 40% by mass, or 0.1 to 20% by mass, or 1 to 10% by mass, or 1.5 to 5% by mass (e.g., 3% by mass or less, preferably 2% by mass or less, preferably 1% by mass or less, preferably 0.1% by mass or less, preferably 0% by mass).

[0248] In embodiments, the acylation reaction described herein is carried out in a solvent-containing medium. As a byproduct, an acylation / functionalization solvent may be generated. In embodiments, based on the weight of the concentrate composition, the acylation and / or functionalization solvent may be present in the concentrate composition at 3% by mass or less, preferably 2% by mass or less, preferably 1% by mass or less, preferably 0.1% by mass or less, preferably 0% by mass. In embodiments, based on the weight of the lubricating oil composition, the functionalization solvent may be present in the lubricating oil composition at 3% by mass or less, preferably 2% by mass or less, preferably 1% by mass or less, preferably 0.1% by mass or less, preferably 0% by mass.

[0249] In the implementation scheme, the acylation agent may be added in a manner that minimizes side reactions, such as reactions with the base oil or other diluents present in the reaction vessel.

[0250] In the implementation scheme, an acylation reaction can occur, wherein an acylated agent (such as maleic acid or maleic anhydride) is added in a continuous or semi-continuous (e.g., batch) feed stream (e.g., added in controlled, relatively equal portions during the reaction time, or added in larger and / or smaller portions at different points in the reaction) to minimize the functionalization of the base oil and other side reactions. As an example, the acylated agent can be added continuously, wherein the amounts of polymer and acylated agent are added in controlled stoichiometric amounts. As another example, the polymer can be added to the reaction vessel in batches, while the acylated agent is added slowly or semi-continuously (e.g., in discrete amounts or portions of 2 or more, 5 or more, 10 or more, 20 or more, 30 or more, 40 or more, 50 or more, 60 or more). Alternatively, the polymer can be added to the reaction vessel in X parts, while the acylating agent can be added in 1.5X or more (e.g., 2X or more, 5X or more, 10X or more, 20X or more, 30X or more, 40X or more, 50X or more, 60X or more). This same effect can also be achieved by diluting or concentrating the polymer solution and / or the acylating agent solution to the same or different degrees.

[0251] Preferably, the acylation agent can be added in a manner that minimizes side reactions, such as in a continuous or semi-continuous manner.

[0252] Side reactions can also be minimized by using a high concentration of polymer (e.g., 45% by weight or more, or 50% by weight or more, or 55% by weight or more, or 60% by weight or more) in the diluent during batch, semi-continuous, or continuous reactor operations. For example, a polymer (e.g., hydrogenated isoprene polymer, such as hydrogenated homopolymer isoprene) can be introduced into batch, semi-continuous, or continuous reactor operations as a solution or suspension (e.g., slurry) in a diluent (e.g., oil (e.g., base oils, such as Group I, II, III, IV and / or V base oils, such as Group II and / or Group III base oils) or alkane solvents or diluents or combinations thereof). The polymer can be present in the solution or suspension at 45% by weight or more (e.g., 50% by weight or more, or 55% by weight or more, or 60% by weight or more) based on the weight of the polymer and diluent.

[0253] In the implementation scheme, side reactions can be minimized as follows: 1) adding the acylating agent in a continuous or semi-continuous manner, and / or 2) introducing the polymer as a solution or suspension in a diluent into batch, semi-continuous or continuous reactor operation, wherein the polymer is present at 45% by weight or more based on the weight of the polymer and the diluent.

[0254] In embodiments, side reactions are minimized optionally by adding the acylating agent in a continuous or semi-continuous manner, and / or by introducing a fully or partially hydrogenated polymer (such as isoprene polymer) as a solution or suspension in a diluent into batch, semi-continuous, or continuous reactor operation, said solution or suspension containing 45% by weight or more (e.g., 50% by weight or more, or 55% by weight or more, or 60% by weight or more) of the fully or partially hydrogenated polymer based on the weight of the fully or partially hydrogenated polymer and the diluent.

[0255] In the embodiments, side reactions are minimized optionally by adding the acylating agent in a continuous or semi-continuous manner, and by introducing a fully or partially hydrogenated polymer (such as isoprene polymer) as a solution or suspension in a diluent into batch, semi-continuous, or continuous reactor operation, said solution or suspension containing 45% by weight or more (e.g., 50% by weight or more, or 55% by weight or more, or 60% by weight or more) of the fully or partially hydrogenated polymer based on the weight of the fully or partially hydrogenated polymer and the diluent.

[0256] Functionalization

[0257] In embodiments, the acylated polymer can react with an alcohol or amine to form an amide, imide, ester, or combination thereof. This reaction can be a condensation composition to form an imide, amide, semiamide, amide-ester, diester, or amine salt. The primary amino group will typically condense to form an amide, or in the case of maleic anhydride, to form an imide. It should be noted that the amine may have a single primary amino group or multiple primary amino groups.

[0258] Suitable amines may include one or more aromatic amines, such as amines in which the carbon atom of the aromatic ring structure is directly attached to an amino nitrogen. The amine may also be aliphatic. In embodiments, aliphatic amines may be used alone, in combination with each other, or in combination with aromatic amines. In some embodiments, the amount of aromatic amine may be major or minor compared to the amount of non-aromatic amine, or in some cases, the composition may be substantially free of aromatic amines. Alternatively, the composition may be substantially free of aliphatic amines.

[0259] Examples of aromatic amines that can be used in this article include one or more N-arylphenylenediamines represented by the following formula:

[0260] R7 is H, -NH aryl, -NH alkylaryl, or a branched or straight-chain hydrocarbon group having about 4 to about 24 carbon atoms, selected from alkyl, alkenyl, alkoxy, aralkyl, or alkylaryl; R9 is -NH2, -(NH(CH2) n ) mNH2, —NHalkyl, —NHaralkyl, —CH2-aryl-NH2, wherein n and m each have a value of about 1 to about 10; and R8 is hydrogen, or an alkyl, alkenyl, alkoxy, aralkyl or alkylaryl having about 4 to about 24 carbon atoms.

[0261] Suitable N-arylphenylenediamines include N-phenylphenylenediamines (NPPDA), such as N-phenyl-4,4-phenylenediamine, N-phenyl-1,3-phenylenediamine, N-phenyl-1,2-phenylenediamine, and N-naphthyl-1,4-phenylenediamine. Other derivatives of NPPDA, such as N-propyl-N'-phenylphenylenediamine, may also be included.

[0262] In the embodiments, the amine reacting with the acylated polymer is an amine having at least 3 or 4 aryl groups and which can be represented by the following formula:

[0263] Independent of each variable, R 1 It can be hydrogen or C l To C5 alkyl (usually hydrogen); R 2 It can be hydrogen or C l To C5 alkyl (usually hydrogen); U can be an aliphatic, alicyclic or aromatic group, provided that when U is aliphatic, the aliphatic group can be a straight-chain or branched alkylene group containing 1 to 5 or 1 to 2 carbon atoms; and w can be 1 to 10, or 1 to 4, or 1 to 2 (usually 1).

[0264] Other examples of aromatic amines include aniline, N-alkylanilines such as N-methylaniline and N-butylaniline, di-(p-methylphenyl)amine, naphthylamine, 4-aminodiphenylamine, N,N-dimethylphenyldiamine, 4-(4-nitro-phenylazo)aniline (Disperse Orange 3), sulfadiazine, 4-phenoxyaniline, 3-nitroaniline, 4-aminoacetaniline, phenyl 4-amino-2-hydroxybenzoate (phenylamino salicylate), N-(4-amino-5-methoxy-2-methyl-phenyl)-benzamide (Glass Violet B), N-(4-amino-2,5-dimethoxy-phenyl)-benzamide (Glass Blue RR), N-(4-amino-2,5-diethoxy-phenyl)-benzamide (Glass Blue BB), N-(4-amino-phenyl)-benzamide, and 4-phenylazoaniline. Suitable amines are mentioned in and incorporated herein by reference in U.S. Patent No. 7,790,661.

[0265] In the implementation scheme, the compound condensed with the acylated polymer can be represented by the following formula:

[0266] Where X is an alkylene group containing approximately 1 to approximately 4 carbon atoms; R 2 R3 and R 4 It is a hydrocarbon group.

[0267]

[0268] Where X is an alkylene group containing approximately 1 to approximately 4 carbon atoms; R 3 and R 4 It is a hydrocarbon group.

[0269] Alternatively, the amine can be an amine having at least four aromatic groups and an aldehyde (such as formaldehyde). The aromatic amine can be represented by the following formula:

[0270] Among them, R 1 Is it hydrogen or C? 1-5 Alkyl (usually hydrogen); R 2 Is it hydrogen or C? 1-5 Alkyl (usually hydrogen); U is an aliphatic, alicyclic, or aromatic group, optionally wherein when U is aliphatic, the aliphatic group may be a straight-chain or branched alkylene group containing 1, 2, 3, 4, or 5, or 1 to 2 carbon atoms; and w is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9, such as 0, 1, 2, or 3, or 0 or 1 (usually 0). For further information on such amines, see, for example, US 2017 / 0073606, paragraphs

[0064] -

[0070] on page 5 and European Patent No. 2 401 348.

[0271] Examples of compounds capable of condensing with an acylating agent and further having a tertiary amino group include, but are not limited to: dimethylaminopropylamine, N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, N,N-dimethylaminoethylamine, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, isobutanediamine, pentapentanediamine, hexanediamine, heptananediamine, diethylenetriamine, dipropylenetriamine, dibutyltriamine, triethylenetetramine, tetraethylenepentane, pentaethylenehexamine, hexamethylenetetramine and bis(hexamethylene)triamine, diaminobenzene, diaminopyridine or mixtures thereof. Compounds capable of condensing with an acylating agent and further having a tertiary amino group may further include aminoalkyl-substituted heterocyclic compounds, such as 1-(3-aminopropyl)imidazolium and 4-(3-aminopropyl)morpholine, 1-(2-aminoethyl)piperidine, 3,3-diamino-N-methyldipropylamine, and 3',3-aminobis(N,N-dimethylpropylamine). Another example of compounds capable of condensing with an acylating agent and having a tertiary amino group includes alkanolamines, including but not limited to triethanolamine, triethanolamine, N,N-dimethylaminopropanol, N,N-diethylaminopropanol, N,N-diethylaminobutanol, N,N,N-tri(hydroxyethyl)amine, and N,N,N-tri(hydroxymethyl)amine.

[0272] In this embodiment, the polymer can react with a polyether aromatic compound. Typically, the polyether aromatic compound has at least two functional groups, each capable of reacting with a monocarboxylic acid or its ester, or a dicarboxylic acid, its anhydride or ester, or a mixture thereof. In this embodiment, the polyether aromatic compound is derived from an aromatic compound containing at least one amine group, and wherein the polyether is capable of reacting with a monocarboxylic acid or its ester, or a dicarboxylic acid, its anhydride or ester.

[0273] Examples of suitable polyether aromatic amines include compounds having the following structures:

[0274] Wherein A represents an aromatic amine structural moiety, wherein the ether group is connected via at least one amine group on the aromatic structural moiety; R1 and R6 are independently hydrogen, alkyl, alkylaryl, aralkyl or aryl or mixtures thereof; R2, R3, R4 and R5 are independently hydrogen or alkyl or mixtures thereof containing about 1 to about 6 carbon atoms; and a and x are independently integers from about 1 to about 50.

[0275] Acylated polymers can react with polyetheramines or polyether polyamines. Typical polyetheramine compounds contain at least one ether unit and are chain-terminated with at least one amine moiety. Polyether polyamines can be based on polymers derived from C2-C6 epoxides such as ethylene oxide, propylene oxide, and butane oxide. Examples of polyether polyamines are sold under the Jeffamine™ brand and are available from Hunterman Corporation.

[0276] The amines that can be used in combination with acylated polymers include one or more of the following: N-phenyldiamines (such as N-phenyl-1,4-phenylenediamine, N-phenyl-p-phenylenediamine (also known as 4-amino-diphenylamine, ADPA), N-phenyl-1,3-phenylenediamine, N-phenyl-1,2-phenylenediamine), nitroaniline (such as 3-nitroaniline), N-phenylethylenediamine (such as N1-phenylethylene-1,2-diamine), N-aminophenylacetamide (such as N-(4-aminophenyl)acetamide), morpholinopropylamine (such as 3-morpholinopropyl-1-amine), and aminoethylpiperazine (such as 1-(2-aminoethyl)piperazine).

[0277] In the embodiments, the functionalization (e.g., amination) reactions described herein can be carried out in a diluent (e.g., a base oil or an alkane solvent). As a byproduct, a functionalized diluent (e.g., a functionalized base oil) can be generated. It is considered that the functionalized diluent (e.g., a functionalized base oil) may contain reaction products of an acylated diluent (e.g., an acylated base oil) and an amine to form an amide, an imide, or a combination thereof.

[0278] Preferably, based on the weight of the concentrate composition, the reaction product of the acylation diluent (such as acylated oil) with an amine or alcohol to form an amide, imide, ester, or combination thereof may be present in the concentrate in an amount of 40% by weight or less, or 20% by weight or less, or 10% by weight or less, or 5% by weight or less, or 3% by mass or less, preferably 2% by mass or less, preferably 1% by mass or less, preferably 0.1% by mass or less, preferably 0% by mass (e.g., 0 to 40% by mass, or 0.01 to 40% by mass, or 0.1 to 20% by mass, or 1 to 10% by mass, or 1.5 to 5% by mass).

[0279] Preferably, based on the weight of the lubricating oil composition, one or more functionalized base oils, such as acylated diluents (e.g., acylated base oils), react with amines or alcohols to form amides, imides, esters, or combinations thereof, and the reaction product may be present in the lubricating oil composition in an amount of 0.01 to 40% by mass, or 0.1 to 20% by mass, or 1 to 10% by mass, or 1.5 to 5% by mass (e.g., 3% by mass or less, preferably 2% by mass or less, preferably 1% by mass or less, preferably 0.1% by mass or less, preferably 0% by mass).

[0280] In embodiments, the functionalization (e.g., amination) reactions described herein can be carried out in a solvent-containing medium. A functionalized solvent can be generated as a byproduct. In embodiments, based on the weight of the concentrate composition, the functionalized solvent may be present in the concentrate composition at 3% by mass or less, preferably 2% by mass or less, preferably 1% by mass or less, preferably 0.1% by mass or less, preferably 0% by mass. In embodiments, based on the weight of the lubricating oil composition, the functionalized solvent may be present in the lubricating oil composition at 3% by mass or less, preferably 2% by mass or less, preferably 1% by mass or less, preferably 0.1% by mass or less, preferably 0% by mass.

[0281] In the implementation scheme, the acylated base oil / solvent can be removed prior to functionalization.

[0282] Functionalized polymers can be homopolymers of C4 or C5 olefins, such as homopolymers of butadiene and isoprene.

[0283] In the implementation scheme, the functionalized polymer may be a homopolymer of isoprene, or a copolymer of isoprene and less than 5 mol% (e.g., less than 3 mol%, less than 1 mol%, less than 0.1 mol%) of comonomer.

[0284] The functionalized polymer may comprise or be a copolymer of isoprene and one or more of the following: styrene, methyl-styrene, 2,3-dimethyl-butadiene, 2-methyl-1,3-pentadiene, myrcene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, 2-phenyl-1,3-pentadiene, 3-phenyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2-hexyl-1,3-butadiene, 3-methyl-1,3-hexadiene, 2-benzyl-1,3- Butadiene, 2-p-tolyl-1,3-butadiene, 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2,4-heptadiene, 1,3-octadiene, 2,4-octadiene, 3,5-octadiene, 1,3-nonadiene, 2,4-nonadiene, 3,5-nonadiene, 1,3-decadiene, 2,4-decadiene and 3,5-decadiene, (optionally, the comonomer is present in amounts of less than 20 mol%, less than 5 mol%, such as less than 3 mol%, such as less than 1 mol%, such as less than 0.1 mol%).

[0285] In the implementation scheme, the functionalized polymer contains 10 (e.g., 9, 8, 7, 6, 5, 4, 3, 2, 1) wt% or less of styrene monomer based on the weight of the functionalized polymer.

[0286] In the implementation scheme, styrene repeating units may be absent in the functionalized polymer.

[0287] In the implementation scheme, the functionalized polymer may be a block copolymer or a graded block copolymer that does not contain styrene blocks.

[0288] In the implementation scheme, the functionalized polymer may be a block copolymer or a graded block copolymer containing isoprene (or composed of or substantially composed of isoprene).

[0289] In an embodiment, the functionalized polymer may be a block copolymer or a graded block copolymer containing 50% by weight or more of isoprene based on the copolymer.

[0290] In the implementation scheme, the functionalized polymer may be containing C 4-5 Conjugated dienes (or those derived from C) 4-5 Conjugated dienes are composed of or are essentially composed of C 4-5 The conjugated diene composition preferably contains 50 (e.g., 60, 70, 80, 90, 95, 98) or more C based on the weight of the copolymer. 4-5 Block copolymers or graded block copolymers of conjugated dienes.

[0291] In an embodiment, the functionalized polymer may be a copolymer containing 50 (e.g., 60, 70, 80, 90, 95, 98) or more wt% of isoprene based on the copolymer weight.

[0292] In an embodiment, the functionalized polymer may be a copolymer containing 50 (e.g., 60, 70, 80, 90, 95, 98) wt% or more of butadiene based on the copolymer weight.

[0293] In an implementation, the functionalized polymer may be a copolymer comprising 50 (e.g., 60, 70, 80, 90, 95, 98) or more by weight of butadiene and isoprene based on the copolymer weight.

[0294] In the embodiments, the functionalized polymer may be a diblock copolymer containing at least one isoprene homopolymer or copolymer block.

[0295] Optionally, butadiene repeating units may be absent in the functionalized polymer.

[0296] Optionally, the functionalized polymer may not be homopolymer isobutylene.

[0297] Optionally, the functionalized polymer may not be a copolymer of isoprene and butadiene.

[0298] Typically, the polymeric conjugated diene in a functionalized polymer comprises monomer units that have been inserted into the growing polymer chain via conjugated and non-conjugated addition. In an embodiment, through... 13 According to C NMR measurements, based on the total number of conjugated addition and non-conjugated insertions, the functionalized polymer contains at least about 50% of the insertions by conjugated addition, such as at least about 75% of the insertions by conjugated addition, such as about 80% of the insertions by conjugated addition, such as about 85% to about 100% of the insertions by conjugated addition.

[0299] Insertion of isoprene is most commonly achieved through 2,1-insertion, 1,4-insertion (trans and cis), and 3,4-insertion. (via 1 (Measurement of insertion geometry by H NMR). 1H NMR measurements show that the functionalized isoprene polymer contains at least about 50% 1,4-intercalation, such as at least about 75% 1,4-intercalation, such as at least about 80% 1,4-intercalation, such as at least about 90% 1,4-intercalation, such as at least about 95% 1,4-intercalation, or such as at least 98% 1,4-intercalation, based on the total amount of 2,1-intercalation, 1,4-intercalation, and 3,4-intercalation. For the purposes of this disclosure: 1) the phrase “1,4-intercalation” includes 1,4-intercalation and 4,1-intercalation, 2) the phrase “2,1-intercalation” includes 2,1-intercalation and 1,2-intercalation, and 3) the phrase “3,4-intercalation” includes 3,4-intercalation and 4,3-intercalation.

[0300] The functionalized polymer can be a homopolymer or a copolymer. Optionally, the functionalized polymer comprises a homopolymer or copolymer of isoprene. The copolymer can be a random copolymer, a graded block copolymer, a star copolymer, or a block copolymer.

[0301] The functionalized polymer may typically have 20,000 to 150,000 g / mol, or 20,000 to about 150,000 g / mol, or 30,000 to about 125,000 g / mol, or 35,000 to about 100,000 g / mol, or 40,000 to 80,000 g / mol of Mn (GPC-PS).

[0302] The unfunctionalized polymer typically has an Mn / Mw ratio of 1.0 to 2, such as 1.1 to 1.5, 1.1 to 1.3, or 1.1 to 1.2 (GPC-PS). As functionalization proceeds, the Mw / Mn ratio may broaden.

[0303] The functionalized polymer may typically have a Mw / Mn ratio of 1 to 3, or 1 to 2, or greater than 1 to less than 2, or 1.05 to 1.9, or 1.10 to 1.8, or 1.10 to 1.7, or 1.12 to 1.6, or 1.13 to 1.5, or 1.15 to 1.4, or 1.15 to 1.3 (GPC-PS). Alternatively, the functionalized polymer may typically have a Mw / Mn ratio of 1 or greater than 1 to less than 2 (e.g., less than 1.8, less than 1.7, less than 1.6, less than 1.4, less than 1.2, less than 1.15, less than 1.12, less than 1.10).

[0304] In the implementation, the functionalized polymer may have a saponification value (SAP) of 25 (e.g., 28, 30, 32, 34) mgKOH / g or greater as determined by ASTM D94.

[0305] In the embodiments, the functionalized polymer may contribute 17% or more (e.g., 20% or more, e.g., 17 to 40%, e.g., 20 to 30%) of the saponification value of the lubricating oil composition.

[0306] In the embodiments, the functionalized polymer may have an average functionality of 1.4 to 20 FG graft / polymer chains, such as 1.4 to 15 FG graft / polymer chains, such as 3 to 12.5 FG graft / polymer chains, such as 4 to 10 FG graft / polymer chains, as determined by GPC-PS.

[0307] Functionalized polymers may have an average functionality of 15 (e.g., 14, 13, 12, 11, 10, 9, 8, 7 or 6) or fewer FG graft / polymer chains as determined by GPC-PS.

[0308] Functionalized polymers may have an average functionality of one (e.g., 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, or 4.0) or more FG graft / polymer chains as determined by GPC-PS.

[0309] Functionalized polymers may have an average functionality of 1 (e.g., 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, or 4.0) to 15 (e.g., 14, 13, 12, 11, 10, 9, 8, 7, or 6) FG graft / polymer chains as determined by GPC-PS.

[0310] In the implementation, the functionalized polymer may have an aromatic content of 5% or less, such as 3% or less, such as 1% or less, such as 0% based on the polymer weight.

[0311] In embodiments, the functionalized polymer may comprise branched Cw having Mn of 20,000 to 500,000 g / mol with a Mn having a Mw / Mn of 2 or less, such as 1 to 2.0, as determined by GPC-PS. 4-5 Acylated polymers of monomers.

[0312] In the embodiments, the functionalized polymer may have a number-average molecular weight (Mn) of 20,000 (e.g., 25,000, 30,000, 35,000, 40,000) g / mol or greater as determined by GPC-PS.

[0313] In some embodiments, the functionalized polymer may have a weight-average molecular weight (Mw) of 50,000 (e.g., 40,000, or 35,000) g / mol or less, as determined by GPC-PS. In other embodiments, the functionalized polymer may have a weight-average molecular weight (Mw) of 1,000 to 50,000 g / mol, or 5,000 to 40,000 g / mol, as determined by GPC-PS.

[0314] In the embodiments, the functionalized polymer may have a z-average molecular weight (Mz) (GPC-PS) of 5,000 to 150,000 g / mol, such as 10,000 to 150,000 g / mol, such as 15,000 to 70,000 g / mol, such as 20,000 to 150,000 g / mol, or 20,000 to about 150,000 g / mol, or 30,000 to about 125,000 g / mol, or 35,000 to about 100,000 g / mol, or 40,000 to 80,000 g / mol, or 40,000 to 60,000 g / mol.

[0315] In embodiments, the functionalized polymer may have a gel content of less than about 5% by weight, less than 3% by weight, less than 2% by weight, less than 1% by weight, less than 0.5% by weight, less than 0.1% by weight, or 0% by weight, wherein the gel content is measured by determining the amount of material extractable from the polymer using boiling xylene (or cyclohexane) as an extractant. The percentages of soluble and insoluble (gel) materials in the polymer composition are determined as described herein.

[0316] In the embodiments, the functionalized polymer may have a functionality distribution (Fd) value of 3.5 or less (e.g., 3.4 or less, such as 1 to 3.3, such as 1.1 to 3.2, such as 1.2 to 3.0, such as 1.4 to 2.9, determined by GPC-PS, the functionality distribution (Fd) value being determined as described in the Examples section below) and an average functionality of 1.4 to 20 FG graft / polymer chains, such as 1.4 to 15 FG graft / polymer chains, such as 3 to 12.5 FG graft / polymer chains, such as 4 to 10 FG graft / polymer chains, as determined by GPC-PS.

[0317] This disclosure relates to amide, imide, and / or ester functionalization containing C 4-5 Alkenes (basically composed of C) 4-5 Alkenes or composed of C 4-5The hydrogenated / saturated polymer (olefin composition) having a Mw / Mn ratio of less than 2, a functionality distribution (Fd) value of 3.5 or less (e.g., 3.4 or less, e.g., 1 to 3.3, e.g., 1.1 to 3.2, e.g., 1.2 to 3.0, e.g., 1.4 to 2.9, as determined by GPC-PS), and wherein if the polymer before functionalization is a C4 olefin polymer, such as polyisobutylene, polybutadiene or copolymers thereof (preferably polyisobutylene or copolymers of isobutylene and butadiene), the C4 olefin polymer has a Mn of 10,000 g / mol or greater (GPC-PS), and if the polymer before functionalization is a C4 / C5 copolymer of isoprene and butadiene, the copolymer has a Mn greater than 25,000 Mn (GPC-PS).

[0318] This disclosure also relates to hydrogenated / saturated polymers containing 90 mol% or more of isoprene repeating units functionalized with amides, imides, and / or esters, having a Mw / Mn ratio of less than 2, a functionality distribution (Fd) value of 3.5 or less (e.g., 3.4 or less, such as 1 to 3.3, such as 1.1 to 3.2, such as 1.2 to 3.0, such as 1.4 to 2.9, as determined by GPC-PS), and wherein the unfunctionalized polymer has an Mn of 30,000 g / mol or greater (GPC-PS).

[0319] This disclosure also relates to hydrogenated / saturated isoprene homopolymers functionalized with amides, imides, and / or esters, having a Mw / Mn ratio of less than 2, a functionality distribution (Fd) value of 3.5 or less (e.g., 3.4 or less, such as 1 to 3.3, such as 1.1 to 3.2, such as 1.2 to 3.0, such as 1.4 to 2.9, as determined by GPC-PS), and wherein the unfunctionalized polymer has an Mn of 30,000 g / mol or greater (as determined by GPC-PS).

[0320] The lubricating compositions according to this disclosure may further comprise one or more additives, such as detergents, friction modifiers, antioxidants, pour point depressants, defoamers, viscosity modifiers, dispersants, corrosion inhibitors, anti-wear agents, extreme pressure additives, demulsifiers, sealing compatibilizers, sealing swelling agents, additive diluents, base oils, etc. Specific examples of such additives are described, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, 3rd Edition, Volume 14, pp. 477-526, and several will be discussed in more detail below.

[0321] D. Friction modifier

[0322] Friction modifiers are any materials that can alter the coefficient of friction of surfaces lubricated by any lubricant or fluid containing such materials. If desired, friction modifiers, also known as friction reducers, lubricity agents, or oiliness agents, and other such agents that alter the ability of base oils, formulations of lubricating compositions, or functional fluids to modulate the coefficient of friction of lubricated surfaces, can be effectively used in conjunction with the base oils or lubricating compositions disclosed herein. The combination of friction modifiers that reduce the coefficient of friction with the base oils and lubricating compositions of this disclosure is particularly advantageous.

[0323] Exemplary friction modifiers may include, for example, organometallic compounds or materials or mixtures thereof. Exemplary organometallic friction modifiers that can be used in the lubricant formulations of this disclosure include, for example, tungsten and / or molybdenum compounds, such as molybdenum amines, molybdenum diamines, organotungstates (such as Molyvan™ W-324 from Vanderbilt Chemicals LLC), molybdenum dithiocarbamate, molybdenum dithiophosphate, molybdenum amine complexes, molybdenum carboxylates, etc., and mixtures thereof. Examples of available molybdenum-containing compounds may conveniently include molybdenum dithiocarbamate, such as trinuclear molybdenum compounds as described in PCT Publication No. WO 98 / 26030, molybdenum sulfides, and molybdenum dithiophosphate. (Dimers Sakura Lube 515, 525 and MOlyvan 3000 dimers)

[0324] Other known friction modifiers include oil-soluble organomolybdenum compounds (Moly van 855). Such organomolybdenum friction modifiers can also provide antioxidant and anti-wear benefits to lubricant compositions. Examples of such oil-soluble organomolybdenum compounds include dithiocarbamates, dithiophosphates, dithiophosphonites, xanthates, thioxanthates, sulfides, and mixtures thereof. Particularly preferred are molybdenum dithiocarbamate, dialkyl dithiophosphate molybdenum, alkyl xanthate molybdenum, and alkyl thioxanthate molybdenum.

[0325] Alternatively, the molybdenum compound can be an acidic molybdenum compound. These compounds react with basic nitrogen compounds as determined by ASTM test D664 or D2896 titration procedures and are typically hexavalent. Examples include molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkali metal molybdates and other molybdenum salts, such as sodium hydrogen molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide, or similar acidic molybdenum compounds.

[0326] The molybdenum compounds that can be used in the compositions disclosed herein include organomolybdenum compounds of the formula Mo(R"OCS2)4 and Mo(R"SCS2)4, wherein R" is an organic group selected from alkyl, aryl, aralkyl, and alkoxyalkyl groups that typically have 1 to 30 carbon atoms, preferably 2 to 12 carbon atoms, and most preferably alkyl groups having 2 to 12 carbon atoms. Dialkyl dithiocarbamates of molybdenum are particularly preferred.

[0327] Another class of organomolybdenum compounds that can be used in the lubricating compositions of this disclosure are trinuclear molybdenum compounds, especially those of the formula Mo3S k L n Q z Those and mixtures thereof, wherein L is an independently chosen ligand having an organic group having a sufficient number of carbon atoms to make the compound soluble or dispersible in oil, n is 1 to 4, k is 4 to 7, Q is selected from neutral electron-donating compounds such as water, amines, alcohols, phosphine, and ethers, and z is 0 to 5 and includes non-stoichiometric values. At least 21 carbon atoms, such as at least 25, at least 30, or at least 35 carbon atoms, should be present in all ligands / organic groups.

[0328] The lubricating oil compositions that can be used in all aspects of this disclosure preferably contain at least 1 ppm, at least 10 ppm, at least 30 ppm, at least 40 ppm, and more preferably at least 50 ppm of molybdenum. Suitably, the lubricating oil compositions that can be used in all aspects of this disclosure contain no more than 1000 ppm, no more than 750 ppm, or no more than 500 ppm of molybdenum. The lubricating oil compositions that can be used in all aspects of this disclosure preferably contain 10 to 1000, such as 30 to 750 or 40 to 500 ppm of molybdenum (as measured by molybdenum atoms). Alternatively, the lubricating oil compositions that can be used in all aspects of this disclosure preferably contain 0 ppm of Mo.

[0329] For more information on available Mo-containing friction modifiers, see U.S. Patent No. 10,829,712 (Column 8, line 58 through Column 11, line 31).

[0330] Ashless friction modifiers are present in and are well known in the lubricant compositions of this disclosure, and include esters formed by reacting carboxylic acids and anhydrides with alkanols, and amine-based friction modifiers. Other available friction modifiers typically include polar end groups (e.g., carboxyl or hydroxyl groups) covalently bonded to lipophilic hydrocarbon chains. Esters of carboxylic acids and anhydrides with alkanols are described in U.S. Patent No. 4,702,850. Examples of other conventional organic friction modifiers are described by M. Belzer in "Journal of Tribology" (1992), Vol. 114, pp. 675-682, and by M. Belzer and S. Jahanmir in "Lubrication Science" (1988), Vol. 1, pp. 3-26. Generally, the total amount of organic ashless friction modifiers in the lubricants according to this disclosure, based on the total mass of the lubricant composition, does not exceed 5% by mass, preferably not more than 2% by mass, and more preferably not more than 0.5% by mass.

[0331] Exemplary friction modifiers that can be used in the lubricating compositions described herein include, for example, alkoxylated fatty acid esters, alkanolamides, polyol fatty acid esters, boronized glycerol fatty acid esters, fatty alcohol ethers, and mixtures thereof.

[0332] Exemplary alkoxylated fatty acid esters include, for example, polyoxyethylene stearate, fatty acid polyethylene glycol ester, etc. These may include polyoxypropylene stearate, polyoxybutylene stearate, polyoxyethylene isostearate, polyoxypropylene isostearate, polyoxyethylene palmitate, etc.

[0333] Exemplary alkanolamides include, for example, diethylalkanolamide laurylate, diethylalkanolamide palmitate, etc. These may include diethylalkanolamide oleate, diethylalkanolamide stearate, diethylalkanolamide oleate, polyethoxylated hydrocarbon amides, polypropoxylated hydrocarbon amides, etc.

[0334] Exemplary polyol fatty acid esters include, for example, glyceryl monooleate, saturated mono-, di-, and tri-glycerides, glyceryl monostearate, etc. These may include polyol esters, hydroxyl-containing polyol esters, etc.

[0335] Exemplary boronized glycerol fatty acid esters include, for example, boronized glycerol monooleate, boronized saturated mono-, di-, and triglycerides, boronized glycerol monostearate, etc. In addition to glycerol polyols, these may also include trimethylolpropane, pentaerythritol, sorbitan, etc. These esters can be polyol monocarboxylic acid esters, polyol dicarboxylic acid esters, and sometimes, polyol tricarboxylic acid esters. Preferred esters include glycerol monooleate, glycerol dioleate, glycerol trioleate, glycerol monostearate, glycerol distearate, and glycerol tristearate, and their respective glycerol monopalmitates, glycerol dipalmitates, and glycerol tripalmitates, as well as their respective isostearates, linoleates, etc. Ethoxylated, propoxylated, and / or butoxylated fatty acid esters of polyols (especially using glycerol as the base polyol) may be used herein.

[0336] Exemplary fatty alcohol ethers include, for example, stearyl ether, myristyl ether, etc. Alcohols, including those having C3 to C4, can be used. 50 Those alcohols with a certain number of carbon atoms can be ethoxylated, propoxylated, or butoxylated to form the corresponding aliphatic alkyl ethers. The base alcohol moiety is preferably stearyl, myristyl, or C... 11 -C 13 Hydrocarbons, oleyl groups, isostearyl groups, etc.

[0337] The useful concentration of friction modifiers can be from 0.01% by mass to 5% by mass, or from about 0.01% by mass to about 2.5% by mass, or from about 0.05% by mass to about 1.5% by mass, or from about 0.051% by mass to about 1% by mass. The concentration of molybdenum-containing materials is generally described as the Mo metal concentration. The favorable concentration of Mo can be from 25 ppm to 700 ppm or more, and is generally preferred in the range of 50-200 ppm. All types of friction modifiers can be used alone or in combination with the materials disclosed herein. Mixtures of two or more friction modifiers or mixtures of friction modifiers with alternative surfactants are also generally desirable. For example, combinations of Mo-containing compounds with polyol fatty acid esters, such as glyceryl monooleate, can be used here.

[0338] E. Antioxidants

[0339] Antioxidants delay the oxidative degradation of base oils during use. Such degradation can lead to deposits on metal surfaces, sludge formation, and increased viscosity in lubricants. A wide variety of oxidation inhibitors can be used in lubricant compositions. See, for example, Lubricants and Related Products, Klamann, Wiley VCH, 1984; U.S. Patents 4,798,684 and 5,084,197.

[0340] Available antioxidants include hindered phenols. These phenolic antioxidants can be ash-free (metal-free) phenolic compounds or neutral or basic metal salts of certain phenolic compounds. Typical phenolic antioxidant compounds are hindered phenols containing sterically hindered hydroxyl groups, including derivatives of dihydroxyaryl compounds, wherein the hydroxyl groups are ortho- or para-positioned relative to each other. Typical phenolic antioxidants include those affected by C... 6+ Alkyl-substituted hindered phenols and their alkylene coupling derivatives. Examples of this type of phenolic material include 2-tert-butyl-4-heptylphenol; 2-tert-butyl-4-octylphenol; 2-tert-butyl-4-dodecylphenol; 2,6-di-tert-butyl-4-heptylphenol; 2,6-di-tert-butyl-4-dodecylphenol; 2-methyl-6-tert-butyl-4-heptylphenol; and 2-methyl-6-tert-butyl-4-dodecylphenol. Other available hindered mono-phenolic antioxidants may include, for example, hindered 2,6-di-alkyl-phenol propionate derivatives. Bis-phenolic antioxidants may also be advantageously used here. Examples of ortho-coupled phenols include 2,2'-bis(4-heptyl-6-tert-butyl-phenol); 2,2'-bis(4-octyl-6-tert-butyl-phenol); and 2,2'-bis(4-dodecyl-6-tert-butyl-phenol). Para-coupled bisphenols include, for example, 4,4'-bis(2,6-di-tert-butylphenol) and 4,4'-methylene-bis(2,6-di-tert-butylphenol).

[0341] An effective amount of one or more catalytic antioxidants may also be used. A catalytic antioxidant comprises an effective amount of a) one or more oil-soluble organometallic compounds; and an effective amount of b) one or more substituted diphenylamines (such as N,N'-diaryl-o-phenylenediamine) compounds, or c) one or more hindered phenolic compounds; or a combination of b) and c). Catalytic antioxidants that may be used herein are more fully described in U.S. Patent No. 8,048,833.

[0342] Available non-phenolic oxidation inhibitors include aromatic amine antioxidants, which can be used as is or in combination with phenols. Typical examples of non-phenolic antioxidants include alkylated and non-alkylated aromatic amines, such as R8R9R. 10 N is an aromatic monoamine, wherein R8 is an aliphatic, aromatic, or substituted aromatic group, R9 is an aromatic or substituted aromatic group, and R 10 It is H, alkyl, aryl or R 11 S(O)XR 12 , where R 11 It is an alkylene, alkenylene, or arylene alkyl group, R 12It is alkyl or alkenyl, aryl or alkylaryl, and x is 0, 1 or 2. The aliphatic group R8 may contain 1 to about 20 carbon atoms, preferably about 6 to 12 carbon atoms. This aliphatic group is typically a saturated aliphatic group. Preferably, R8 and R9 are both aromatic or substituted aromatic groups, and the aromatic group may be a fused-ring aromatic group, such as naphthyl. Aromatic groups R8 and R9 may be linked to other groups such as S.

[0343] Typical aromatic amine antioxidants have alkyl substituents containing at least about 6 carbon atoms. Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl, and decyl. Generally, aliphatic groups do not contain more than about 14 carbon atoms. Common types of amine antioxidants that can be used in this composition include diphenylamines (such as di(C...)... 8-14 (-alkyl-substituted diphenyl)amines, such as di(nonylphenyl)amine, phenylnaphthylamine, phenothiazine, iminodibenzylamine, and diphenylphenyldiamine. Mixtures of two or more aromatic amines are also available. Polymeric amine antioxidants may also be used. Specific examples of aromatic amine antioxidants that can be used in this disclosure include: p,p'-dioctyldiphenylamine; tert-octylphenyl-α-naphthylamine; phenyl-α-naphthylamine; and p-octylphenyl-α-naphthylamine.

[0344] Sulfur-containing antioxidants can also be used here. In particular, one or more oil-soluble or oil-dispersible sulfur-containing antioxidants can be used as antioxidant additives. For example, sulfurized alkylphenols and their alkali metal or alkaline earth metal salts are also antioxidants available herein. Suitably, the lubricating oil compositions of this disclosure may include one or more of the sulfur-containing antioxidants providing the lubricating oil composition with an amount of sulfur of 0.02 to 0.2, preferably 0.02 to 0.15, more preferably 0.02 to 0.1, and even more preferably 0.04 to 0.1% by mass based on the total mass of the lubricating oil composition. Optionally, the oil-soluble or oil-dispersible sulfur-containing antioxidant is selected from sulfurized C4 to C6. 25 Olefins, sulfurized aliphatic compounds (C7 to C6) 29 Hydrocarbon fatty acid esters, ashless sulfurized phenolic antioxidants, sulfur-containing organomolybdenum compounds, and combinations thereof. For further information on sulfurized materials that can be used as antioxidants herein, see U.S. Patent No. 10,731,101 (column 15, line 55 through column 22, line 12).

[0345] Antioxidants that can be used in this article include hindered phenols and / or aryl amines. These antioxidants can be used alone or in combination, depending on their type.

[0346] Typical antioxidants include: Irganox™ L67, Irganox™ L135, Ethanox™ 4702, Lanxess Additin™ RC 7110; Ethanox™ 4782J; Irganox™ 1135, Irganox™ 5057, sulfurized lard, and palm oil fatty acid methyl esters.

[0347] Based on the weight of the lubricating composition, the antioxidant additive may be used in an amount of about 0.01 to 10 (or 0.01 to 5, or 0.01 to 3) wt%, or about 0.03 to 5 wt%, or 0.05 to less than 3 wt%.

[0348] The compositions according to this disclosure may contain additives with different enumerated functions and also have a secondary effect as antioxidants (e.g., phosphorus-containing anti-wear agents (such as ZDDP) may also have an antioxidant effect). These additives are not considered antioxidants in determining the amount of antioxidants in the lubricating oil compositions or concentrates described herein.

[0349] F. Pour point depressant

[0350] If desired, conventional pour point depressants (also known as lubricating oil flow improvers or LOFI) may be added to the compositions disclosed herein. These pour point depressants can be added to the lubricating compositions disclosed herein to reduce the minimum temperature required for the fluid to flow or pour. Examples of suitable pour point depressants include polymethacrylates, polyacrylates, polyacrylamides, condensation products of halogenated paraffins and aromatic compounds, vinyl carboxylate polymers, and terpolymers of dialkyl fumarate, vinyl fatty acid esters, and allyl vinyl ethers. U.S. Patent Nos. 1,815,022; 2,015,748; 2,191,498; 2,387,501; 2,655,479; 2,666,746; 2,721,877; 2,721,878; and 3,250,715 describe available pour point depressants and / or their preparation. Based on the weight of the lubricating composition, such an additive can be used in an amount of about 0.01 to 5% by mass, preferably about 0.01 to 1.5% by mass.

[0351] G. Defoamer

[0352] Defoamers can be advantageously added to the lubricant compositions described herein. These agents prevent or delay the formation of stable foams. Organosilicones and / or organic polymers are typical defoamers. For example, polysiloxanes, such as silicone oils or polydimethylsiloxanes, provide defoaming properties.

[0353] Defoamers are available and can be used in minor amounts, such as 5% by mass or less, 3% by mass or less, 1% by mass or less, 0.1% by mass or less, such as 5% by mass to 0.1 ppm, such as 3% by mass to 0.5 ppm, such as 1% by mass to 10 ppm.

[0354] For example, the lubricating oil composition may contain a defoamer comprising a polyalkylsiloxane, such as a polydialkylsiloxane, wherein the alkyl group is C1-C. 10 Alkyl groups, such as polydimethylsiloxane (PDMS), also known as silicone oils. Alternatively, siloxanes are poly(R... 3 )siloxane, wherein R 3 It is one or more identical or different straight-chain, branched or cyclic hydrocarbon groups, such as alkyl or aryl, which typically have 1 to 20 carbon atoms. Possibly, for example, the lubricating oil composition comprises a polymeric siloxane compound according to Formula 1, wherein R... 1 and R 2 Independently, it is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl, phenyl, naphthyl, alkyl-substituted phenyl or its isomers (such as methyl, phenyl), and n is 2 to 1000, such as 50 to 450, or such as 40 to 100.

[0355] Additionally or alternatively, the lubricating oil composition may contain organically modified siloxanes (OMS), such as those with organic groups like polyethers (e.g., ethylene oxide-propylene oxide copolymers) or long-chain hydrocarbon groups (e.g., C... 11 -C 100 Alkyl) or aryl (e.g., C6-C) 14 Aryl) modified siloxanes. Possibly, for example, the lubricating oil composition comprises an organically modified siloxane compound according to Formula 1, wherein n is 2 to 2000, such as 50 to 450 (or such as 40 to 100), and wherein R... 1 and R 2 Same or different, where R is optional 1 and R 2 Each is an independent organic group, such as those selected from polyethers (e.g., ethylene oxide-propylene oxide copolymers) and long-chain hydrocarbon groups (e.g., C...). 11 -C 100 Alkyl) or aryl (e.g., C6-C) 14 An organic group consisting of an aryl group. Preferably, R 1 and R 2 One of them is CH3.

[0356] Formula 1

[0357] Based on the total weight of the lubricant composition, a siloxane according to Formula 1 is incorporated to provide approximately 0.1 to less than approximately 30 ppm Si, or approximately 0.1 to approximately 25 ppm Si, or approximately 0.1 to approximately 20 ppm Si, or approximately 0.1 to approximately 15 ppm Si, or approximately 0.1 to approximately 10 ppm Si. More preferably, it is in the range of approximately 3-10 ppm Si.

[0358] In the embodiments described herein, silicone defoamers available from Dow Corning Corporation and Union Carbide Corporation, such as Dow Corning FS-1265 (1000 centipoise), Dow Corning DC-200, and Union Carbide UC-L45, are permitted. Silicone defoamers permitted herein include polydimethylsiloxanes, fluorosilicone materials, phenyl-methylpolysiloxanes, linear, cyclic, or branched siloxanes, silicone polymers and copolymers, and / or organo-silicone copolymers. Alternatively, siloxane polyether copolymer defoamers available from OSI Specialties, Inc. of Farmington Hills, Michigan may be used or included. One such material is sold as SILWET-L-7220. Other available silicone-containing agents include those disclosed in EP 3 366 755 A1.

[0359] Acrylic polymer defoamers can also be used here. Typical acrylic defoamers include polyacrylate defoamer known as PC-1244, available from Monsanto Polymer Products Co. Preferred acrylic polymer defoamers for use herein are PX™ 3841 (i.e., alkyl acrylate polymer), also known as Mobilad™ C402, available from Dorf Ketl.

[0360] In the implementation scheme, a combination of silicone defoamer and acrylate defoamer may be used, such as at a silicone defoamer / acrylate defoamer weight ratio of about 5:1 to about 1:5, see, for example, U.S. Patent Application Publication No. 2021 / 0189283.

[0361] H. Viscosity improver

[0362] Viscosity improvers (also known as viscosity index improvers or viscosity modifiers) may be included in the lubricating compositions described herein. Viscosity improvers provide lubricants with high-temperature and low-temperature operability. These additives provide shear stability at elevated temperatures and acceptable viscosity at low temperatures. Suitable viscosity improvers include high molecular weight hydrocarbons, polyesters, and viscosity improver dispersants (also known as dispersant viscosity improvers or DVMs) that can act as both viscosity improvers and dispersants. Typical molecular weights of these polymers are between about 10,000 and 1,500,000 g / mol, more typically about 20,000 to 1,200,000 g / mol, and even more typically between about 50,000 and 1,000,000 g / mol.

[0363] Examples of suitable viscosity modifiers are linear or radial (star-shaped) polymers and copolymers of methacrylates, butadiene, olefins, or alkylated styrene. Polyisobutylene is a commonly used viscosity modifier. Another suitable viscosity modifier is polymethacrylate (e.g., copolymers of alkyl methacrylates of various chain lengths), some of which also act 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 acrylates of various chain lengths). Specific examples include styrene-isoprene or styrene-butadiene type polymers with molecular weights from 50,000 to 200,000 g / mol.

[0364] Copolymers that can be used as viscosity modifiers include those available under the trade name "PARATONE™" (such as "PARATONE™ 8921", "PARATONE™ 68231", and "PARATONE™ 8941") from Chevron Oronite Company LLC; those available under the trade name "HiTEC™" (such as HiTEC™ 5850B and HiTEC™ 5777) from Afton Chemical Corporation; and those available under the trade name "Lubrizol™ 7067C" from The Lubrizol Corporation. Hydrogenated polyisoprene radial (star-shaped) polymers that can be used as viscosity modifiers herein include those available from Infineum International Limited, for example, under the trade names "SV200™" and "SV600™". Hydrogenated diene-styrene block copolymers that can be used as viscosity modifiers herein are available from Infineum International Limited, for example, under the trade name "SV150™".

[0365] Polymers that can be used as viscosity modifiers in this article include polymethacrylate or polyacrylate polymers, such as linear polymethacrylate or polyacrylate polymers, such as those available under the trade name "Viscoplex™" (e.g., Viscoplex™ 6-954) from Evonik Industries, or star-shaped polymers available under the trade name Asteric™ (e.g., Lubrizol™ 87708 and Lubrizol™ 87725) from Lubrizol Corporation.

[0366] Vinyl aromatic polymers that can be used as viscosity modifiers in this document can be derived from vinyl aromatic monomers, such as styrene monomers, like styrene. Exemplary vinyl aromatic copolymers that can be used in this document can be represented by the following general formula: AB, where A is a polymeric block mainly derived from a vinyl aromatic monomer (such as styrene) and B is a polymeric block mainly derived from a conjugated diene monomer (such as isoprene).

[0367] Vinyl aromatic polymers that can be used as viscosity modifiers may have a kinematic viscosity at 100°C of 20 cSt or lower, such as 15 cSt or lower, such as 12 cSt or lower, but may be diluted (e.g. in Group I, II and / or III base oils) to a higher kinematic viscosity at 100°C, such as up to 40 cSt or higher, such as 100 cSt or higher, such as 1000 cSt or higher, such as 1000 to 2000 cSt.

[0368] Dispersant viscosity modifiers that may be used herein include amide, imide, and / or ester-functionalized partially or fully saturated C-containing compounds as described in U.S. Patent Application USSN 18 / 480,571, filed October 4, 2023 (the entire contents of which are incorporated herein by reference). 4-5 Polymers of olefins. Preferred DVMs include polymers referred to as "functionalized polymers" as described in USSN 18 / 480,571, and are preferably polymers of the functionalized hydrogenated polyisoprene family for use in lubricating oil compositions. In an advantageous form, the lubricating oil compositions described herein optionally further include 0.2 to 2.0% by mass, or 0.4 to 1.8% by mass, or 0.6 to 1.6% by mass, or 0.8 to 1.4% by mass, or 1.0 to 1.2% by mass of one or more of the functionalized polymers described in 18 / 480,571 as dispersants and viscosity improvers, wherein the functionalized polymer comprises amides, imides, and / or esters functionalized partially or fully saturated C-containing polymers. 4-5The polymer of the olefin has: i) a Mw / Mn of less than 2, or less than 1.8, or less than 1.6; ii) a functionality distribution (Fd) value of 3.5 or less, or 3.2 or less, or 3.0 or less, or 2.5 or less; and iii) a prefunctionalized polymer with Mn of 10,000 g / mol or more, or 15,000 g / mol or more, or 20,000 g / mol or more, or 25,000 g / mol or more (GPC-PS), optionally provided that if the prefunctionalized polymer is a copolymer of isoprene and butadiene, the copolymer has Mn greater than 25,000 g / mol, or 30,000 g / mol or more, or 35,000 g / mol or more, or 40,000 g / mol or more (GPC-PS). (GPC-PS was performed as described in U.S. Patent Application USSN 18 / 480,571, filed October 4, 2023). For the functionalized polymers described herein in 18 / 480,571, the average functionality [also referred to as the average functionality value (Fv)] and functionality distribution (Fd) values ​​were determined by gel permeation chromatography using polystyrene standards as described in the experimental portion of U.S. Patent Application USSN 18 / 480,571, filed October 4, 2023. The functionalized polymers described herein in 18 / 480,571 may comprise at least 50%, or at least 60%, or at least 70% of a monomer (such as isoprene monomer) with 1,4-intercalation. Furthermore, the functionalized polymers that can be used in 18 / 480,571 herein may comprise partially or fully saturated homopolymer isoprene containing one or more amine side groups and having, prior to functionalization, 25,000 to 100,000 g / mol, or 35,000 to 90,000 g / mol, or 45,000 to 80,000 g / mol, or 55,000 to 75,000 g / mol of Mn (GPC-PS) and at least 50%, or at least 60%, or at least 70% of 1,4-intercalation. The functionalized polymers that can be used in 18 / 480,571 herein may be devoid of styrene repeating units, or devoid of butadiene repeating units, or not homopolymer isobutylene, or not a copolymer of isoprene and butadiene.

[0369] Other available DVMs include functionalized olefin copolymers (such as amine-functionalized ethylene-propylene copolymers). For other available DVMs, see US 5,663,126, US 6,187,721, US 5,874,389; WO 97 / 47709; US 6,300,289; US 6,686,321; WO 99 / 21902; US 2002 / 0183456; US 2004 / 0043909; WO 03 / 099890; US2008 / 0139423; US2008 / 0293600; WO 2006 / 116663; US 2004 / 0043909; and US 2010 / 0162981.

[0370] Vinyl aromatic polymer concentrates prepared in base oils (such as in Group I, II, and / or III base oils) that can be used as viscosity improvers may have a kinematic viscosity at 100°C of 40 cSt or higher, such as 100 cSt or higher, such as 1000 cSt or higher, such as 1000 to 2000 cSt. Further dilution in base oils (such as in Group I, II, and / or III base oils) can reduce the viscosity at 100°C, such as to 20 cSt or lower, such as 15 cSt or lower, such as 12 cSt or lower.

[0371] Typically, based on the total weight of the formulated lubricant composition, the viscosity improver may be used in amounts from about 0.01 to about 10% by mass, such as from about 0.1 to about 7% by mass, such as from 0.1 to about 4% by mass, such as from about 0.2 to about 2% by mass, such as from about 0.2 to about 1% by mass, and such as from about 0.2 to about 0.5% by mass.

[0372] Viscosity improvers are typically added as concentrates to bulk diluent oils. In "as delivered" polymer concentrates, the "as delivered" viscosity improver typically contains 20% to 75% by mass of active polymer for polymethacrylate or polyacrylate polymers, or 8% to 20% by mass of active polymer for olefin copolymers, hydrogenated polyisoprene star polymers, or hydrogenated diene-styrene block copolymers.

[0373] I. Dispersant

[0374] During engine operation, oil-insoluble oxidation byproducts are generated. Dispersants help retain these byproducts in solution, thereby reducing their deposition on metal surfaces. The dispersants used in the formulations of the lubricating compositions described herein can be ashless or ash-forming in nature. Preferably, the dispersant is ashless. A so-called ashless dispersant is an organic material that does not substantially form ash during combustion. For example, metal-free dispersants or boronized metal-free dispersants are considered ashless. Conversely, metal-containing detergents tend to form ash during combustion.

[0375] Dispersants used herein typically contain polar groups attached to a relatively high molecular weight hydrocarbon chain. These polar groups typically contain at least one element selected from nitrogen, oxygen, or phosphorus. A typical hydrocarbon chain contains 40 to 500, e.g., 50 to 400 carbon atoms. When used in the context of a functionalized polymer acting as a dispersant, the molecular weight is typically reported relative to the base polymer before modification. For example, the molecular weight of the PIBSA-PAM dispersant is typically reported relative to the base polymer before functionalization with an acylating agent (maleic acid or anhydride) and functional groups (such as polyamines). Therefore, the molecular weight of a dispersant as used herein is typically specified as the molecular weight of the base polymer from which the dispersant is derived.

[0376] (poly)olefin succinic acid derivative dispersant

[0377] One particularly available class of dispersants includes (poly)alkenyl succinic acid derivatives, typically prepared by reacting long-chain hydrocarbon-substituted succinic acid compounds (usually hydrocarbon-substituted succinic anhydrides) with polyhydroxy or polyamino compounds. The long-chain hydrocarbon group constituting the lipophilic portion of the molecule (which provides oil solubility) is typically a polyisobutylene group (this long-chain hydrocarbon group, such as the polyisobutylene group, typically has 400 to 3000 g / mol of Mn, such as 450 to 2500 g / mol). Numerous examples of this type of dispersant are commercially and literaryally well-known. Exemplary U.S. patents describing such dispersants include U.S. patent numbers 3,172,892; 3,215,707; 3,219,666; 3,316,177; 3,341,542; 3,444,170; 3,454,607; 3,541,012; 3,630,904; 3,632,511; 3,787,374 and 4,234,435. Other types of dispersants are described in U.S. Patent Nos. 3,036,003; 3,200,107; 3,254,025; 3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,413,347; 3,697,574; 3,725,277; 3,725,480; 3,726,882; 4,454,059; 3,329,658; 3,449,250; 3,519,565; 3,666,730; 3,687,849; 3,702,300; 4,100,082; and 5,705,458. Further descriptions of dispersants that may be used herein can be found, for example, in European patent applications 0 471 071 and 0 451 380, which are incorporated herein by reference.

[0378] Hydrocarbon-substituted succinic acids and hydrocarbon-substituted succinic anhydride derivatives are available dispersants. In particular, succinimides, succinates, or succinate amides prepared by reacting hydrocarbon-substituted succinic acids or anhydrides (typically having at least 25 carbon atoms in the hydrocarbon substituent, such as 28 to 400 carbon atoms) with at least one equivalent of a polyhydroxy or polyamino compound (such as an alkyleneamine) are especially suitable for this purpose. Hydrocarbon-substituted succinic acids and hydrocarbon-substituted succinic anhydride derivatives may have a number average molecular weight of at least 400 g / mol, such as at least 900 g / mol, such as at least 1500 g / mol, such as 400 to 4000 g / mol, such as 800 to 3000 g / mol, such as 2000 to 2800 g / mol, such as about 2100 to 2500 g / mol, and such as about 2200 to about 2400 g / mol.

[0379] The succinimides particularly suitable for use in this article are formed by a condensation reaction between 1) a hydrocarbon-substituted succinic anhydride, such as polyisobutylene succinic anhydride (PIBSA); and 2) a polyamine (PAM). Examples of suitable polyamines include: polyalkylene polyamines, polyalkylene polyamines, hydroxyl-substituted polyamines, polyoxyethylene polyamines, and combinations thereof. Examples of polyamines include tetraethylenepentamine, pentaethylenehexamine, tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), N-phenyl-p-phenylenediamine (ADPA), and other polyamines having an average of 5, 6, 7, 8, or 9 nitrogen atoms per molecule. Mixtures in which the average number of nitrogen atoms per polyamine molecule is greater than 7 are generally referred to as heavy polyamines or H-PAM and are available by trade names such as HPA™ and HPA-X™ from Dow Chemical, and by E-100™ from Huntsman Chemical, etc. Examples of hydroxylated polyamines include N-hydroxyalkyl-alkylene polyamines, such as N-(2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)piperazine, and / or N-hydroxyalkylated alkylene diamines of the type described, for example, in U.S. Patent No. 4,873,009. Examples of polyoxyethylene polyamines include polyoxyethylene and / or polyoxypropylene diamines and triamines (and their co-oligomers) having an average Mn of about 200 to about 5000 g / mol. Products of this type are available under the trade name Jeffamine™. Representative examples of available succinimides are shown in U.S. Patent Nos. 3,087,936; 3,172,892; 3,219,666; 3,272,746; 3,322,670; 3,652,616; 3,948,800; and 6,821,307; and Canadian Patent No. 1,094,044.

[0380] The dispersant may comprise one or more optional boronized higher molecular weight (Mn 1600 g / mol or greater, such as 1800 to 3000 g / mol) succinimides and one or more optional boronized lower molecular weight (Mn less than 1600 g / mol) succinimides, wherein the higher molecular weight may be 1600 to 3000 g / mol, such as 1700 to 2800 g / mol, such as 1800 to 2500 g / mol, such as 1850 to 2300 g / mol; and the lower molecular weight may be 600 to less than 1600 g / mol, such as 650 to 1500 g / mol, such as 700 to 1400 g / mol, such as 800 to 1300 g / mol, such as 850 to 1200 g / mol, such as 900 to 1150 g / mol, such as 900 to 1000 g / mol. Higher molecular weight succinimid dispersants may be present in the lubricating composition in amounts of 0.5 to 10% by mass, or 0.8 to 6% by mass, or 1.0 to 5% by mass, or 1.5 to 5% by mass, or 1.5 to 4.0% by mass; lower molecular weight succinimid dispersants may be present in the lubricating composition in amounts of 1 to 5% by mass, or 1.5 to 4.8% by mass, or 1.8 to 4.6% by mass, or 1.9 to 4.6% by mass, or 2% by mass or more, such as 2 to 5% by mass. The lower molecular weight succinimid may differ from the higher molecular weight succinimid by 500 g / mol or more, such as 750 g / mol or more, such as 1000 g / mol or more, such as 1200 g / mol or more, such as 500 to 3000 g / mol, such as 750 to 2000 g / mol, or such as 1000 to 1500 g / mol.

[0381] Succinates that can be used as dispersants include those formed by condensation reactions between hydrocarbon-substituted succinic anhydrides and alcohols or polyols. For example, the condensation product of hydrocarbon-substituted succinic anhydrides and pentaerythritol is a usable dispersant.

[0382] The succinate amides available herein are formed via a condensation reaction between a hydrocarbon-substituted succinic anhydride and an alkanolamine. Suitable alkanolamines include ethoxylated polyalkyl polyamines, propoxylated polyalkyl polyamines, and polyalkenyl polyamines, such as polyethylene polyamines and / or propoxylated hexamethylenediamines. Representative examples are shown in U.S. Patent No. 4,426,305.

[0383] Hydrocarbon-bridged aryloxy alcohol esters of hydrocarbon-substituted succinic anhydrides (such as PIBSA) may also be used as dispersants herein. Information on such dispersants can be found in U.S. Patent No. 7,485,603, particularly columns 2, lines 65 through 6, lines 22 and 23, lines 40 through 26, lines 46. Specifically, methylene-bridged naphthoxyethanol (i.e., 2-hydroxyethyl-1-naphthol ether (or hydroxyl-terminated naphthol ethylene oxide oligomer ether)) PIBSA esters may be used herein.

[0384] The molecular weights of the hydrocarbon-substituted succinic anhydrides used in the preceding paragraphs are typically 350 to 4000 g / mol, such as 400 to 3000 g / mol, 450 to 2800 g / mol, or 800 to 2500 g / mol. The aforementioned (poly)alkenyl succinic acid derivatives can undergo post-reaction reactions with various reagents, such as sulfur, oxygen, formaldehyde, and carboxylic acids like oleic acid.

[0385] The dispersant may be present in the lubricant in an amount of 0.1% to 20% by mass, such as 0.2% to 15% by mass, such as 0.25% to 10% by mass, such as 0.3% to 5% by mass, such as 1.0% to 3.0% by mass of the lubricating oil composition.

[0386] The aforementioned (poly)alkenyl succinic acid derivatives can also be post-reacted with boron compounds such as boric acid, borate esters or highly borated dispersants to form borated dispersants that typically have a reaction product of about 0.1 to about 5 moles of boron per mole of dispersant.

[0387] Dispersants that may be used in this article include boronized succinimides, including those derivatives from monosuccinimides, bissuccinimides, and / or mixtures of monosuccinimides and bissuccinimides, wherein the alkyl succinimides are derived from hydrocarbylene groups having about 300 to about 5000 g / mol, or about 500 to about 3000 g / mol, or about 1000 to about 2000 g / mol of Mn, such as polyisobutylene, or mixtures of such hydrocarbylene groups typically having high-terminal vinyl groups.

[0388] The boron-containing dispersant may be present in the lubricating composition at 0.01% to 20% by mass, or 0.1% to 15% by mass, or 0.1% to 10% by mass, or 0.5% to 8% by mass, or 1.0% to 6.5% by mass, or 0.5% to 2.2% by mass.

[0389] The boron-containing dispersant may be present in the composition in amounts of 15 ppm to 2000 ppm, or 25 ppm to 1000 ppm, or 40 ppm to 600 ppm, or 80 ppm to 350 ppm of boron.

[0390] Borated dispersants can be used in combination with non-borated dispersants and can be the same as or different from the non-borated dispersants. In one embodiment, the lubricating composition may include one or more boron-containing dispersants and one or more non-borated dispersants, wherein the total amount of the dispersants may be from 0.01% to 20% by mass, or 0.1% to 15% by mass, or 0.1% to 10% by mass, or 0.5% to 8% by mass, or 1.0% to 6.5% by mass, or 0.5% to 2.2% by mass of the lubricating composition, and wherein the ratio of boron-containing dispersant to non-borated dispersant may be from 1:10 to 10:1 (weight:weight), or 1:5 to 3:1, or 1:3 to 2:1.

[0391] The dispersant may contain one or more borated or unborated poly(alkenyl)succinimides, wherein the polyalkenyl group is derived from polyisobutylene and the imide is derived from a polyamine ("PIBSA-PAM").

[0392] The dispersant may comprise one or more PIBSA-PAMs, wherein the PIB is derived from polyisobutylene having a Mn concentration of 600 to 5000, such as 700 to 4000, such as 800 to 3000, such as 900 to 2500 g / mol, and the polyamine is derived from hydrocarbon-substituted polyamines such as tetraethylenepentamine, pentaethylenehexamine, tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), N-phenyl-p-phenylenediamine (ADPA), and other polyamines having an average of 5, 6, 7, 8, or 9 nitrogen atoms per molecule. The dispersant may be boronized, typically at a level of up to 4% by mass, such as 1 to 3% by mass. The dispersant may comprise one or more boronized PIBSA-PAMs and one or more non-boronized PIBSA-PAMs. The dispersant may comprise one or more borated PIBSA-PAMs derived from PIBs having 700 to 1800 g / mol (e.g., 800 to 1500 g / mol) of Mn, and one or more non-borated PIBSA-PAMs derived from PIBs having greater than 1800 to 5000 g / mol (e.g., 2000 to 3000 g / mol) of Mn.

[0393] The dispersant may comprise PIBSA derived from PIB having 700 to 5000 g / mol (e.g., 800 to 3000 g / mol) of Mn and one or more borated or non-borated PIBSA-PAM derived from PIB having 700 to 5000 g / mol of Mn.

[0394] The dispersant may comprise PIBSA derived from PIB having 700 to 5000 g / mol (e.g., 800 to 3000 g / mol) of Mn, one or more borated PIBSA-PAM derived from PIB having 700 to 1800 g / mol (e.g., 800 to 1500 g / mol) of Mn, and one or more non-borated PIBSA-PAM derived from PIB having greater than 1800 to 5000 g / mol (e.g., 2000 to 3000 g / mol) of Mn. The dispersant may comprise PIBSA derived from PIB having 700 to 5000 g / mol (e.g., 800 to 3000 g / mol) of Mn, one or more non-boronized PIBSA-PAM derived from PIB having 700 to 1800 g / mol (e.g., 800 to 1500 g / mol) of Mn, and one or more boronized PIBSA-PAM derived from PIB having greater than 1800 to 5000 g / mol (e.g., 2000 to 3000 g / mol) of Mn.

[0395] The dispersant may contain one or more borated or non-borated PIBSA-PAM and one or more hydrocarbon-bridged aryloxy alcohols of PIBSA ester.

[0396] The dispersant may contain one or more borated PIBSA-PAM and one or more non-borated PIBSA-PAM.

[0397] The dispersant may comprise one or more optional boronized higher molecular weight (Mn 1600 g / mol or greater, such as 1800 to 3000 g / mol) PIBSA-PAM and one or more optional boronized lower molecular weight (Mn less than 1600 g / mol) PIBSA-PAM, wherein the higher molecular weight may be 1600 to 3000 g / mol, such as 1700 to 2800 g / mol, such as 1800 to 2500 g / mol, such as 1850 to 2300 g / mol; and the lower molecular weight may be 600 to less than 1600 g / mol, such as 650 to 1500 g / mol, such as 700 to 1400 g / mol, such as 800 to 1300 g / mol, such as 850 to 1200 g / mol, such as 900 to 1150 g / mol, such as 900 to 1000 g / mol. Higher molecular weight PIBSA-PAM dispersants may be present in the lubricating composition in amounts of 0.5 to 10% by mass, or 0.8 to 6% by mass, or 1.0 to 5% by mass, or 1.5 to 5% by mass, or 1.5 to 4.0% by mass; lower molecular weight PIBSA-PAM dispersants may be present in the lubricating composition in amounts of 1 to 5% by mass, or 1.5 to 4.8% by mass, or 1.8 to 4.6% by mass, or 1.9 to 4.6% by mass, or 2% by mass or more, such as 2 to 5% by mass.

[0398] Mannich base dispersant

[0399] Mannich base dispersants used herein are typically produced by the reaction of an amine component, a hydroxy aromatic compound (substituted or unsubstituted, such as alkyl-substituted), such as alkylphenols, and an aldehyde, such as formaldehyde. See U.S. Patent Nos. 4,767,551 and 10,899,986. Processing aids and catalysts, such as oleic acid and sulfonic acid, may also be part of the reaction mixture. Representative examples are shown in U.S. Patent Nos. 3,697,574; 3,703,536; 3,704,308; 3,751,365; 3,756,953; 3,798,165; 3,803,039; 4,231,759; 9,938,479; 7,491,248; and 10,899,986 and PCT Publication No. WO 01 / 42399.

[0400] polymethacrylate or polyacrylate derivative dispersants

[0401] Polymethacrylate or polyacrylate derivatives are another class of dispersants that can be used herein. These dispersants are typically prepared by reacting a nitrogen-containing monomer with a methacrylate or acrylate containing 5-25 carbon atoms in its ester group. Representative examples are shown in U.S. Patent Nos. 2,100,993 and 6,323,164. Polymethacrylate and polyacrylate dispersants are typically of low molecular weight.

[0402] The lubricating compositions disclosed herein typically contain 0.1% to 20% by mass, such as 0.2% to 15% by mass, such as 0.25% to 10% by mass, such as 0.3% to 5% by mass, or 2.0% to 4.0% by mass of a lubricating oil composition. Alternatively, the dispersant may be present in 0.1% to 5% by mass, or 0.01% to 4% by mass of the lubricating composition.

[0403] For further information on dispersants that may be used in this document, see U.S. Patent No. 10,829,712, column 13, line 36 through column 16, line 67, and U.S. Patent No. 7,485,603, column 2, line 65 through column 6, line 22, column 8, line 25 through column 14, line 53, and column 23, line 40 through column 26, line 46.

[0404] The compositions according to this disclosure may contain additives with different enumerated functions and also have a second effect as dispersants (e.g., the viscosity improvers described above may also have a dispersant effect). These additives are not considered dispersants when determining the amount of dispersant in the lubricating oil compositions or concentrates described herein.

[0405] J. Corrosion inhibitors / rust preventants

[0406] Corrosion inhibitors, also known as rust inhibitors or anti-rust agents, are used to mitigate the corrosion of metals and are often referred to as metal deactivators or metal passivators. Some corrosion inhibitors can also be characterized as antioxidants.

[0407] Suitable corrosion inhibitors may include nitrogen- and / or sulfur-containing heterocyclic compounds, such as triazoles (e.g., benzotriazole), substituted thiadiazoles, imidazoles, thiazoles, tetraazoles, hydroxyquinolines, oxazolines, imidazoles, thiophenes, indoles, indazoles, quinolines, benzoxazines, dithiols, oxazoles, oxatriazoles, pyridines, piperazines, triazines, and any one or more derivatives thereof. A specific corrosion inhibitor is benzotriazole with the following structure:

[0408] Where R 8 (Hydrogen) is absent or can be straight-chain or branched, saturated or unsaturated C1 to C2. 20Hydrocarbon group or substituted hydrocarbon group. It may contain a ring structure that is alkyl or aryl in nature and / or contain heteroatoms such as N, O or S. Examples of suitable compounds may include benzotriazole, alkyl-substituted benzotriazole (e.g., tolyltriazole, ethylbenzotriazole, hexylbenzotriazole, octylbenzotriazole, etc.), aryl-substituted benzotriazole, alkylaryl- or arylalkyl-substituted benzotriazole, and combinations thereof. For example, the triazole may contain benzotriazole and / or alkylbenzotriazole, wherein the alkyl group contains 1 to about 20 carbon atoms, or 1 to about 8 carbon atoms. Non-limiting examples of such corrosion inhibitors may contain benzotriazole, triazole such as tolyltriazole and / or optionally, substituted benzotriazole, such as Irgamet™ and Irgamet™ 39 available from BASF of Ludwigshafen, Germany. Preferred corrosion inhibitors may contain benzotriazole and / or tolyltriazole.

[0409] Additionally or alternatively, the corrosion inhibitor may include one or more substituted thiadiazoles with the following structures:

[0410] Where R 15 and R 16 The group is independently hydrogen or hydrocarbon, and can be aliphatic or aromatic, including cyclic, alicyclic, aralkyl, aryl, and alkylaryl groups, wherein each w is independently 1, 2, 3, 4, 5, or 6 (preferably 2, 3, or 4, such as 2). These substituted thiadiazoles are derived from the 2,5-dimercapto-1,3,4-thiadiazole (DMTD) molecule. Many derivatives of DMTD have been described in the art, and any such compound may be included in the fluid used in this disclosure. For example, U.S. Patent Nos. 2,719,125; 2,719,126; and 3,087,937 describe the preparation of various 2,5-bis-(hydrodithio)-1,3,4-thiadiazoles.

[0411] Additionally or alternatively, the corrosion inhibitor may include one or more other DMTD derivatives, such as carboxylic acid esters, wherein R 15 and R 16 It can be attached to the sulfur atom of a sulfide via a carbonyl group. The preparation of these sulfide-containing DMTD derivatives is described, for example, in U.S. Patent No. 2,760,933. DMTD derivatives prepared by the condensation of DMTD with an α-haloaliphatic carboxylic acid having at least 10 carbon atoms are described, for example, in U.S. Patent No. 2,836,564. This method produces DMTD derivatives in which R... 15 and R 16 It is HOOC-CH(R) 19 ) (R 19(It is a hydrocarbon group). DMTD derivatives, which are further prepared by amidation or esterification of these terminal carboxylic acid groups, are also available.

[0412] The preparation of 2-alkyldithio-5-mercapto-1,3,4-thiadiazole is described, for example, in U.S. Patent No. 3,663,561.

[0413] One class of DMTD derivatives may include a mixture of 2-alkyldithio-5-mercapto-1,3,4-thiadiazole and 2,5-bis-alkyldithio-1,3,4-thiadiazole. Such mixtures may be sold under the trade name HiTEC™ 4313 and are available from Afton Chemical Company.

[0414] The preparation of 2-alkyldithio-5-mercapto-1,3,4-thiadiazole is described, for example, in U.S. Patent No. 3,663,561.

[0415] Additionally or alternatively, corrosion inhibitors may include those having structure B (OR) 46 )3 trifunctional borate esters, wherein each R 46 They can be the same or different. Since this borate ester is generally ideally compatible with the non-aqueous medium of the composition, each R... 46 It may specifically contain hydrocarbon C1-C8 structural moieties. For compositions in which non-aqueous media are contained or are lubricating oil base oils, better compatibility is generally achieved, for example, when each hydrocarbon structural moieties are at least C4. Non-limiting examples of such corrosion inhibitors therefore include, but are not limited to, triethyl borate, tripropyl borate such as triisopropyl borate, tributyl borate such as tri-tert-butyl borate, tripentyl borate, trihexyl borate, trioctyl borate such as tri-(2-ethylhexyl) borate, monohexyl dibutyl borate, and combinations thereof.

[0416] When used, corrosion inhibitors may contain substituted thiadiazoles, substituted benzotriazoles, substituted triazoles, trisubstituted borate esters, or combinations thereof.

[0417] Other corrosion inhibitors that can be used to mitigate water damage may be aliphatic alkyl ethers derived from alkyl alcohols, including those with C3 to C4 carbon numbers. 50 Those alkyl alcohols have been ethoxylated, propoxylated, or butoxylated to form the corresponding aliphatic alkyl ethers. The base alcohol moiety is preferably stearyl, myristyl, or C... 11 -C 13 Hydrocarbon groups, oleyl groups, isostearyl groups, etc. Available ethoxylated alcohols include ethoxylated lauryl alcohol (such as Berol™ 1214), nonylphenol ethoxylates, C6 to C6 ethoxylated alcohols, etc. 20 Ethoxylated straight-chain alcohols and / or Surfonic™ L24-4, Huntsman.

[0418] When needed, corrosion inhibitors can be used in any effective amount, but when used, they can typically be used in amounts from about 0.001% to 5.0% by weight, for example, from 0.005% to 3.0% by weight or from 0.01% to 1.0% by weight, based on the weight of the composition. Alternatively, such additives can be used in amounts from about 0.01% to 5% by weight, preferably from about 0.01% to 1.5% by weight, based on the weight of the lubricating composition.

[0419] In some embodiments, the composition containing 3,4-oxypyridone may be substantially free of (e.g., 0, or less than 0.001% by mass, 0.0005% by mass or less, with no intentional addition and / or absolutely free of) triazoles, benzotriazoles, substituted thiadiazoles, imidazoles, thiazoles, tetrazolium, hydroxyquinoline, oxazoline, imidazoline, thiophene, indole, indazole, quinoline, benzoxazine, dithiol, oxazole, oxatriazole, pyridine, piperazine, triazine, their derivatives, combinations thereof, or all corrosion inhibitors.

[0420] The compositions according to this disclosure may contain additives with different enumerated functions and also have a secondary effect as corrosion inhibitors. These additives are not considered corrosion inhibitors when determining the amount of corrosion inhibitor in the lubricating oil compositions or concentrates described herein.

[0421] K. Anti-wear agents and zinc dihydrodithiophosphate compounds

[0422] The lubricating oil compositions disclosed herein may contain one or more anti-wear agents that reduce friction and excessive wear. Any anti-wear agent known to those skilled in the art may be used in this lubricating oil composition. Non-limiting examples of suitable anti-wear agents include dithiophosphates and / or dithiocarbamates (such as metal (e.g., Pb, Sb, Mo, etc.) salts of dithiophosphate and / or metal (e.g., Zn, Pb, Sb, Mo, etc.) salts of dithiocarbamate), metal (e.g., Zn, Pb, Sb, Mo, etc.) salts of fatty acids, boron compounds, phosphate esters, phosphites, amine salts of phosphate esters or thiophosphate esters, reaction products of dicyclopentadiene and thiophosphate, and combinations thereof.

[0423] In embodiments, the anti-wear agent is or comprises a dialkyl dithiophosphate metal salt. The metal of the dialkyl dithiophosphate metal salt can be an alkali metal or an alkaline earth metal, or aluminum, lead, tin, manganese, nickel, or copper. In some embodiments, the hydrocarbon group of the dialkyl dithiophosphate metal salt has about 3 to about 22 carbon atoms, about 3 to about 18 carbon atoms, about 3 to about 12 carbon atoms, or about 3 to about 8 carbon atoms, and can be alkyl, substituted alkyl, aryl, or substituted aryl. In embodiments, the alkyl group is straight-chain and / or branched.

[0424] Available anti-wear agents also include substituted or unsubstituted thiophosphates, whose salts include metal-containing compounds, such as metal dithiophosphate compounds selected from dialkyl-, diaryl-, and / or alkylaryl-dithiophosphates.

[0425] In the implementation scheme, the anti-wear compound may be a zinc dithiocarbamate complex, such as zinc dithiocarbamate as shown in the following formula:

[0426] Among them, each R I Independently, it is a straight-chain, cyclic, or branched, saturated or unsaturated aliphatic hydrocarbon moiety having 1 to about 10 carbon atoms, where n is 0, 1, or 2, L is a ligand saturating the coordination layer of zinc, and x is 0, 1, 2, 3, or 4. In some embodiments, the ligand L is selected from water, hydroxides, ammonia, amino groups, amide groups, alkylthiolates, halides, and combinations thereof.

[0427] Anti-wear additives that can be used in this article also include boron-containing compounds such as borate esters, boronized fatty amines, boronized epoxides, alkali metal (or mixed alkali metal or alkaline earth metal) borates and boronized perbasal metal salts.

[0428] Anti-wear additives are typically used in amounts from about 0.01% by mass to about 5% by mass, from about 0.05% by mass to about 3% by mass, from about 0.4% by mass to about 1.2% by mass, from about 0.1% by mass to about 1% by mass, preferably from about 0.5% by mass to about 1.0% by mass, more preferably from about 0.6% by mass to about 0.8% by mass, although more or less may generally be used more or less.

[0429] The compositions according to this disclosure may contain additives with different enumerated functions and also have a secondary effect as anti-wear agents (e.g., component B, the zinc diphosphate compound described above, may also have an anti-wear effect). These additives are not considered anti-wear agents when determining the amount of anti-wear agent in the lubricating oil compositions or concentrates described herein.

[0430] In the embodiments, the one or more alkyl zinc dithiophosphate compounds are dialkyl zinc dithiophosphate compounds (ZDDP), such as dialkyl zinc dithiophosphate compounds. The alkyl groups in the alkyl zinc dithiophosphate compound (such as dialkyl zinc dithiophosphate compound) can be the same or different alkyl groups. The alkyl groups in the dialkyl zinc dithiophosphate compound can be the same or different alkyl groups.

[0431] The dialkyl dithiophosphate zinc compounds that can be used in this article are generally derived from the formula Zn[SP(S)(OR]]. 1 (OR) 2 )]2 indicates that R1 and R 2 Independently for C 1-30 Hydrocarbon groups, such as C 1-18 Hydrocarbon groups, such as C1-C 18 Alkyl and / or C1-C 24 alkyl-aryl, and / or C 5-30 Aryl, such as C2-C 12 Alkyl or aryl (such as C) 4- C 12 Alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl, phenyl, naphthyl, alkyl-substituted phenyl groups or their isomers. Hydrocarbon groups (such as alkyl groups) can be straight-chain (linear), cyclic and / or branched.

[0432] For ease of reference, when a zinc dithiophosphate compound (such as dialkyl zinc dithiophosphate and dialkyl zinc dithiophosphate) is referred to as being derived from one or more alcohols, it should be understood that it is the hydrocarbon group (such as alkyl) that is derived from the alcohol. Zinc dithiophosphate compounds (such as dialkyl zinc dithiophosphate) can be derived from primary alcohols, secondary alcohols, or mixtures thereof. In embodiments, the hydrocarbon group of zinc dithiophosphate is derived from one or more primary alcohols, one or more secondary alcohols, and / or a combination of primary and secondary alcohols. Specifically, C1-C 18 Primary alcohols, C1-C 18 Mixtures of primary alcohols, C1-C 18 Secondary alcohols, C1-C 18 Mixtures of secondary alcohols, and / or C1-C 18 Primary alcohols and C1-C 18 Mixtures of secondary alcohols can be used to prepare the hydrocarbon-based zinc dithiophosphate compounds described herein.

[0433] Alcohols used to generate dialkyl dithiophosphate zinc compounds include those with the following hydrocarbon groups: R z -OH represents an alcohol, where R... z It is one or more of the following groups: C 1-30 Hydrocarbon groups, such as C 1-18 Hydrocarbon groups, such as C1-C 18 Alkyl and / or C1-C 24 alkyl-aryl, and / or C 5-30 Aryl, such as C2-C 12 Alkyl or aryl (such as C) 4- C 12Alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl, phenyl, naphthyl, alkyl-substituted phenyl groups or their isomers, wherein the hydrocarbon group (such as alkyl) can be straight-chain (linear), cyclic, and / or branched. In a preferred embodiment, the alcohol used to generate the dialkyl dithiophosphate zinc compound includes, but is not limited to, one or more of ethanol, 2-propanol, butanol, sec-butanol, pentanol, hexanol such as 4-methyl-2-pentanol, n-hexanol, n-octanol, 2-ethylhexanol, alkylaryl alcohols (such as alkylated phenols), etc.

[0434] Available zinc dithiophosphates include those from The Lubrizol Corporation under the trade names "LZ™ 677A", "LZ™ 1095" and "LZ™ 1371", Chevron Oronite under the trade name "OLOA™ 262", and Afton Chemical under the trade name "HiTEC™ 7169".

[0435] Dialkyl zinc dithiophosphate compounds (such as dialkyl zinc dithiophosphate compounds, such as dialkyl zinc dithiophosphate compounds) are typically used in amounts from about 0.01% by mass to about 5% by mass, from about 0.05% by mass to about 3% by mass, from about 0.4% by mass to about 1.2% by mass, from about 0.1% by mass to about 1.0% by mass, preferably from about 0.5% by mass to about 1.0% by mass, more preferably from about 0.6% by mass to about 0.8% by mass, based on the total weight of the lubricating composition, although more or less may generally be used advantageously.

[0436] In the embodiments, the dialkyl dithiophosphate zinc compound includes secondary ZDDP (i.e., derived from secondary alcohols) and is present in the lubricating oil composition in an amount of 0.1 to 5.0% by weight of the total weight of the lubricating composition.

[0437] In an embodiment, the dialkyl dithiophosphate zinc compound comprises a mixture of primary and secondary ZDDPs (i.e., a mixture derived from primary and secondary alcohols, or a mixture of ZDDPs derived from primary alcohols and ZDDPs derived from secondary alcohols) and is present in the lubricating oil composition at about 0.1 to 5.0% by weight of the total weight of the lubricating composition.

[0438] Examples of dialkyl dithiophosphate zinc compounds that may be used in this article include one or more compounds represented by the following general formula:

[0439] In the above formula, R 7 and R 8Each of these terms independently represents a primary or secondary alkyl group having 3 to 22 carbon atoms, or an alkylaryl group substituted with an alkyl group having 3 to 18 carbon atoms. Examples of primary or secondary alkyl groups having 3 to 22 carbon atoms include primary propyl or secondary propyl, primary butyl or secondary butyl, primary pentyl or secondary pentyl, primary hexyl or secondary hexyl, primary heptyl or secondary heptyl, primary octyl or secondary octyl, primary nonyl or secondary nonyl, primary decyl or secondary decyl, primary dodecyl or secondary dodecyl, primary tetradecyl or secondary tetradecyl, primary hexadecyl or secondary hexadecyl, primary octadecyl or secondary octadecyl, primary eicosyl or secondary eicosyl, etc. Examples of alkylaryl groups substituted with an alkyl group having 3 to 18 carbon atoms include propylphenyl, pentylphenyl, octylphenyl, nonylphenyl, dodecylphenyl, etc.

[0440] The lubricating compositions according to this disclosure may further comprise one or more additives, such as detergents, friction modifiers, antioxidants, pour point depressants, defoamers, viscosity modifiers, dispersants, corrosion inhibitors, anti-wear agents, extreme pressure additives, demulsifiers, sealing compatibilizers, additive diluents, base oils, etc. Specific examples of such additives are described, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, 3rd edition, Volume 14, pp. 477-526, and several will be discussed in more detail below.

[0441] L. Demulsifier

[0442] Demulsifiers that may be used herein include trialkyl phosphates, and various polymers and copolymers of ethylene glycol, ethylene oxide, propylene oxide, and mixtures thereof. Additionally, demulsifiers that may be used herein include those described in U.S. Patent No. 10,829,712 (column 20, lines 34-40). Typically, small amounts of demulsifying components may be used herein. Preferred demulsifying components are described in European Patent No. 330,522. These are obtained by reacting an alkylene oxide with an adduct obtained from the reaction of a diepoxide with a polyol. Such additives may be used in amounts from about 0.001 to 5% by mass, preferably from about 0.01 to 2% by mass.

[0443] M. Sealing compatibilizer

[0444] Other optional additives include sealing compatibilizers such as organophosphates, aromatic esters, aromatic hydrocarbons, esters (e.g., butyl benzyl phthalate), and polybutenyl succinic anhydride. Such additives can be used in amounts from about 0.001 to 5% by mass, preferably from about 0.01 to 2% by mass. In embodiments, the sealing compatibilizer is a sealing swelling agent, such as PIBSA (polyisobutylene succinic anhydride), or a sulfolene derivative, such as ExxonMobil Necton-37™ (FN 1380) and ExxonMobil Mineral Seal Oil™ (FN 3200).

[0445] N. Extreme pressure agent

[0446] The lubricating oil composition disclosed herein may contain one or more extreme pressure agents that prevent seizing of sliding metal surfaces under extreme pressure conditions. Any extreme pressure agent known to those skilled in the art may be used in this lubricating oil composition. Typically, extreme pressure agents are compounds that can chemically bond with metals to form a surface film that prevents asperities on relative metal surfaces from welding under high loads. Non-limiting examples of suitable extreme pressure agents include sulfurized animal or vegetable fats or oils, sulfurized animal or vegetable fatty acid esters, fully or partially esterified esters of trivalent or pentavalent phosphorus-containing acids, sulfurized alkenes, dialkyl polysulfides, sulfurized Diels-Alder adducts, sulfurized dicyclopentadiene, sulfurized or co-sulfurized mixtures of fatty acid esters and monounsaturated alkenes, co-sulfurized blends of fatty acids, fatty acid esters and α-olefins, functionally substituted dialkyl polysulfides, thioaldehydes, thioketones, epithiolated compounds, thioacetal derivatives, co-sulfurized blends of terpenes and acyclic alkenes, and polysulfide olefin products, amine salts of phosphate esters or thiophosphate esters, and combinations thereof. The amount of the extreme pressure agent may be from about 0.01% by mass to about 5% by mass, from about 0.05% by mass to about 3% by mass, or from about 0.1% by mass to about 1% by mass, based on the total weight of the lubricating oil composition.

[0447] O. Non-base oil unsaturated hydrocarbons

[0448] The lubricating oil compositions disclosed herein may contain one or more unsaturated hydrocarbons. These unsaturated hydrocarbons are distinct from any base oils (Group I, II, III, IV, and / or V lubricating oil base oils) and / or viscosity improvers that may be present in the composition, and always possess at least one unsaturated hydrocarbon per molecule (typically only one in the case of linear α-olefins or LAOs). While not bound by theory, it is believed that unsaturation can provide antioxidant and / or sulfur-capturing functions, which may complement and / or replace one or more antioxidant additives and / or one or more corrosion inhibitor additives; however, unsaturated hydrocarbons (LAOs) generally do not provide the sole antioxidant and sole corrosion inhibitor functions in lubricating oil compositions. Non-limiting examples of unsaturated hydrocarbons may include one or more unsaturated C... 12 -C 60 Hydrocarbons (such as C) 12 -C 48 Hydrocarbons, C 12 -C 36 Hydrocarbons, C 12 -C 30 Hydrocarbons or C 12 -C 24 Hydrocarbons). Other non-limiting examples of unsaturated hydrocarbons may include polyisobutylene oligomers / polymers and / or blends thereof that retain (or are modified post-polymerization to exhibit) (near) terminal unsaturation. When present, unsaturated hydrocarbons may be present in amounts of 0.01 to 5% by mass (particularly 0.1 to 3% by mass, or 0.1 to 1.5% by mass) based on the total weight of the lubricating oil composition.

[0449] In embodiments, the LOC comprises one or more α-olefins having 8 to 36 carbon atoms, such as 8 to 24 carbon atoms, more preferably 10 to 20 carbon atoms, more preferably 12 to 20 carbon atoms, and even more preferably 14 to 18 carbon atoms, such as linear α-olefins (LAO). In embodiments, the LOC comprises a mixture of linear α-olefins having 8 to 24 carbon atoms, more preferably 10 to 20 carbon atoms, more preferably 12 to 20 carbon atoms, and even more preferably 14 to 18 carbon atoms. In embodiments, the LOC comprises a mixture of linear α-olefins having 14 or more carbon atoms. In embodiments, the LOC may comprise 0.001 to 15% by weight (particularly 0.15 to 10% by weight, or 0.20% to 5% by weight, or 0.25% to 2% by weight) of one or more C8 to C96 olefins based on the weight of the lubricating composition. 36 α-olefins. In embodiments, the LOC may comprise 0.001 to 15% by weight (particularly 0.15 to 10% by weight, or 0.20% to 5% by weight, or 0.25% to 2% by weight) of one, two, three, four, five or more C8 to C9 olefins based on the weight of the lubricating composition. 36α-olefins, such linear α-olefins having 8 to 24 carbon atoms, more preferably 10 to 20 carbon atoms, more preferably 12 to 20 carbon atoms, and more preferably 14 to 18 carbon atoms.

[0450] When a lubricating oil composition contains one or more of the additives discussed above, the additives are typically incorporated into the composition in an amount sufficient to enable it to perform its intended function. Typical amounts of such additives that can be used in this disclosure, particularly for crankcase lubricants, are shown in the table below.

[0451] It should be noted that many additives are shipped by the additive manufacturer as concentrates containing one or more additives, along with a certain amount of base oil or other diluent. Therefore, the weights in the table below, as well as other quantities mentioned herein, refer to the amount of the active ingredient (i.e., the non-diluent portion of that ingredient). The weight percentages (mass %) shown below are based on the total weight of the lubricating oil composition.

[0452]

[0453] The additives mentioned above are typically commercially available materials. These additives can be added individually, but are usually pre-combined in additive packages available from lubricant additive suppliers. Additive packages with various components, proportions, and properties are available, and the selection of a suitable additive package will take into account the intended use of the final composition.

[0454] fuel composition

[0455] This disclosure also relates to a method for lubricating a hydrogen-fired internal combustion engine in a passenger or commercial vehicle during engine operation, comprising: (i) providing the vehicle crankcase lubricating oil composition described herein to the crankcase of the vehicle hydrogen internal combustion engine; (ii) providing hydrogen-containing fuel in the vehicle hydrogen internal combustion engine; and (iii) burning the fuel in the vehicle hydrogen internal combustion engine, such as a spark-ignition or compression-ignition two-stroke or four-stroke reciprocating engine.

[0456] This disclosure also relates to a fuel composition comprising the lubricating oil composition described herein and a hydrogen-containing fuel, wherein the hydrogen fuel may include hydrogen selected from green hydrogen, blue hydrogen, gray hydrogen, brown hydrogen, or combinations thereof. The hydrogen-containing fuel may optionally include other non-hydrogen-containing fuels, including but not limited to natural gas, propane, gasoline, renewable fuels, or combinations thereof. The renewable fuel component may be made from vegetable oils (such as palm oil, rapeseed oil, soybean oil, jatropha oil), microbial oils (such as algal oil), animal fats (such as edible oils, animal fats, and / or fish fats), and / or biogas. Renewable fuels refer to biofuels made from biological resources formed through contemporary biological processes. In one embodiment, the renewable fuel component is made using a hydrotreating process. Hydrotreating involves various reactions in which molecular hydrogen reacts with other components, or components undergo molecular transformation in the presence of molecular hydrogen and a solid catalyst. These reactions include, but are not limited to, hydrogenation, hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrocracking, and isomerization. Renewable fuel components can have different distillation ranges to provide the desired properties for the component according to its intended use.

[0457] use

[0458] The lubricating compositions disclosed herein can be used to lubricate mechanical engine components by adding lubricants, particularly in hydrogen-fired internal combustion engines, such as spark-ignition or compression-ignition two-stroke or four-stroke reciprocating hydrogen-fired engines. Typically, they are crankcase lubricants, such as passenger car engine oils or heavy-duty engine lubricants.

[0459] In particular, the lubricating compositions disclosed herein are suitable for the lubrication of the crankcase of compression-ignition hydrogen-fired internal combustion engines, such as heavy-duty engines.

[0460] In particular, the lubricating composition disclosed herein is suitable for the lubrication of the crankcase of a spark-ignition turbocharged hydrogen-fired internal combustion engine.

[0461] In the implementation scheme, the lubricating oil disclosed herein is used in a spark-assisted high-compression hydrogen-fired internal combustion engine.

[0462] In embodiments, the lubricating compositions disclosed herein are suitably used for the lubrication of the crankcase of a hydrogen-fired engine in a heavy-duty vehicle (i.e., a heavy-duty vehicle with a gross vehicle weight rating of 10,000 pounds or more).

[0463] In particular, the lubricant formulations disclosed herein are especially suitable for use in compression-ignition hydrogen-fired internal combustion engines, i.e., heavy-duty engines, that use low-viscosity oils, such as API FA-4 and future oil categories where wear protection of valve mechanisms becomes challenging.

[0464] The lubricating compositions described herein can also be used as lubricants for natural gas engines [for example, natural gas is the fuel on which the engine runs, commonly referred to as GEO or (natural) gas engine oil].

[0465] The lubricating compositions described herein can be used to lubricate mechanical engine components by adding a lubricant, particularly in hydrogen-fired internal combustion engines, such as spark-ignition or compression-ignition two-stroke or four-stroke reciprocating engines.

[0466] The lubricating composition described herein is particularly suitable for hydrogen-fired internal combustion engines that are prone to piston-liner wear due to prolonged operation, thus extending engine life.

[0467] The lubricating composition described herein can also be used as a lubricant for ammonia-fueled engines, etc. [For example, ammonia fuel (or a combination of hydrogen and ammonia fuel, or a combination of ammonia and hydrocarbon fuel, such as gasoline or diesel fuel) is the fuel burned in the internal combustion engine].

[0468] This disclosure further relates to the following additional implementation schemes: Additional implementation plans / projects 1. A method for reducing abnormal combustion events during engine operation of a hydrogen-fired internal combustion engine (HICE), comprising: a) providing the hydrogen-fired internal combustion engine with a lubricating oil composition comprising or a mixture of the following components: i) a base oil having a viscosity KV100 of less than or equal to 12 cSt and an amount of greater than 50% by weight of the composition, and comprising Group I base oil, Group II base oil, Group III base oil, Group IV base oil, or a combination thereof; ii) an over-alkaline metal-containing detergent comprising an over-alkaline metal salicylate detergent, an over-alkaline metal phenolate detergent, or a combination thereof, having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500 and being contained at a treatment level providing the composition with a total metal content between 100 and 5000 ppm by weight and a total soap content between 0.15% by weight and 8.0% by weight; and iii) The lubricating oil composition has a total sulfate ash content of less than or equal to 2.0% by weight, a total phosphorus level of less than or equal to 0.120% by weight, and an SAE viscosity grade of 25W-X, 20W-X, 15W-X, 10W-X, 5W-X, or 0W-X, wherein X represents any one of 8, 12, 16, 20, 30, 40, 50, or 60; b) supplying hydrogen-containing fuel to the hydrogen-fired internal combustion engine; and c) burning the fuel in the hydrogen-fired internal combustion engine.

[0469] 2. The method of Project 1, further comprising: d) measuring the number of abnormal pre-ignition events during combustion (1000 rpm, 12 bar BMEP and 1.85 air-fuel ratio (AFR)), wherein the number of pre-ignition events per 1,000 engine cycles is less than or equal to 10.

[0470] 3. The method of Project 1-2, further comprising: d) measuring the number of abnormal pre-ignition events during combustion (1200 rpm, 18 bar BMEP and 2.05 air-fuel ratio (AFR)) and wherein the number of pre-ignition events per 1,000 engine cycles is less than or equal to 5.

[0471] 4. The methods of Projects 1-3, wherein the frequency of abnormal pre-ignition events during combustion in a hydrogen-fired internal combustion engine (HICE) operating at 100% load is reduced by at least 20% compared to comparable lubricating oil compositions that do not include the aforementioned overly alkaline metal-containing detergent.

[0472] 5. The methods of Projects 1-4, wherein the metal of the peralkaline metal salicylate detergent, the peralkaline metal phenolate detergent, or a combination thereof is selected from calcium, magnesium, sodium, potassium, and lithium.

[0473] 6. The methods of Items 1-5, wherein the superalkaline metal-containing detergent is a superalkaline calcium salicylate detergent.

[0474] 7. The methods of items 1-6, wherein the base oil comprises a Group I base oil, a Group II base oil, or a combination thereof and is contained in greater than 80% by weight of the composition.

[0475] 8. The method of Project 7, wherein the base oil is substantially free of Group IV base oils.

[0476] 9. The method of Project 8, wherein the base oil is substantially free of Group III base oils.

[0477] 10. The methods of items 1-9, wherein the lubricating oil composition further comprises a dispersant, a dispersant viscosity improver, or a combination thereof.

[0478] 11. The method of item 10, wherein the dispersant or dispersant viscosity improver comprises an amide, an imide, and / or an ester-functionalized, partially or fully saturated C-containing... 4-5 Polymers of olefins having: i) a Mw / Mn ratio of less than 2, ii) a functionality distribution (Fd) value of 3.5 or less, and iii) a pre-functionalized polymer Mn of 10,000 g / mol or greater.

[0479] 12. The method of Item 10, wherein the dispersant comprises one or more optionally boronized higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersants (Mn 1600 g / mol or greater), one or more optionally boronized lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersants (Mn less than 1600 g / mol), or a combination thereof, and wherein the treatment level of the dispersant is 1.0 to 15.0 by weight of the lubricating oil composition.

[0480] 13. The method of item 12, wherein the higher molecular weight PIBSA-PAM is boronized, the lower molecular weight PIBSA-PAM is boronized or a combination thereof, and is contained at a treatment level of providing the lubricating oil composition with 20 ppm to 700 ppm by weight of boron.

[0481] 14. The method of items 1-13, wherein the lubricating oil composition further comprises a corrosion inhibitor selected from substituted thiadiazoles, substituted benzotriazoles, substituted triazoles, trisubstituted borate esters, ethoxylated lauryl alcohol, nonylphenol ethoxylates, C6 to C6... 20 Ethoxylated straight-chain alcohols or combinations thereof, and contained at a treatment level of 0.001% to 5.0% by weight of the lubricating oil composition.

[0482] 15. The method of items 1-14, wherein the lubricating oil composition further comprises one or more zinc dialkyl dithiophosphate (ZDDP) compounds; and wherein the treatment level of said one or more ZDDP compounds is from about 0.4% by weight to about 1.5% by weight of the lubricating oil composition.

[0483] 16. The method of Item 15, wherein the hydrocarbon group of the zinc dithiophosphate is derived from one or more primary alcohols, one or more secondary alcohols, or a combination of primary and secondary alcohols.

[0484] 17. The method of items 1-16, wherein the lubricating oil composition further comprises one or more of the following components: one or more functional polymers; one or more friction modifiers; one or more antioxidants; one or more pour point depressants; one or more defoamers; one or more viscosity modifiers; one or more other dispersants; one or more other over-alkaline metal-containing detergents; one or more corrosion inhibitors; one or more rust inhibitors; one or more sealing swelling agents; and / or one or more anti-wear agents.

[0485] 18. The method of Items 1-17, wherein the hydrogen comprises green hydrogen, blue hydrogen, gray hydrogen, brown hydrogen, or a combination thereof.

[0486] 19. The methods of items 1-18, wherein the fuel further comprises natural gas, propane, gasoline for vehicles, renewable fuels, or combinations thereof.

[0487] 20. The method of Items 1-19, wherein the fuel supplied to the engine comprises at least 25% by mass hydrogen based on the fuel mass.

[0488] 21. The method of Items 1-20, wherein the fuel supplied to the engine comprises at least 50% by mass hydrogen based on the fuel mass.

[0489] 22. The method of items 1-21, wherein the fuel supplied to the engine comprises essentially 100% by mass hydrogen based on a fuel mass meter.

[0490] 23. The method of items 1-22, wherein the hydrogen-containing fuel and the lubricating oil composition are combined in the combustion chamber of the hydrogen-fired internal combustion engine to form a fuel composition.

[0491] 24. The method of items 1-23, wherein the hydrogen-containing fuel and the lubricating oil composition are combined to form a fuel composition before being injected into the combustion chamber of the hydrogen-fired internal combustion engine (HICE).

[0492] 25. The method of Items 1-24, wherein the hydrogen-fired internal combustion engine (HICE) is spark-ignition or compression-ignition type.

[0493] 26. The method of Items 1-25, wherein the hydrogen-burning internal combustion engine is a heavy-duty or light-duty internal combustion engine.

[0494] 27. The method of Items 1-26, wherein the hydrogen-burning internal combustion engine is a stationary internal combustion engine.

[0495] 28. The method of items 1-27, further comprising providing a turbocharger or supercharger prior to the hydrogen-fired internal combustion engine.

[0496] 29. The method of Items 1-28, wherein the hydrogen-fired internal combustion engine (HICE) operates at a BMEP of 12 to 18 bar and an air-fuel ratio (AFR) of 1:1 to 3:1.

[0497] 30. The method of items 1-29, wherein the lubricating oil composition is used as a passenger vehicle lubricant (PVL), a commercial vehicle lubricant (CVL), or a marine engine lubricant.

[0498] 31. A lubricating oil composition for hydrogen-fired internal combustion engines (HICE), comprising or derived from a mixture of the following components: i) a base oil having a KV100 of less than or equal to 12 cSt and comprising more than 50% by weight of the composition, and comprising Group I, Group II, Group III, Group IV base oils or combinations thereof; ii) a super-alkaline metal-containing detergent comprising a super-alkaline metal salicylate detergent, a super-alkaline metal phenolate detergent or combinations thereof, having a total base number (KOH / g) of greater than or equal to 9 and less than or equal to 500 and providing the composition with a total base number (KOH / g) of 100 to 5000 by weight. The processing level includes total metals between 0.15 wt% and total soap between 8.0 wt%; and the lubricating oil composition has a total sulfate ash content of less than or equal to 2.0 wt%, a total phosphorus level of less than or equal to 0.120 wt%, and an SAE viscosity grade of 25W-X, 20W-X, 15W-X, 10W-X, 5W-X, or 0W-X, where X represents any one of 8, 12, 16, 20, 30, 40, 50, or 60.

[0499] 32. The composition of item 31, wherein the composition reduces the number of abnormal pre-ignition events during combustion in a hydrogen-fired internal combustion engine (HICE) measured at 1000 rpm, 12 bar BMEP and 1.85 air-fuel ratio (AFR) to less than or equal to 10 events per 1,000 engine cycles.

[0500] 33. The compositions of items 31-32, wherein the compositions reduce the number of abnormal pre-ignition events during combustion in a hydrogen-fired internal combustion engine (HICE) measured at 1200 rpm, 18 bar BMEP and 2.05 air-fuel ratio (AFR) to less than or equal to 5 events per 1,000 engine cycles.

[0501] 34. The compositions of items 31-33, wherein, compared with comparable lubricating oil compositions excluding the aforementioned overly alkaline metal-containing detergent, the compositions reduce the number of abnormal pre-ignition events during combustion in a hydrogen-fired internal combustion engine (HICE) operating at 100% load by at least 20%.

[0502] 35. The compositions of items 31-34, wherein the metal of the superalkaline metal salicylate detergent, the superalkaline metal phenolate detergent, or a combination thereof is selected from calcium, magnesium, sodium, potassium, and lithium.

[0503] 36. The compositions of items 31-35, wherein the superalkaline metal-containing detergent is a superalkaline calcium salicylate detergent.

[0504] 37. The compositions of items 31-36, wherein the base oil comprises a Group I base oil, a Group II base oil, or a combination thereof and is contained in greater than 80% by weight of the composition.

[0505] 38. The composition of item 37, wherein the base oil is substantially free of Group IV base oils.

[0506] 39. The composition of item 38, wherein the base oil is substantially free of Group III base oils.

[0507] 40. The compositions of items 31-39, wherein the lubricating oil composition further comprises a dispersant, a dispersant viscosity improver, or a combination thereof.

[0508] 41. The composition of item 40, wherein the dispersant or dispersant viscosity improver comprises an amide, an imide, and / or an ester-functionalized, partially or fully saturated C-containing... 4-5 Polymers of olefins having: i) a Mw / Mn ratio of less than 2, ii) a functionality distribution (Fd) value of 3.5 or less, and iii) Mn of the unfunctionalized polymer of 10,000 g / mol or greater.

[0509] 42. The composition of item 40, wherein the dispersant comprises one or more optionally boronized higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersants (Mn 1600 g / mol or greater), one or more optionally boronized lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersants (Mn less than 1600 g / mol), or a combination thereof, and wherein the treatment level of the dispersant is 1.0 to 15.0 by weight of the lubricating oil composition.

[0510] 43. The composition of item 42, wherein the higher molecular weight PIBSA-PAM is boronized, the lower molecular weight PIBSA-PAM is boronized, or a combination thereof, and is contained at a treatment level of providing the lubricating oil composition with 20 ppm to 700 ppm by weight of boron.

[0511] 44. The compositions of items 31-43, wherein the lubricating oil composition further comprises a corrosion inhibitor selected from substituted thiadiazoles, substituted benzotriazoles, substituted triazoles, trisubstituted borate esters, ethoxylated lauryl alcohol, nonylphenol ethoxylates, C6 to C4 compounds. 20 Ethoxylated straight-chain alcohols or combinations thereof, and contained at a treatment level of 0.001% to 5.0% by weight of the lubricating oil composition.

[0512] 45. The compositions of items 31-44, wherein the lubricating oil composition further comprises one or more zinc dialkyl dithiophosphate (ZDDP) compounds; and wherein the treatment level of said one or more ZDDP compounds is from about 0.4% by weight to about 1.5% by weight of the lubricating oil composition.

[0513] 46. ​​The composition of item 45, wherein the hydrocarbon group of the zinc dithiophosphate is derived from one or more primary alcohols, one or more secondary alcohols, or a combination of primary and secondary alcohols.

[0514] 47. The compositions of items 31-46, wherein the lubricating oil composition further comprises one or more of the following components: one or more functional polymers; one or more friction modifiers; one or more antioxidants; one or more pour point depressants; one or more defoamers; one or more viscosity modifiers; one or more dispersants; one or more other superalkaline metal detergents; one or more corrosion inhibitors; one or more rust inhibitors; one or more sealing swelling agents; and / or one or more anti-wear agents.

[0515] 48. The compositions of items 31-47, wherein the lubricating oil composition is used as a passenger vehicle lubricant (PVL), a commercial vehicle lubricant (CVL), or a marine engine oil.

[0516] 49. The compositions of items 31-48, wherein the hydrogen-burning internal combustion engine is a heavy-duty internal combustion engine, a light-duty internal combustion engine, or a stationary internal combustion engine.

[0517] 50. A method of lubricating a hydrogen-fired internal combustion engine, comprising supplying the engine with a lubricating oil composition according to any one of items 31 to 49.

[0518] 51. A concentrate comprising or a mixture thereof: 1% to 95% by weight of one or more base oils having a KV100 of 12 cSt or less and comprising Group I, Group II, Group III, Group IV base oils or combinations thereof; and 5% to 99% by weight of a super-alkaline metal-containing detergent based on the weight of the concentrate, comprising a super-alkaline metal salicylate detergent, a super-alkaline metal phenolate detergent or combinations thereof, having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500.

[0519] 52. The concentrate of item 51, further comprising combining said concentrate with a base oil to form a lubricating oil composition, said lubricating oil composition comprising: i) a base oil having a KV100 of less than or equal to 12 cSt and comprising more than 50% by weight of said composition, comprising Group I base oil, Group II base oil, Group III base oil, Group IV base oil, or a combination thereof; ii) An over-alkaline metal-containing detergent comprising an over-alkaline metal salicylate detergent, an over-alkaline metal phenolate detergent, or a combination thereof, having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500 and being contained at a treatment level providing the composition with a total metal content between 100 and 5000 ppm by weight and a total soap content between 0.15% by weight and 8.0% by weight; and wherein the lubricating oil composition has a total sulfate ash content less than or equal to 2.0% by weight, a total phosphorus level less than or equal to 0.120% by weight, and an SAE viscosity grade of 25W-X, 20W-X, 15W-X, 10W-X, 5W-X, or 0W-X, wherein X represents any one of 8, 12, 16, 20, 30, 40, 50, or 60; and wherein the composition will be used in 1000 The composition reduces the number of abnormal pre-ignition events in a hydrogen-fired internal combustion engine (HICE) during combustion, measured at rpm, 12 bar BMEP, and 1.85 air-fuel ratio (AFR), to less than or equal to 10 events per 1,000 engine cycles; and the composition further reduces the number of abnormal pre-ignition events in a hydrogen-fired internal combustion engine (HICE) during combustion, measured at 1200 rpm, 18 bar BMEP, and 2.05 air-fuel ratio (AFR), to less than or equal to 5 events per 1,000 engine cycles.

[0520] 53. The concentrate of items 51-52, wherein, compared with a comparable lubricating oil composition excluding the aforementioned overly alkaline metal-containing detergent, the composition reduces the number of abnormal pre-ignition events during combustion in a hydrogen-fired internal combustion engine (HICE) operating at 100% load by at least 20%.

[0521] The following non-limiting embodiments are provided to illustrate this disclosure.

[0522] Example

[0523] Test program

[0524] The sulfate ash (“SASH”) content was measured according to ASTM D 874.

[0525] The contents of phosphorus, calcium, zinc and silicon were measured according to ASTM D 5185.

[0526] For Example 1 below, the following method was used to measure the pre-ignition test of the lubricating oil composition regarding abnormal combustion events. Abnormal combustion events (pre-ignition) were determined as follows: Data on pre-ignition occurrence were generated using a port-fueled Daimler OM936 7.7-liter 6-cylinder engine, modified for hydrogen fuel operation with a reduced compression ratio of 10-12:1, upgraded fuel injectors and turbocharger systems, adjusted blow-by system to prevent high concentrations of hydrogen in the crankcase, and adapted to a modified CNG-based engine control system for lean-burn operation. The engine was operated at a brake mean effective pressure of 12 to 18 bar, an engine speed of approximately 1000 to 1200 rpm, and an air-fuel ratio (AFR) of 1.85 to 2.05. For each cycle (one cycle consists of two piston cycles (up / down, up / down)), peak pressure and combustion mass fraction data were collected for the duration of each cycle. Post-processing of the data includes calculating combustion parameters, verifying that operating parameters are within target limits, and detecting pre-ignition events (statistical procedures outlined below). Outliers, representing potential pre-ignition occurrences, are collected from the data. For each pre-ignition cycle, recorded data include peak pressure (PP), MFB03.5 (crank angle at 3.5% fuel mass fraction), cycle number, and engine cylinder. A cycle is considered to have a pre-ignition event if both the crank angle and cylinder PP corresponding to the fuel's MFB03.5 are outliers. Outliers are determined relative to the distribution of the specific cylinder and test segment in which they occur. The determination of "outliers" is an iterative process involving calculating the mean and standard deviation of PP and MFB03.5 for each segment and cylinder; and cycles where the parameters exceed the mean by n standard deviations. The number of standard deviations n used as the limit for determining outliers is a function of the number of cycles in the test and is calculated using the Grubbs outlier test. Outliers are identified in the severe tail of each distribution. In other words, if n is the number of standard deviations obtained from the Grubbs outlier test, then outliers for PP are considered to be values ​​exceeding the average peak pressure plus n standard deviations. Similarly, outliers for MFB03.5 are considered to be values ​​below the average MFB03.5 minus n standard deviations. Further examination of the data ensures that outliers indicate pre-ignition and not some other abnormal combustion event or electrical sensor error.

[0527] For Example 3 below, the following method was used to measure the pre-ignition test of the lubricating oil composition regarding abnormal combustion events. Abnormal combustion events (pre-ignition) were determined as follows: Pre-ignition was measured using a turbocharged, direct-injection Mercedes M274 2.0-liter 4-cylinder engine modified for hydrogen fuel operation, equipped with HDEV4 series gasoline injectors and modified ignition coils. A 3mm diameter side-mounted feed nozzle was integrated into the intake port of cylinder 4. Test oil was metered into the intake port using a peristaltic pump. The engine was operated at approximately 1550 rpm at a brake mean effective pressure of 14 bar, an air-fuel ratio (AFR) of 1.7, and an intake temperature of 75°C. The test procedure consisted of a 10-minute pre-conditioning phase without refueling, followed by a 10-minute refueling period at a rate of approximately 0.3 g / kWh, and a final 10-minute post-conditioning phase without refueling. Data collected during the duration of this test were analyzed to determine the frequency of pre-ignition occurrence. The analysis of pre-ignition frequency was conducted as follows: For each cycle (one cycle consists of two piston cycles (up / down, up / down)), peak pressure and combustion mass fraction data were collected for the duration of each cycle. Post-processing of the data included calculating combustion parameters, verifying that operating parameters were within target limits, and detecting pre-ignition events (statistical procedures outlined below). Outliers, representing potential pre-ignition events, were collected from the above data. Data from cylinder 4 was analyzed to confirm pre-ignition events caused by the test fuel. For each pre-ignition cycle, recorded data included peak pressure (PP), MFB05 (crank angle at 5% combustion mass fraction), cycle number, and engine cylinder. If both the crank angle and cylinder PP corresponding to the fuel's MFB05 were outliers, the cycle was considered to have a pre-ignition event. Outliers were determined relative to the distribution of a specific cylinder during the pre-fitting phase. Outliers for PP were identified as values ​​exceeding the average peak pressure plus 3 standard deviations. Similarly, outliers for MFB05 were identified as values ​​below the average MFB05 minus 3 standard deviations. Further examination of the data is needed to ensure that outliers indicate pre-ignition rather than some other abnormal combustion event or electrical sensor error.

[0528] As used in this article, mean effective braking pressure (BMEP) is the average effective pressure calculated from measured braking torque. The term "braking" refers to the actual torque or power available at the engine flywheel, measured on a dynamometer. Therefore, BMEP is a measure of the engine's effective power output. BMEP is defined as the work done during an engine cycle divided by the engine swept volume; engine torque normalized to engine displacement, and can be calculated using the following formula: BMEP = (2 Tn) / (Vd), where T is torque (Nm), n is the number of revolutions per cycle, and Vd is displacement (m). 3 For a 4-stroke engine, n is 2; for a 2-stroke engine, n is 1. The unit is bar.

[0529] As used herein, differential pressure scanning calorimetry (PDSC) is a test used to measure the effect of a lubricating oil composition on the pre-ignition tendency of hydrogen-containing fuels, wherein the effect is credited, debited, or neutral. The test method used to measure the oxidation onset time (in minutes) of a lubricating oil composition at 200°C is ASTM Test Method D6186. When used in hydrogen-fired internal combustion engines, a longer PDSC oxidation onset time of the lubricating oil composition is generally associated with improved pre-ignition performance (credit). See also: STLE 2019, Fuel Economy Low Viscosity Engine Oil Compatible with Low Speed ​​Pre-Ignition Performance This supports the view that higher PDSC oxidation time is associated with a lower tendency for anomalous pre-ignition events.

[0530] Example 1

[0531] Oil 1 of the present invention and Comparative Oils 1 and 2 were prepared to form the lubricating oil compositions included in Table 1 below, and pre-ignition tests were evaluated according to the above procedure. The pre-ignition tests were performed under the following conditions: 1) Condition 1 - 75,000 cycles at 1000 rpm, 1.85 AFR, and 12 bar BMEP; or 2) Condition 2 - 40,000 cycles at 1200 rpm, 2.05 AFR, and 18 bar BMEP. Data collected during the duration of the tests were analyzed to determine the frequency of pre-ignition. The data are reported in Table 1 below.

[0532] Table 1

[0533] Figure 2 This is a bar chart showing the number of pre-ignition events per 1000 cycles (measured at 1000 rpm, 12 bar BMEP and 1.85 air-fuel ratio (AFR)) of the lubricating oil composition of the present invention and a comparative lubricating oil composition in Example 1 of a hydrogen-fired internal combustion engine (HICE) versus the type of detergent soap in the lubricating oil composition, which shows a clear gain (credit) of salicylate detergent. Figure 3 Table 1 above shows the number of pre-ignition events per 1000 cycles (measured at 1200 rpm, 18 bar BMEP, and 2.05 air-fuel ratio (AFR)) of the lubricating oil composition of the present invention and a comparative lubricating oil composition in Example 1 of a hydrogen-fired internal combustion engine (HICE) versus the type of detergent soap in the lubricating oil composition, which shows a clear gain (credit) of salicylate detergent. Figure 2 and 3The results of the pre-ignition tests show that, compared to the two comparative lubricant compositions tested (no detergent, calcium sulfonate detergent), the lubricant composition of the present invention, including calcium salicylate detergent, exhibits a surprising and unexpected reduction in the number of pre-ignition events per 1000 cycles. This is the opposite of the effect seen in gasoline-fueled compression ignition engines, where metal sulfonate detergents are generally considered to provide improved low-speed pre-ignition compared to metal salicylate detergents. The inventors have unexpectedly discovered the opposite effect observed in hydrogen-fired internal combustion engines.

[0534] Example 2

[0535] Lubricating oil compositions were prepared according to Table 2 below, differing only in the inclusion of the superbasic metal detergent in the composition. Specifically, the soap type of the superbasic metal detergent (salicylate, sulfonate, phenolate) was varied, while all other components remained constant across the three oils. The lubricating oil compositions were then tested at 200°C using differential pressure scanning calorimetry according to the PDSC test procedure described above. As mentioned above, a higher oxidation induction time generally indicates a lower tendency for abnormal pre-ignition events, as described above.

[0536] Table 2

[0537] Figure 4 This is a bar graph showing the oxidation induction time at 200°C for the lubricating oil compositions of Example 2 with different soap types, measured by differential pressure scanning calorimetry (PDSC). It displays a clear gain for salicylate and phenolate detergents (of this invention) relative to sulfonate detergents (comparative). (See Table 2 above.) Figure 4 The PDSC oxidation induction time test results show that, compared with the tested comparative lubricating oil composition (calcium sulfonate detergent), the lubricating oil composition of the present invention, including calcium salicylate detergent and calcium phenolate detergent, exhibits a surprising and unexpected increase in oxidation induction time. This is contrary to the effect seen in gasoline-fueled compression ignition engines, where metal sulfonate detergents are generally considered to provide improved low-speed pre-ignition compared to metal salicylate and metal phenolate detergents. The inventors have unexpectedly discovered that the opposite effect is observed in hydrogen-fueled internal combustion engines.

[0538] Example 3

[0539] Lubricating oil compositions (3 comparative and 2 of the present invention) were prepared according to Table 3 below, differing only in the inclusion of the perbasic metal detergent in the composition. Specifically, the soap type (sulfonate, phenolate) of the perbasic metal detergent was varied, while all other components remained constant across the five oils. All five lubricating oils had equivalent compositions, differing only in the amount and type of perbasic detergent added. Comparative oil 1 and oil 1 of the present invention were formulated to provide equal amounts of calcium to the lubricating oil, differing only in the soap type (sulfonate vs. phenolate). Comparative oil 2 and oil 2 of the present invention each contained 5% by weight of perbasic detergent, differing only in the soap type (sulfonate vs. phenolate). Comparative oil 3 was equivalent to comparative oils 1 and 2, except that no perbasic detergent was present.

[0540] Pre-ignition tests were conducted on all five oils under the following conditions: 1550 rpm, 14 bar BMEP, 1.70 air-fuel ratio (AFR), and an intake air temperature of 75°C. Data collected during the test period were analyzed using the aforementioned data analysis procedure to determine the frequency of pre-ignition. Data for the three comparative lubricants and the two lubricants of this invention are reported in Table 3 below.

[0541] Based on the pre-ignition test data in Table 3, it was surprisingly and unexpectedly found that, compared with comparable lubricants that included or did not contain superalkaline calcium sulfonate detergents, superalkaline calcium phenol detergents provided a significant reduction in abnormal combustion events such as pre-ignition.

[0542] Table 3

[0543] All documents described herein are incorporated herein by reference to the extent that they do not contradict this document, including any priority documents and / or test procedures. It will be apparent from the foregoing general description and specific embodiments that various modifications may be made without departing from the spirit and scope of the invention, although the forms of the invention have been illustrated and described. Accordingly, it is not intended to limit the invention. The term “comprising” is considered synonymous with the term “including.” The term “comprising” or any cognate word specifies the presence of the stated feature, step, or integer or component, but does not exclude the presence or addition of one or more other features, steps, integers, components, or groups thereof. Similarly, whenever a composition, element, or group of elements is preceded by the conjunction “comprising,” it is to be understood that we also contemplate the same composition or group of elements preceded by the conjunctions “substantially composed of,” “composed of,” “selected from,” or “is,” and vice versa, where “substantially composed of” allows the inclusion of substances that do not materially affect the characteristics of the composition for its applicability.

Claims

1. A method for reducing abnormal combustion events during the operation of a hydrogen-fired internal combustion engine (HICE), comprising: a) Providing the hydrogen-fired internal combustion engine with a lubricating oil composition comprising or a mixture of the following components: i) A base oil having a viscosity KV100 of less than or equal to 12 cSt and an amount of more than 50% by weight of the composition, and comprising Group I base oil, Group II base oil, Group III base oil, Group IV base oil or a combination thereof. ii) An overly alkaline metal-containing detergent comprising an overly alkaline metal salicylate detergent, an overly alkaline metal phenolate detergent, or a combination thereof, having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500 and being contained at a treatment level providing the composition with a total metal content between 100 and 5000 ppm by weight and a total soap content between 0.15% by weight and 8.0% by weight; and iii) The lubricating oil composition has a total sulfate ash content of less than or equal to 2.0% by weight, a total phosphorus level of less than or equal to 0.120% by weight, and an SAE viscosity grade of 25W-X, 20W-X, 15W-X, 10W-X, 5W-X, or 0W-X, wherein X represents any one of 8, 12, 16, 20, 30, 40, 50, or 60; b) To supply hydrogen-containing fuel to the hydrogen-fired internal combustion engine; and c) Combust the fuel in the hydrogen-fired internal combustion engine.

2. The method according to claim 1, further comprising: d) Measure the number of abnormal pre-ignition events during combustion (1000 rpm, 12 bar BMEP and 1.85 air-fuel ratio (AFR)) and the number of pre-ignition events per 1,000 engine cycles is less than or equal to 10.

3. The method according to claims 1-2, further comprising: d) Measure the number of abnormal pre-ignition events during combustion (1200 rpm, 18 bar BMEP and 2.05 air-fuel ratio (AFR)) and the number of pre-ignition events per 1,000 engine cycles is less than or equal to 5.

4. The method according to claims 1-3, wherein the frequency of abnormal pre-ignition events during combustion in a hydrogen-fired internal combustion engine (HICE) operating at 100% load is reduced by at least 20% compared to comparable lubricating oil compositions that do not include the overly alkaline metal-containing detergent.

5. The method according to claims 1-4, wherein the metal in the peralkaline metal salicylate detergent, the peralkaline metal phenolate detergent, or a combination thereof is selected from calcium, magnesium, sodium, potassium, and lithium.

6. The method according to claims 1-5, wherein the over-alkaline metal-containing detergent is an over-alkaline calcium salicylate detergent, an over-alkaline calcium phenolate detergent, or a combination thereof.

7. The method according to claims 1-6, wherein the base oil comprises a Group I base oil, a Group II base oil, or a combination thereof and is contained in greater than 80% by weight of the composition.

8. The method according to claims 1-7, wherein the lubricating oil composition further comprises a dispersant, a dispersant viscosity improver, or a combination thereof.

9. The method of claim 8, wherein the dispersant or dispersant viscosity improver comprises an amide, an imide, and / or an ester-functionalized, partially or fully saturated C-containing... 4-5 Polymers of olefins having: i) a Mw / Mn ratio of less than 2, ii) a functionality distribution (Fd) value of 3.5 or less, and iii) Mn of the unfunctionalized polymer of 10,000 g / mol or greater.

10. The method of claim 8, wherein the dispersant comprises one or more optionally boronized higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersants (Mn 1600 g / mol or greater), one or more optionally boronized lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersants (Mn less than 1600 g / mol), or a combination thereof, and wherein the treatment level of the dispersant is 1.0 to 15.0 by weight of the lubricating oil composition.

11. The method according to claims 1-10, wherein the lubricating oil composition further comprises a corrosion inhibitor selected from substituted thiadiazoles, substituted benzotriazoles, substituted triazoles, trisubstituted borate esters, ethoxylated lauryl alcohol, nonylphenol ethoxylates, C6 to C6... 20 Ethoxylated straight-chain alcohols or combinations thereof, and contained at a treatment level of 0.001% to 5.0% by weight of the lubricating oil composition.

12. The method according to claims 1-11, wherein the lubricating oil composition further comprises one or more zinc dialkyl dithiophosphate (ZDDP) compounds; and wherein the treatment level of the one or more ZDDP compounds is from about 0.4% by weight to about 1.5% by weight of the lubricating oil composition.

13. The method according to claims 1-12, wherein the lubricating oil composition further comprises one or more of the following components: one or more functional polymers, one or more friction modifiers; one or more antioxidants; one or more pour point depressants; one or more defoamers; one or more viscosity modifiers; one or more other dispersants; one or more other alkaline metal-containing detergents, one or more corrosion inhibitors, one or more rust inhibitors; one or more sealing swelling agents; and / or one or more anti-wear agents.

14. The method according to claims 1-13, wherein the fuel supplied to the engine comprises at least 50% by mass hydrogen based on fuel mass.

15. The method according to claims 1-14, wherein the hydrogen-fired internal combustion engine (HICE) operates at a BMEP of 12 to 18 bar and an air-fuel ratio (AFR) of 1:1 to 3:

1.

16. The method according to claims 1-15, wherein the lubricating oil composition is used as a passenger vehicle lubricant (PVL), a commercial vehicle lubricant (CVL), or a marine engine lubricant.

17. A lubricating oil composition for hydrogen-fired internal combustion engines (HICE), comprising or obtained by mixing the following components: i) A base oil having a KV100 of less than or equal to 12 cSt and an amount of more than 50% by weight of the composition, and comprising Group I base oil, Group II base oil, Group III base oil, Group IV base oil or a combination thereof. ii) An overly alkaline metal-containing detergent comprising an overly alkaline metal salicylate detergent, an overly alkaline metal phenolate detergent, or a combination thereof, having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500 and being contained at a treatment level providing the composition with a total metal content between 100 and 5000 ppm by weight and a total soap content between 0.15% by weight and 8.0% by weight; and The lubricating oil composition has a total sulfate ash content of less than or equal to 2.0% by weight, a total phosphorus level of less than or equal to 0.120% by weight, and an SAE viscosity grade of 25W-X, 20W-X, 15W-X, 10W-X, 5W-X, or 0W-X, wherein X represents any one of 8, 12, 16, 20, 30, 40, 50, or 60.

18. The composition of claim 17, wherein the composition reduces the number of abnormal pre-ignition events during combustion in a hydrogen-fired internal combustion engine (HICE) measured at 1000 rpm, 12 bar BMEP and 1.85 air-fuel ratio (AFR) to less than or equal to 10 events per 1,000 engine cycles.

19. The composition according to claims 17-18, wherein the composition reduces the number of abnormal pre-ignition events in a hydrogen-fired internal combustion engine (HICE) during combustion, measured at 1200 rpm, 18 bar BMEP and 2.05 air-fuel ratio (AFR), to less than or equal to 5 events per 1,000 engine cycles.

20. The composition according to claims 17-19, wherein, compared with comparable lubricating oil compositions excluding the overly alkaline metal-containing detergent, the composition reduces the number of abnormal pre-ignition events during combustion in a hydrogen-fired internal combustion engine (HICE) operating at 100% load by at least 20%.

21. The composition according to claims 17-20, wherein the metal of the perbasic metal salicylate detergent, the perbasic metal phenolate detergent, or a combination thereof is selected from calcium, magnesium, sodium, potassium, and lithium.

22. The composition according to claims 17-21, wherein the over-alkaline metal-containing detergent is an over-alkaline calcium salicylate detergent, an over-alkaline calcium phenolate detergent, or a combination thereof.

23. The composition according to claims 17-22, wherein the base oil comprises a Group I base oil, a Group II base oil, or a combination thereof and is contained in greater than 80% by weight of the composition.

24. The composition according to claims 17-23, wherein the lubricating oil composition further comprises a dispersant, a dispersant viscosity improver, or a combination thereof.

25. The composition of claim 24, wherein the dispersant or dispersant viscosity improver comprises an amide, an imide, and / or an ester-functionalized, partially or fully saturated C-containing... 4-5 Polymers of olefins having: i) a Mw / Mn ratio of less than 2, ii) a functionality distribution (Fd) value of 3.5 or less, and iii) a prefunctionalized polymer Mn of 10,000 g / mol or greater.

26. The composition of claim 24, wherein the dispersant comprises one or more optionally boronized higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersants (Mn 1600 g / mol or greater), one or more optionally boronized lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersants (Mn less than 1600 g / mol), or a combination thereof, and wherein the treatment level of the dispersant is 1.0 to 15.0 by weight of the lubricating oil composition.

27. The composition according to claims 17-26, wherein the lubricating oil composition further comprises a corrosion inhibitor selected from substituted thiadiazoles, substituted benzotriazoles, substituted triazoles, trisubstituted borate esters, ethoxylated lauryl alcohol, nonylphenol ethoxylates, C6 to C6... 20 Ethoxylated straight-chain alcohols or combinations thereof, and contained at a treatment level of 0.001% to 5.0% by weight of the lubricating oil composition.

28. The composition according to claims 17-27, wherein the lubricating oil composition further comprises one or more zinc dialkyl dithiophosphate (ZDDP) compounds; and wherein the treatment level of the one or more ZDDP compounds is from about 0.4% by weight to about 1.5% by weight of the lubricating oil composition.

29. The composition according to claims 17-28, wherein the lubricating oil composition further comprises one or more of the following components: one or more functional polymers; one or more friction modifiers; one or more antioxidants; one or more pour point depressants; one or more defoamers; one or more viscosity modifiers; one or more dispersants; one or more other superalkaline metal detergents; one or more corrosion inhibitors; one or more rust inhibitors; one or more sealing swelling agents; and / or one or more anti-wear agents.

30. A concentrate comprising or a mixture of the following components: One or more base oils, ranging from 1% by weight to less than or equal to 95% by weight, having a KV100 of less than or equal to 12 cSt and comprising Group I base oils, Group II base oils, Group III base oils, Group IV base oils, or combinations thereof; and Based on the weight of the concentrate, 5 to 99% by weight of a super-alkaline metal-containing detergent comprising a super-alkaline metal salicylate detergent, a super-alkaline metal phenolate detergent, or a combination thereof, having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500.

31. The concentrate of claim 30, further comprising combining the concentrate with a base oil to form a lubricating oil composition, the lubricating oil composition comprising: i) A base oil having a KV100 of less than or equal to 12 cSt and comprising more than 50% by weight of the composition, comprising Group I base oil, Group II base oil, Group III base oil, Group IV base oil or a combination thereof. ii) An overly alkaline metal-containing detergent comprising an overly alkaline metal salicylate detergent, an overly alkaline metal phenolate detergent, or a combination thereof, having a total base number (KOH / g) greater than or equal to 9 and less than or equal to 500 and being contained at a treatment level providing the composition with a total metal content between 100 and 5000 ppm by weight and a total soap content between 0.15% by weight and 8.0% by weight; and The lubricating oil composition described herein has a total sulfate ash content of less than or equal to 2.0% by weight, a total phosphorus level of less than or equal to 0.120% by weight, and an SAE viscosity grade of 25W-X, 20W-X, 15W-X, 10W-X, 5W-X, or 0W-X, wherein X represents any one of 8, 12, 16, 20, 30, 40, 50, or 60; and The composition described herein reduces the number of abnormal pre-ignition events during combustion in a hydrogen-fired internal combustion engine (HICE) measured at 1000 rpm, 12 bar BMEP, and 1.85 air-fuel ratio (AFR) to less than or equal to 10 events per 1,000 engine cycles; and The composition described therein reduces the number of abnormal pre-ignition events during combustion in a hydrogen-fired internal combustion engine (HICE) measured at 1200 rpm, 18 bar BMEP and 2.05 air-fuel ratio (AFR) to less than or equal to 5 events per 1,000 engine cycles.

32. The concentrate of claim 31, wherein, compared with a comparable lubricating oil composition excluding the overly alkaline metal-containing detergent, the composition reduces the number of abnormal pre-ignition events during combustion in a hydrogen-fired internal combustion engine (HICE) operating at 100% load by at least 20%.

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